US011542365B2

( 12 ) Amstutz
Unitedet States Patent ( 10 ) Patent No.: US 11,542,365 B2
al . (45 ) Date of Patent : * Jan . 3 , 2023
( 54 ) CURATIVE ( 58 ) Field of Classification Search
None
( 71 ) Applicant: Natural Fiber Welding, Inc. , Peoria , See application file for complete search history.
IL (US )
(56) References Cited
( 72 ) Inventors: Aaron Kenneth Amstutz , Peoria, IL U.S. PATENT DOCUMENTS
(US ) ; Luke Michael Haverhals , Peoria ,
IL (US ); Isaiah Amstutz , Canton, IL 3,873,602 A 3/1975 Katzakian et al .
(US ) ; Skylar Clement , East Peoria, IL 4,769,416 A * 9/1988 Gelling CO8L 19/003
( US ) ; Shang -Min Li , Peoria , IL ( US ) 525/194
( Continued )
( 73 ) Assignee : Natural Fiber Welding, Inc. , Peoria ,
IL (US ) FOREIGN PATENT DOCUMENTS
( * ) Notice: Subject to any disclaimer, the term of this CN 101476166 A 7/2009
patent is extended or adjusted under 35 EP 0788524 A1 8/1997
U.S.C. 154 ( b ) by 0 days. (Continued )
This patent is subject to a terminal dis OTHER PUBLICATIONS
claimer.
( 21 ) Appl. No .: 17/665,224 Altuna - self - healed polymer networks cross -linked epoxidized soy
bean oil— Green Chem . —2013 ( Year: 2013 ) . *
(22 ) Filed : Feb. 4 , 2022 ( Continued )
( 65 ) Prior Publication Data Primary Examiner John Vincent Lawler
(74 ) Attorney, Agent, or Firm — Hamilton IP Law , PC ;
US 2022/0282031 A1 Sep. 8 , 2022 Jay R. Hamilton ; Charles A. Damschen
( 57 ) ABSTRACT
Related U.S. Application Data A curative for epoxidized plant -based oils and epoxidized
( 63 ) Continuation of application No. 17/ 665,185 , filed on natural rubber is created from the reaction between a natu
Feb. 4 , 2022 , now Pat. No. 11,396,578 , which is a rally occurring polyfunctional acid and an epoxidized plant
(Continued ) based oil is disclosed . The curative may be used to produce
at least one of six different materials, wherein each type of
(51 ) Int. Cl. material may be configured as a thermosetting elastomer that
CO8G 63/42 ( 2006.01 ) is crosslinked with B -hydroxyester linkages. The materials
B32B 5/02 ( 2006.01 ) may be configured as a leather -like material, a foam mate
(Continued ) rial, a molded elastomer, a coating, an adhesive, and / or a
(52) U.S. Ci .
rigid or semi- rigid material. Illustrative articles made from
??? any combination of the six materials may be recycled using
C08G 63/42 (2013.01 ) ; B32B 5/022 a mechano - chemical process to de - crosslink the thermoset
(2013.01 ) ; B32B 5/024 (2013.01 ) ; B32B 9/06 ting elastomer.
(2013.01 );
(Continued ) 21 Claims , 32 Drawing Sheets

405

402 -4045

4016
 US 11,542,365 B2
Page 2

Related U.S. Application Data 9,567,311 B2 2/2017 Pajerski

9,765,182 B2 9/2017 Liu
continuation - in - part of application No. 17 / 155,000 , 9,926,426 B2 3/2018 Rust
filed on Jan. 21 , 2021 , and aa continuation - in - part of 10,400,061 B1 9/2019 Amstutz et al .
application No. 17/ 141,900 , filed on Jan. 5 , 2021 , said 10,882,950 B2 1/2021 Amstutz et al .
2002/0092809 A1 7/2002 Ries et al .
application No. 17/ 155,000 is a continuation - in -part 2004/0192859 A1 * 9/2004 Parker CO8L 63/00
of application No. 17/ 129,183 , filed on Dec. 21 , 2020 , 525/438
now Pat . No. 11,407,856 , said application No. 2008/0155857 A1 * 7/2008 Rosen A43B 7/144
17/ 141,900 is a continuation of application No. 2010/0029523 A1 2/2010 Benecke et al .
36/114
16/ 918,646 , filed on Jul. 1 , 2020 , now Pat . No. 2011/0120635 A1 * 5/2011 Jokisch B32B 27/32
10,882,951, said application No. 17 / 129,183 is a 156/500
continuation of application No. 16 /457,352 , filed on
2
2011/0319524 A1 * 12/2011 Leibler CO8L 63/00
Jun . 28 , 2019 , now Pat . No. 10,882,950 , said appli 523/400
cation No. 16 / 918,646 is a continuation - in -part of 2013/0299747 Al 11/2013 Dershem
application No. 16 / 457,352 , filed on Apr. 18 , 2019 , 2014/0228480
2015/0038605
A1
A1
8/2014 Shiraishi et al .
2/2015 Baghdadi
now Pat. No. 10,882,950 , which is a continuation of 2015/0087732 A1 * 3/2015 Liu CO8G 63/42
application No. 16 / 388,693 , filed on Apr. 18 , 2019 , 521/64
now Pat. No. 10,400,061 . 2016/0060386 A1 3/2016 Medoff et al.
2019/0322799 Al 10/2019 Amstutz et al .
( 60 ) Provisional application No. 63 / 297,569 , filed on Jan. 2019/0365028 A1 12/2019 Fakhouri et al .
7,2022 , provisional application No. 63 / 274,443 , filed 2020/0332057 Al 10/2020 Amstutz et al .
on Nov. 1 , 2021, provisional application No. 2021/0108029
2021/0
A1
A1
4/2021
4/2021
Amstutz
Amstutz
et al .
et al .
63 / 145,939 , filed on Feb. 4 , 2021 , provisional 2022/0185954 Al 6/2022 Amstutz et al .
application No. 63 /084,508 , filed on Sep. 28 , 2020 ,
provisional application No. 62 / 989,275 , filed on Mar. FOREIGN PATENT DOCUMENTS
13 , 2020 , provisional application No. 62 / 963,325,
filed on Jan. 20 , 2020 , provisional application No. EP 3157975 A1 4/2017
62/ 869,393 , filed on Jul. 1 , 2019 , provisional EP
EP
2576193
3194466
B1
A1
6/2017
7/2017
application No. 62 / 806,480 , filed on Feb. 15 , 2019 , JP HO2240178 A 9/1990
provisional application No. 62/ 772,744 , filed on Nov. JP H05112765 A 5/1993
29 , 2018 , provisional application No. 62 /772,715 , JP 2001026744 A 1/2001
filed on Nov. 29 , 2018 , provisional application No. WO 2018217996 A1 11/2018
62 / 756,062 , filed on Nov. 5 , 2018, provisional
application No. 62 / 669,483 , filed on May 10 , 2018 , OTHER PUBLICATIONS
provisional application No. 62 / 669,502 , filed on May
10 , 2018 , provisional application No. 62 / 660,943 , Sahoo - bio -based epoxy network — shoe soles Poly.Adv.Tech.
filed on Apr. 21 , 2018 . Mar. 2018 (Year : 2018 ).*
International Searching Authority, International Search Report and
( 51 ) Int . Ci . Written Opinion , NFW- P1014 - ICI - PCT, dated Jun . 16 , 2022 .
B32B 9/06 ( 2006.01 ) Riding Arena Footing Material Selection and Management, Horse
CO8G 63/81 ( 2006.01 ) Facilities , Penn State College of Agricultural Sciences and Coop
B32B 25/10 ( 2006.01 ) erative Extension, p . 1-12 .
B32B 25/12 ( 2006.01)
Altuna et al , Self -healable polymer networks based on the cross
linking of epoxidised soybean oil by an aqueous citric acid solution ,
C08J 3/24 ( 2006.01 ) Green Chemistry, 2013 , 15 , 3360-3366 .
C08C 19/06 ( 2006.01 ) Amstutz et al . , Mechanically Reversible Crosslinked Elastomer.
(52) U.S. CI. Cao , et al , A Ball -Milling -Enabled Reformatsky Reaction ,
CPC B32B 25/10 (2013.01 ) ; B32B 25/12 ChemSusChem Communications, 2019 , 12 , 2554-2557 .
(2013.01 ) ; C08C 19/06 (2013.01 ) ; C08 63/81 Capelot et al . , Catalytic Control of the Vitrimer Glass Transition,
(2013.01 ) ; C08J 3/24 (2013.01 ) ; B32B ACS Macro Letters, 2012 , 1 , 789-792 .
2305/72 ( 2013.01 ) ; B32B 2307/50 ( 2013.01 ) ; Capelot et al , Metal- Catalyzed Transesterification for Healing and
Assembling of Thermosets, Journal of the American Chemical
B32B 2319/00 (2013.01 ) ; C08J 2315/00 Society , 2012 , 134 , 7664-7667 .
( 2013.01 ) Ciezak - Jenkins et al , Mechanochemical Induced Structural Changes
in Sucrose Using the Rotational Diamond Anvil Cell , Journal of
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Mechanochemical Crosslinking , Polymer Chemistry, 2013 , 00 , 1-3 .
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9,179,660 B2 11/2015 Peterson et al . Vitrimer Preparation, Macromolecular Rapid Communication, 2019 ,
9,556,368 B2 1/2017 Li et al . 1800889 , 1-6 .
 US 11,542,365 B2
Page 3

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Lu et al , Dual Cross -Linked Self -Healing and Recyclable Epoxidized
Natural Rubber Based on Multiple Reversible Effects, Sustainable
Chemistry & Engineering , 2019 , 7 , 4443-4455 .
Min Qi et al . Epoxidized soybean oil cured with tannic acid for fully
bio -based epoxy resin . RSC Advances, vol . 8 , 2018 , pp . 26948
2958 , doi.org/10.1039/C8RA03874K .
Montarnal et al , Silica- Like Malleable Materials from Permanent
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Officer E. Klochkova, ISR & Opinion for PCT /US2019 /028184,
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Qiuyu Tang et al. Bio -based epoxy resin from epoxidized soybean
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Ramirez et al , Microstructure of Copolymers Formed by the Reagent
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Tang et al, Malleable, Mechanically Strong, and Adaptive Elasto
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Tanjung Faisal Amri et al . Use of epoxidized natural rubber as a
toughening agent in plastics . Journal of applied polymer science ,
vol . 132 , 2015 , pp . 1-9 , doi.org/10.1002/app.42270.
* cited by examiner
U.S. Patent Jan. 3 , 2023 Sheet 1 of 32 US 11,542,365 B2

excess

**

OH
OH

HO .

Q 10

HO

H-0

FIG . 1
U.S. Patent Jan. 3. 2023 Sheet 2 of 32 US 11,542,365 B2

100
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BA
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104

FIG
.
2A
B
KARATE
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.
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3
.
FIG
U.S. Patent Jan. 3. 2023 Sheet 4 of 32 US 11,542,365 B2

FIG . 4A
U.S. Patent Jan. 3. 2023 Sheet 5 of 32 US 11,542,365 B2

FIG . 4B
U.S. Patent Jan. 3. 2023 Sheet 6 of 32 US 11,542,365 B2

FIG . 4C
U.S. Patent Jan. 3 , 2023 Sheet 7 of 32 US 11,542,365 B2

3
8
9
07

22
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NA
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.
FIG

Now

Q A $

y
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U.S. Patent Jan. 3. 2023 Sheet 8 of 32 US 11,542,365 B2

6
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FIG
U.S. Patent Jan. 3 , 2023 Sheet 9 of 32 US 11,542,365 B2

w 49

wwwwww

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FIG . 7
U.S. Patent Jan. 3 , 2023 Sheet 10 of 32 US 11,542,365 B2

FIG . 8A

FIG . 8B
U.S. Patent Jan. 3 , 2023 Sheet 11 of 32 US 11,542,365 B2

Elongation
)
%
(
9
.
FIG

FRNEoPTeparumtnxfbsildfezaocnrvs
r-fcb*epiolse*rntwpakniedv*
U.S. Patent Jan. 3 , 2023 Sheet 12 of 32 US 11,542,365 B2

10A
.
FIG Albafsdiontydsnehridaplg FIG.10B

Rluabyer Rluabyer
U.S. Patent Jan. 3 , 2023 Sheet 13 of 32 US 11,542,365 B2

bofremailndter

FIG
11
.
rg&etiodngvieosn
U.S. Patent Jan. 3 , 2023 Sheet 14 of 32 US 11,542,365 B2

SRiehlcaeosnt TPeaxtpuer RSPhruebftordm Non-wmatoven WReionfvrcmet PRShruebftordm TPeaxtpuer RSiehlcaeosnt

FIG
12
.

Rimpersgniato
U.S. Patent Jan. 3 , 2023 Sheet 15 of 32 US 11,542,365 B2

wcanrtSeihatcehts mcoutlreahivres ntoextweonrdk

?????
??

sTcanrihetaesct tomowtliehcuelhrs
nextweonrdk
and

Aditonal ESOad ed ctourative 1stmadein step

U.S. Patent Jan. 3. 2023 Sheet 16 of 32 US 11,542,365 B2

"
R

HOR
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rtooeitgurnal
R

mc-eh iacnol
******

Lola

reR
"action

R
U.S. Patent Jan. 3 , 2023 Sheet 17 of 32 US 11,542,365 B2

-M1aumdint5exdroi0narlg mf1asut5eilcr7zaeyld

15e-mnendofaet rianlg
m150-inatleiraeldy
nastic on
cm-siFIG15hecomahwigcenaolsg
rtofbs15a-helarsomticsnektg -m1uadnti5exdridoanrlg rofceovslrinkalg
U.S. Patent Jan. 3 , 2023 Sheet 18 of 32 US 11,542,365 B2

2
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U.S. Patent Jan. 3 , 2023 Sheet 19 of 32 US 11,542,365 B2

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U.S. Patent Jan. 3 , 2023 Sheet 20 of 32 US 11,542,365 B2

Vos 18
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U.S. Patent Jan. 3 , 2023 Sheet 21 of 32 US 11,542,365 B2

C
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203 FIG.20A
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3 M

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U.S. Patent Jan. 3. 2023 Sheet 25 of 32 US 11,542,365 B2

FIG
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U.S. Patent Jan. 3. 2023 Sheet 26 of 32 US 11,542,365 B2

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U.S. Patent Jan. 3 , 2023 Sheet 27 of 32 US 11,542,365 B2

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U.S. Patent Jan. 3 , 2023 Sheet 28 of 32 US 11,542,365 B2

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U.S. Patent Jan. 3 , 2023 Sheet 29 of 32 US 11,542,365 B2

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FIG.24D
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U.S. Patent Jan. 3 , 2023 Sheet 30 of 32 US 11,542,365 B2

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U.S. Patent Jan. 3 , 2023 Sheet 31 of 32 US 11,542,365 B2

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U.S. Patent Jan. 3 , 2023 Sheet 32 of 32 US 11,542,365 B2

