US005650543A
United States Patent 19 11 Patent Number: 5,650,543
Medina 45 Date of Patent: Jul. 22, 1997
54 ETHOXYLATED ACETYLENIC GLYCOLS Primary Examiner-Johann Richter
HAVING LOW DYNAMC SURFACE Assistant Examiner-John D. Peabody, III
TENSION
Attorney, Agent, or Firm-Russell L. Brewer; William F.
75 Inventor: Steven Wayne Medina, Orefield, Pa. Marsh
73) Assignee: Air Products and Chemicals, Inc., 57 ABSTRACT
Alientown, Pa.
This invention relates to ethoxylated acetylenic glycol com
21 Appl. No.: 524,129 positions represented by the formula:
22 Filed: Aug. 31, 1995
Related U.S. Application Data th fH, SH fH,
CH-CH-CH-CH-i-c sC - -CH2-CH2-CH-CH
63 Continuation of Ser. No. 158,672, Nov. 29, 1993, aban O O
doned.
(51 int. C. ... C07C 43/15 (H, (H.
52 U.S. Cl. ............. 568/616
58) Field of Search ......................................... 568/616
fit. Sh
H
| \,H ',
56 References Cited
U.S. PATENT DOCUMENTS
3.268,593 8/1966 Carpenter et al.. wherein m and n are integers and the sum is from 4-12.
4,117249 9/1978 DeSimone et al..
FOREIGN PATENT DOCUMENTS These ethoxylated acetylenic diols are excellent as surfac
tants alone or admixed with other surfactants for use in water
44-20450 9/1969 Japan ..................................... 568/616
borne coatings.
OTHER PUBLICATIONS
Schwartz, Joel “The Importance of Low Dynamic Surface
Tension in Waterborne Coatings” Journal of Coatings Tech
nology (1992). 3 Claims, No Drawings
5,650,543
1. 2
ETHOXYLATED ACETYLENIC GLYCOLS U.S. Pat. No. 4,117.249 discloses acetylenic glycols rep
HAVING LOW DYNAMC SURFACE resented by the structural formula
TENSION
This application is a file-wrapper continuation of appli H th th
cation Ser. No. 08/158,672 filed on Nov. 29, 1993, now CH3-C =CH-CH-CH- HCEC - -CH2-R
abandoned. OH OH
FIELD OF THE INVENTION
wherein R is hydrogen or an alkenyl radical. The acetylenic
This invention relates to ethoxylated acetylenic glycols 10 glycols are acknowledged as having utility as surface active
suitability as a surfactant for aqueous coating systems. agents and they can be used as wetting agents, dispersants,
BACKGROUND OF THE INVENTION
antifoaming nonionic agents and viscosity stabilizers.
In an article, Schwartz, The Importance of Low Dynamic
The waterborne coatings and ink industries require sur 15
Surface Tension in Waterborne Coatings, Journal of Coat
factants that provide excellent surface tension reducing ings Technology (1992), there is discussion of Surface
capabilities for substrate wetting. Equilibrium surface ten tension properties in waterborne coatings and a discussion of
sion performance is important when the system is at rest. dynamic surface tension in such coatings. Equilibrium Sur
End-users also need surfactants with good dynamic perfor face and dynamic surface tension are evaluated for several
mance which is a measure of a surfactant's ability to provide 20 surface active agents including the ethyleneoxide adducts of
wetting under high speed application such as when coatings
are spray applied or inks are printed. acetylenic glycol, e.g., the 4.7-ethyleneoxide the 3.5 mole
Traditional nonionic surfactants such as alkylaryl or alco adduct of 2.47.9-tetramethyl-5-decyne-4,7-diol where the
hol ethoxylates, and ethylene oxide (EO)-propylene oxide number of ethyleneoxide units ranges from about 1.3 to 30,
(PO) copolymers have excellent equilibrium surface tension 25
as well as the acetylenic glycols themselves, and ethyl
performance but are generally characterized as having poor eneoxide adducts of other aromatic and aliphatic alcohols,
dynamic surface tension reduction. In contrast, certain e.g., nonylphenol and lauryl alcohol. At a concentration of
anionic surfactants such as sodium dialkyl sulfosuccinates 0.1% in distilled water, the dynamic surface tension ranges
can provide good dynamic results, but these are very foamy from a low of about 32 to a high of 72 dynes percentimeter.
and impart water sensitivity to the finished coating. 30
Surfactants based on acetylenic glycols such as 2.47.9- SUMMARY OF THE INVENTION
tetramethyl-5-decyne-4,7-diol and its ethoxylates are known
for their good balance of equilibrium and dynamic surface This invention pertains to an ethoxylated 2,5,8,11
tension reducing capabilities with little of the negative tetramethyl-6-dodecyne-5,8-diol. The ethoxylated acety
features of traditional nonionic and anionic Surfactants. The 35 lenic glycol is represented by the formula:
molecules, however, may not provide the very low surface
tension reduction needed for the wetting of contaminated
surfaces or low surface energy substrates. In those cases, fit H ?t it.
end-users may require silicone or fluorocarbon based sur
factants which may be costly, foamy, exhibit poor dynamic
CH-CH-CH-CH-i-c
O
E --CH-CH-CH-CH
O
40
performance and often cause adhesion problems.
The following patents and articles describe various acety
lenic alcohols and their ethoxylates as surface active agents:
U.S. Pat. No. 3.268,593 discloses ethyleneoxide adducts (H. SH:
of tertiary acetylenic alcohols represented by the structural 45
t s
formula H H
.
R - -CE - -R4
is wherein m and n are integers and the sum is from 2-50,
preferably 4-10.
H(OCH2CH2O O(CH2CH2).H
50 There are significant advantages associated with the
ethoxylated acetylenic glycol of this invention and these
advantages include:
wherein R and R are alkyl radicals having from 3-10 