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 US 11,542,365 B2
1 2
CURATIVE STATEMENT REGARDING FEDERALLY
SPONSORED RESEARCH OR DEVELOPMENT
CROSS REFERENCE TO RELATED
APPLICATIONS No federal funds were used to develop or create the
5 invention disclosed and described in the patent application .
The present non - provisional utility patent application is a
continuation of and claims priority from U.S. patent appli BACKGROUND
cation Ser. No. 17 / 665,185 filed on Feb. 4 , 2022 , ( now U.S.
Pat . No. 11,396,578 ) which application is a continuation Various manufacturing methods are utilized for footwear
in -part of and claims priority from U.S. patent application 10 construction depending on the complexity of the final
Ser. No. 17/ 141,900 filed on Jan. 5 , 2021 , which application design . The simplest designs may utilize only one or two
was a continuation of and claimed priority from U.S. patent discrete types of materials as seen in flip -flops, slides ,
application Ser. No. 16 / 918,646 filed on Jul. 1 , 2020 (now sandals, and CrocsTM . In these types of footwear one mate
rial can serve for the entire footbed and either the same or
U.S. Pat . No. 10,882,951 ) , which application was a continu 15 a different material may be used for the top straps. At the
ation -in -part of and claimed priority from U.S. patent appli other extreme, some performance running shoes or hiking
cation Ser. No. 16 /457,352 filed on Jun . 28 , 2019 (now U.S. boots may use 10-20 different types of materials for their
Pat . No. 10,882,950) , which application is a continuation of specialized attributes.
and claims priority to U.S. patent application Ser. No. It is desirable to be able to create footwear that is entirely
16 /388,693 filed on Apr. 18 , 2019 ( now U.S. Pat . No. 20 recyclable without requiring deconstruction of the shoe .
10,400,061 ) , which application claimed priority from pro- This may be relatively easy to achieve in simple designs that
visional U.S. App. Nos . 62 / 660,943 filed on Apr. 21 , 2018 ;
2 may be molded of one particular thermoplastic (whether
62 / 669,483 filed on May 10 , 2018 ; 62/ 669,502 filed on Ma foamed , solid , or both ). In more complex footwear that
10 , 2018 ; 62 /756,062 filed on Nov. 5 , 2018 ; 62 /772,744 filed contain an upper of one type of material and aa midsole foam
on Nov. 29 , 2018 ; U.S. Pat . No. 62,772,715 filed on Nov. 29 , 25 of another type of material and an outsole rubber of another
2018 ; and 62/ 806,480 filed on Feb. 15 , 2019. The U.S. type of material the recycling of such a shoe requires
patent application Ser. No. 16/ 918,646 filed on Jul . 1 , 2020 deconstruction . U.S. Ser. No. 11 / 026,477 discloses a shoe
( now U.S. Pat. No. 10,882,951 ) also claimed priority from that is comprised of bio - based and / or recycled materials and
provisional U.S. App . Nos . 62 / 989,275 filed on Mar. 13 , 30 seeks to minimize the number of discrete material types; but
2020 and 62/ 869,393 filed on Jul. 1 , 2019. The U.S. patent such shoe still ultimately requires deconstruction at the
end -of - life in order to be fully recycled.
application Ser. No. 17 / 665,185 filed on Feb. 4 , 2022 is also
a continuation - in -part of and claims priority from U.S. BRIEF DESCRIPTION OF THE DRAWINGS
patent application Ser. No. 17 / 155,000 filed on Jan. 21 ,
2021 , which application was a continuation - in -part of and 35 The accompanying drawings , which are incorporated in
claimed priority from U.S. patent application Ser. No. and constitute a part of this specification, illustrate embodi
17 / 129,183 filed on Dec. 21 , 2020 , (now U.S. Pat . No. ments and together with the description , serve to explain the
11,396,578 ) which application is a continuation of and principles of the methods and systems .
claims priority from U.S. application Ser. No. 16/ 457,352 FIG . 1 is a chemical reaction formula and schematic for
filed on Jun . 28 , 2019 (now U.S. Pat. No. 10,882,950 ) , 40 at least one illustrative embodiment of the curative disclosed
which application claimed priority from and is a continua-
a herein .
tion of U.S. application Ser. No. 16 /388,693 filed on Apr. 18 , FIG . 2A is an illustration of an epoxidized natural rubber
2019 now U.S. Pat. No. 10,400,061 , which application based material produced using a relatively lower viscosity
claimed priority from provisional U.S. App . Nos . 62/660 , resin that was allowed to penetrate throughout the flannel
943 filed on Apr. 21 , 2018 ; 62/ 669,483 filed on May 10 , 45 substrate resulting in a suede or brushed - looking surface.
2018 ; 62 / 669,502 filed on May 10 , 2018 ; 62 /756,062 filed FIG . 2B is an illustration of an epoxidized natural rubber
on Nov. 5 , 2018 ; 62 /772,744 filed on Nov. 29 , 2018 ; U.S. based material produced using a relatively higher viscosity
Pat . No. 62,772,715 filed on Nov. 29 , 2018 ; and 62 / 806,480 resin that was allowed to only penetrate partly through the
filed on Feb. 15 , 2019. The U.S. patent application Ser. No. flannel substrate resulting in a glossy polished - looking sur
17 / 155,000 filed on Jan. 21 , 2021 also claimed priority from 50 face.
provisional U.S. App . Nos . 63 /084,508 filed on Sep. 28 , FIG . 3 is an image of an epoxidized natural rubber-based
2020 and 62/ 963,325 filed on Jan. 20 , 2020. The U.S. patent material produced in accordance with the present disclosure .
FIGS . 4A , 4B , and 4C are views of portion of an epoxi
application Ser. No. 17 / 665,185 filed on Feb. 4 , 2022 ( now dized natural
U.S. Pat. No. 11,396,578 ) also claims priority from provi 55 with the present rubber -based material produced in accordance
sional Pat. App . Nos . 63 / 145,939 filed on Feb. 4 , 2021 ; of wallet wherein disclosure that may be used for construction
63 /274,443 filed on Nov. 1 , 2021 ; and 63 / 297,569 filed on rubber -based material each version of the epoxidized natural
Jan. 7 , 2022 , all of which previous applications are incor is made with a different texture .
FIG . 5 is a view of a plurality of pieces of a epoxidized
porated by reference herein in their entireties. natural rubber -based material produced in accordance with
FIELD OF THE INVENTION
60 the present disclosure that may be used for construction of
wallet .
FIG . 6 is a view of the plurality of pieces of the epoxi
The present disclosure related to methods for producing dized natural rubber -based material produced in accordance
natural products that may be made utilizing the curative with the present disclosure assembled as a simple credit card
disclosed herein . The natural products have physical prop- 65 wallet or carrier having the appearance , rigidity and strength
erties similar to synthetic coated fabrics, leather - based prod- as one of ordinary skill would expect with natural animal
ucts , and foam products. hide leather.
 US 11,542,365 B2
3 4
FIG . 7 is a resin impregnated fabric that may be utilized Similarly, when values are expressed as approximations, by
in accordance with the present disclosure . use of the antecedent “ about," it will be understood that the
FIG . 8A is a top view of a ball made according to the particular value forms another embodiment. It will be further
present disclosure. understood that the endpoints of each of the ranges are
FIG . 8B is a side view of a ball made according to the 5 significant both in relation to the other endpoint, and inde
present disclosure. pendently of the other endpoint.
FIG . 9 provides a graphical representation for two stress “ Optional ” or “ optionally " means that the subsequently
strain curves of two different ENR -based materials . described event or circumstance may or may not occur, and
FIG . 10A provides a depiction of an ENR -based material that the description includes instances where said event or
configured with inherent functionality for engaging a belt 10 circumstance occurs and instances where it does not.
buckle . “ Aspect ” when referring to a method, apparatus, and /or
FIG . 10B provides a depiction of the ENR -based material component
from FIG . 10A after engage ent with a belt buckle. thereof does not mean that limitation , function
FIG . 11 provides a depiction of an ENR - based material rather that it is oneetc.partreferred
ality, component
of a
to as an aspect is required, but
particular illustrative disclosure
having grooves and ridges formed therein . 15
and not limiting to the scope of the method , apparatus,
FIG . 12 provides a depiction of an illustrative embodi and
ment of a molding system that may be used for certain ing /claims or component thereof unless so indicated in the follow
.
ENR -based materials .
FIG . 13 shows a chemical representation of a cured 20 tion , the word "the
Throughout description and claims of this specifica
comprise ” and variations of the word , such
thermoset material.
FIG . 14 shows a chemical representation of mechano- as " comprising ” and “ comprises,” means “ including but not
chemical reversibility. limited to ,” and is not intended to exclude , for example,
FIGS . 15a - f provide a series of images during the other components, integers or steps. “ Exemplary ” means “ an
mechano - chemical processing of thermoset material. example of ” and is not intended to convey an indication of
FIG . 16 shows a series of rheometer data from
that is repeatedly mechano -chemically processed .
material 25 a preferred or ideal embodiment. “ Such as ” is not used in a
restrictive sense , but for explanatory purposes.
FIG . 17 shows a series of rheometer data for increasing Disclosed are components that can be used to perform the
cure temperatures. disclosed methods and apparatuses.
FIG . 18 shows pancake - like discs of foam product pro- These and other components are disclosed herein , and it
duced
sure .
according to one embodiment of the present disclo- 30 is understood that when combinations, subsets, interactions ,
groups , etc. of these components are disclosed that while
FIG . 19 shows a gradient of porosity associated with specific reference of each various individual and collective
variation in curing temperature. combinations and permutation of these may not be explicitly
FIG . 20 shows a foam slab made according to various disclosed, each is specifically contemplated and described
aspects of the present disclosure . 35
herein , for all methods and apparatuses. This applies to all
FIG . 20A is aa detailed view of a portion of the foam slab aspects of this application including, but not limited to , steps
shown in FIG . 20 .
FIG . 21 shows an illustrative method of making the foam in disclosed methods. Thus, if there are a variety of addi
slab shown in FIGS . 20 & 20A . tional steps that can be performed it is understood that each
FIG . 22 shows material( s) manufactured with compounds 40 of these additional steps can be performed with any specific
according to the present disclosure that has been ground for embodiment or combination of embodiments of the dis
recycling closed methods .
FIGS . 23A - 23D provide schematic representations of four The present methods and apparatuses may be understood
steps for an illustrative method of making one type of article . more readily by reference to the following detailed descrip
FIGS . 24A - 24D provide schematic representations of four 45 tion of preferred aspects and the examples included therein
steps of another illustrative method of making one type of and to the Figures and their previous and following descrip
article . tion . Corresponding terms may be used interchangeably
FIGS . 25A - 25F provide schematic representations of four when referring to generalities of configuration and /or cor
steps of another illustrative method of making one type of 50 responding components, aspects, features, functionality ,
article . methods and / or materials of construction , etc. those terms.
DETAILED DESCRIPTION
It is to be understood that the disclosure is not limited in
its application to the details of construction and the arrange
Before the present methods and apparatuses are disclosed ments of components set forth in the following description
and described , it is to be understood that the methods and 55 or illustrated in the drawings. The present disclosure is
apparatuses are not limited to specific methods, specific capable of other embodiments and of being practiced or of
components , or to particular implementations. It is also to be being carried out in various ways . Also , it is to be understood
understood that the terminology used herein is for the that phraseology and terminology used herein with reference
purpose of describing particular embodiments /aspects only to device or element orientation ( such as , for example, terms
and is not intended to be limiting . 60 like “ front” , “ back ” , “ up ” , “ down ”, “ top ” , “ bottom ” , and the
As used in the specification and the appended claims , the like ) are only used to simplify description, and do not alone
singular forms “ a," " an , ” and “the” include plural referents indicate or imply that the device or element referred to must
unless the context clearly dictates otherwise . Ranges may be have a particular orientation . In addition , terms such as
expressed herein as from “ about ” one particular value , “ first ” , “ second ” , and “ third ” are used herein and in the
and / or to “ about ” another particular value . When such a 65 appended claims for purposes of description and are not
range is expressed , another embodiment includes from the intended to indicate or imply relative importance or signifi
one particular value and / or to the other particular value . cance .
 US 11,542,365 B2
5 6
produce different end products. For example, when the
Element Description Element Number curative is used with epoxy -containing monomeric resins
Natural leather - like material ( suede finish ) 100 (e.g. , EVOs ) it functions to build molecular weight that is
Natural leather - like material ( glossy finish ) 100 ' integral to the backbone of the resultant polymer and there
Fabric
Fabric extension
102
103
5 fore may be referred to as a pre -polymer in such applica
Polymer 104 tions . In another example, when the curative is used in
Expanding foam 200 applications having pre - existing high molecular weight
Floating platen
Lifting platen
210
220
epoxy -containing polymer ( e.g. , as disclosed below herein )
Mold 400 10
the curative is functioning primarily to link those pre
Sole preform 401a existing high molecular weight polymers and therefore may
Sole
Foam injection aperture
401b be referred to simply as a curative in such applications .
Strap
4010
402 Finally, when the curative is used in applications having
Adhesive material 403 both substantial amounts of epoxy -containing monomer and
Foam footbed preform 404a 15 some portion of pre -existing high molecular weight epoxy
Foaming / foamed footbed 404b containing polymer it functions both to build molecular
Metal plate 405
weight and to link pre - existing high molecular weight poly
Foaming compound mold 406
Injection port 406? . mers and therefore may be referred to as a pre -polymer
Injection barrel 407 curative .
Last 408
Preformed upper 409 20 It has been found that the creation of a curative can
eliminate the risk of porosity due to solvent evaporation
during the curing process . Furthermore, the oligomeric
1. Curative (Pre-Polymer) curative may incorporate substantially all of the polyfunc
Disclosed is a curative comprised of an epoxidized tri tional carboxylic acid so that no additional curative is
glyceride (which may bea a plant -based oil such as vegetable 25 required during the curing process . For example, citric acid
and / or nut oil ( s ) and / or a microbial oil such as that produced is not miscible in epoxidized soybean oil ( ESO ) but they
by algae or yeast) , naturally occurring polyfunctional car may be made to react with each other in a suitable solvent.
boxylic acids , and at least some grafted hydroxyl - containing The amount of citric acid may be selected so that the
solvent. Examples of such epoxidized triglycerides com
prised of plant-based oils include epoxidized soybean oil 30 curative is created so that substantially all of the epoxide
groups of the ESO in the curative are reacted with carboxylic
( ESO ) , epoxidized linseed oil (ELO ), epoxidized corn oil , acid groups of the citric acid . With sufficiently excess citric
epoxidized cottonseed oil , epoxidized canola oil ,epoxidized
rapeseed oil , epoxidized grape seed oil, epoxidized poppy acid , the pre - polymerization extent may be limited so that no
seed oil , epoxidized tongue oil, epoxidized sunflower oil, gel fraction is formed . That is , the target species of the
epoxidized safflower oil, epoxidized wheat germ oil, epoxi- 35 capped curative is a -product
low molecular
formedweight
by the(oligomeric ) citric -acid
dized walnut oil , and other epoxidized vegetable oils boxylic ester reaction between car
acid groups on the citric acid with epoxide groups on
( EVOs ). Generally, any polyunsaturated triglyceride with an
iodine number of 100 or greater may be epoxidized and used the ESO . The solvent used for the reaction medium contains
with the curative as disclosed herein without limitation at least some portion of a hydroxyl -containing solvent (i.e. ,
unless otherwise indicated in the following claims . Such 40 an alcohol) that is grafted unto at least some of the polyfunc
epoxidized triglycerides are generally known to be biode- tional carboxylic acid during the creation of the curative .
gradable. Examples of naturally occurring polyfunctional Although specific illustrative embodiments may denote one
acids include citric acid , tartaric acid, succinic acid, malic type of alcohol (e.g. , IPA , ethanol, etc. ), such embodiments
acid, maleic acid, and fumaric acid . Although specific illus- are not meant to be limiting in any way unless otherwise
trative embodiments may denote one type of oil and / or acid , 45 indicated in the following claims .
such embodiments are not meant to be limiting in any way Illustrative oligomeric curatives may be created with
unless otherwise indicated in the following claims . weight ratios of ESO to citric acid in the range of 1.5 : 1
The curative as disclosed herein is a reaction product 0.5 : 1 , which corresponds to a molar ratio of epoxide groups :
between an epoxidized vegetable oil ( s ) and a naturally carboxylic acid groups of approximately 0.43 : 1 ( for a
occurring polyfunctional carboxylic acid conducted in a 50 weight ratio of 1.5 : 1 ) to 0.14 : 1 ( for the weight ratio of 0.5 : 1).
solvent that is capable of solubilizing both the epoxidized In on illustrative embodiment a weight ratio of ESO : citric
vegetable oil ( s ) and a naturally occurring polyfunctional acid is 1 : 1 , which gives a molar ratio of epoxide groups:
carboxylic acid, wherein the solvent contains at least some carboxylic acid groups of 0.29 : 1 . If too much ESO is added
portion of a hydroxyl- containing solvent ( i.e. , an alcohol ) during curative creation , the solution may gel and further
that reacts with at least some portion of the carboxylic acid 55 incorporation of ESO to create the target resin becomes
functional groups that are contained on the polyfunctional impossible. Note that on a weight basis , stoichiometric
carboxylic acid . The curative is an oligomeric structure of equivalent amounts of epoxide groups on the ESO (molecu
carboxylic -acid -capped epoxidized vegetable oil , heretofore lar weight of -1000 g /mol, functionality of 4.5 epoxide
called a pre -polymer curative. The curative is a viscous groups per molecule ) and carboxylic acid groups on the
liquid that is soluble in unmodified epoxidized vegetable oil 60 citric acid (molecular weight 192 g/mol , functionality of 3
and other epoxidized plant - sourced polymers ( e.g. , epoxi- carboxylic groups per molecule) occur at a weight ratio of
dized natural rubber ). 100 parts of ESO to about 30 parts of citric acid . A weight
Generally the terms “ curative , ” “ pre -polymer,” and “ pre- ratio of ESO : citric acid above 1.5 : 1 may build a curative
polymer curative ” are used to denote the same and / or similar with excessive molecular weight (and hence viscosity )
chemical structure as disclosed in this Section 1. However, 65 which limits its ability to be incorporated into unmodified
the function of the curative, pre - polymer, and pre - polymer epoxidized vegetable oil or epoxidized natural rubber . If the
curative may be different in different applications thereof to weight ratio of ESO : citric acid is below 0.5 : 1 it has been
 US 11,542,365 B2
7 8
found that there is so much excess citric acid that after denim ), knitted substrates, and non - woven substrates with
solvent evaporation, ungrafted citric acid may precipitate out limitation unless indicted in the following claims .
out of solution . In other embodiments, the resin may be coated onto a
In addition to controlling the ratio of ESO to citric acid , non - stick surface (e.g. , silicone or PTFE ) or texture paper at
through experimentation it has been found that selective 5 a consistent layer thickness. After the film has been coated
control of the amount of alcohol used as a solvent may also to an even layer, a layer of backing material may be laid on
be used to tailor the physical properties of the resulting top of the liquid resin . The liquid resin may wick into the
elastomer made with the curative . The alcohol solvent itself fabric layer ( i.e. , backing material) creating a permanent
is incorporated into the elastomer by forming ester linkages bond with the fabric during curing. The article may then be
with the polyfunctional carboxylic acid . A mixture of two or 10 placed in an oven to complete the cure of the resin . Tem
more solvents may be used to tailor the amount of grafting peratures for curing may be preferably 60 ° C. - 100 ° C. , or
of a hydroxyl-containing solvent onto the citric acid - capped even more preferably 70 ° C. - 90 ° C. for aa duration of 4 hr - 24
oligomeric curative. A schematic depiction of the chemical hr. Longer cure times are also permissible. Alternatively, the
reaction for making an illustrative embodiment of the cura- liquid resin may be applied onto a non - stick surface ( e.g. ,
tive disclosed herein is shown in FIG . 1 . 15 silicone or PTFE) or texture paper at a consistent layer
For example , and without restriction or limitation , iso- thickness after which fabric may be laid on top of the liquid
propyl alcohol ( IPA ), ethanol, or other suitable alcohol resin and then another non - stick surface may be laid on top
without limitation unless otherwise indicated in the follow- of the resin and fabric. This assembly may be placed in a
ing claims may be used as a component of aa solvent system heated molding press to complete the cure . Cure tempera
used to miscibilize citric acid with ESO . IPA , ethanol, or 20 tures within a press may optionally be higher than in an oven
other suitable alcohol are capable of forming an ester because the molding pressure minimizes the creation of
linkage via a condensation reaction with citric acid . Since bubbles (voids ) in the final article . Cure temperatures within
citric acid has three carboxylic acids , such grafting reduces a press may be between 80 ° C. - 170 ° C. , or even more
the average functionality of the citric acid molecules that are preferably, 100 ° C. - 150 ° C. for aa duration of 5 minutes -60
reacting with the ESO . This is beneficial in creating an 25 minutes, or more preferably between 15 minutes -45 min
oligomeric structure that is more linear and therefore less utes .
highly branched . Acetone may be used as one component of The resin may be optically clear with a slight yellow hue .
a solvent system used to miscibilize citric acid with ESO , Resin that has no pigment added may be used to create
but unlike IPA or ethanol, acetone itself is not capable of oil - cloth like materials that allow for fabrics to be made
being grafted onto the citric acid- capped oligomeric cura- 30 water resistant and wind resistant while still allowing the
tive . Indeed , during creation of the oligomeric curative it has fabric patterns to be visible within the resin . Coated fabrics
been found that the reactivity of the pre - polymer is deter- made according to this embodiment may be cured either in
mined , in part, by the ratio of the alcohol to acetone that may an oven (without press molding ) or may be cured within a
be used to solubilize citric acid with ESO . That is , in reaction heated press . Such coated fabrics may be used for garments,
mixtures with the similar amounts of citric acid and ESO ,a 35 particularly for outerwear, or for waterproof accessories;
curative created from a solution with a relatively high ratio including , but not limited to , purses , handbags, backpacks,
of alcohol to acetone creates a curative with longer, less- duffle bags , luggage , briefcases , hats, and the like .
highly -branched structures than curative created from a Novel embossed items have been created using the resin
solution with a relatively low ratio of alcohol to acetone described in this disclosure in combination with non -woven
under similar reaction conditions . 40 mats comprised of virgin or recycled textile fibers. Specifi
Generally , a curative may be adapted for use with addi- cally, non- woven webs from about 7 mm thick to about 20
tional unmodified epoxidized vegetable oil to yield a mm thick may be impregnated by resins prepared according
castable resin . The improved methodology disclosed by to this disclosure . After impregnation , the non -woven webs
Applicant herein results in substantially porosity - free elas- may be pressed in a heated hydraulic press to a nominal
tomeric products. 45 pressure of between 10 psi - 250 psi , or even more preferably
2. Coated Materials
A. Summary
between 25 psi - 100 psi . The non -woven web with resin may
be pressed between silicone release liners , one of which may
The curative as disclosed immediately above may func- have an embossing pattern therein . The embossing pattern
tion as a pre -polymer and may be mixed with additional may have relief characteristics of a depth between 1 mm - 6
epoxidized vegetable oil to be used as a resin which may be 50 mm , or more preferably between 2 mm and 4 mm in depth .
applied to various backing materials /backing layers to yield When resin prepared according to this disclosure is further
a leather - like material with excellent tear strength, flexibil- pigmented with a structural color pigment, e.g. , mica pig
ity, dimensional stability, and fabrication integrity. Through- ments of various shades — many of which have pearlescent
out this disclosure , the terms “ backing material” and “ back- qualities and such resin is molded into a non -woven web
ing layer ” may be used interchangeably depending the 55 with an embossing pattern , it has been found to create
specific context. However, for certain articles disclosed aesthetically pleasing patterned articles. The structural color
herein a backing material may be comprised of a resin- has been found to preferentially align at embossing features
impregnated backing layer. According to one illustrative to create sharp contrasts and visual depth corresponding to
embodiment of aa coated material utilizing the pre - polymer, the embossed pattern . Alternatively, and without restriction
one illustrative fabric backing material/backing layer may be 60 unless so indicated in the following claims , mineral pig
a woven cotton flannel (as depicted in FIGS . 2A & 2B and ments from other source rocks and processes may be
described in more detail below ) . If the resin is formulated to included in the casting resin to impart color to articles made
be relatively low in viscosity, exposed flannel may persist according to the present disclosure .
above the resin -coated fabric core . This imparts a warm Resin coated fabrics made also be created according to
texture to the surface of the article. Other fabric backing 65 one embodiment of the present disclosure using roll - to -roll
material /backing layer may include woven substrates of processing. In a roll - to -roll process of textured , coated
various kinds ( e.g. , plain weave , twill, sateen weave , fabrics , including leather - like materials, the texture paper is
 US 11,542,365 B2
9 10
often used as a carrier film to move both the resin and the internal mold release agent). The resulting resin was poured
fabric through an oven for a specific duration of time . The over cellulosic fabric and allowed to cure at -120 ° C. for
resin according to the present disclosure may require cure 10-30 minutes. After initial cure , the material was placed in
times that are longer than PVC or polyurethane resins that an 80 ° C. oven for overnight post - curing ( ~ 16 hours ) . The
are currently used in the art, thus the line speeds may be 5 surface of the material was then sanded smooth (and option
correspondingly slower or the cure ovens may be made ally polished) . The resulting material was found to have
longer to effect a longer cure time . Vacuum degassing of the leather - like attributes .
resin prior to casting may allow for higher temperatures to
be used for curing ( due to less residual solvent, moisture , Third Illustrative Embodiment and Method
and trapped air) that would speed up the cure time and thus 10
the line pull rate . Pre -polymer creation has been conducted by dissolving
Alternatively, certain catalysts are known in the art to 50 parts of citric acid in 100 parts of warm IPA , accelerated
speed up the carboxylic acid addition to epoxide groups. by mixing. After dissolution of the citric acid, 50 parts of
Base catalysts may be added to the resin ; some example ESO is added to the stirring solution . The mixture is kept on
catalysts include pyridine , isoquinoline, quinoline, N , N- 15 a hot plate while the IPA evaporated under continuous heat
dimethylcyclohexylamine, tributylamine, N -ethylmorpho- and stirring. Such solutions have been created multiple times
line, dimethylaniline, tetrabutyl ammonium hydroxide, and with various hot plate temperatures and air flow conditions .
similar molecules . Other quaternary ammonium and phos- Even after extended times of heating and stirring, it has
phonium molecules are known catalysts for the carboxylic repeatedly been found that the amount of reaction product is
acid addition to epoxide groups. Various imidazoles are 20 greater than the mass of the ESO and citric acid alone .
likewise known as catalysts for this reaction . Zinc salts of Depending on the rate of IPA evaporation (determined at
organic acids are known to improve the cure rate as well as least by air flow , mixing rate , and hot plate temperature )
impart beneficial properties, including improved moisture between 2.5 and 20 parts of the IPA has been found to be
resistance , to the cured films. ( See Werner J. Blank, Z. A. He grafted onto the citric - acid capped oligomeric pre -polymer.
and Marie Picci , “ Catalysis of the Epoxy - Carboxyl Reac- 25 Furthermore, solvent blends of acetone and IPA may be used
tion ” , Presented at the International Waterborne, High - Sol-
? as the reaction medium wherein the ratio between acetone
ids and Powder Coatings Symposium , Feb. 21-23 , 2001. ) and IPA determines the amount of residual carboxylic acid
Accordingly, any suitable catalyst may be used without functional groups on the pre - polymer as well as the amount
limitation unless otherwise indicated in the following 30
of branching in the pre -polymer. Higher amounts of IPA
claims . create more linear structures by lowering the effective
B. Illustrative Embodiments functionality of the citric acid by capping some of the
Although the illustrative embodiments and methods that carboxylic acid functional groups by grafting IPA unto the
follow include specific reaction parameters (e.g. , tempera- citric acid via an ester linkage as referenced in FIG . 1. Lower
tures, pressures, reagent ratios, etc. ) , those embodiments and 35
amounts of IPA create more highly branched structures with
methods are for illustrative purposes only and in no way more residual carboxylic acid functional groups .
limit the scope of the present disclosure unless otherwise
indicated in the following claims . Fourth Illustrative Embodiment and Method
First Illustrative Embodiment and Method Pre -polymer creation has been conducted by dissolving
40 50 parts of citric acid in 100 parts of warm IPA , accelerated
To make a first illustrative embodiment of a coated by mixing. After dissolution of the citric acid, 50 parts of
material using the pre -polymer ( that is , the curative as ESO and 15 parts of dewaxed blonde shellac is added to the
disclosed previously above ) , 18 parts of citric acid were stirring solution . The mixture is kept on aa hot plate the while
dissolved into 54 parts of warm IPA . To this solution, only IPA evaporated under continuous heat and stirring. The
12 parts of ESO is added . The IPA was evaporated with 45 shellac was found to increase the viscosity of the resulting
continuous heating and stirring (above ~ 85 ° C. ) . This was pre -polymer.
found to make aa viscous liquid that could be heated to above
120 ° C. without gelation ( even for long periods of time ) . Fifth Illustrative Embodiment and Method
This viscous liquid pre -polymer was allowed to cool below
80 ° C. To this viscous liquid , 88 parts of ESO is added . The 50 Pre -polymer creation has been conducted by dissolving
final liquid resin will polymerize to a solid elastomeric 45 parts of citric acid in 90 parts of warm IPA , accelerated
product in 1-5 minutes at ~ 150 ° C. The coated material by mixing. After dissolution of the citric acid, 45 parts of
(which may serve as a substitute for natural animal-hide ESO is added to the stirring solution . The mixture is kept on
leather) may be formed as a reaction product using an a hot plate while the IPA evaporated under continuous heat
epoxidized triglyceride and the pre - polymer without limita- 55 and stirring.
tion unless otherwise indicated in the following claims .
Sixth Illustrative Embodiment and Method
Second Illustrative Embodiment and Method
Pre -polymer creation has been conducted by dissolving
For this illustrative embodiment, 30 parts of citric acid 60 45 parts of citric acid in 30 parts of warm IPA and 60 parts
were dissolved into 60 parts of warm IPA . To this solution , of acetone , accelerated by mixing . After dissolution of the
20 parts of ESO were slowly added while stirring. The IPA citric acid, 45 parts of ESO is added to the stirring solution .
was evaporated with continuous heating and stirring ( above The mixture is kept on a hot plate while the acetone and IPA
85 ° C. , and preferably above 100 ° C. ) . This viscous pre- evaporated under continuous heat and stirring. Such solu
polymer was allowed to cool below 80 ° C . ( preferably below 65 tions have been created multiple times with various hot plate
70 ° C. ) and 80 parts of ESO were added along with various temperatures and air flow conditions . Even after extended
structural color pigments and 0.5 parts of zinc stearate ( as an times of heating and stirring, it has repeatedly been found
 US 11,542,365 B2
11 12
that the amount of reaction product is greater than the mass and stirring. After dissolution of the citric acid , 20 parts of
of the ESO and citric acid alone , but the amount of grafted ESO was added to the solution along with 5 parts of shellac .
IPA is less than in pre-polymer created according to the fifth The pre -polymer created after evaporation of the solvents
illustrative embodiment (even though the ratio of ESO : citric was then cooled . The pre - polymer was mixed with an
acid is 1 : 1 toin both
according casesillustrative
the fifth ). Furthermore , pre-polymer
embodiment createdin
is lower 5 additional 80 parts of ESO to bring the total amount of ESO
viscosity compared to pre -polymer created according to the to 100 parts. The mixed resin was then cast on a silicone mat
sixth illustrative embodiment. to make a transparent sheet. The mechanical properties of
Generally , it is contemplated that the greater content of the material were found by tensile testing according to
IPA during the pre -polymer creation allowed more IPA to be 10 ASTM D412 . The tensile strength was found to be 11.3 MPa
grafted onto carboxylic -acid sites on the citric acid , thus and the elongation was 33 % , which gives a calculated
lowering the average functionality of the citric acid and thus modulus of 34 MPa . As can be seen from the tenth illustra
creating a less highly branched oligomeric pre -polymer. In tive embodiment, by appropriate design of the pre -polymer
no circumstance have reaction conditions been found that and the final resin mixture, a plastic material with the
capping of the citric acid with IPA to such an extent that final 15 attributes of high strength and high modulus may be created
curing of the resin is prohibited . by the methods of the present disclosure.
Seventh Illustrative Embodiment and Method Eleventh Illustrative Embodiment and Method
The pre- polymer created in the fourth illustrative embodi 20 The pre -polymer of the sixth illustrative embodiment was
ment was mixed with additional ESO to bring the total mixed with additional ESO to bring the total calculated
calculated amount of ESO to 100 parts. This mixture was amount of ESO to 100 parts. The mixed resin was then cast
found to cure into a transparent, elastomeric resin . Tensile on a silicone mat to make a transparent sheet. The mechani
testing according to ASTM D412 found that the tensile
strength was 1.0 MPa with an elongation at break of 116 % . cal properties of the material were found by tensile testing
25 according to ASTM D412 . The tensile strength was found to
Eight Illustrative Embodiment and Method be 0.4 MPa and the elongation was 145 % , which gives a
calculated modulus of 0.28 MPa .
Pre -polymer was created by dissolving 45 parts of citric As can be seen from the eleventh illustrative embodiment,
acid in 20 parts of IPA and 80 parts of acetone under heating by appropriate design of the pre - polymer and the final resin
and stirring. After dissolution of the citric acid , 35 parts of 30 mixture, a high elongation elastomeric material by be cre
ESO was added to the solution along with 10 parts of ated by the methods of the present disclosure. Therefore , by
shellac . The pre -polymer created after evaporation of the appropriate design of the pre -polymer, the inventive meth
solvents was then cooled . The pre -polymer was mixed with ods may be used produce materials ranging from stiff,
an additional 65 parts of ESO to bring the total amount of plastic - like materials to high - elongation elastomeric mate
ESO to 100 parts. The mixed resin was then cast on a 35 rials. Generally, higher amounts of IPA grafted during pre
silicone mat to make a transparent sheet . The mechanical polymer formation lowers the stiffness of the resulting
properties of the material were found by tensile testing material. Higher amounts of dissolved shellac yield stronger
according to ASTM D412 . The tensile strength was found to materials with somewhat higher stiffness . Citric acid amount
be 1.0 MPa and the elongation was 104 % , which gives a ( relative to the final mixed recipe ) may be used either above
calculated modulus of 0.96 MPa . 40 stoichiometric balance or below to lower the modulus. Citric
acid amounts near stoichiometric balance (~ 30 parts by
Ninth Illustrative Embodiment and Method weight to 100 parts by weight ESO ) generally yield the
stiffest materials; unless offset by high levels IPA grafting of
Pre -polymer was created by dissolving 45 parts of citric the carboxylic acid groups during pre -polymer formation .
acid in 5 parts of IPA and 80 parts of acetone under heating 45 One of the beneficial attributes of animal -based leather is
and stirring. After dissolution of the citric acid , 35 parts of its flexibility over a wide range of temperatures. Synthetic
ESO was added to the solution along with 10 parts of polymer based leather substitutes based on PVC or poly
shellac. The pre -polymer created after evaporation of the urethane may become particularly stiff at temperatures
solvents was then cooled . The pre -polymer was mixed with below -10 ° C. or below -20 ° C. ( based on testing according
an additional 65 parts of ESO to bring the total amount of 50 to CFFA - 6a —Cold Crack Resistance Roller method ).
ESO to 100 parts . The mixed resin was then cast on a Materials prepared according to some of the embodiments of
silicone mat to make a transparent sheet . The mechanical the present disclosure may have poor cold crack resistance .
properties of the material were found by tensile testing In the following examples, formulations are given that
according to ASTM D412 . The tensile strength was found to improve cold crack resistance . Cold crack resistance may be
be 1.8 MPa and the elongation was 62%, which gives a 55 improved by adding a flexible plasticizer. Some natural
calculated modulus of 2.9 MPa . As can be seen from the vegetable oils may exhibit good low temperature flow ,
eighth and ninth illustrative embodiments, the lower amount especially preferred may be polyunsaturated oils . Such oils
of IPA present during pre -polymer creation yields a pre- may be any non -epoxidized triglycerides ( such as those
polymer that creates a more highly crosslinked resin with disclosed in Section 1 above ) having relatively high iodine
higher modulus and lower elongation . These reaction prod- 60 numbers (e.g. , greater than 100 ) without limitation unless
ucts are more plastic - like and less rubber - like in their otherwise indicated in the following claims . Alternatively,
material attributes. monounsaturated oils may be added as plasticizers ; one
illustrative oil may be castor oil which is found to be
Tenth Illustrative Embodiment and Method thermally stable and less prone to becoming rancid . Addi
65 tionally, the fatty acids and fatty acid salts of these oils may
Pre -polymer was created by dissolving 25 parts of citric be used as a plasticizer. Accordingly, the scope of the present
acid in 10 parts of IPA and 80 parts of acetone under heating disclosure is in no way limited by the presence of or
 US 11,542,365 B2
13 14
particular chemistry of a plasticizer unless otherwise indi- be used in applications where animal -hide leather and/ or
cated in the following claims . synthetic resin - coated fabrics are used today. Such applica
Another approach is to use a polymeric additive that may tions may include belts , purses , backpacks, shoes , table tops ,
impart improved low temperature flexibility. A preferred seating, and the like without limitation unless otherwise
polymeric additive may be Epoxidized Natural Rubber 5 indicated in the following claims . Many of these articles are
( ENR ). ENR is available commercially in different grades consumable items that if made from synthetic material
with various levels of epoxidation, for example 25 % epoxi alternatives are non -biodegradable and are non - recyclable.
dation of the double bonds yields grade ENR - 25 , 50 % If such items are instead made according to the present
epoxidation of the double bonds yields grade ENR - 50 . disclosure , they would be biodegradable and thus not create
Higher levels of epoxidation increase the glass transition
temperature , Tg. It is advantageous for the T , to remain as 10 a disposal problem as the biodegradability of similarly
prepared polymers made from ESO and natural acids has
low as possible for the most improvement in cold crack been studied and shown . Shogren et al . , Journal of Polymers
resistance in the final resin , so ENR - 25 may be the preferred and the Environment, Vol. 12 , No. 3 , July 2004. Further
grade for use as a polymeric plasticizer. Even lower levels
of epoxidation may be advantageous for further lowering of more, unlike animal -hide leather, which requires significant
the cold crack temperature in the final resin . However, the 15 processing to be made durable and stable ( some of which
scope of the present disclosure is not so limited unless uses toxic chemicals ), the materials disclosed herein may
otherwise indicated in the following claims . require less processing and will use environmentally
friendly chemicals. Additionally, animal-hide leather is lim
Twelfth Illustrative Embodiment and Method ited in size and may contain defects that render large pieces
20 inefficient to produce. The material disclosed herein does not
ENR - 25 was mixed with ESO on a two -roll rubber have the same kind of size limitations .
compounding mill . It was found that ESO could slowly be A cross - sectional depiction of the resulting material when
added until a total of 50 parts of ESO could be added to 100 a liquid resin precursor such as those described for various
parts of ENR - 25 before the viscosity dropped so far that illustrative embodiments and methods above was applied to
further mill mixing was impossible . This gooey material was 25 cotton flannel fabric that was placed over aa heated surface ( a
then transferred to containers for further mixing in aa Flack hot plate ) is shown in FIGS . 2A & 2B . The resin was found
tek® Speedmixer. A flowable mixture was achieved when a to react in 1-5 minutes when the surface temperature of the
total of 300 parts of ESO was finally incorporated into 100 hot plate was ~ 130 ° C. - 150 ° C. The viscosity of the resin
parts of ENR - 25 . The mixture created did not phase segre may be controlled by the time allowed for polymerization
gate.
The material of the twelfth illustrative embodiment may 30 prior to pouring over the surface. By controlling the viscos
be mixed in a single step by a number of means known in ity , the degree of penetration into the surface may be
the art, without restriction or limitation unless indicated in controlled to achieve various effects in the resultant product.
the following claims . Specifically, so - called Sigma Blade For example, a lower viscosity resin may penetrate through
mixers may be used to create a homogenous mixture of ENR out the fabric 102 and leave a suede or brushed - looking
and ESO in a single step . Likewise , a kneader, such as a Buss 35 surface as shown in FIG . 2A to create a natural leather - like
Kneader, by used to create such mixtures in a continuous material 100 having a suede finish . A higher viscosity resin
mixer - type arrangement which is well known to one of may penetrate only partly through the fabric 102 and result
ordinary skill in the art. The homogeneous mixture may be in a glossy, polished - looking surface as shown in FIG . 2B to
mixed with pre - polymers as described in prior examples to create a natural leather -like material 100 ' having a glossy
create a spreadable resin that may be used as a leather - like 40 finish . In this way, variations may be created that mimic
material with improved cold crack resistance. Additionally, natural animal -hide leather products. As shown in contrast
materials created with ENR -modified ESO as disclosed by ing FIGS . 2A & 2B , the natural leather - like material 100
the twelfth illustrative embodiment may exhibit improved having a suede finish 100 may exhibit a larger number of
tear strength , elongation , and abrasion resistance when com- fabric extensions 103 extending from the fabric 102 through
pared to resins that do not contain ENR . 45 the polymer 104 than does the natural leather - like material
100 ' having a glossy finish . In the natural leather - like
C. Additional Treatments material 100 ' having a glossy finish , the majority of fabric
extensions 103 may terminate within the polymer 104 .
Articles produced according to this disclosure may be Alternatively, an article with a suede - like (i.e. , relatively
finished by any means known in the art . Such means include, 50 soft) surface without resin may be created by embedding
but are not limited to , embossing, branding, sanding, abrad- flannel in a non- miscible paste (e.g. , silicone vacuum
ing , polishing, calendering, varnishing, waxing , dyeing, grease ) that is coated on a hot plate. The resin can then be
pigmenting, and the like unless otherwise indicated in the poured over the surface of the flannel but will not penetrate
following claims . Exemplary results may be obtained by through the non- miscible paste . After curing, the non -mis
impregnating the resin of the present disclosure onto fabric 55 cible paste may be removed from the article leaving that
or a non- woven mat and curing such article . After curing the surface with aa suede - like feeling. One of ordinary skill will
article , the surfaces may be sanded to remove imperfections therefore appreciate that a natural leather - like material as
and expose some portion of the substrate. Such surfaces disclosed herein may be produced as the reaction product
exhibit characteristics very analogous to animal -hide between an epoxidized vegetable oil and a naturally occur
leather ,as exemplified by FIGS . 3-7 . The surfaces then may 60 ring polyfunctional acid impregnated upon a cotton flannel
be treated with natural oil or wax protectants, subject to a substrate, without limitation or restriction , wherein the
particular application . article thus formed has the reaction product impregnated
only partly through the substrate with substantially unim
D. Applications/ Illustrative Products pregnated flannel on one side of the article . Although cotton
65 flannel was used in these examples, any suitable flannel
Coated fabrics, ENR -based materials, and / or oil cloth - like and / or fabric may be used including but not limited to those
materials produced according to the present disclosure may made from linen , hemp, ramie, and other cellulosic fibers
 US 11,542,365 B2
15 16
without limitation unless otherwise indicated in the follow- ing surfaces, and room dividers; in garments , including
ing claims . Additionally, non -woven substrates may be used jackets, shoes , and belts ; in accessory items, including
as well recycled substrates ( upcycled ). Brushed knits may be handbags, purses , luggage , hats, and wallets ; and may be
used to impart additional stretch to the resultant article . useful in residential decorations, including wallcoverings,
Random mats (e.g. , Pellon, also known as batting) may be 5 floor coverings, furniture surfaces, and window treatments.
advantageously used as a substrate for certain articles . In
another illustrative embodiment, a textile backing layer
Materials made according to the present disclosure may be
used in any of those applications or other applications
and / or backing material may be configured from a protein- disclosed herein or later occurring depending on the suit
based fiber, which fibers include but are not limited to of ability of the material without limitation unless otherwise
wool , silk , alpaca fiber, qiviut , vicuna fiber, llama wool , 10 indicated in the following claims . Additionally, current
cashmere, and angora unless otherwise indicated in the applications that are served by animal - based leather may be
following claims. considered potential applications for materials made accord
Additional illustrative products that may be made accord- ing to the present disclosure.
ing to the present disclosure are shown in FIGS . 3-8B . A Furthermore, current applications that are served by pet
depiction of a sheet of material that may serve as a natural 15 rochemical-based flexible films; notably those served by
leather - like material is shown in FIG . 3 , and FIGS . 4-6 show PVC and polyurethane - coated fabrics, may be considered
various natural leather - like materials that may be used to potential applications for materials made according to the
construct a wallet . The material in FIGS . 4A , 4B , & 4C is present disclosure . In addition, the resin as disclosed herein
shown with a plurality of apertures made therein , which is substantially free of any off -gassing vapors when cured
apertures may be made with a conventional drill without 20 according to the times and temperatures as disclosed herein .
limitation unless otherwise indicated in the following Therefore, applications that are thicker than traditional films
claims . Contrasting FIGS . 4A , 4B , & 4C shows that the may also be served by the resins prepared according to the
2

method for making the material may be configured to impart present disclosure. For example, the resin may be used to
a wide variety of textures thereon, which textures include cast three - dimensional items in suitable molds . A top view
but are not limited to smooth, grainy, soft, etc. ( e.g. , similar 25 of such a three -dimensional item configured as a ball made
to that of various animal -hide leathers) unless otherwise according to the present disclosure is provided in FIG . 8A ,
indicated in the following claims . and aa side view thereof is shown in FIG . 8B . The ball may
The material pieces shown in FIGS . 5 & 6 may be cut be resin -based and may be produced from epoxidized soy oil
using a laser cutter. Unlike animal - hide leather, the laser and citric acid- based recipes along with structural color
cutting did not char or degrade the edges of the natural 30 pigments. Simple tests indicate it has very low rebound and
leather - like material along the cutline . A finished wallet is expected to have excellent vibration absorption qualities .
constructed of a natural leather -like material made according Prior art three -dimensional cast resin items are typically
to the present disclosure is shown in FIG . 6. The separate made of styrene - extended polyester ( orthophthalic or isoph
pieces shown in FIG . 5 may be conventionally assembled thalic systems ). Such items may currently consist of two
( e.g. , sewn ) to construct a simple credit card wallet or carrier 35 part epoxies or two - part polyurethane resins . Such items
( as shown in FIG . 6 ) having the appearance, rigidity, and may currently consist of silicone casting resins . One
strength as one would expect in aa similar article made from example of an application currently served by two - part
animal -hide leather. The natural leather - like material may be epoxies is the thick - film coating of tables and decorative
sewn and / or otherwise processed into a finished product inlays , wherein the epoxy may be selectively pigmented to
using conventional techniques without limitation unless 40 create a pleasing aesthetic design. Such applications have
otherwise indicated in the following claims . As shown in been successfully duplicated with casting resins created
FIG . 7 and as described in detail above , a fabric may be according to the present disclosure. Furthermore, small
impregnated with a resin to provide various characteristics chess pieces have been successfully cast from resins created
to an article made according to the present disclosure. according to the present disclosure without detrimental
Additionally, the resin produced according to the present 45 off-gassing or trapped air. Accordingly, a wide array of
disclosure may be pigmented to match the coloration of applications exist for various materials made according to
natural animal -hide leather. Of particular utility are struc- the present disclosure and the specific intended use of the
tural color pigments and / or mineral pigments that do not final article produced by any method disclosed herein is not
contain any harmful substances . One such example of illus limited to a particular application unless otherwise indicated
trative structural color pigments is Jaquard PearlEx® pig- 50 in the following claims .
ments . It has been found that the blending of structural color
pigments at relatively low loadings creates aa natural leather E. Resinous Coatings, Products, and Methods
like material that has excellent visual aesthetics . Another
such illustrative example of a suitable pigment may be In various illustrative embodiments disclosed herein ,
procured from Kreidezeit Naturfarben , GmbH . Furthermore, 55 natural products may have physical properties similar to
it has been found that lightly sanding the resultant surface synthetic coated fabrics, animal - based leather products, and
results in a material that strongly resembles tanned & dyed foam products. As disclosed the physical properties of the
animal -hide leather. natural products may be further enhanced to improve flex
Although certain examples disclosed herein may be con- ibility .
figured to utilize only one layer of fabric, other illustrative 60
samples have been created with multiple fabric layers to BACKGROUND
create thicker leather - like products . Since the reaction
between epoxide groups and carboxylic groups does not Coatings are present on many consumer goods where
create any condensation by -products, there is no inherent such coatings are applied to provide surface protection
limit to the cross - sectional thickness that may be created . 65 and / or coloration . In addition , in some consumer goods , the
Generally, resin - coated fabrics and non- wovens are used in coating may serve primarily to improve the haptics ( that is ,
applications such as office furniture , including seating , writ- the tactile feel) of a surface . In one class of materials,
 US 11,542,365 B2
17 18
namely animal -based leather and leather - like materials, sur- tends to make the material more grippy, which negatively
face coatings may be provided to provide surface protection , impacts the haptics of an article.
coloration , and improved haptics . For animal-based leather, Therefore , it is desired to have an article construction that
such coatings may be substantially absorbed into the sub- has a base material with a low T g, and a coating with a
strate and complement the natural haptics of the leather. 5 relatively higher T , while the coating ought to retain enough
Such coatings may be based on oils , waxes, and / or polymers flexibility to avoid cracking at low temperatures. Addition
(both natural and synthetic ). In the creation of petrochemi ally, testing the coefficient of friction in such a way that
cal -based leather alternatives (e.g. , those based on PVC or captures data consistent with what is observed with human
PU) , coatings may or may not be required , but when used , hands is challenging. Generally, tests between animal- based
they are generally also petrochemical-based. In the devel- 10 leather and stainless- steel sheets and between animal-based
leather and silicone sheets give data that does not correlate
opment of a non -petrochemical and non - animal - based with
leather alternative, that is a material based entirely on that athe order of magnitude in coefficient of friction ( COF )
plant -derived ingredients, it may also be desired to provide based leather hand
human would detect . In contrast, testing animal
a coating that provides additional surface protection , color 15 shows similar static aand
against PTFE - coated - fiberglass baking sheet
ation , and /or improved haptics to the non -petrochemical and while also giving a relativelydynamic low
coefficients of friction
absolute value that reflects
non - animal - based leather alternative . the feeling of the human hand. Taking that same test method
Summary and applying it to materials produced according to various
methods disclosed in U.S. Pat . No. 10,400,061 gives the data
20 shown in Table 1 .
Generally , an illustrative embodiment of a coating may be
created entirely from plant-derived ingredients. This coating TABLE 1
may be particularly well suited for use on leather - like Test results for an animal- based leather
materials created from epoxidized natural rubber - based for and two leather - like materials.
mulations but is not so limited unless otherwise indicated in 25
the following claims . The coating created according to the Test material Counter- surface Dynamic COF Static COF
present disclosure may be configured as substantially the Resin - coated plant PTFE Coated 0.15 0.59
reaction product between epoxidized vegetable oil and a based leather Fiberglass
polyfunctional naturally occurring acid ( such as citric acid ) Uncoated plant-based PTFE Coated 0.44 0.46
as further disclosed in U.S. Pat . No. 10,400,061 . The coating 30 Red
leatherLeather
based- onSmooth
ENR PTFEFiberglass
Coated 0.17 0.17
has been found to greatly improve the haptics of the products Front Fiberglass
thus coated .
ILLUSTRATIVE EMBODIMENTS AND From Table 1 we see that animal -based leather has aa low
DETAILED DESCRIPTION 35 static and dynamic COF while an uncoated plant-based
leather material based on ENR has a relatively higher COF.
Animal -based leather materials exhibit a haptic quality In the first row we see data that coating such material with
that is particularly smooth to the touch , even for textured resin that is aa reaction product between epoxidized soybean
articles. has been found that the relationship between the oil (ESO ) and citric acid ( various illustrative embodiments
dynamic coefficient of friction and static ( or “ breakaway ” ) 40 ofwhich may be produced by methods disclosed in U.S. Pat.
coefficient of friction is key to quantifying this attribute. In No. 10,400,061 ) lowers the dynamic COF to a value closer
generally, rubbery materials tend to have high grip , which to animal - based leather. This results in a haptic quality that
may be reflected in both the actual values of the coefficients is considerably improved when compared to the uncoated
of friction ( static and dynamic ), while the static coefficient ENR -based leather - like material.
of friction is generally significantly higher than the dynamic 45 Specifically, the coating used for resin -coated plant-based
coefficient of friction . leather in Table 1 may be formulated by making a curative
Certain leather - like materials ( which are substitutes for as disclosed in U.S. Pat . No. 10,400,061 and then mixing
animal -based leather ) have been found to exhibit character- that curative with additional ESO to make a temperature
istic rubber - like coefficient -of - friction values ; especially curable resin . In the first stage of curative manufacture, citric
when such materials are formulated with epoxidized natural 50 acid is dissolved in isopropyl alcohol , ethanol, or a combi
rubber (ENR) . Formulations based on ENR with a 25 % nation of acetone and alcohol-containing solvent. In the
epoxidation level tend to have higher friction than formu- second stage of curative manufacture ESO or similar epoxy
lations based on ENR with a 50 % epoxidation level. This is containing plant -based triglyceride oil is added to the dis
consistent with polymer theory that correlates the glass solved citric acid solution and allowed to react while simul
transition temperature ( T.) with the coefficient of friction. 55 taneously removing the miscibilizing solvent. An illustrative
That is , higher T , results in lower coefficient of friction
g curative formulation may use 50 parts of citric acid to 50
while lower To results in higher coefficient of friction . It has parts of ESO to 400 parts of miscibilizing solvent. After the
been documented that roughly each increased percentage curative has been formed and the miscibilizing solvent
change in epoxidation degree increases the Tg by one degree evaporated , then roughly 100 parts of curative is mixed with
Celsius . The coefficient of friction effect of changes in T g, is 60 another 100 parts of ESO to make the coating resin . Such
due to the rate at which polymer chains can rearrange to coating resin may be further diluted with solvent to make it
engage the contacting surface . Unfortunately, many con- easier to spray or spread . An example dilution for easy
sumer goods require a material with a low Tg, to prevent spreading may entail mixing the resin with an equal mass of
articles from becoming stiff or brittle at reduced ambient isopropyl alcohol, ethanol, or acetone . Subsequently, the
temperatures ( as may be encountered in the winter ). Thus, 65 dilution solvent is allowed to evaporate, and the resin - coated
the Tg, of the material formulated for low temperature substrate may be placed into an oven or a heated press to
flexibility (based on ENR with lower epoxidation levels ) complete the curing reaction between the curative and the
 US 11,542,365 B2
19 20
epoxidized plant-based triglyceride oil . In one illustrative based rubber substrates as may be used in wallets , handbags,
embodiment, the coating resin may require 10 minutes to purses , shoes , belts , and similar consumer items that may be
cure at 150 ° C. The texture of the coating resin may be normally made of leather or PU / PVC faux leather without
determined by textured release paper or textured silicone limitation unless otherwise indicated in the following
sheets to give the desired appearance and haptics without 5 claims . Illustrative embodiments of a coating disclosed
limitation unless otherwise indicated in the following herein may be particularly advantageous in being used to
claims . coat ENR -based rubber because of the inherent material
Another illustrative embodiment of a coating configured compatibility between coating and substrate . For example,
according to the methods disclosed herein is comprised of a and without limitation unless otherwise indicated in the
resin coating formulation that may be produced based on the 10 following claims , it has been found that thin coatings ( e.g. ,
ratio of 100 parts of curative with 100 parts of ESO , which less than 200 microns) as applied using textured silicone or
may be further modified for easy application. Specifically, texture paper are flexible enough to withstand bending at
such mixture may be diluted with acetone , isopropyl alco- -15 ° C. without delamination or cracking ; whereas such
hol , or ethanol at a ratio of 1 : 1 (mixed resin :solvent) up to coating materials when subject to bending at low tempera
1:20 (mixed resin :solvent ). Generally, any chemically suit- 15 tures as a bulk material ( thickness greater than 500 microns )
able solvent having a boil point from approximately 55 are prone to cracking.
degrees Celsius to approximately 85 degrees Celsius may be Untextured oven- curing such coatings may result in a
used with various illustrative embodiments of a coating glossy surface that has less desirable haptics when compared
without limitation unless otherwise indicated in the follow- to press -cured and textured coatings. In some illustrative
ing claims . Thinner dilutions may enable easy spraying of 20 embodiments, the press - curing of the coating may occur
thin coatings while thicker dilutions may be more appropri- concurrently with the curing of the substrate ENR -based
ate for roll -coating. In another illustrative embodiment, it rubber material. In other illustrative embodiments, the sub
has been found that the inclusion of a thickening polymer strate may be cured in a first step , the coating applied in a
may aid in both the haptics of the cured film and in second step , and the coating cured against textured silicone
preventing the resin from squeezing out during the molding 25 or texture paper in a third step .
step . Such thickening polymers may include, but are not In other illustrative embodiments, the resin coating may
limited to unless otherwise indicated in the following be applied directly to fabrics to provide water resistance . In
claims , shellac , cellulose acetate, cellulose acetate phthalate, such illustrative embodiments, a higher dilution level of the
hydroxypropyl cellulose , and other naturally occurring or coating solution (e.g. , ~ 3-6 % solids ) may yield a fabric with
naturally derived polymers (without limitation unless oth- 30 water resistance while retaining the flexible hand of the
erwise indicated in the following claims ) that are soluble in fabric . Higher solids contents may yield more barrier resis
acetone, isopropyl alcohol, ethanol, or other suitable solvent tance with a stiffening of the substrate.
without limitation unless otherwise indicated in the follow- Materials made and /or coated according to any teaching
ing claims . Generally, any thickener having the desired of this disclosure may be used as flooring, exercise mats ,
effect on the coating during use for its intended application 35 bedding , shoe insoles , shoe outsoles , or sound absorption
may be used to create an illustrative embodiment of the panels without limitation unless otherwise indicated in the
coating disclosed herein without limitation unless otherwise following claims.
indicated in the following claims . Materials made and /or coated according to any teaching
Release additives such as waxes may be included in the of this disclosure may be molded into complex three
resin coating to improve haptics and help release from 40 dimensional articles and multi -laminated articles. Three
texture paper. In one illustrative embodiment olive wax has dimensional articles may also consist of multiple material
been found to be particularly advantageous for such pur- formulations arranged at various locations within an article
poses . In other illustrative embodiments as disclosed herein , to provide functionality required for each location .
ultra -violet (UV ) light stabilizing additives such as micro- The resilient memory foam based on vegetable oil may be
TiO , or nano - Ti0 , may be added to improve the light
2 45 used in applications where polyurethane is used today. Such
stability of the coating and protect the underlying material, applications may include shoes , seating, flooring, exercise
without departure from spirit of this disclosure and without mats , bedding, sound absorption panels, and the like without
limitation unless otherwise indicated in the following limitation unless otherwise indicated in the following
claims . claims . Many of these articles are consumable items that if
It has been found that curing said coating resin by 50 made from synthetic polyurethane foams are non -biodegrad
molding it between an ENR -based rubber substrate as dis- able and are non - recyclable . If such items are made from the
closed in U.S. Pat . No. 10,400,061 and textured silicone or material disclosed herein , they would be biodegradable and
texture paper yields and appearance and haptic quality that thus not create a disposal problem .
are particularly well suited for consumer goods that require Although the methods described and disclosed herein may
low dynamic COF, low gloss , and a “ dry ” hand . 55 be configured to utilize a coating comprised of a natural
It is generally understood that the T , of materials corre- materials, the scope of the present disclosure, any discrete
g
lates to the COF and the resin coating as disclosed herein has process step and / or parameters therefor, and / or any appara
a Tg higher than epoxidized natural rubber, even at the 50 % tus for use therewith is not so limited and extends to any
epoxidation level. Furthermore, the resin coating may have beneficial and / or advantageous use thereof without limita
a relatively higher crosslink density and thus may exhibit 60 tion unless so indicated in the following claims .
less conformability to the human hand . These attributes may 3. Epoxidized Rubber
contribute to the preferred “ hand ” of the material.
A. Summary
INDUSTRIAL APPLICABILITY
65 Coated fabrics prepared as disclosed in Section 2 above
Various illustrative embodiments of resin coatings as use a liquidous viscosity resin that allows such materials to
disclosed herein may be particularly suited to coating ENR- flow into fabric and non -woven substrates . The resulting
 US 11,542,365 B2
21 22
cured materials have mechanical properties that reflect B. Illustrative Methods and Products
highly - branched structures with limited polymer flexibility
between crosslinks (modest strength and modest elonga- Epoxidized natural rubber (ENR) is a commercially avail
tion ). One means of increasing the mechanical properties is able product under the tradename Epoxyprene® ( Sanyo
to begin with polymeric materials that have more linear 5 Corp. ). It is available in two grades with 25 % epoxidation
structures and can be cured with lower cross - link density. and 50 % epoxidation , ENR - 25 and ENR - 50 respectively .
The incorporation of shellac resin (which is a high molecular However, in certain embodiments it is contemplated that an
weight natural resin ) in coated fabric recipes was found to ENR with aa level of epoxidation between 3 % and 50 % may
improve strength and elongation but was also found to make be used without limitation unless otherwise indicated in the
the materials more plastic . Material formulations as dis- 10 following claims . One of ordinary skill will appreciate that
closed in Section 3 — Epoxidized Rubber are able to exhibit ENR may also be produced from protein denatured or
removed latex starting products. During the epoxidation of
excellent mechanical properties (very high strength and natural rubber, it has been found that the allergen activity is
higher elongation ) without compromising material flexibil significantly reduced — the literature for Epoxyprene dis
ity at room temperature ( e.g. , ~ 15 ° C. - 30 ° C. ) . 15 closes that the Latex Allergen Activity is only 2-4 % of that
A natural material based on epoxidized natural rubber of untreated natural
( ENR ) is disclosed that contains no animal -based substances tial improvement forrubber those
latex products. This is a substan
that may experience latex aller
and is substantially free of petrochemical -containing mate gies . ENR is used in materials
rials . In certain embodiments this natural material may serve impart elongation, strength , andoflowthetemperature
present disclosure to
flexibility
as a leather - like material (which may be a substitute for 20 to the products disclosed and claimed .
animal -hide leather and / or petrochemical -based leather - like ENR is traditionally cured with chemistries that are
products (e.g. , PVC , polyurethane, etc.) without limitation common in the rubber compound literature , e.g. , sulfur cure
unless otherwise indicated in the following claims . Further- systems , peroxide cure systems , and amine cure systems.
more , the natural material based on ENR as disclosed herein According to the present disclosure, a specially prepared
may be configured to be substantially free of allergens that 25 curative with carboxylic acid functionality is prepared to be
may cause sensitivity in certain people . The material dis- used as the curative as fully disclosed in Section 1 above .
closed herein is more cost effective and scalable than other There are a number of naturally occurring polyfunctional
proposed materials for petrochemical - free vegan leather. carboxylic acid containing molecules , including but not
With certain treatments the natural material may also be limited to citric acid , tartartic acid, succinic acid , malic acid ,
made water resistant, heat resistant, and retain flexibility at 30 maleic acid, and fumaric acid . None of these molecules are
low temperatures . This set of beneficial attributes may apply miscible in ENR and thus have limited effectivity and utility.
to any natural material based on ENR that is produced It has also been found that a curative of, for example , citric
according the present disclosure and which additional acid, and an epoxidized vegetable oil may be prepared that
treatments are applied , as suitable to a particular application , is soluble in ENR . Specifically, curatives of epoxidized
as disclosed and discussed herein . 35 soybean oil ( ESO ) and citric acid have been prepared with
In at least one embodiment, an elastomeric material may an excess of citric acid to prevent gelation of the ESO . Citric
be formed to include at least a primary polymeric material acid itself is not miscible in ESO , but it has been advanta
further comprised of epoxidized natural rubber and a cura- geously been discovered that solvents such as isopropyl
tive comprised of a reaction product between a polyfunc- alcohol , ethanol, and acetone ( for example but without
tional carboxylic acid and an epoxidized vegetable oil as 40 limitation unless otherwise indicated in the following
disclosed in Section 1- Curative . The elastomeric material claims ) may make a homogeneous solution of citric acid and
may also be formed wherein the primary polymeric material ESO . In this solution , the excess citric acid is made to react
is greater in volumetric proportion in comparison to the with the ESO and create a carboxylic -acid - capped oligo
curative . The elastomeric material may also be formed to meric material ( that is still liquid ) as shown in FIG . 1. The
wherein the epoxidized natural rubber has a degree of 45 miscibilizing solvent contains at least some hydroxyl-con
epoxidation between 3 % and 50% without limitation unless taining ( i.e. , alcohol ) solvent that at least partially reacts
otherwise indicated in the following claims. Another with some of the carboxylic acid functional groups on the
embodiment of the elastomeric material may be comprised citric acid . The majority of the solvent is removed with
of a primary polymeric material comprised of epoxidized elevated temperature and / or vacuum — leaving behind a
natural rubber and a cure system that is not sulfur - based nor 50 curative that may be used as a miscible curative for the ENR .
peroxide -based, and wherein the cure system contains over By thus constructing the curative, the resultant material is
90 % reactants from biological sources. substantially free of petrochemical - sourced inputs .
In another embodiment, an article may be formed from
the reaction product of epoxidized natural rubber and a First Illustrative Embodiment and Process for the
curative wherein the curative is the reaction product between 55 Creation of Curative that is Used in the Preparation
a naturally occurring polyfunctional carboxylic acid and an of ENR - Based Material
epoxidized vegetable oil . In another embodiment, an article
comprised of epoxidized natural rubber with fillers including Curative was prepared by dissolving 50 parts of citric acid
cork powder and precipitated silica may be formed and the in a warm blend of 50 parts of isopropyl alcohol and 30 parts
article may be molded as a sheet with leather - like texture. In 60 of acetone . After the citric acid was dissolved , 15 parts of
another embodiment, an article may be formed wherein the shellac flakes ( blonde dewaxed ) were added to the mixture
reaction product further contains fillers of cork powder and along with 50 parts of ESO . The mixture was heated and
silica . In another embodiment, the article may be formed or stirred continually until all the volatile solvents had evapo
configured such that two or more layers of the reaction rated . It is noteworthy that the total residual volume is
product have substantially different mechanical properties 65 greater than that of the citric acid , ESO , and shellac
and the mechanical property differences are due to differ- meaning that some of the isopropyl alcohol (IPA ) is grafted
ences in filler composition. onto the citric acid capped curative ( via an ester linkage ).
 US 11,542,365 B2
23 24
Varying the ratio of IPA to acetone can vary the degree of ered textiles ) was added. This mixture was made on a
IPA grafting onto the curative . two - roll rubber mill according to normal compounding
practices. The mixture was sheeted out and molded at 110 °
Second Illustrative Embodiment and Process for C. for 30 minutes. It was found to be fully cured and
ENR - Based Material 5 additionally had a very high extensional modulus in accor
dance with the fiber content .
Epoxidized Natural Rubber with 25 % epoxidation (ENR
25 ) was mixed at 100 parts of rubber to 30 parts of the Seventh Illustrative Embodiment and Process for
curative as prepared in the first embodiment. In addition, 70 10
ENR - Based Material
parts of ground cork powder ( MF1 from Amorim ) was
added as a filler. This mixture was made on a two - roll rubber Epoxidized Natural Rubber with 25 % epoxidation ( ENR
mill according to normal compounding practices. The mix- 25 ) was mixed at 100 parts of rubber to 60 parts of the
ture was sheeted out and molded at 110 ° C. for 30 minutes. curative as prepared in embodiment 1. In addition, 35 parts
It was found to be properly cured, with similar elongation 15 of ESO was added as a reactive plasticizer. In addition , 350
and strain recovery as sulfur and peroxide cure systems. parts of ground cork powder ( MF1 from Amorim ) was
Third Illustrative Embodiment and Process for
added as a filler. Additionally, 30 parts of garneted fiber
ENR - Based Material ( from recovered textiles ) was added . This mixture was made
on a two - roll rubber mill according to normal compounding
Epoxidized Natural Rubber with 25 % epoxidation (ENR- 20 practices
C. for 30
. The mixture was sheeted out and molded at 110 °
minutes. It was found to be fully cured , rigid, and
25 ) was mixed at 100 parts of rubber to 45 parts of the additionally had a relatively high extensional modulus in
curative as prepared in the first embodiment. In addition, 70
parts of ground cork powder ( MF1 from Amorim ) was accordance with the fiber content .
added as a filler. This mixture was made on a two -roll rubber
mill according to normal compounding practices. The mix 25 Creation Eighth Illustrative Embodiment and Process for the
ture was sheeted out and molded at 110 ° C. for 30 minutes . of Curative that is Used in the Preparation
It was found to be fully cured , but with some attributes of of ENR - Based Material
over -crosslinked systems , including lower tear resistance Curative was prepared by dissolving 50 parts of citric acid
and very high resilience .
30 in a warm blend of 110 parts of isopropyl alcohol . After the
Fourth Illustrative Embodiment and Process for citric acid was dissolved, 50 parts of ESO was added to the
ENR - Based Material mixture along with 10 parts of Beeswax . The mixture was
heated and stirred continually until all the volatile solvents
Epoxidized Natural Rubber with 25 % epoxidation (ENR- had evaporated. The total residual volume is greater than
25 ) was mixed at 100 parts of rubber to 15 parts of the 35 that of the citric acid , ESO , and beeswax — meaning that
curative as prepared in the first embodiment. In addition , 70 some of the isopropyl alcohol ( IPA ) is grafted onto the citric
parts of ground cork powder ( MF1 from Amorim ) was acid capped curative (via an ester linkage ). The reduced
added as a filler. This mixture was made on a two - roll rubber liquid mixture was added to fine precipitated silica ( Ultrasil
mill according to normal compounding practices. The mix- 7000 from Evonik ) to make aa 50 wt % dry liquid concentrate
ture was sheeted out and molded at 110 ° C. for 30 minutes . 40 (DLC ) for easy addition in subsequent processing .
It was found to be cured, but with a relatively low state - of
cure; with attributes such as low resilience and poor strain Ninth Illustrative Embodiment and Process for
recovery . ENR - Based Material
Fifth Illustrative Embodiment and Process for 45 Epoxidized Natural Rubber with 25 % epoxidation (ENR
ENR - Based Material 25 ) was mixed at 100 parts of rubber to 50 parts of the
curative DLC as prepared in the eighth illustrative embodi
Epoxidized Natural Rubber with 25 % epoxidation ( ENR- ment along with 30 additional parts of fine precipitated
25 ) was mixed at 100 parts of rubber to 30 parts of the silica . It was found that mixing of the curative DLC prepared
curative as prepared in the first embodiment. In addition, 70 50 in eighth illustrative embodiment eliminated some stickiness
parts of ground cork powder ( MF1 from Amorim ) was in processing that was experienced when mixing in curative
added as a filler. Additionally, 20 parts of garneted fiber that was not pre - dispersed as a DLC . The resulting mixture
( from recovered textiles ) was added . This mixture was made was cured in a press at -50 psi at 110 ° C. for 30 minutes to
on a two - roll rubber mill according to normal compounding make a translucent slab .
practices. The mixture was sheeted out and molded at 110 ° 55 The material of this embodiment was found to have
C. for 30 minutes. It was found to be fully cured and attributes that are analogous to those found in animal - hide
additionally had a relatively high extensional modulus in leather ; including slow recovery after folding, vibration
accordance with the fiber content. damping attributes, and high tear strength . It is believed that
the total silica loading ( 55 parts) and this particular curative
Sixth Illustrative Embodiment and Process for 60 contribute to the “ lossy ” characteristics of this material.
ENR - Based Material Without wishing to be bound by theory, it is possible that the
level of total silica loading is approaching the percolation
Epoxidized Natural Rubber with 25 % epoxidation (ENR- threshold and creating particle -particle interactions that are
25 ) was mixed at 100 parts of rubber to 30 parts of the creating the lossy attributes without limitation unless other
curative as prepared in embodiment 1. In addition , 60 parts 65 wise indicated in the following claims . This is a preferred
of ground cork powder ( MF1 from Amorim ) was added as mechanism to reliance on polymer formulations that expe
a filler. Additionally, 80 parts of garneted fiber ( from recov- rience a Tg near room temperature ( e.g. , ~ 15 ° C. - 30 ° C. ) as
 US 11,542,365 B2
25 26
a means to create a lossy material, as such an approach TABLE 2 - continued
would lead to poor cold crack resistance .
Acceptable and Preferred Ranges of Other Ingredients .
Tenth Illustrative Embodiment and Process for Acceptable Range
ENR - Based Material 5
Preferred Range
(Percent of Total (Percent of Total
Ingredient Product Weight) Product Weight)
Epoxidized Natural Rubber with 25 % epoxidation (ENR
25 ) was mixed at 100 parts of rubber to 30 parts of so - called Cork
Colorant
3-10
0-15
0-70
0-50
“ cottonized ” hemp fiber, this mixture was mixed on a Precipitated Silica 15-35 0-50
two - roll mill using a tight nip to get an even dispersion of 10 EVO 0-10 0-30
fiber. To this masterbatch 50 parts of the curative DLC as Non -reactive vegetable oil 0-10 0-30
prepared in the eighth illustrative embodiment along with 30 Odorant 0.5-3 0-10
additional parts of fine precipitated silica . The resulting Vitamin E /antioxidant 0.2-2 0-4
mixture was cured in a press at ~ 50 psi at 110 ° C. for 30 Mineral filler (e.g. , clay ) 0-15 0-50
minutes to make a translucent slab . The material of the tenth
illustrative embodiment was found to have similar attributes 15 Variations in the other ingredients: clay, precipitated
as the material of the ninth illustrative embodiment with the silica , additional epoxidized soybean oil , castor oil , and / or
change of having much lower elongation at break and much amount of curative may be used to vary the modulus of a
higher modulus in accordance with the fiber loading. batch /recipe within a range that is characteristic of tradi
Eleventh Illustrative Embodiment and Process for 20 tional rubber recipes. By those well versed in rubber com
ENR - Based Material pounding it is recognized that formulations of rubber may be
selectively compounded with hardnesses ranging from
A black batch of ENR -based material was prepared by approximately 50 Shore up to about 90 Shore A. The
mixing ENR - 25 with coconut charcoal to achieve the illustrative formulations show that these compounds fall
desired black color. In addition to the black colorant, other 25 within the range of expected performance for epoxidized
ingredients were added to yield a processible batch of natural rubber. Furthermore, it is known that traditionally
rubber. Other ingredients may include clay, precipitated compounded natural rubber may achieve strength values
silica , additional epoxidized soybean oil , castor oil , essential from 10-25 MPa . The eleventh illustrative embodiment
oil odorants , tocopheryl ( Vitamin E as a natural antioxi displays physical properties in line with traditionally com
dant ), and curative. This material was then cured in a 30 pounded natural rubber.
tensile -plaque mold at 150 ° C. for 25 minutes to complete
the curing Materials made according to this disclosure may further
be reinforced with continuous fiber to make stronger prod
Twelfth Illustrative Embodiment and Process for ucts . Methods for reinforcement may include but are not
ENR - Based Material 35 limited to use of both woven textiles, non- woven textiles ,
unidirectional strands, and plied unidirectional layers unless
A brown batch of ENR - based material was prepared by otherwise indicated in the following claims . Reinforcement
mixing ENR - 25 with cork powder to achieve the desired may preferably come from natural fibers and yarns . Illus
brown color and texture . In addition to the cork , other trative yarns may include , but are not limited to , cotton, jute ,
ingredients were added to yield a processible batch of 40 hemp, ramie, sisal , coconut fiber, kapok fiber, silk , or wool
rubber. Other ingredients may include clay, precipitated and combinations thereof unless otherwise indicated in the
silica , additional epoxidized soybean oil , essential oil odor- following claims . Regenerated cellulose fibers such as vis
ants, tocopheryl ( Vitamin E — as a natural antioxidant ), and cose rayon , Modal® (a specific type of viscose , by Lenzing),
pre -polymer curative. This material was then cured in a Lyocell ( also known as Tencel® , by Lenzing), or Cupram
tensile - plaque mold at 150 ° C. for 25 minutes to complete 45 monium Rayon may also be used without limitation or
the curing restriction , as suitable for a particular application, unless
Tensile stress - strain curves are shown in FIG . 9 for otherwise indicated in the following claims . Alternatively,
materials prepared according to the eleventh and twelfth reinforcement may require the strength of synthetic fiber
embodiments . It can be seen that the cork - filled brown batch yarns based on para - aramids, meta -aramids, polybenzimi
( twelfth embodiment) is higher in modulus than the black 50 dazole , polybenzoxazole , and similar high strength fibers. In
batch ( eleventh embodiment) for this particular example. In another illustrative embodiment, a reinforcement layer and /
these two illustrative embodiments, the brown batch ( twelfth or material may be configured from a protein -based fiber,
embodime had a Shore A hardness of 86 while the black which fibers include but are not limited to of wool , silk ,
batch ( eleventh embodiment) had aa Shore A hardness of 79 . alpaca fiber, qiviut , vicuna fiber, llama wool , cashmere, and
The optimalto amount
according of theapplication
the specific additional materials may-based
of the ENR vary 55 angora unless otherwise indicated in the following claims.
Illustrative natural yarns may beneficially be treated by the
material, and various ranges for same are shown in Table 2 . natural fiber welding process to improve their strength ,
reduce their cross - sectional diameter, and improve fiber - to
TABLE 2 elastomer bonding characteristics. Such yarns may be plied
Acceptable and Preferred Ranges of Other Ingredients . 60 into threads that provide interpenetration features between
reinforcement and elastomer as well as improve the strength
Preferred Range Acceptable Range of the reinforcement. For certain applications it may be
Ingredient
(Percent of Total
Product Weight)
( Percent of Total preferred to provide reinforcement by unidirectional rein
Product Weight) forcement in plied layers as compared to woven and knit
ENR - 25 40-60 20-90 65 reinforcement. It has been found that such woven and knit
Curative 2-10 1-50 reinforcement may improve product stiffness but may nega
tively impact tear strength by creating stress -concentration
 US 11,542,365 B2
27 28
features around yarns and fibers . In contrast, unidirectional ing , polishing, calendering, varnishing, waxing , dyeing,
reinforcement at various ply angles may avoid such stress pigmenting, and the like unless otherwise indicated in the
concentrating features. In a related way, non -woven mats following claims . Such articles may be configured to exhibit
may be used as reinforcement as they do not contain characteristics very analogous to animal- hide leather. The
regularly oriented stress -concentrating features but do 5 surfaces then may be treated with natural oil or wax pro
enable long reinforcement fiber lengths at high fiber volume tectants, subject to a particular application .
fractions. In aa related way, integrally mixed fiber content has
been found to improve stiffness but decrease tear strength at D. Applications/Additional Illustrative Products
certain volume and weight fractions. Tear strength improve
ment is observed when total fiber content exceeds 50 phr (in 10 Articles molded with materials according to this disclo
traditional rubber compounding nomenclature ), especially sure may be used as plant -based alternatives to petrochemi
with even dispersion and good retention of fiber length cal -based leather - like products and /or animal- hide leather
during processing. products. In one illustrative embodiment the articles may be
Molding and curing of materials according to the present molded substantially as sheets with various textures accord
disclosure has been found to require only modest pressure to 15 ing to the desired application . The sheets may be used in
achieve porosity - free articles. While traditional rubber cure durable goods such as upholstery, seating, belts , shoes,
systems evolve gasses and thus require molding pressures handbags, purses , backpacks, straps, equestrian gear, wal
generally greater than 500 psi and often closer to 2000 psi , lets , cellular phone cases , and similar articles without limi
the compounds disclosed herein only require molding pres- tation unless otherwise indicated in the following claims .
sure of 20 psi - 100 psi , or more specifically 40 psi - 80 psi to 20 Alternatively, such materials may be molded directly to the
achieve consolidation and porosity - free articles. The actual shape of the final article in applications such as shoe soles ,
required pressure may be dependent more on the amount of shoe toes , shoe heal cups , shoe uppers , purses , horse saddles
material flow and detail required in the final article . Such and saddle components, helmet coverings, chair armrests,
low molding pressures allow the usage of much lower and similar articles.
tonnage presses that are correspondingly less expensive . 25 Materials according to this disclosure may be overmolded
Such pressures also allow much less expensive tooling; even onto resilient materials and thus be used as flooring, exercise
embossed texture papers have been found to create suitable mats , or sound absorption panels. Similarly, those materials
patterns in elastomeric materials made according to this could be overmolded onto garments as , for example, a knee
disclosure and such texture papers are found to be reusable patch or elbow patch for improved abrasion resistance for a
for multiple cycles without loss of pattern detail. The 30 region of a garment. Likewise, motorcycle garments ( e.g. ,
material edge strength has been found to be adequate even chaps) and equestrian gear may be overmolded of materials
when using open - sided tooling — this allows for faster tool according to this disclosure to provide improved local
cleaning and significantly reduced tooling costs . abrasion resistance and protection.
The low molding pressures further allow for such elasto- Materials according to this disclosure may be molded into
meric materials to be molded directly onto the surface of 35 complex three - dimensional articles and multi - laminated
resilient and porous core substrates. For example, the mate- articles. That is , certain formulations according to this
rial may be overmolded onto non -woven insulative mats as disclosure may provide improved tear strength, while other
a resilient flooring product or automotive interior product formulations according this disclosure may provide
that exhibits soft - touch and sound absorption characteristics . improved abrasion resistance . Such formulations may be
Similarly, the product may be overmolded onto softwoods or 40 laminated and co - molded to provide articles with improved
similar low compressive strength substrates without damage overall performance compared with an article made of only
to the substrate . one formulation . Three - dimensional articles may be molded
As previously described, certain catalysts are known in to provide additional product features, attachment points ,
the art to speed up the carboxylic acid addition to epoxide and other functionality without limitation unless otherwise
groups and such may be used in formulating recipes accord- 45 indicated in the following claims . Three -dimensional
ing to the present disclosure without limitation unless oth- articles may also consist of multiple formulations arranged
erwise indicated in the following claims . at various locations within an article to provide functionality
Animal -hide leather has distinctive characteristics in required for each location .
terms of elongation, resiliency, loss modulus, and stiffness One example of such molded - in functionality is shown in
that are different than a regularly compounded elastomer .In 50 FIGS . 10Aa& 10B , which provides a perspective view of a
particular, animal - hide leather may be folded back on itself portion of a belt made of an ENR -based material. Specifi
without cracking - largely independent of temperature . That cally, in FIG . 10A , a tapered feature ( shown on the right
is , it does not have a material phase that becomes brittle at hand side of FIG . 10A) may be molded into a sheet that is
low temperatures. Animal -hide leather also has vibration later slit into belt sections . The reduced thickness ( which
damping characteristics that are less common with regularly 55 may be due to the absence of a backing material/backing
compounded elastomeric compounds. Animal- hide leather layer (e.g. , non -woven mat) in the area having reduced
has slow recovery after creasing or folding, but does gen- thickness ) allows for a folded buckle retention area that is
erally recover completely with minimal plastic deformation . substantially similar in thickness to belt sections that are not
These attributes may be mimicked in materials compounded folded over on itself, which is shown in FIG . 10B where the
according to the present disclosure in the illustrative 60 reduced - thickness area has been engaged with a buckle .
embodiments and methods for same disclosed herein . Additionally, the region that is folded back onto itself may
be preferentially bonded in place with additional resin or
C. Additional Treatments ENR -based material molded between the folded region with
a cure cycle that is similar to that used during the initial
Articles produced according to this disclosure may be 65 molding of the sheet.
finished by any means known in the art . Such means include Shown in FIG . 11 are a series of retention grooves and
but are not limited to embossing, branding, sanding , abrad- ridges that may be molded into the end of the belt to provide
 US 11,542,365 B2
29 30
a friction -based retention feature . That is , some belts made woven products provide relatively good tear strength when
with woven nylon or other textiles are tightened and retained compared to tight woven fabrics . In another illustrative
on the wearer by friction between ribs woven into the belt embodiment, a reinforcement layer (woven or non -woven)
and a metal bar used in the clasp . Such features may be may be configured from a protein -based fiber, which fibers
advantageous in that they prevent stress risers from devel- 5 include but are not limited to of wool , silk , alpaca fiber,
oping around punched holes used for retention in common qiviut , vicuna fiber, llama wool , cashmere , and angora
belt buckles . Retention grooves & ridges and / or other fea- unless otherwise indicated in the following claims .
tures for retaining the position of a portion of a belt easily ENR - based materials configured for use as leather sub
molded into a belt sheet by the creation of matching features stitutes may be used in applications where animal- hide
in the mold tooling (which may be silicone or metal) when 10 leather is used today. Such applications may include belts ,
making an ENR - based material according to the present purses , backpacks, shoes, table tops , seating, and the like
disclosure . without limitation unless otherwise indicated in the follow
ENR - based materials configured for use as a belt may be ing claims . Many of these articles are consumable items that
made in sheets and may be produced by molding according if made from petrochemical-based leather -like products are
to the pattern illustrated in FIG . 12. As shown in FIG . 12 , the 15 non -biodegradable and are non -recyclable . If such items are
sheet may be comprised of various layers, wherein each made from the material disclosed herein , they would be
outside layer of the sheet may be comprised of an ENR- biodegradable and thus not create a disposal problem . Fur
based material ( e.g. , " sheeted rubber preform ” in FIG . 12 ) thermore , unlike animal - hide leather, which requires signifi
with one or more fibrous backing materials /backing layers cant processing to be made durable and stable ( some of
positioned therebetween. The backing materials may be
comprised of a woven reinforcement or a non- woven mat in
20 which uses toxic chemicals ), the materials disclosed herein
may require less processing and will use environmentally
the illustrative embodiment shown in FIG . 12 , but any friendly chemicals. Additionally, animal- hide leather is lim
suitable backing material/backing layer may be used without ited in size and may contain defects that render large pieces
limitation unless otherwise indicated in the following inefficient to produce. The material disclosed in at least one
claims . At least one of the backing materials may be a coated 25 embodiment herein does not have the same kind of size
fabric (as shown in FIG . 12 for the layer labeled “ non - woven limitations as the reaction between epoxide groups and
mat ” ), which may be constructed in accordance with Section carboxylic groups does not create any condensation by
2 described herein above . Texture paper may be positioned products, there is no inherent limit to the cross - sectional
adjacent one or both ENR - based material layers to provide thickness that may be created .
the desired aesthetics to the outer layers of the sheet and 30 In another application for material produced according to
resulting article . Finally, a silicone release sheet may be the present disclosure, the leather substitute material (which
positioned adjacent one or both texture papers for ease of may be configured as an ENR -based material) may be used
use . for footwear, specifically the upper portion of the footwear.
It has been found that the relatively low required pressure Generally, it is contemplated that leather substitute material
to yield a properly cured specimen utilizing ENR -based 35 may be engaged with a fabric backing. In one illustrative
materials allows for the use of low - cost paper and silicone embodiment the fabric backing may be comprised of Rayon
tooling. So - called texture papers are used in polyurethane (e.g. , Tencel, Lyocell, etc. ) , and in another illustrative
and vinyl leather alternatives to achieve the desired texture. embodiment the fabric backing may be comprised of canvas ,
It has been found that these texture papers likewise are hemp, or other suitable material. It is contemplated that the
effective in creating patterns in ENR -based materials as 40 optimal fabric backing may vary depending on the specific
disclosed herein . An advantageous molding configuration is application and is therefore in no way limiting to the scope
shown in FIG . 12 , wherein release silicone sheets are of the present disclosure unless otherwise indicated in the
provided as the top - most and bottom -most layers in the following claims . It is further contemplated that for at least
sandwich that is molded under temperature and pressure . If some applications, the leather substitute material and fabric
the " outside ” faces of the belt are desired to be textured , 45 backing may have the following characteristics:
texture paper may be provided next to the silicone sheets . Tensile Strength (ASTM D 5035-2011 ) 600 N / 5 cm ,
These may advantageously be treated with aa release aid to Elongation ( ASTM D 5035-2011 ) 80% +/ - 20
promote easy release and reuse of the texture paper. Silicone Color fastness to rubbing ( crocking) ( ISO 20433 : 2012 ) ,
and vegetable oil have both been found to be effective in Dryz4 and Wet24
release and reuse of the texture paper but any suitable release 50 Bonding Strength of coated material/between leather sub
agent may be used without limitation unless otherwise stitute material (which may be configured as an ENR
indicated in the following claims . based material) layer and the fabric backing material,
The uncured rubber pre - form sheets may be loaded into 2.5 N /mm
the sandwich next to the texture paper ( s ). Between the Bally Flex at room temperature ( e.g. , -15 ° C. - 30 ° C. ) .
rubber pre - form sheets a non - woven mat and /or woven 55 ASTM D 6782-13 (23 + 1 ) , 100,000 cycles , Pass
reinforcement layer ( s) may be provided. In one illustrative Abrasion — Taber (ASTM D 3884-09 , H - 22 , 1000 g ,
embodiment, the non -woven mat may comprise recycled > 1000 cycles ) , Pass
textiles , hemp fibers , coconut coir fibers, or other environ- Color fastness to wash (ISO - 105 - C06 : 2010) , zb 4
mentally benign ( biodegradable ) fibers, and /or combinations However, such characteristics are not meant to be limiting
thereof without limitation unless otherwise indicated in the 60 in anyway and are for illustrative purposes only unless
following claims . In one illustrative embodiment the woven otherwise indicated in the following claims .
reinforcement layer may comprise jute burlap or similar Generally, it has been observed through testing that when
open -structure woven product that is high in strength and silica is added as a type of filler with the leather substitute
biodegradable . In another illustrative embodiment so - called material (which may be configured as an ENR - based mate
cotton monk's cloth may be also used as a woven reinforce- 65 rial ), the result may be a higher cohesive strength within the
ment layer without restriction unless otherwise indicated in leather substitute material layer than is shown in a leather
the following claims . In some configurations open - structure substitute material layer without a silica filler. It has also
 US 11,542,365 B2
31 32
been observed that a silica filler may aide with fatigues flexibility of the ENR while delivering the haptics associated
life /bally flex, which may be evident specifically when rice with a polymer having a Tg nearer room temperature ( e.g. ,
hulls are also used as a filler. Additionally, because silica ~ 15 ° C. -30 ° C. ) .
does not hide certain characteristics of other materials (e.g. , In another embodiment, disclosed is a combination of a
silica provides a certain degree of translucency in certain 5 plant -based all -natural polymer that can be combined with
applications as a filler material ), when used with rice hulls, ENR and another optional plasticizer that further suppresses
the speckles, texture , and / or other characteristics of the rice the glass transition temperature to impart excellent low
hulls ( or other filler materials in other illustrative embodi temperature flexibility ( down to -10 ° C. or lower ).
ments ) may be more pronounced than when filler materials
other than silica are used . It is contemplated that rice hull ash 10 ingDisclosed is an illustrative method of selectively revers
may be used in place of silica as a filler in certain applica referred to herein as crosslinks
covalent chemical
“ de -
(which reversing may also
crosslinking ”) in a thermoset
tions to achieve desirable characteristics of the resulting material through mechano - chemical processing using low
material.
It has further been found that using Tencel as a backing temperature (e.g. , less than 70 ° C. ) and high shear, which
fabric results in the composite material (i.e. , leather substi- 15 may be performed by gap
passing a thermoset
) of a two material repeat
tute adhered to a fabric backing) exhibits a higher tensile edly (
through a narrow
approximately 1.25 : 1
(< 1 mm
friction ratio ) or
- roll rubber
through mixing
mill
in an
elongation compared to using cotton as a backing fabric . internal mixer. The method has been found to cause scission
However, the specific configuration of the backing fabric primarily to crosslinks to partially reverse the cure . Such
and / or leather substitute material, method of adhering the
various layers, dimensions, etc. may also affect the charac- 20 mechano - chemically modified thermoset may be used as one
teristics of same without limitation unless otherwise indi- constituent in a mixture with ENR to yield a leather - like
cated in the following claims . alternative material with improved haptics .
4. Mechano - Chemically Modified Thermoset Material As used herein , the term “ thermoset material ” is meant to
A. Background include all thermosets without limitation unless otherwise
Leather -like materials based on synthetic polymers such 25 indicated in the following claims, including those thermo
sets that are made via resin ( liquid ) precursors , gum precur
as polyurethane ( PU) and polyvinyl chloride (PVC ) are well
known in the art. These materials have been formulated to sors , semi- solid precursors , thermoplastic precursors, and / or
have haptics that mimic , in many ways , the feel of animal combinations thereof.
leather . Animal leather is a collagen -based structure that is Various methods exist for determining the power -per
usually filled with waxes and oils that impart both softness 30 unit - volume of thermoset material required to selectively
and a slick surface termed " buttery” by those in the art. break the crosslinks in the thermoset material disclosed
PVC , for example, may achieve similar haptics by the herein , and the scope of the present disclosure is in way
combination of the polymer itself that may have a glass limited by a specific method for determining same unless
transition temperature, Tg , above room temperature ( e.g. , otherwise indicated in the following claims . In one illustra
greater than ~ 23 ° C. ) combined with plasticizers that drop 35 tive method for determining the aforementioned power -per
the bulk material stiffness so that it remains flexible well unit - volume of thermoset material, the thermoset material
below room temperature (e.g. , less than ~ 23 ° C. ) . PU , in may be mixed on a two -roll mill with a nip gap of 0.5 mm .
another example , may achieve similar haptics by the com- The power consumption may be approximately 5000 W ( 5
bination of so - called hard block domains ( with a Tg above kW) . As the thermoset material fills the nip width of 30 cm ,
room temperature) and soft block domains (with a Tg below 40 it may be assumed that the majority of power input into the
room temperature) synthesized into the polymer backbone. thermoset material happens below a nip gap of 1.5 mm
In these examples, there is a phase or constituent with a Tg because experiments show very little mechano -chemical
above room temperature (collagen, PVC polymer, and PU de -crosslinking at this nip gap or larger. For mills configured
hard blocks ) and a phase or constituent with a Tg below with rolls with a radius of 75 mm ( 6 - inch rolls ) , this
room temperature ( tanning agents and oils for animal 45 corresponds to an arc of approximately 13 ° ( +/– 6.5 ° around
leather, plasticizers for PVC , and soft block domains for the point of closest approach ). One may accordingly esti
PU) . This combination of phases or constituents that have a mate that the volume of material within this nip gap across
Tg above room temperature and phases or constituents with the width of the mill is approximately 7.5 ml . Therefore, a
a Tg below room temperature and may yield a favorable reasonable estimate of the instantaneous power input to
haptic combining softness of the bulk article without impart- 50 enable mechano -chemical de - crosslinking is 5000 W / 0.0075
ing a “ grippy ” surface . liters = 6.67x105 W / 1.
Materials based on natural rubber or other related poly- However, in some instances, the power consumption on
mers , such as epoxidized natural rubber, tend to have a the two -roll mill may be as low as 2000 W (2 kW) . The mill
polymer phase with a single Tg that is below room tem- geometry and nip gap remain the same and the mill width
perature ; thus compounds based on natural rubber (NR ) or 55 remains the same. In these instances , the instantaneous
epoxidized natural rubber ( ENR ) tend to have a “ grippy ” power input to enable mechano -chemical de - crosslinking
surface that is undesirable when developing a leather -alter- may be 2000 W /0.0075 liters =2.67x105 W / 1.
native material. It would be desirable to combine the ben- Through experimentation , the lowest shear variation that
eficial low temperature flexibility and softness that comes has been observed to selectively de - crosslink the thermoset
from NR or ENR with a slick or buttery surface haptic for 60 material through a mechano - chemical process mechano
the creation of a leather - alternative material. chemical de -crosslinking may occur with a minimum nip
gap of 0.8 mm with an estimated power consumption of
B. Summary 2000 W ( 2 kW ). In this instance, the estimated volume of
thermoset material experiencing the high shear near the nip
Disclosed is a combination of a plant -based all -natural 65 may be as much as approximately 10 ml . In this example, the
polymer that can be combined with ENR to yield a poly- instantaneous power input to enable mechano - chemical de
meric mixture that maintains the excellent low temperature crosslinking may be 2000 W /0.01 liters =2x105 W / 1.
 US 11,542,365 B2
33 34
In the preceding illustrative embodiments, the mechano- curative demonstrating that the curative is not only selec
chemical de - crosslinking may be characterized by very high tively broken, but also that the carboxylic -acid functionality
instantaneous power -per - volume shear mixing followed by and epoxide functionality are regenerated during the break
periods of cooling so that the temperature of the thermoset ing of the crosslinks. Such mechanically induced regenera
material that is being mixed never exceeds approximately
70 ° C. ( above which temperature the thermoset material
5 tionDisclosed
of curativeis thefunctionality has not before been disclosed.
combination of virgin epoxidized natural
may begin re -curing, that is , re -crosslinking ). On aa two - roll rubber and mechanically masticized thermoset material
mill , the high -shear mixing zone has been estimated to be (which may be configured as a thermoset resin ) that was
happening over an arc length of approximately 13 ° , thus by formed as the reaction product between an epoxidized
deduction the estimated low - shear or no -shear cooling time 10 plant -sourced triglyceride and a naturally occurring
occurs during the remaining periphery of the roll (i.e. , the polyfunctional carboxylic acid . Such reaction product may
remaining approximately 347 ° of travel ). Accordingly, the be preferably produced according to the methods disclosed
high shear time may be experienced by the thermoset Section 2–Coated Fabrics, though the scope thereof is not
material for approximately 13/360 , or 3.6 % of the total so limited unless otherwise indicated in the following
mixing time . In this way, the maximum material temperature 15 claims . The mechanically masticized thermoset material
may be limited , despite having instantaneous times of very may function as the curative for the virgin epoxidized
high -power input (per volume). natural rubber. Such mechanical masticization of the ther
Disclosed is a reaction product between an epoxidized moset material and mixing of the recipe has been found to
plant- sourced triglyceride (an example of which may be be able to occur concurrently.
epoxidized soybean oil ( ESO ) ) and a naturally occurring 20
polyfunctional carboxylic acid ( an example of which may be C. Detailed Description
citric acid) wherein the thermoset reaction product contains
B -hydroxyesters as the linkages between the epoxidized Thermoset materials ( and specifically, thermoset resins )
plant-sourced triglyceride and the naturally occurring and thermoset elastomers are well known in the art. In most
polyfunctional carboxylic acid . It has been unexpectedly 25 cases , the covalent bonds formed between molecules have
discovered that the B -hydroxyester linkages may be selec strength characteristics that are commensurate with the
tively and reversibly broken by mechanical shear only. That strength characteristics within the precursor molecules . In
is , the thermoset matrix sourced from small and highly such materials , mechanical shear results in turning the
branched precursor molecules may be transformed into a thermoset material into a granule or powder that may be
millable gum by the action of high - shear mixing . Such 30 used as a filler in new materials, but is not capable of
mechanically masticized thermoset has been found to be returning the thermoset material into a high molecular
capable of being re - cured into a thermoset by the re- weight gum , having characteristics substantially the same or
application of heat without the addition of additional cura- even similar to the starting precursor material ( s ). Some
tive functionality ( that is , without the addition of virgin ionically crosslinked materials, when formed by the coor
epoxidized plant-sourced triglyceride or carboxylic -acid 35 dination of charges along the polymer backbone, may be
functionality ) made to flow under either high shear or the application of
Disclosed is an epoxidized natural rubber that is cross- very high temperatures, but this type of reversible thermoset
linked by a carboxylic -acid containing curative . Crosslinks behavior is not known among covalently bonded thermoset
between the epoxide groups and the carboxylic -acid curative materials.
form B -hydroxyesters. Such B -hydroxyesters are known to 40 It is known in the art that crosslinks between the epoxide
be capable of thermally -induced transesterification reac- groups and a carboxylic - acid curative form B -hydroxyesters.
tions . Such reactions have been used to1 make so - called Such B -hydroxyesters are known to be capable of thermally
“ self-healing” and recyclable thermosets . In the prior art, it induced transesterification reactions. Such reactions have
has been assumed that transesterification reactions proceed been used to make so - called “ self-healing ” and recyclable
in a sort of zero - sum rearrangement where the total number 45 thermosets. In the prior art, it has been assumed that trans
of linkages is generally stable , Leibler et . al states , “ The esterification reactions proceed in a sort of zero - sum rear
underlying concept is to allow for reversible exchange rangement where the total number of linkages is generally
reactions by transesterification that rearrange the network stable , Leibler et . al states “ The underlying concept is to
topology while keeping constant the total number of links allow for reversible exchange reactions by transesterifica
and the average functionality of cross - links .”2?? 50 tion that rearrange the network topology while keeping
1
" Self -healable polymer networks based on the cross - linking of epoxidized
soybean oil by an aqueous citric acid solution ” , Facundo I. Altuna, Valeria
constant the total number of links and the average function
Pettarin , Roberto J. J. Williams, Green Chem ., 2013 , 15 , 3360
ality of cross -links.”
2 “ Silica -Like Malleable Materials from Permanent Organic Networks ” , D. It has been unexpectedly discovered that B -hydroxyester
crosslinks may be selectively and reversibly broken (i.e. ,
Montarnal, M. Capelot, F. Tournilhac and L. Leibler, Science, 2011 , 334 ,
965-968 . 55 de - crosslinked ) by mechanical shear only . That is , a ther
It has been unexpectedly discovered that by pairing a high moset material with linkages that are B -hydroxyesters, as
molecular weight polymer based on a carbon -carbon back- shown in the cured thermoset resin of FIG . 13 ( wherein
bone with crosslinks of B -hydroxyesters, the crosslinks may small arrows on the right side of the figure show reactive
be selectively and reversibly broken by mechanical shear sites in for the compound ), may be mechanically processed
only. That is , a high molecular weight elastomer such as 60 by very high shear such that the thermoset material may be
epoxidized natural rubber that has been crosslinked (vulca- masticized as the crosslinks are selectively broken in such a
nized ) through B -hydroxyesters may be mechanically pro- way that their initial functionality is regenerated . The resul
cessed by very high shear such that the high molecular tant masticized thermoset may be re - cured without addi
weight linear rubber may be substantially retained while the tional curative demonstrating that the curative is not only
crosslinks are selectively broken in such a way that their 65 selectively broken , but also that the carboxylic -acid func
initial functionality is regenerated. The resultant re - milled tionality and epoxide functionality are regenerated during
rubber may be re -molded without the addition of additional the breaking of the crosslinks as shown in FIG . 15. Such
 US 11,542,365 B2
35 36
mechanically induced regeneration of curative functionality It can be seen that the state of cure increases with increasing
has not before been disclosed . temperature to 200 ° C. There is some small evidence of
i . Regenerated Thermoset Materials Based on Epoxidized reversion at 200 ° C. At 225 ° C. , we see an initial cure that
Natural Rubber is followed by rapid reversion that is nearly complete at the
It has been unexpectedly discovered that by pairing a high 5 end of the 30 - minute test . This is evidence that the cross
molecular weight polymer based on a carbon - carbon back- linking bonds are substantially weaker than the epoxidized
bone ( such as epoxidized natural rubber ) with crosslinks of natural rubber itself, which has an onset of thermo -oxidation
B -hydroxyesters, the crosslinks are selectively and revers- at approximately 250 ° C. Therefore , we may surmise that
ibly broken by mechanical shear only. That is , a high mechanical stresses are capable of breaking the weaker
molecular weight elastomer such as epoxidized natural 10 subset of covalent bonds — in this case , the B -hydroxyester
rubber that has been crosslinked ( vulcanized ) through B -hy- crosslinks.
droxyesters may be mechanically processed by very high ii . Regenerated Thermoset Materials Based on Epoxi
shear such that the high molecular weight linear rubber may dized Plant Oil and Naturally Occurring Polyfunctional Acid
be substantially retained while the crosslinks are selectively It has been unexpectedly discovered that the reaction
broken in such a way that their initial functionality is 15 product of two small molecules (such as epoxidized soybean
regenerated. The resultant re -milled rubber, which has been oil (ESO ) and citric acid ), wherein the covalent linkages
de - crosslinked (also called devulcanized ), may be re -molded between the molecules of the thermoset material (which for
without additional curative demonstrating that the curative this illustrative embodiment is configured as a thermoset
is not only selectively broken, but also that the carboxylic resin ) are B -hydroxyesters, may be transformed into a mill
acid functionality and epoxide functionality are regenerated 20 able gum by mechanical shear only. That is , a highly
during the breaking of the crosslinks. Such mechanically branched elastomer may be transformed into a more linear
induced regeneration of curative functionality has not before and extensible material through the reversible fracture of a
been disclosed . subset of the B -hydroxyester covalent linkages as shown in
A rubber compound of epoxidized natural rubber (ENR- FIG . 15. This millable gum may furthermore be used advan
25 ) and a carboxylic -acid functional curative as disclosed in 25 tageously in two or more ways . In one preferred illustrative
Section 1 above may be mixed with additional fillers and embodiment, the millable gum may be subsequently com
additives as may be common in the art . In one illustrative bined with any number of fillers, plasticizers, or functional
embodiment, the compound contains powdered cork and additives and then re - cured — without the addition of addi
precipitated silica . A series of rheometer traces is shown in tional epoxidized plant - sourced triglyceride ( such as ESO )
FIG . 16 from a moving die rheometer ( MDR) as measured 30 or naturally occurring polyfunctional carboxylic acid ( such
at 150 ° C. for 30 minutes. The initial trace shows a char as citric acid) . In another preferred illustrative embodiment,
acteristic cure curve with a brief induction time and then the millable gum may be sheeted out without combination
marching modulus for the 30 -minute cure . The rheometer with additional fillers, plasticizers , or functional additives
sample was then subject to remilling on a lab - scale ( 6 " and then re -cured as a transparent film ( either by itself or in
diameterx12 " wide) two -roll rubber mill . After a few passes 35 contact with backing fabric or other backing material ). In
through the mill wherein the sample exhibited nervy behav another preferred illustrative embodiment, the millable gum
ior, it gradually became flowable in a similar way to uncured may be subsequently combined with virgin epoxidized natu
rubber under continued mixing . The second rheometer curve ral rubber wherein the epoxidized natural rubber is cross
( “ second trace ” on FIG . 16 ) on this particular sample shows linked through the action of the regenerated carboxylic acid
asame
higherfinalinitial modulus but thereafter cures to roughly the 40
stiffness at a similar rate . This particular sample
functionality that was achieved through the mechanical
shear of the thermoset material.
of material was subsequently remilled again and cured By way of illustration, and without limitation unless so
again . This was repeated eleven times — the sixth and elev indicated in the following claims , various processes and
enth cure traces are shown in FIG . 16. It can be seen that the parameters thereof are described in detail below . The values
general shape of the cure curve is similar for all re- curing 45 for the parameters given below are for illustrative purposes
experiments; the modulus drops as the number of recycling only and are in no way limiting unless otherwise indicated
loops increases, but each time , the sample was shown to be in the following claims . Other parameter values , methods,
capable of re - curing without the addition of more curative . equipment, etc. may be used without limitation unless
The twelfth cure curve (“ twelfth trace , added curative ” on otherwise indicated in the following claims .
FIG . 16 ) reflects the addition of a small amount of curative 50
that was able to increase the modulus of the sample. Example 1
The series of cure curves of FIG . 16 shows that the
compound may be de - crosslinked by the application of 100 parts of Citric Acid, 100 parts of ESO , and 400 parts
mechanical shear only without the addition of heat ( that is , of Isopropyl Alcohol ( IPA ) are charged into a vacuum
the rolls of the two - roll mill were not heated for any of these
experiments ). Furthermore , the rheometer traces show that
55 capable reactor vessel . The mixture is slowly heated over the
course of 8 hours with constant stirring and under modest
the curative is capable of re -crosslinking the epoxidized vacuum (> 50 Torr ). The IPA is condensed during the reac
natural rubber after mechanical de - crosslinking. In contrast tion period and removed from the solution . At the end of the
to prior literature on transesterification, it has been shown reaction period, when substantially all of the unbound and
that the total number of crosslinks do not need to be 60 unreacted IPA is removed, the temperature of the reactor
maintained to regenerate solid materials with mechanical vessel rises quickly and the reaction is halted when the
integrity. The curative may regenerate itself after being reaction product reaches 110 ° C.
sheared apart by mechanical forces.
In another set of experiments, the same recipe that was Example 2
used in FIG . 16 was subject to rheometry at a series of 65
increasing temperatures. This data is shown in FIG . 17 for 109 parts of the reaction product of Example 1 is mixed
the temperatures of 150 ° C. , 175 ° C. , 200 ° C. , and 225º C. with 100 parts of ESO to yield a curable resin . This resin
 US 11,542,365 B2
37 38
may be cured overnight at 80 ° C. or within two hours at 125 ° rice hulls, activated carbon, activated charcoal, kaolin clay,
C. to make an elastomeric solid . metakaolin clay, precipitated silica , talc , mica , corn starch ,
Example 3 mineral pigments, and /or various combinations thereofwith
out limitation unless otherwise indicated in the following
5 claims ; the plasticizers may include both reactive plasticiz
The cured elastomeric solid of Example 2 is passed ers such as epoxidized soybean oil , semi-reactive plasticiz
repeatedly through a tight nip on a rubber mill . The friction ers such as glycerol, propylene glycol , and castor oil , and
ratio is 1.25 : 1 and the nip is set to less than 0.5 mm . After non - reactive plasticizers such as naturally occurring triglyc
a few passes , the powdery material begins to masticate and eride plant -based oils and / or various combinations thereof
within about 3-7 minutes of mixing a millable gum is 10 without limitation unless otherwise indicated in the follow
generated. This millable gum may be sheeted out and ing claims ; the functional additives may include antioxidants
re - cured as a transparent sheet or it may be combined with ( such as tocopherol acetate ( Vitamin E) ) , UV absorbers
fillers, plasticizers , and / or functional additives to yield a ( such as sub -micron TiO2 ) , antiozonants, cure retarders
compound that may be cured under heat (e.g. 150 ° C. for 5 ( such as alkali sodium salts and powdered soda glass ) , cure
minutes ) to make a thermoset elastomer . The millable gum 15 tions
accelerators (such a certain zinc chelates ), and/or combina
thereof without limitation unless otherwise indicated in
may be combined with epoxidized natural rubber ( ENR) and
ENR -based compounds and act as a curative for the ENR . the following claims . Materials made by such processing
steps and with such ingredients have been found to have
Example 4
20
excellent flexibility down to -10 ° C. and buttery haptics.
109 parts of the reaction product of Example 1 is mixed Example 7
with 100 parts of ESO along with 7 parts of propylene glycol
and 3.5 parts of olive -derived emulsifying wax to yield a 80 parts of ENR - 50 is mixed with 21 parts of the cured
curable resin . This resin may be cured overnight at 80 ° C. or resin of Example 4 in the previous section . It has been found
within two hours at 125 ° C. to make an elastomeric solid . 25 that there is sufficient shear during the mixing of the ENR - 50
with the cured resin of Example 4 that the cured resin is
Example 5 mechano -chemically broken down (de -crosslinked ) and thus
becomes a source of carboxylic acid functionality that is
The cured elastomeric solid of Example 4 is passed capable of curing the ENR - 50 . This mixture of elastomeric
repeatedly through a tight nip on a rubber mill . The friction 30 gum materials may be further combined with fillers, plasti
ratio is 1.25 : 1 and the nip is set to less than 1 mm . After a cizers, and functional additives to yield a compound that
few passes , the powdery material begins to masticate and may then be cured as an elastomeric solid .
within about 3-7 minutes of mixing a millable gum is The molded materials produced according to Example 6
generated . This millable gum may be sheeted out and and Example 7 have attributes that allow them to be used as
re - cured as a transparent sheet or it may be combined with 35 leather - substitute materials . The blend of a relatively low Tg
fillers, plasticizers , and /or functional additives to yield a materials such as ENR - 50 with a relatively higher Tg
compound that may be cured under heat (e.g. 150 ° C. for 5 material such as the masticized resin yields a bulk material
minutes) to make a thermoset elastomer. The material of with excellent haptics and low temperature flexibility down
example 5 is more easily masticated than the material of to at least -10 ° C. Furthermore, the bulk material glass
example 3. The millable gum may be combined with epoxi- 40 transition temperature can be lowered by incorporating a
dized natural rubber (ENR) and ENR - based compounds and plasticizer such as propylene glycol without negatively
act as a curative for the ENR . impacting the tactile properties of the material . Instead , it
iii . Thermoset Material Blends Based on Virgin ENR and has been found that a plasticizer such as propylene glycol
Regenerated Thermoset Materials Based on Epoxidized (which can be made with a catalytic process known as
Plant Oil and Naturally Occurring Polyfunctional Acid 45 hydrogenolysis to readily convert plant -sourced glycerin
By combining the technology of mechano -chemically and hydrogen to propylene glycol ) acts as both a plasticizer
regenerated thermoset materials ( where such materials have and aid to the creation of " buttery ” haptics by lowering the
been found to regenerate the original chemical functionality surface friction .
of epoxide groups and carboxylic acid groups) with virgin In these examples, it has been found that the combination
ENR , the regenerated functionality is able to cure (i.e. , 50 of high molecular weight ENR and masticized resin yields
crosslink ) the epoxide groups in the ENR without the an optimal balance of green strength , low temperature
addition of additional curative. This is laid out in the flexibility, and room temperature flexibility. Without wish
following examples . ing to be bound by theory, it is believed that there may exist
domains within the final compound that remain rich in the
Example 6 55 resin -based starting thermoset and domains that are more
rich in ENR . The mixture of domains may limit the localized
40 parts of ENR - 50 is mixed with 63 parts of the cured extensibility of the compound, thus reducing the sensation
resin of Example 4 in the previous section . It has been found of grippiness. In support of this theory, remilled resin as
that there is sufficient shear during the mixing of the ENR- 50 illustrated in FIG . 15 was stirred into ethanol overnight; the
with the cured resin of Example 4 that the cured resin is 60 resultant solution showed some small curdled material in the
mechano - chemically broken down ( de - crosslinked ) and thus bottom of the container that would not dissolve . This sug
becomes a source of carboxylic acid functionality that is gests that during the remilling operation, a portion of the
capable of curing the ENR -50 . This mixture of elastomeric thermoset material is mechano - chemically modified through
gum materials may be further combined with fillers , plasti- shear and once the shear drops below a certain threshold , the
cizers, and functional additives to yield a compound that 65 remaining thermoset material does not experience sufficient
may then be cured as an elastomeric solid . In one illustrative shear to break the B -hydroxyester crosslinks. Therefore , the
embodiment, the fillers may include cork powder, ground de - crosslinking is not homogeneously distributed through
 US 11,542,365 B2
39 40
out the material; i.e. some crosslinked domains survive the additional virgin material addition enables closed- loop
remilling process . As a result , the combined ENR and manufacturing in a way not previously envisioned for ther
remilled resin compound will have some portion of previ- moset materials. Importantly, such materials may be still
ously crosslinked resin that survive the mixing process and biodegradable and may be sourced from plant-based raw
act as domains that impart a locally higher Tg and thus less 5 ingredients without the inclusion of petrochemically derived
grippy haptic . precursors .
In another illustrative embodiment it may be desirable to The use of pre -cured thermoset material as a curative for
configure the material such that it exhibits a relatively high ENR is particularly advantageous from a processing stand
Tg , and one illustrative method for increasing the Tg of an point. It has been found that the curative as disclosed in
ENR -50 rubber compound is disclosed below, but other 10 Section 1 and then applied in Section 3 may impart sticki
suitable methods for increasing the Tg of an ENR - 50 rubber
compound according to the present disclosure may be used ness to some of the compounds, especially during mixing .
without limitation unless otherwise indicated in the follow The use of pre - cured thermoset resin as disclosed herein
ing claims . Generally , ENR -50 has a Tg of -24 ° C. as significantly reduces the stickiness of the batch during
prepared. It has been unexpectedly discovered that a stan- 15 the
processing and likewise reduces the tackiness/ grippiness of
molded article .
dard compound based on ENR - 50 with mineral fillers ( e.g. , 5. Foam Material
clay and tale ) along with a curative that is made in accor
dance with methods disclosed elsewhere in this application ; A. Background
i.e. , a reaction product of a naturally occurring polyfunc Most resilient foam products that are commercially avail
tional carboxylic acid (e.g. , citric acid) along with an epoxi- 20 able are based on synthetic polymers , specifically polyure
dized triglyceride (e.g. , ESO ) may be further made to have thane. A key attribute that differentiates so - called memory
plastic - like attributes such that the resulting material may be foam from other foam products is the glass transition
configured as a rigid or semi-rigid material. In one illustra- temperature ( T. ) of the polymer. Rigid foams are generally
tive embodiment, these attributes were found to arise when comprised of polymers with a T , well above room tempera
g
phytic acid is incorporated into the recipe at loadings as low 25 ture , an illustrative example of such a product is polystyrene
as 2 phr and then subjected to a heat treatment. Such a foam (often used in rigid insulation boards and insulated
compound was mixed and molded and found to have initial drinking cups ) . Flexible and springy foams are generally
properties of 11.9 MPa tensile strength and 120 % elonga- comprised of polymers with a T g, well below room tempera
tion . After heat treating at 100 ° C. for 168 hrs , the compound ture, an exemplary example of such a product is a car door
was found to be a rigid plastic with aa strength of 14.8 MPa 30 weather seal based on ethylene -propylene rubber (EPR /
and an elongation of 16.7 % . It was found that reheating the EPDM) . Natural products may be likewise found in both
compound (from room temperature (e.g. , -15 ° C. - 30 ° C. ) to rigid and flexible /springy categories. Balsa wood is a gen
60 ° C. ) decreased the stiffness and increased the elongation ; erally porous and foam -like material that is substantially
thus, the heat treatment did not merely cause embrittlement rigid at room temperature (e.g. , -15 ° C. - 30 ° C. ) . Natural
( characteristic of heat aging of elastomers ) but rather caused 35 rubber latex may be foamed by either the Talalay or Dunlop
a dramatic shift in the Tg from the original -24 ° C. to >20 ° process to make a flexible and springy foam product that is
C. Such a rigid or semi- rigid ( e.g. , plastic ) material may substantially comprised of naturally occurring polymers. To
further be filled with fibrous reinforcements to further date , there is no widespread naturally occurring foam that
improve the tensile strength of the material . has a T g, near room temperature (e.g. , -15 ° C. - 30 ° C. ) to
5. Applicability 40 yield a lossy foam that is the key attribute of memory foam
The recycling of thermoset materials is a particularly materials .
challenging problem for the polymer -materials industry. Natural materials that make flexible foam products today
Some proposed solutions for this challenge have included are often based on natural rubber latex . To make latex
solvent -induced depolymerization, grinding of waste and products stable to temperature excursions , the polymer must
re - integration with new binder, and thermal depolymeriza- 45 be vulcanized ( i.e. , crosslinked ). Vulcanization of natural
tion . None of these solutions are easy to integrate into rubber may occur through a few known methods; most often
existing manufacturing processes . In contrast, the mechani- sulfur vulcanization may be used , but peroxide or phenolic
cally induced de - crosslinking of the thermoset material cure systems may likewise be used . Although sulfur and zinc
according to this disclosure utilizes the very same equipment oxide cure systems may be capable of vulcanizing natural
and methodology used to mix the material in the first place . 50 rubber latex , very often other chemicals are added to
Thereby, an article may be molded using low percentages of increase the cure rate , limit reversion , and provide other
reclaimed material all the way up to 100 % reclaimed mate- functional benefits ( e.g. , anti-oxidants, anti -ozonates, and / or
rial . Such materials may be utilized in articles substantially UV stabilizers ). These additional chemicals may create
identical to articles manufactured with virgin material. chemical sensitivities in certain individuals. Also , natural
In the manufacturing of leather - like materials, it has been 55 rubber latex itself may cause allergic reactions in certain
advantageously found that the inclusion of at least some individuals due to the natural proteins that exist in the latex .
reclaimed and recycled material results in a sheet product Similar natural rubber latex formulations may likewise be
having a naturally occurring texture that is particularly used as a glue for fibrous mats to create a resilient foam -like
pleasing having surface undulations on the scale of 1-10 product. Notably , coconut fiber may be bonded together by
mm that do not require any texture in the mold . Such surface 60 natural rubber latex into a non - woven mat to provide a
undulations may be similar to that exhibited by bison or cushion or mattress material that is substantially all - natural
buffalo leather products and is highly desirable for many in origin . Despite various claims in the prior art of being “ all
applications. natural ,” the cure system and additives to the natural rubber
The ability to integrate waste material (e.g. , product may contain synthetic chemicals that may create chemical
trimming, flawed articles, articles that have reached the end 65 sensitivities in certain individuals; furthermore, the natural
of their useful life, etc. ) into articles without significant loss rubber latex itself may cause allergic reactions in certain
of mechanical properties and without the requirement of individuals due to the residual protein .
 US 11,542,365 B2
41 42
Furthermore, footwear midsoles are most often made amounts of epoxide groups on the ESO and carboxylic acid
from EVA foam for performance footwear. EVA foams have groups on the citric acid occur at a weight ratio of 100 parts
low -density, high -energy resiliency, decent compression set , of ESO to about 30 parts of citric acid . A ratio of ESO : citric
and are easy to form and process . EVA is a petrochemical acid above 1.5 : 1 may build a pre -polymer curative with
polymer that is not bio -based nor biodegradable. Accord- 5 excessive molecular weight ( and hence viscosity ) which
ingly, it would be desirable to have a foam that meets the limits its usefulness as a casting resin . If the ratio of
energy rebound ( resiliency ) and compression set attributes ESO : citric acid is below 0.5 : 1 it has been found that there is
of EVA while being 100% bio -based . so much excess citric acid that after solvent evaporation,
ungrafted citric acid may precipitate out of solution .
B. Summary 10
In addition to controlling the ratio of ESO to citric acid,
according to the present disclosure it has been found that
A foam product based on epoxidized vegetable oil is selective control of the amount of alcohol used as a solvent
disclosed wherein the pre -polymer curative is likewise com- may also be used to tailor the physical properties of the
prised of naturally occurring and naturally derived products resulting elastomeric foam . It has been found that the
of biological origin . The foam product disclosed is created 15 alcohol solvent may itself be incorporated into the elastomer
without the use of additional foaming agent. The foamed by forming ester linkages with the polyfunctional carboxylic
product may be created with or without the requirement of acid that are reversible and thus gas - evolving when the
whipping in air into the pre - cured liquid resin . The foam material is cured at a temperature higher than that required
product disclosed may have a T8, near room temperature to make a porosity - free product. A mixture of two or more
(e.g. , ~ 15 ° C. - 30° C. ) , thus providing a lossy product. 20 solvents may be used to tailor the amount of grafting of an
Additionally, the foam product may be formulated to have a alcohol -containing solvent onto the citric acid - capped oli
T g, below room temperature (e.g. , less than ~23 ° C. ) to gomeric pre -polymer curative.
provide a flexible, springy product. Memory foam attributes For example, and without restriction or limitation unless
may be attained by polymers prepared according to this otherwise indicated in the following claims , isopropyl alco
disclosure . Such polymers are reaction products of the 25 hol ( IPA ) or ethanol may be used as a component of a
pre -polymer curative as described herein above and epoxi- solvent system used to miscibilize citric acid with ESO . IPA
dized vegetable oils , reaction mixtures may also contain or ethanol are capable of forming an ester linkage via a
other natural polymers and modified natural polymers as condensation reaction with citric acid . Since citric acid has
described in further detail below. three carboxylic acids , such grafting reduces the average
In certain embodiments, the foam product may contain a 30 functionality of the citric acid molecules that are reacting
certain fraction of epoxidized natural rubber. Notably, the with the ESO . This is beneficial in creating an oligomeric
process that creates epoxidized natural rubber also reduces structure that is more linear and therefore less highly
the free protein that may create allergic reactions in certain branched . Acetone may be used as one component of a
individuals. The reduction in allergic response for epoxi- solvent system used to miscibilize citric acid with ESO , but
dized natural rubber compared to untreated natural rubber is 35 unlike IPA or ethanol, acetone itself is not capable of being
greater than 95 % . grafted onto the citric acid -capped oligomeric pre -polymer
Disclosed is a castable resin comprising EVO ( and /or any curative . Indeed , during creation of the oligomeric pre
suitable epoxidized triglyceride as disclosed above) com- polymer curative it has been found that the reactivity of the
bined with the pre -polymer curative (as disclosed above in pre -polymer curative is determined , in part, by the ratio of
Section 1 ) , and in one illustrative embodiment ENR that has 40 IPA or ethanol to acetone that may be used to solubilize citric
been solubilized in the EVO . acid with ESO . That is , in reaction mixtures with the similar
It has been found that a pre -polymer curative, as disclosed amounts of citric acid and ESO , a pre -polymer curative
in Section 1 , can be created that eliminates the risk of created from a solution with a relatively high ratio of IPA or
porosity when cured within a certain temperature range , but ethanol to acetone creates a lower viscosity product than
that evolves gas during the curing process when conducted 45 pre -polymer curative created from a solution with a rela
within a second higher temperature range . Furthermore , the tively low ratio of IPA or ethanol to acetone under similar
oligomeric pre -polymer curative may incorporate substan- reaction conditions . Also , the amount of IPA or ethanol
tially all of the polyfunctional carboxylic acid so that no grafted on the pre -polymer curative determines the extent to
additional solvent is required during the curing process. For which such IPA or ethanol is evolved when the formulated
example , citric acid is not miscible in ESO but they may be 50 resin is foamed at a temperature higher than that required to
made to react with each other in a suitable solvent. The make a porosity - free resin product.
amount of citric acid may be selected so that the pre - polymer
curative is created so that substantially all of the epoxide C. Illustrative Methods and Products
groups of the ESO in the pre -polymer curative are reacted
with carboxylic acid groups of the citric acid . With suffi- 55 Illustrative blends that create resilient memory foams
ciently excess citric acid, the pre -polymerization extent may have been created from a combination of inputs that include
be limited so that no gel fraction is formed . That is , the target a pre -polymer curative, a liquid blend of epoxidized natural
pre -polymer curative is aa low molecular weight ( oligomeric ) rubber and epoxidized vegetable oil and may contain
citric - acid capped ester -product formed by the reaction unmodified epoxidized vegetable oil .
between carboxylic acid groups on the citric acid with 60 In aa first illustrative embodiment of a foam material, the
epoxide groups on the ESO . resilient memory foam is produced using a pre -polymer
Illustrative oligomeric pre -polymer curatives may be cre- curative creation and by dissolving 50 parts of citric acid in
ated with weight ratios of ESO to citric acid in the range of 125 parts of warm IPA , accelerated by mixing ( again with
1.5 : 1-0.5 : 1 . If too much ESO is added during pre - polymer reference to FIG . 1 ) . After dissolution of the citric acid , 50
curative creation, the solution may gel and further incorpo- 65 parts of ESO is added to the stirring solution . The solution
ration of ESO to create the target resin becomes impossible. is preferably mixed and reacted at temperatures of 60 °
Note that on a weight basis , stoichiometric equivalent C. - 140 ° C. with optional use of mild vacuum ( 50-300 Torr ).
 US 11,542,365 B2
43 44
One illustrative batch was mixed in a jacketed reactor vessel gas , likely removal of the grafted IPA , at temperatures at or
with a jacket temperature of 120 ° C. ( solution temperatures above 200 ° C. As previously described , certain catalysts are
of ~70 ° C. - 85 ° C. ) and the citric acid grafting onto ESO known in the art to speed up the carboxylic acid addition to
occurred concurrently with IPA evaporation. At the end of epoxide groups and such may be used in formulating recipes
the reaction sequence it was discovered that roughly 12 parts 5 according to the present disclosure without limitation unless
of IPA was grafted onto the combined 100 parts of ESO and
citric acid . Accordingly, temperatures above the boiling otherwise indicated in the following claims .
Referring now to FIGS . 20 & 20A , shown therein is a
point of IPA and application of vacuum could no longer foam that is suitable for certain footwear applications ,
yield IPA condensate in the condensing system . Calculations wherein the foam is substantially or completely free of
reveal that of the starting carboxylic acid sites on the citric 10 petrochemical inputs and does not require petrochemical
acid, roughly 31 % reacted with epoxide groups on the ESO blowing agents. A slab of such foam is shown generally in
( assuming all of the epoxides were converted during the FIG . 20 and a detailed view of an exterior surface and a
reaction to ester linkages ), roughly 27 % of the carboxylic cross - section thereof is shown in FIG . 20A . This foam is
acid sites reacted with IPA to form pendant esters , and based on epoxidized natural rubber and is cured with a
roughly 42 % remain unreacted and available for crosslink-
ing the resin in a subsequent processing step . However, these 15 curative that is made according to the preceding description.
calculations are for illustrative purposes only and in no way Additionally, this foam may be made into slabs with a
limit the scope of the present disclosure unless otherwise thickness between approximately 2.5 mm and 25 mm in
indicated in the following claims . which the heat transfer may be accomplished with heated
In a second illustrative embodiment of a foam material, plates applied to the two planar surfaces.
20 Referring
the resilient memory foam was created via a rubber -con now to FIG . 21 , which provides a depiction of
taining resin precursor. Epoxidized natural rubber may be one illustrative embodiment of a method of making such a
included in resin -based formulations at levels below twenty foam , the heated plate on top ( floating platen 210 ) may be
five weight percent ( 25 wt % ) and still yield a pourable sized and / or configured to exert between 0.5 psi and 2.0 psi
liquid. Creation of the rubber - containing precursor may be 25 vertical pressure on the expanding foam 200 to keep it from
developing non -planar attributes and to keep any large air
done in two - stages without requiring the use of a solvent for pockets (that may be introduced by mixing and / or sheeting)
rubber dissolution . In the first stage 100 parts of epoxidized from growing into large defect sites . The expanding foam
natural rubber ( ENR - 25 ) are mixed with 50 parts of ESO 200 may be positioned between the floating platen 210 and
using rubber mixing techniques (a two - roll mill or internal
mixer ). This yields a very soft gum that cannot effectively be
further mixed on rubber processing equipment, but with the
30 lifting platen 220. However, other methods of making a
foam with the desired characteristics and according to the
application of heat (e.g. , 80º C. ) additional ESO may be present disclosure without limitation unless otherwise indi
mixed into the rubber with a Flacktek Speedmixer or alter cated in the following claims .
native low -horsepower equipment (e.g. , a sigma -blade TABLE 3
mixer) to create a flowable liquid containing 25 % ENR - 25 35
and 75 % ESO . Illustrative Ranges of Ingredients .
A third illustrative embodiment of a foam material may Ingredient Parts per Hundred Rubber Ingredient Class
also produce aa resilient memory foam -type creation . In this
embodiment, the foamable resin is produced via mixing and ENR -25 100 Polymer
curing. For this illustrative embodiment, 40 parts of pre- 40 Starch
Cork powder 0-40
0-100
Filler
Filler
polymer curative from the first illustrative embodiment of a Precipitated Silica 0-10 Filler
foam material was added to 80 parts of rubber - containing Epoxidized Soybean Oil 0-10 Plasticizer
resin from the second illustrative embodiment. The resulting Castor Oil 0-10 Plasticizer
combination was then mixed with Flacktek Speedmixer Plant - Based Wax 0-1 Release Aid
until a homogeneous solution was obtained ( about 10 min- 45 Curative (as defined
herein above )
5-20 Curative
utes of mixing ) . This resin was cured using the following
two procedures:
1. Resin cured on 200 ° C. (nominal temperature) hot As shown in Table 3 , a foam produced according to the
griddle (PTFE coated) just like a pancake . The material present disclosure may include a varying array of ingredi
foamed to a relatively homogenous article with 50 ents, and the specific ingredients and their relative propor
memory -foam characteristics ; specifically, lossy tions within the foam in no way limit the scope of the present
behavior. A depiction of the resulting material is shown disclosure unless otherwise indicated in the following
in FIG . 13 . claims . In one illustrative embodiment, epoxidized natural
2. Resin was vacuum degassed after mixing and placed on rubber 25 ( ENR - 25 ) may be mixed with fillers such as cork
the same 200 ° C. hot griddle. In this instance , porosity 55 powder, corn starch , silica , plasticizing oils , and curative
was observed over the heating element (measured prepared according to the present disclosure as described in
temperature 210 ° C. ) but no porosity was observed detail herein above . This mixture may be sheeted out on a
over the region of the griddle without the heating two - roll mill or calendar to a thickness roughly half of the
element (measured temperature 180 ° C. ) . Depictions of final target thickness. The calendered sheet may be placed
the resulting materials are shown in FIG . 14 . 60 between two heated steel plates for both curing (vulcaniza
From these two procedures, it is clear that there may be tion) and foaming. In one illustrative embodiment, a mul
two sources of porosity. One source may involve small tiple - daylight platen press , such as that shown in FIG . 16 ,
bubbles of air that are incorporated during mixing . Addi- may be used in which the weight of a single platen exerts
tional experimentation has shown that the presence of ENR- between 0.5 psi and 2.0 psi on the calendered sheet.
25 in the resin is an important contributor to stabilizing this 65 While the mixture expands , the heat from the top ( float
incorporated air and preventing bubble coalescence during ing ) platen 210 and bottom ( fixed ), or lifting platen 220
the curing stage . The second source of porosity is evolved convey heat into the compound to simultaneously cure the
 US 11,542,365 B2
45 46
rubber. The cure time may be directly impacted by the polymer ( s) are bio -based ( i.e. , coming from agricultural
thickness of the sheet and may be between 5 minutes and 2 sources , either in entirety or in substantial majority ) with
hours (wherein longer cure times may be required for thicker nominal or no detectable synthetic and / or petroleum -based
slabs ) . The curing temperature is preferably between 120 ° C. compounds. Such types of materials include , but are not
and 180 ° C. , or even more preferably between 130 ° C. and 5 limited to unless otherwise indicated in the following
170 ° C. , and even more preferably between 140 ° C. and claims : a foam material that is applicable to midsole and / or
160 ° C. without limitation unless otherwise indicated in the insole components , a solid molded material that is appli
following claims . After curing, a slab of foam made accord tocable to the outsole, a sheet-good material that is applicable
the upper components, an adhesive material that may be
ing to the present disclosure may exhibit performance attri
butes as shown in Table 3. However , a foam produced 10 used to bond components together, a coating material that
according to the present disclosure may be configured to may be used to provide preferred haptics and possibly coat
exhibit other properties and / or other values and / or ranges of textile material (s ), a textile material (used as a knit upper for
the properties shown in Table 4 without limitation unless example or a backer for the sheet - good material ), and / or a
otherwise indicated in the following claims . rigid or semi-rigid material (which may be used for various
15 components such as buckles , clasps , eyelets, zippers , loops ,
TABLE 4 eye stays , clips , and / or similar components without limita
tion unless otherwise indicated in the following claims ) .
Illustrative properties of a foam made Another object of illustrative embodiments of the present
according to the present disclosure . disclosure is to provide a mechanical processing technology
Dynamic 20 that may render said materials reformable into a new article
Density Resiliency Compression Set Energy Efficiency comprising one homogeneous blend of the various types of
input materials used in the entire article . It is a further object
0.35-0.55 g /cm3 >20 % > 10 % > 60 %
of illustrative embodiments of the present disclosure to
provide a mechanical processing technology that utilizes
Foams made according to this disclosure may be used in 25 mechano -chemical reactions that render the blended types of
footwear midsoles , insoles , and foam padding for tongues at input materials capable of being remolded (using thermoset
various thicknesses. Of particular utility may be the use of molding chemistries) into a new article. Other objects of
foams according to this disclosure in footwear midsoles . illustrative embodiments of the present disclosure may be
Foams produced according to the present disclosure may be utilized , inherent, and / or expressed herein without limitation
applicable to other products without limitation unless oth- 30 unless otherwise indicated in the following claims.
erwise indicated in the following claims. Materials that may be suitable for inclusion in such
illustrative embodiments of a footwear article include, but
D. Applications /Additional Illustrative Products are not limited to unless otherwise indicated in the following
claims , those manufactured according to technologies dis
Materials according to this disclosure may be used as 35 closed in U.S. Pat . Nos . 10,400,061 ; 10,882,950 ; 10,882 ,
flooring, exercise mats , bedding, shoe insoles , shoe outsoles , 951 , and other related pending applications by the same
or sound absorption panels without limitation unless other- inventor( s ). Such materials may utilize a mechano -chemi
wise indicated in the following claims . cally reversible thermoset curative. Materials utilizing this
Materials according to this disclosure may be molded into technology (both epoxidized polymer (s ) and B -hydroxyes
complex three - dimensional articles and multi - laminated 40 ters as cure sites ) are able to be homogeneously combined
articles. Three - dimensional articles may also consist of regardless of the starting form ; either sheet good , molded
multiple material formulations arranged at various locations component, foam , coating material, rigid or semi- rigid mate
within an article to provide functionality required for each rial, or adhesive interlayer without limitation unless other
location . wise indicated in the following claims .
The resilient memory foam based on vegetable oil may be 45 Generally, at least six types of materials may be manu
used in applications where polyurethane is used today. Such factured according to the present disclosure, which materials
applications may include shoes, seating, flooring, exercise may be used in various articles as disclosed herein or as
mats , bedding, sound absorption panels, and the like without suitable for the particular material or combinations ofmate
limitation unless otherwise indicated in the following rials without limitation unless otherwise indicated in the
claims . Many of these articles are consumable items that if 50 following claims . These various material types may share at
made from synthetic polyurethane foams are non -biodegrad- least a common chemistry in that each may include B -hy
able and are non -recyclable. If such items are made from the droxyester linkages, and that in various illustrative embodi
material disclosed herein , they would be biodegradable and ments each type of material may be constructed with only
thus not create a disposal problem . naturally occurring compounds (and without use of any
6. Additional Articles 55 animal - hide leather) yet exhibit the performance character
Summary istics desired for a wide range of applications. That is , the
One object of various embodiments of the present disclo- materials may be completely petro -chemical, synthetic
sure is to provide methods of manufacture for various chemical, and / or animal -hide leather free yet simultaneously
articles ( including but not limited to footwear unless other- perform similar to or better than the prior art materials. The
wise indicated in the following claims), wherein an article 60 commonality in chemistry among the various materials
may be comprised of various types of materials that all disclosed herein may result in various advantages, including
utilize the same class (es ) of polymer( s ) for all functional but not limited to the miscibility of virtually any combina
components therein . That is , the continuous polymer phase tion and / or configuration of the various materials during a
of all types of materials are compatible with each other. mechano - chemical process ( such as that disclosed herein for
Additionally, another object of illustrative embodiments 65 recycling materials ) without limitation unless otherwise
of the present disclosure is to provide such types of materials indicated in the following claims . The materials may be
that all utilize the same class (es ) of polymer ( s) wherein said bonded to one another during processing in any order,
 US 11,542,365 B2
47 48
number, layers, thicknesses , configuration, etc. suitable for material, third material, fourth material, fifth material, and /
2

the material and particular application thereof without limi- or sixth material; the second material may be bonded to the
tation unless otherwise indicated in the following claims . third material, fourth material, fifth material, and / or sixth
A first material may be configured as a leather - like material; the third material may be bonded to the fourth
material as described in detail herein above, wherein the 5 material, fifth material, and/or sixth material; the fourth
leather - like material may serve as a substitute for applica- material may be bonded to the fifth material and /or sixth
tions currently served by synthetic leathers and / or animal- material; and the fifth material may be bonded to the sixth
hide leathers without limitation unless otherwise indicated in material in any suitable combination , ordering, and / or lay
the following claims . Such a material may be comprised of ering without limitation unless otherwise indicated in the
a
a thermosetting elastomer that is crosslinked with B -hy- 10 following claims . Additionally, an article may include more
droxyester linkages, wherein said first material is defined as than one layer of a specific type of material separated by
being a leather - like material with a glass transition tempera- layers for other types of material ( e.g. , a layer of the second
ture generally below room temperature ( e.g. , less than ~ 23 ° material sandwiched between two layers of the first mate
C. ) , wherein said first material may be configured as gen- rial) in any suitable configuration without limitation unless
erally planar and having a thickness between about 0.3 mm 15 otherwise indicated in the following claims . The common
and 2.5 mm but without limitation unless otherwise indi chemistry among the six materials, and particularly the
cated in the following claims . B -hydroxyester linkages , allow any and all combinations of
A second material may be comprised of the same ther- the six materials to be miscible during certain types of
mosetting elastomer that is crosslinked with B -hydroxyester recycling as described in detail below, including but not
linkages, wherein the second material may be defined as 20 limited to mechano - chemical processing (which may serve
being a foam material with a glass transition temperature to selectively and / or reversibly break or the B -hydroxyester
generally not greater than room temperature or just above linkages or “ de - crosslink ” the material) unless otherwise
room temperature ( e.g. , around ~23 ° C. or between -20 ° and indicated in the following claims .
~ 30 ° C. ) and having a density less than 0.7 g/ cc but without Detailed Description
limitation unless otherwise indicated in the following 25 An illustrative embodiment of a footwear article produced
claims . according to the present disclosure may contain one or more
A third material may be comprised of the same thermo- types of materials that utilize a polymer matrix that is
setting elastomer that is crosslinked with B -hydroxyester molded and cured wherein B -hydroxyesters are crosslinks
linkages, wherein the third material may defined as being a between epoxidized polymer inputs. An illustrative embodi
molded elastomer material with a glass transition tempera- 30 ment of a footwear article according to this disclosure may
ture generally not greater than room temperature or just over contain textile components without limitation as well unless
room temperature ( e.g. , around -23 ° C. or between -20 ° and otherwise indicated in the following claims . In one illustra
~ 30 ° C. ) , wherein the third material may be cast and / or tive embodiment, said textile components are preferably
molded in aa three - dimensional in shape but without limita- made from bio -based inputs such as : cotton , regenerated
tion unless otherwise indicated in the following claims . 35 cellulose , various animal fibers (wool, silk , alpaca fiber,
A fourth material may be comprised of the same thermo- etc. ) , protein fibers ( soy protein , casein) , and man -made
setting elastomer that is crosslinked with B -hydroxyester bio - based fibers ( e.g. polyhydroxyalkanoates, polylactic
linkages, wherein the fourth material may be defined as acid ) without limitation unless otherwise indicated in the
being a coating material with a glass transition temperature following claims . For certain applications it may be prefer
generally below room temperature (e.g. , less than ~23 ° C. ) , 40 able to utilize foams based on epoxidized natural rubber
wherein the fourth material may be configured with a (ENR) as the continuous polymer matrix that are cured
thickness from 10 to 100 microns but without limitation ( vulcanized ) via B -hydroxyesters. In one illustrative appli
unless otherwise indicated in the following claims . cation a preferred curative may be prepared according to
A fifth material may be comprised of the same thermo- U.S. Pat . No. 10,400,061 which is incorporated by reference
setting elastomer that is crosslinked with B -hydroxyester 45 herein in its entirety.
linkages, wherein the fifth material may be defined as being Mechano - chemical recycling of footwear articles as
an adhesive material with a glass transition temperature manufactured according to illustrative embodiments of the
generally below room temperature (e.g. , less than ~23 ° C. ) , present disclosure may involve at least two steps : ( 1 ) the
and wherein the fifth material has aa thickness of 1 mm or less pre - shredding of the footwear article; (2 ) subjecting the
but without limitation unless otherwise indicated in the 50 shredded material to high - shear mixing ( such as may be
following claims . Further, it is contemplated that the adhe- accomplished by a two -roll mill as is commonly used in
sive material may generally be positioned between two rubber mixing or an internal mixer as is commonly used in
substrates, wherein either substrate may be one of the other rubber mixing ) ; ( 3 ) shaping the homogenously mixed elas
materials disclosed herein but without limitation unless tomeric material to an appropriately sized pre - form (whether
otherwise indicated in the following claims. 55 through calendering or extrusion or other suitable process );
A sixth material may be comprised of the same thermo- and / or 4 ) molding a desired article through heat and pressure
setting elastomer that is crosslinked with B - hydroxyester to yield a formed thermoset material.
linkages, wherein the sixth material is defined as being a
rigid or semi- rigid material with a glass transition tempera I. Foams
ture generally greater than room temperature ( e.g. , greater 60
than ~23 ° C. ) , and wherein the sixth material is substantially Foams are used in footwear components as midsoles ,
non - crystalline in structure but without limitation unless insoles , tongue padding, and /or around the cuff area. Foams
otherwise indicated in the following claims . of various thicknesses and densities are possible within the
These six materials may be bonded to one another in inventive framework disclosed herein . In one illustrative
nearly any combination to fabricate an article having a 65 embodiment, foams may be manufactured by mixing an
desired set of characteristics and / or functional attributes . ENR -based batch of material containing a substantial ( > 10
That is , the first material may be bonded to the second wt % ) content of cork powder. It has been discovered that
 US 11,542,365 B2
49 50
certain kinds of cork powder can be incorporated into may be used to make a sheet preform that is substantially
ENR -based recipes and entrain trapped air that may expand free of large trapped - air pockets.
upon low -pressure curing to yield foams with densities less
than 0.75 g /cc. Even more preferably, certain recipes may be II . Outsoles
subject to low -pressure curing and achieve densities less 5
than 0.6 g/cc . Even more preferably, certain recipes have Outsoles used in many footwear articles are 3 -dimension
discovered that, even though they contain no chemical ally molded components that comprise features that provide
blowing agents , still achieve densities less than 0.5 g/cc . traction, provide wear material, and interface with the other
In one particular illustrative embodiment, a recipe con- 10
components of the shoe. Rubber outsoles are well known in
taining 100 parts of ENR was combined with a total of 35 the art; they are often made of thermoset (i.e. vulcanized )
parts of various cork powders along with 15 parts of natural elastomers but may also be made from thermoplastic elas
plasticizers, 10 parts of precipitated silica , and curative (as tomers ( TPE ) of which there are many subtypes that may
further described in U.S. Pat. No. 10,400,061 ) to yield a be suitable , including but not limited to : ethylene vinyl
recipe that was sheeted out and cured with low pressure 15 acetate copolymers (EVA ), styrene butadiene styrene ( SBS ) ,
( 0.5-4 psi ) , It has been found that pressure - free curing may styrene ethylene butadiene styrene ( SEBS ) , other styrenic
result in sheets that are not smooth and may have large block copolymers ( generically TPS ) , polyether block amide
trapped - air pockets. Low -pressure curing may result in an ( TPA ), copolyester ( TPC ) , thermoplastic polyurethane
optimal balance of sufficient pressure to reduce the propen ( TPU ), thermoplastic polyolefins ( TPO ). Additionally, out
sity of large trapped - air pockets to expand while still allow- 20 soles may be made from thermoplastic vulcanizates ( TPV );
ing for the expansion of air to create pores on the 0.1-3 mm compounds that contain crosslinked rubber within a ther
size scale . Curing temperatures may be 120 ° C. - 180 ° C. , or moplastic matrix . The highest performing outsoles are made
even more preferably between 130 ° C. - 170 ° C. , and in some from thermoset elastomers . Among the most common ther
cases between 140 ° C. - 160 ° C. Concurrent with the curing moset elastomers that may be used for outsoles , natural
process the expansion of the entrained air to form the 25 rubber (NR) , styrene butadiene rubber ( SBR) , butadiene
porosity. That is , the sheet (or article) may be placed in an rubber (BR) , and ethylene propylene diene monomer
oven at one ( higher) density and the sheet (or article ) (EPDM) are the most widely used . Polychloroprene (CR ) or
expands with the application of heat to reach the target acrylonitrile butadiene rubber (NBR ) may be used for oil
thickness and a second (lower ) density. Immediately after resistant sole formulations.
expansion, and even during expansion, the curing reaction 30 According to an illustrative embodiment of the present
may be instigated and may act to chemically fix the new disclosure , a preferred thermoset elastomer outsole formu
dimensions in -place . In one illustrative embodiment, a sheet lation may be based on epoxidized natural rubber ( ENR ).
that is placed into an oven or between hot plates at 5 mm ENR is commercially available in two grades : ENR - 25 and
thickness may expand to a sheet that is 9-11 mm in thickness ENR - 50 , which are differentiated by their respective degrees
after expansion and curing. Surprisingly, it has been found 35 of epoxidation; 25 % of the double bonds are converted to
that vertical pressure applied to a preform may be sufficient epoxides in ENR - 25 while 50 % of the double bonds are
to constrain lateral growth while allowing vertical growth . converted to epoxides in ENR - 50 . According to one illus
That is , the thickness of the sheet may grow while the lateral trative embodiment, ENR - 25 may be used for the outsole
dimensions remain relatively unchanged . base rubber. ENR may be crosslinked ( vulcanized ) through
If oven curing is used, it may be preferable to have a 40 means known in the art for unsaturated elastomers ; includ
preheated metal plate to place on top of the foaming sheet to ing but not limited to sulfur vulcanization , peroxide vulca
apply the target pressure range ( 0.5-4 psi ) . In one illustrative nization , alkylphenol vulcanization ( so - called “ resin cure ”) ,
embodiment, a custom molded shape may be created by and radiation vulcanization . Additionally, because ENR con
manufacturing a preform of dimensions roughly half as thick tains epoxy functional groups , there are other cure mecha
as the final target thickness (including any convolutions or 45 nisms that may be used that are uniquely suited to reactions
variations in thickness required ), placing a preheated metal with the epoxy functionality. Polyfunctional amines ,
mold on the top of preform , and allowing said preform to polyfunctional acids , and polyphenol compounds may all be
expand to the final target shape. In one illustrative embodi- used to crosslink epoxidized polymers such as ENR . Among
ment, said custom molded shape may be aa shoe midsole . In simple polyfunctional molecules that may be used to cross
this instance , the midsole preform may be created by press- 50 link ENR , the bio - based PriamineTM molecules from
ing the rubber compound into a shape that is substantially Croda — all polyfunctional amines- are one pathway.
similar to the contours of the final midsole - but roughly half Another group of polyfunctional molecules that may be used
of the final target thickness. The midsole preform may then to crosslink ENR are the polyfunctional carboxylic acids .
be placed between two heated metal molds ( one side may be For certain illustrative embodiments , preferred naturally
a simple plate) to both foam the material and cure the 55 occurring or naturally derived polyfunctional carboxylic
material concurrently. The heat from the metal molds ( again ,acids include, but are not limited to unless otherwise indi
one side may be a simple plate ) will cause the entrained air cated in the following claims , citric acid , tartaric acid ,
to expand and increase the thickness of the rubber, reducing succinic acid , malic acid, maleic acid, oxalic acid , azelaic
the density, and the rubber will cure . acid, dodecanedioic acid , malonic acid , sebacic acid , glu
For articles that do not require complex contours, the 60 taric acid , glucaric acid , fumaric acid , crocetin , muconic
creation of sheet preforms may be created by calendering or acid, citraconic acid, mesaconic acid , itaconic acid , glutinic
extruding the rubber compound to a thickness that is less acid, glutamic acid , aspartic acid , acetonedicarboxylic acid ,
than the final target thickness. That is , a 5 mm calendered aconitic acid , agaric acid , and phytic acid . Another class of
sheet may foam to a final thickness of 9-11 mm . In some potential curatives are those that are reaction products
instances, the thickness of the final foam would require a 65 between a polyfunctional naturally occurring carboxylic
preform thickness that is beyond the range of control that is acid and an epoxidized plant oil ; such reaction products are
possible with calendering. In such cases , sheet extrusion further disclosed in U.S. Pat . No. 10,400,061 .
 US 11,542,365 B2
51 52
When outsoles are manufactured with certain classes of a sufficiently vulcanized adhesive . In one illustrative
curatives according to this disclosure, those compounds are embodiment, the adhesive may be catalyzed before usage so
able to be recycled according to mechano - chemical process- that temperatures lower than 100 ° C. and times less than 30
ing and are miscible with other articles, whether they be minutes are sufficient to cure the adhesive .
foams or sheet goods , that utilize closely related cure 5 In another illustrative embodiment of a suitable adhesive
systems and polymer types. For example, an outsole that is prepared according to the present disclosure , the adhesive
manufactured with ENR that is cured with polyfunctional may be a 1 - part ( 1K) thermosetting system that comprises a
carboxylic acids may be mechno -chemically recycled con- material that is partially reacted to completion at one tem
currently (and miscibly ) with aa foam or sheet - good (used as perature (e.g. a first reaction temperature of ~ 40 ° C. - 60 ° C. )
a shoe upper) that also is made using ENR that is cured with 10 and then cooled to a temperature for storage that is less than
polyfunctional carboxylic acids . This is true whether the room temperature (e.g. , less than -23 ° C. ) and preferably
ENR of one component ( or subcomponent) is ENR - 25 and stored at refrigerated temperatures (e.g. , less than ~ 5 ° C. ) ,
another compa (or subcomponent) of the shoe utilizes and even more preferably stored at deeper freezing tempera
ENR - 50 as the base rubber. Furthermore, ENR - based com- tures (e.g. , less than ~ -15 ° C. ) . This 1K thermosetting
ponents ( or subcomponents ) may be mechno -chemically 15 system may be reacted at the first reaction temperature with
processed concurrently ( and miscibly ) with materials that a naturally occurring polyfunctional carboxylic acid and an
are reaction products between polyfunctional carboxylic epoxidized plant -based triglyceride. At this first reaction
acids and epoxidized plant oils . Various types of such temperature , the naturally -occurring polyfunctional carbox
mechano - chemical processing are disclosed in U.S. Pat . No. ylic acid ( e.g. citric acid) may be miscibilized with the
10,882,951 . 20 epoxidized plant-based triglyceride ( e.g. epoxidized soy
Outsole thermoset elastomer compounds formulated bean oil , ESO ) with a miscibilizing solvent ( e.g. acetone,
according to this disclosure may utilize fillers that are only isopropyl alcohol , or ethanol ). At the first reaction tempera
bio -based and mineral based . Non -marking soles may be ture, it has been found that a stable intermediate product may
formulated without carbon black as a filler; instead they may be created that creates a pre -polymer in stoichiometric
use precipitated silica as the primary reinforcing agent. 25 balance but that is not completely polymerized. After that
Alternatively, rice husk ash may be used as an alternative first reaction is progressed sufficiently — in one illustrative
silica source that imparts similar primary reinforcing ben- embodiment this may take 16-32 hours, or more preferably
efits. In some illustrative embodiments, mineral fillers that this may take 20-28 hours the temperature may be lowered
may be used include talc , mica , wollastonite , clay ( s ) , sepi- to a second temperature at which residual miscibilizing
olite , muskovite, and other silicates and aluminates . In some 30 solvent may be vacuum extracted . This second temperature
illustrative embodiments that do not require translucency, may be between ~ 15 ° C. - 40 ° C. , or more preferably between
agricultural byproducts may be used as fillers. Common ~20 ° C. - 30 ° C. At this second (lower ) temperature , the
agricultural byproducts include, but are not limited to , reaction rate may be considerably slowed such that the
materials such as cork powder, ground rice hulls, ground solvent may be removed without causing excessive pre
coir fiber, cellulosic powders , various ground nut powders, 35 polymer growth ( and thus viscosity increase) . After the
and ground grasses (e.g. Miscanthus powder ). In general, solvent has been removed (which in on illustrative embodi
high performance outsole compounds may contain some ment may be performed by vacuum) , the reaction product
primary reinforcing filler ( s) and may contain various extend- may be stored at sub - ambient temperatures ( as already
ing fillers that improve processing but do not significantly described ). This 1K thermosetting adhesive system may be
impact strength and abrasion performance attributes . 40 applied to various articles, article components, and /or foot
wear components and then cured ( vulcanized ) at ~ 100 °
III . Manufacture of Adhesive C. - 150 ° C. in less than 30 minutes to set the adhesive joint.
In one illustrative embodiment, the adhesive may be cata
Many types of footwear are constructed using adhesives. lyzed before usage so that temperatures lower than 100 ° C.
Adhesives may serve as fixturing aids to supplement sewing, 45 and times less than 30 minutes are sufficient to cure the
they may be the primary attachment medium between mid- adhesive .
soles and shoe uppers ( and /or other footwear / article com
ponents ), they may be the primary attachment medium IV . Coated Textiles
between midsoles and outsoles ( and /or other footwear/ ar
ticle components ), and they may be used to secure foxing or 50 Generally, for some applications it may be desirable to
other elements to the outside of the shoe surface. Many configure one or more portions of an article as a coated
adhesives in use for footwear construction are elastomeric textile . Specifically , but without limitation unless otherwise
and function as contact adhesives (with high initial tack ). indicated in the following claims , all or a portion of a shoe
Many are solvent - based to facilitate dispensing and spread- upper may be comprised of a coated textile.
ing the adhesive. Many are heat -cured thermosets. Most all 55 In an illustrative method for manufacturing such aa coated
adhesives in current use are petrochemical -based. textile , a resin prepared according to the present disclosure
According to the present disclosure, am entire class of may be diluted in a solvent. The resulting solution may be
adhesives based on illustrative embodiments of bio -based applied to a fabric and / or textile via any suitable method
resins may be used in various articles / footwear. In one using any suitable apparatus unless otherwise indicated in
illustrative embodiment, the adhesive may be aa 2 -part (2K)
thermosetting system that comprises a curative prepared as
60 the following claims. It is contemplated that for some
applications the solution may be sprayed , rolls, or padded
disclosed in U.S. Pat . No. 10,400,061 and an epoxidized onto the fabric and / or textile .
plant-based oil . In one illustrative embodiment, the adhesive After the solution is applied to the fabric and /or textile ,
is solvent - free and substantially petrochemical - free . In one the solvent may be allowed to evaporate and the resin may
illustrative embodiment the epoxide & carboxylic acid reac- 65 be cured . The solvent evaporation may be achieved under
tion is catalyzed to allow for a thermosetting reaction to ambient pressure and / or temperature or under reduced pres
occur at ~ 100 ° C. - 150 ° C. in less than 30 minutes to yield sure and / or increased temperature without limitation unless
 US 11,542,365 B2
53 54
otherwise indicated in the following claims . The resin cure addition , illustrative embodiments of the thermosetting
may be achieved under ambient pressure and /or temperature polymers of this disclosure may be mechano -chemically
or under increased temperature and / or pressure without recyclable using high -shear low -temperature mixing
limitation unless otherwise indicated in the following process (es) as disclosed in U.S. Pat . No. 10,882,951 . It has
claims . 5 been found that incorporation of fabrics (e.g. , a cotton upper
In one illustrative embodiment of a method of manufac- or a cellulosic backing fabric for aa leather - like material) does
turing a coated fabric and / or textile , but without limitation not inhibit the mechano - chemical recyclability as such fab
unless otherwise indicated in the following claims , the rics are dispersed into the resultant mixed product and act as
coated fabric and / or textile may be manufactured without a fibrous reinforcement to the compound .Therefore, an illus
solvent or with a minimal amount of solvent. In such a 10 trative embodiment of a footwear article contemplated by
method, an aqueous emulsion may be prepared with a resin this disclosure may include two or more instances of mate
configured as those previously described herein above, rials types ( e.g. , a foam and an outsole , or a foam / outsole
wherein the aqueous emulsion may subsequently be applied unit and an ENR - based material upper ( fabric -backed or
to the fabric and /or textile . In such a method, the aqueous not ) , or a foam and an outsole with a fabric upper , etc. ) ,
emulsion may be prepared using a solvent - free or solvent- 15 wherein such materials may be co -molded, or alternatively
poor resin that may be mixed under relatively high -shear bonded with an adhesive from same family of thermosetting
conditions with a suitable surfactant. Utilizing the proper polymers. The mechano -chemically recyclable attribute of
amount of dilution of resin in the aqueous emulsion and the ENR - based material curative or resin - based adhesive (as
proper application of the aqueous emulsion to the fabric discussed herein ) may enable the entire footwear article to
and / or textile (e.g. , small enough emulsion droplets, flow 20 be subject to the same mechano -chemical recycling treat
rates and flow characteristics of aqueous emulsion , etc.) may ment without requiring separation of the constituent com
result in the desired attributes of the coated fabric and / or ponents .
textile (e.g. , adequate coverage , penetration of the fabric In one illustrative embodiment of an article configured
and / or textile , etc.) . according to the present disclosure the article may be
After application of the aqueous emulsion to the fabric 25 configured as a slide sandal having the above - referenced
and / or textile, the treated fabric and / or textile may be combination of materials . In this embodiment, three con
allowed to dry under ambient pressure and /or temperature or stituent components may include an outsole , a foam , and an
under reduced pressure and / or increased temperature with- ENR -based material strap . The outsole may be molded in a
out limitation unless otherwise indicated in the following compression mold as is commonly practiced in the art. The
claims . The resin cure may be achieved under ambient 30 outsole may be comprised of an ENR -based compound that
pressure and / or temperature or under increased temperature is cured with curative formulated according to U.S. Pat . No.
and / or pressure without limitation unless otherwise indi- 10,400,061 . A strap also made from an ENR -based com
cated in the following claims. pound that is cured with curative formulated according to
The resulting coated textile and / or fabric may exhibit U.S. Pat . No. 10,400,061 may be provided. The strap may
various desirable attributes, including but not limited to , 35 optionally be fabric backed , made by co -molding a fabric
increased waterproof attributes, increased durability, backer with an ENR - based compound that is cured with
increased strength , and / or combinations thereof unless oth- curative formulated according to U.S. Pat . No. 10,400,061 .
erwise indicated in the following claims . Said strap may in one illustrative embodiment be adhesively
bonded between the outsole and a foam footbed . In one
V. Integration into Footwear / Articles (Examples of 40 embodiment, after molding the outsole , it may be coated on
Various Styles) the backside with an adhesive as disclosed herein . In one
embodiment, an uncured foam preform may be placed on
Footwear is often created by combining multiple material pre -molded and adhesive - coated outsole, a heated weight
types; most often from various material families . In some placed thereon may provide sufficient pressure ( -0.5-4 psi )
instances, the various material types ( foam , fabric , strap- 45 to cause vulcanization between the outsole and the foam and
ping , etc.) may be made from the same (or closely related ) yet still allow the foam preform to concurrently “ rise ” (that
material families. For example, a shoe may use a polyester is , actually grow in thickness and thereby become a less
fabric upper, be closed with polyester fiber laces , it may use dense foam ) and cure (i.e. vulcanize ).
a polyester co -polymer foam , and perhaps could even use a In one illustrative embodiment a preferred curing and
polyester co -polymer thermoplastic elastomer outsole . In 50 foaming temperature may be between 110 ° C. - 170 ° C. , or
such instances, the entire shoe (made of related thermoplas- even more preferably between 120 ° C. - 160 ° C. , for between
tics ) could hypothetically be recycled by melting all the 10-90 minutes, or even more preferably between 15-60
constituents and molding a new article ( shoe component or minutes. In such a method, the shape of the top heated
alternative article ) out of the blended material. In such a weight may determine the final shape and contour of the
case , there may be some limitations in regards to the
performance suitability of the available options for the
55 footbed while controlling the growth of the foam . A slide
sandal made according to this embodiment may consist of
various components when trying to keep all the materials in three variations of the same material family ( four if the
the same family. Additionally, there may be certain compo- adhesive is included ), which yields an article that may be
nents ( such as those listed above , but without limitation subject to mechano - chemical recycling at the end of its life .
unless otherwise indicated in the following claims ) that are
better served by thermoset polymers instead of thermoplas-
60 Alternatively, according to this illustrative embodiment, the
slide sandal is comprised of non -petrochemically derived
tic polymers . Also , the most commonly used thermoplastic materials and thus may be returned to the ground for
polymers used in footwear components are neither biobased biodegradation .
nor biodegradable. Referring now to FIGS . 23A - 23D , which provide sche
9

An illustrative embodiment of the present disclosure 65 matic representations of four steps for an illustrative method
provides for the combination of multiple material types of making one type of article , the illustrative article therein
drawn from a common family of thermosetting polymers. In may be configured as a slide sandal. Generally, in aa first step
 US 11,542,365 B2
55 56
as shown in FIG . 23A , a compression mold technique may using an injection barrel 407 for injection molding thereof
be used to create a pair of outsoles , wherein the compression adjacent the adhesive material 403 on the outsole ( s )/ sole ( s )
molding process may be completed at a specific 401b .
temperature (s ), pressure ( s ), and / or ranges thereof. A sole In yet another illustrative embodiment of an article
preform 401a may be positioned in a mold 400 at a specific 5 according to the present disclosure that may be configured as
temperature and pressure for a specific amount of time to rial footwear, a shoe may be manufactured using multiple mate
create a sole (or outsole ) 401b . In a second step as shown in menttypes from the same family. Such an illustrative embodi
may be configured with an upper using a leather -like
FIG . 23B an adhesive material 403 may be applied to one material , an outsole , and a midsole . In this illustrative
surface of the outsole ( s) 401b to affix a strap 402 to the embodiment
outsole 401b . A third step is shown in FIG . 23C , wherein an 10 ENR - 50
, a pre -molded outsole may be made using an
based compound and cured with curative formu
uncured foam - in -place layer ( foam footbed preform 404a )
may be applied over an upward - facing surface of the outsole lated according to U.S. Pat. No. 10,400,061 . That outsole/
sole 401b may optionally be coated with adhesive material
401b , such that the foam -in - place layer may cover one or 403 as disclosed herein on the backside of the outsole . A
more terminal ends of the strap 402. Finally, in a fourth step 15 mold 406 may be provided that contains the outsole/sole
a
as shown in FIG . 23D , a metal plate (which may be 401b and also has a heated last 408 around which is wrapped
pre -heated ) 405 may be positioned on the foam footbed the pre -manufactured and / or preformed upper 409 (which
preform 404a to facilitate the foaming process and / or to may be configured to not entirely envelop the last 408 , but
generate crosslinking of the material to create a foaming only in - part ). The last 408 may form one half of the mold
foamed footbed 404b , and the article may be placed in an 20 cavity (within the shoe) and the outsole / sole 401b (and the
oven for curing side of the tool that holds it ) may form the other half of the
In an illustrative embodiment of an article configured as mold cavity. The pre -manufactured /preformed upper 409
a log - like shoe (c uially referred to oftentimes by the may be pinched between the last 408 and the outsole half of
trademark Crocs® ), an outsole / sole 401b may in aa first step the mold cavity, thus creating a cavity into which a foaming
be pre -molded using an ENR - 50 based compound and cured 25 compound may be injected . The foaming compound may be
with curative formulated according to U.S. Pat. No. 10,400 , injected through the outsole half of the mold or directly
061. That outsole / sole 401b may optionally be coated with through the last side of the tool to fill the space between the
adhesive material 403 as disclosed herein on the backside of pre -molded outsole/ sole 401b and the last 408 ; while entrap
the outsole/ sole 401b . That adhesive material 403 - coated ping and bonding to the upper 409 that is wrapped around
outsole / sole 4016 may be placed in a rubber injection 30 the last 408 (at least in -part). In this manufacturing process ,
molding tool that is fabricated to form the entire body of the insolefoaming
the compound may serve as the midsole ( and /or
) and subsequently may initiate bonding to and
clog -like shoe . In this illustrative embodiment, a foaming between the outsole / sole 401b and upper 409 .
compound may be injected into the heated mold and the Referring now to FIGS . 25A - 25F, which provide sche
combination
shear (duringofinjection
heat from) may
the tooling
result and heat generatedandby 35 matic representations of six steps of another illustrative
in vulcanization
foaming of the compound and concurrent curing of the method of making one type of article , the illustrative article
therein may be configured as a shoe having a distinct sole
adhesive - coated outsole to the foamed shoe body. It may be and upper portion. Generally , in a first step as shown in FIG .
preferred to avoid the use of any petrochemical blowing 25A , a compression mold technique may be used to create
agents to create the thermoset foam and instead rely on 40 a pair of outsole ( s )/ soles 4016 , wherein the compression
moisture in compounded ingredients that turn to steam molding process may be completed at a specific
during the molding and curing process. Lignocellulosic temperature ( s ), pressure ( s ), and / or ranges thereof. In a sec
fillers and starches are two classes of illustrative fillers that ond step as shown in FIG . 25B an adhesive material 403 may
may carry controlled levels of moisture that may generate be applied to one surface of the outsole ( s )/ sole ( s ) 401b .
steam during molding and curing that gives rise to foams. 45 Additionally, a foam injection aperture 401c may be fash
This technology ( steam expanded starch ) is known in the ioned in a portion of each outsole/ sole 401b if not done in
food industry (e.g. to make " corn puffs ” ) but has not been step one . A third step is shown in FIG . 25C , wherein a
used as a formulation approach in thermoset elastomers to portion of a shoe preformed upper 409 portion may be
create foams. wrapped around a portion of the outsole ( s )/sole ( s ) 401b .
Referring now to FIGS . 23A - 23D , which provide sche- 50 In a fourth step as shown in FIG . 250 , the upper 409
matic representations of four steps of another illustrative portion of the shoe and outsole / sole 401b may be inverted
method of making one type of article, the illustrative article for positioning in aa mold 406 , which may be configured as
therein may be configured as an injection -molded clog or a foaming compound mold 406. In a fifth step shown in FIG .
Croc® - type shoe . Generally, in a first step as shown in FIG . 25E , the outsole/ sole 401b and upper 409 may be positioned
24A , a compression mold technique may be used to create 55 with respect to a mold 406. Finally, FIG . 25F shows aa sixth
a pair of outsole ( s ) or soles 401b from one or more sole step wherein aa midsole compound ( which may be configured
preforms 401a using a mold 400 , wherein the compression as a foaming compound and / or foaming material as dis
molding process may be completed at a specific closed in detail herein without limitation unless otherwise
temperature ( s ), pressure ( s ), and / or ranges thereof. In a sec- indicated in the following claims ) may be injected into the
ond step as shown in FIG . 24B an adhesive material 403 may 60 foam injection aperture 401c formed in the outsole / sole
be applied to one surface of the outsole ( s )/ soles 401b . A 401b . However, the preceding examples of illustrative meth
third step is shown in FIG . 24C , wherein the outsole ( s )/ soles ods of manufacture for an article configured as a shoe are in
9

401b with adhesive material 403 applied thereto may be no way limiting to the scope of the present disclosure unless
positioned within an injection molding tool or foaming otherwise indicated in the following claims
compound mold 406. Finally, in a fourth step as shown in 65 These three illustrative embodiments of articles and
FIG . 24D a foaming compound may be injected into the method for making same are neither exhaustive nor exclu
foaming compound mold 406 through an injection port 406a sive but are meant to serve as examples of the types of
 US 11,542,365 B2
57 58
construction that may be utilized to combine multiple mate- tions of elastomeric solids/molded components, elastomeric
rial types wherein all the material types are of the same foams, rigid or semi- rigid plastic - like materials, adhesives,
broad material family, and the present disclosure is not coatings, and / or flexible sheet goods (e.g. , leatherlike mate
limited to articles configured as footwear unless otherwise rials and / or textiles ) that may also be manufactured and / or
indicated in the following claims . The common cure system, 5 recycled according to the methods disclosed herein . For
relying on a reaction between a carboxylic acid and an example, a handbag with elastomeric corner protectors ,
epoxide to facilitate crosslinking with B -hydroxyester link sheet good sides , and a foam bottom may, by analogy, be
ages , may enable co -mingling and bonding of the various manufactured and /or recycled according to the methods
form factors of the material - whether it be an elastomeric disclosed herein . Accordingly, the present disclosure may be
outsole compound , an adhesive layer, a leather - like sheet
good, a rigid or semi-rigid and/ orplastic -like material, 10 applicable to bags of nearly any kind, including but not
and / or a foam . Textiles may be incorporated without limi limited to purses , clutches , satchels, messenger bags ,
pouches, backpacks, knapsacks, and / or similar bags / sacks
tation into the construction of such aa shoe unless otherwise
indicated in the following claims. without limitation unless otherwise indicated in the follow
ing claims . A computer backpack or bag may also be
VI . Method of Recycling 15 manufactured using a combination of elastomeric solid
corner protectors and handles, sheet good sides , and foam
Illustrative embodiments of articles made according to the bumpers to protect electronics ; such an article may be
present disclosure that are configured as footwear articles manufactured and / or recycled according to the methods
may contain polymers that are thermosets manufactured disclosed herein , as may any other suitable article without
with similar cure ( vulcanization ) chemistry. The particular 20 limitation unless otherwise indicated in the following
cure chemistry, described in detail in U.S. Pat. No. 10,400 , claims .
061 , is unique in its ability to make elastomers that may be Additional articles may be manufactured utilizing various
mechano - chemically recycled according to U.S. Pat . No. combinations of the six materials having a common chem
10,882,951 . This method of recycling may utilize a very istry of B -hydroxyester linkages, wherein such articles
high specific power input while simultaneously limiting the 25 include but are not limited to furniture and its components
heating of the material.
The recycling of articles (which may be configured as and (e.g. , coverings, cushions , structural members, etc. ) , luggage
footwear) that utilizes materials disclosed herein may be pers,itshandles components (e.g. , exterior coverings, cushions , bum
, clasps , buckles , zippers , etc. ), electronics
subject to mechano - chemical recycling without requiring
any pretreatment apart from the removal of metallic hard cases and / or accessories (e.g. , mobile phone, tablet, and / or
ware that may have been added to the article (as to not 30 mobile computer cases and / or covers ) , and / or similar
articles without limitation unless otherwise indicated in the
damage the processing equipment) so as to create a metallic following claims .
free mixture . In one illustrative embodiment, the mechano Also , by analogy, such articles that are combinations of
chemical recycling may be conducted in two stages . In the materials from the same material family, using the same cure
first stage , articles ( e.g. , footwear) to be recycled may be fed
into an internal rubber mixer. The rubber mixer may be used 35 system , but be manifest in different material forms any
to break down the articles (e.g. , footwear) and make a such article may be recycled by the mechano -chemical
homogeneous mixture — in practice , the mixer may not be method . The mixture of those input materials may likewise
able to deliver the specific energy required to render the be rendered into a millable gum compound and thus be
mixture a millable gum (due to the clearance limitations in moldable into a new article without limitation unless other
a rubber mixer and the heat build -up therein ) , but it is 40 wise indicated in the following claims .
capable of making a rubber fluff, an illustrative embodiment Although the methods described and disclosed herein may
of which is depicted in FIG . 22 . be configured to utilize a curative comprised of a natural
In a second stage , this fluff may be fed to aa two - roll rubber materials, the scope of the present disclosure, any discrete
mill with a nip set to 0.2 mm - 2.0 mm , or more preferably to process step and /or parameters therefor, and / or any appara
0.4 mm - 1.6 mm . The mill must be set with a friction ratio of 45 tus for use therewith is not so limited and extends to any
1.1-1.5 or even more preferably between 1.2-1.4 to create
the energy input requirements to create a millable gum . beneficial tion unless
and / or advantageous use thereof without limita
so indicated in the following claims .
However, other values for these clearances may be used in The materials used to construct the apparatuses and / or
other embodiments without limitation unless otherwise indi components thereof for a specific process will vary depend
cated in the following claims . A two - roll rubber mill allows
for the combination of sufficient cooling (to prevent scorch , 50 thating on the specific application thereof, but it is contemplated
i.e. , re -curing ) and the specific energy required. After the thereofpolymers , natural materials, and / or combinations
may be especially useful in some applications .
mixture is rendered a millable gum compound, it may be
molded again into a new article ; either a component of Accordingly, the above -referenced elements may be con
footwear or another article appropriate to the properties of structed of any material known to those skilled in the art or
the material ( now a mixture of various inputs which may 55 later developed, which material is appropriate for the spe
include ground -up textiles that were part of the recycled cific application of the present disclosure without departing
article ( e.g. , footwear ) ). from the spirit and scope of the present disclosure unless so
In another illustrative embodiment, the recycling may be indicated in the following claims .
conducted in a single stage wherein the article (e.g. , foot- Having described preferred aspects of the various pro
wear) may be delivered directly to a two -roll mill and the 60 cesses , apparatuses, and products made thereby, other fea
entire shredding, blending, and creating of a millable gum tures of the present disclosure will undoubtedly occur to
compound are all achieved in one step . those versed in the art, as will numerous modifications and
alterations in the embodiments and / or aspects as illustrated
VII . Example Articles herein , all of which may be achieved without departing from
65 the spirit and scope of the present disclosure . Accordingly,
In this disclosure , particular focus has been placed on the methods and embodiments pictured and described herein
footwear, but there are analogous articles that are combina- are for illustrative purposes only, and the scope of the
 US 11,542,365 B2
59 60
present disclosure extends to all processes, apparatuses , The invention claimed is :
and / or structures for providing the various benefits and / or 1. An article comprising:
features of the present disclosure unless so indicated in the a . a second material comprising a thermosetting elastomer
following claims. that is crosslinked with B -hydroxyester linkages,
While the chemical process , process steps , components 5 wherein said second material is defined as being a foam
thereof, apparatuses therefor, products made thereby, and material with a glass transition temperature not greater
impregnated substrates according to the present disclosure than about 25 ° C. and a density less than 0.7 g / cc;
have been described in connection with preferred aspects b . aa third material comprising said thermosetting elasto
and specific examples, it is not intended that the scope be mer that is crosslinked with B -hydroxyester linkages,
limited to the particular embodiments and / or aspects set 10 wherein said third material is defined as being a molded
forth , as the embodiments and / or aspects herein are intended elastomer material with a glass transition temperature
in all respects to be illustrative rather than restrictive . not greater than about 25 C , wherein said third material
Accordingly, the processes and embodiments pictured and is three -dimensional in shape; and,
c . a fifth material comprising said thermosetting elastomer
described herein are no way limiting to the scope of the 15 that is crosslinked with B -hydroxyester linkages,
present disclosure unless so stated in the following claims . wherein said fifth material is defined as being an
Although several figures are drawn to accurate scale , any adhesive material with a glass transition temperature
dimensions provided herein are for illustrative purposes only below room temperature, wherein said fifth material
and in no way limit the scope of the present disclosure unless has a thickness of 1 mm or less , and wherein said fifth
so indicated in the following claims . It should be noted that 20 material is positioned between and bonded to said
the welding processes , apparatuses and / or equipment there second material and said third material.
for, and / or impregnated and reacted upon substrates pro- 2. The article according to claim 1 further comprising a
duced thereby are not limited to the specific embodiments fourth material, said fourth material comprising said ther
pictured and described herein , but rather the scope of the mosetting elastomer that is crosslinked with B -hydroxyester
inventive features according to the present disclosure is 25 linkages, wherein said fourth material is defined as being a
defined by the claims herein . Modifications and alterations coating material with a glass transition temperature below
from the described embodiments will occur to those skilled room temperature, wherein said fourth material has a thick
in the art without departure from the spirit and scope of the ness from 10 to 100 microns , wherein said fourth material is
present disclosure. bonded to said second , said third , or said fifth material.
Any of the various features, components, functionalities, 30 3. The article according to claim 2 further comprising a
advantages, aspects , configurations, process steps , process sixth material, said sixth material comprising said thermo
parameters, etc. of a chemical process, a process step , a setting elastomer that is crosslinked with B -hydroxyester
substrate, and / or a impregnated and reacted substrate , may linkages, wherein said sixth material is defined as being a
be used alone or in combination with one another depending rigid or semi- rigid material with a glass transition tempera
on the compatibility of the features , components , function- 35 ture greater than room temperature, wherein said sixth
alities , advantages, aspects , configurations, process steps , material is substantially non - crystalline in structure , wherein
process parameters, etc. Accordingly, an infinite number of said sixth material is bonded to said first, said second , said
variations of the present disclosure exist . Modifications third , said fourth, or said fifth material.
and / or substitutions of one feature , component, functional- 4. The article according to claim 1 wherein said thermo
ity, aspect , configuration , process step , process parameter, 40 setting elastomer is the reaction product between a naturally
etc. for another in no way limit the scope of the present occurring polyfunctional carboxylic acid and an epoxidized
disclosure unless so indicated in the following claims . triglyceride.
It is understood that the present disclosure extends to all 5. The article according to claim 1 wherein a crosslinking
alternative combinations of one or more of the individual with B -hydroxyester linkages of said thermosetting elasto
features mentioned , evident from the text and / or drawings , 45 mer is effected using a reaction product between a naturally
and / or inherently disclosed . All of these different combina- occurring polyfunctional carboxylic acid and an epoxidized
tions constitute various alternative aspects of the present triglyceride.
disclosure and / or components thereof. The embodiments 6. The article according to claim 1 wherein said thermo
described herein explain the best modes known for practic- setting elastomer that is crosslinked with B - hydroxyester
ing the apparatuses, methods, and / or components disclosed 50 linkages is further defined as being capable of de-crosslink
herein and will enable others skilled in the art to utilize the ing of said B -hydroxyester linkages via a mechano -chemical
same. The claims are to be construed to include alternative process.
embodiments to the extent permitted by the prior art. 7. The article according to claim 1 further comprising a
Unless otherwise expressly stated in the claims , it is in no first material, said first material comprising a thermosetting
way intended that any process or method set forth herein be 55 elastomer that is crosslinked with B -hydroxyester linkages ,
construed as requiring that its steps be performed in a wherein said first material is defined as being a leather - like
specific order. Accordingly , where aa method claim does not material with a glass transition temperature below room
actually recite an order to be followed by its steps or it is not temperature, wherein said first material is planar having a
otherwise specifically stated in the claims or descriptions thickness between about 0.3 mm and 2.5 mm .
that the steps are to be limited to a specific order, it is no way 60 8. The article according to claim 7 further comprising a
intended that an order be inferred, in any respect. This holds fourth material, said fourth material comprising said ther
for any possible non - express basis for interpretation, includ- mosetting elastomer that is crosslinked with B - hydroxyester
ing but not limited to : matters of logic with respect to linkages, wherein said fourth material is defined as being a
arrangement of steps or operational flow ; plain meaning coating material with a glass transition temperature below
derived from grammatical organization or punctuation; the 65 room temperature, wherein said fourth material has a thick
number or type of embodiments described in the specifica- ness from 10 to 100 microns , wherein said fourth material is
tion . bonded to said second , said third , or said fifth material.
 US 11,542,365 B2
61 62
9. The article according to claim 8 further comprising a temperature greater than room temperature, wherein said
sixth material, said sixth material comprising said thermo- sixth material is substantially non -crystalline in structure,
setting elastomer that is crosslinked with B -hydroxyester wherein said sixth material is bonded to said first, said
linkages, wherein said sixth material is defined as being a second , said third, said fourth , or said fifth material.
rigid or semi- rigid material with a glass transition tempera 15. The footwear article according to claim 12 wherein
5

ture greater than room temperature , wherein said sixth said thermosetting elastomer is the reaction product between
material is substantially non -crystalline in structure , wherein a naturally occurring polyfunctional carboxylic acid and an
said sixth material is bonded to said first, said second , said epoxidized triglyceride .
third10., said fourth , according
or said fifthto material 16. The footwear article according to claim 12 wherein a
The article claim 7.wherein said article
10 crosslinking with B -hydroxyester linkages of said thermo
setting elastomer is effected using a reaction product
is further defined as a footwear article .
11. The article according to claim 1 wherein said article is between
acid and
a naturally occurring polyfunctional carboxylic
an epoxidized triglyceride.
further defined as a slide sandal.
12. A footwear article comprising: 17. The footwear article according to claim 12 wherein
a . a second material comprising a thermosetting elastomer 15 said
droxyester linkages is furtherthat
thermosetting elastomer is crosslinked
defined as being with B -hyof
capable
that is crosslinked with B -hydroxyester linkages , de -crosslinking of said B -hydroxyester linkages via a
wherein said second material is defined as being a foam mechano -chemical process.
material with a glass transition temperature not greater 18. The footwear article according to claim 12 further
than about 25 ° C. and a density less than 0.7 g /cc;
b. a third material comprising said thermosetting elasto- 20 thermosetting
comprising a firstelastomer
materialthat
, saidisfirstcrosslinked
material comprising
with B -hya
mer that is crosslinked with B -hydroxyester linkages, droxyester linkages
wherein said third material is defined as being aa molded being a leather - like ,material
wherein said first material is defined as
elastomer material with a glass transition temperature ture below room temperaturewith ,
a glass transition tempera
wherein said first material is
not greater than about 25 ° C. , wherein said third 25 planar having a thickness between about 0.3 mm and 2.5
material is three - dimensional in shape; and,
c . a fifth material comprising said thermosetting elastomer mm19.. The footwear article according to claim 18 further
that is crosslinked with B -hydroxyester linkages, comprising a fourth material, said fourth material compris
wherein said fifth material is defined as being an ing said thermosetting elastomer that is crosslinked with
adhesive material with a glass transition temperature B -hydroxyester
below room temperature, wherein said fifth material 30 defined as beinglinkages a
, wherein said fourth material is
coating material with a glass transition
has aa thickness of 1 mm or less , and wherein said fifth temperature below room temperature , wherein said fourth
material is positioned between and bonded to said material has a thickness from 10 to 100 microns , wherein
second material and said third material.
13. The footwear article according to claim 12 further said fourth material is bonded to said second , said third, or
comprising a fourth material, said fourth material compris- 35 said20.fifthThematerial . article according to claim 19 further
footwear
ing said thermosetting elastomer that is crosslinked with comprising a sixth material, said sixth material comprising
B -hydroxyester linkages, wherein said fourth material is said thermosetting
defined as being a coating material with a glass transition droxyester linkages,elastomer wherein
that is crosslinked with B -hy
said sixth material is defined as
temperature below room temperature , wherein said fourth being a rigid or semi- rigid material with a glass transition
material has a thickness from 10 to 100 microns , wherein 40 temperature greater than room temperature
said fourth material is bonded to said second , said third , or sixth material is substantially non - crystalline, wherein said
in structure,
said fifth material.
14. The footwear article according to claim 13 further wherein, said said sixth material is bonded to said first, said
comprising a sixth material, said sixth material comprising second third , said fourth , or said fifth material.
said thermosetting elastomer that is crosslinked with B -hy- 45 said21.article
The footwear article according to claim 12 wherein
is further defined as a slide sandal.
droxyester linkages, wherein said sixth material is defined as
being a rigid or semi- rigid material with a glass transition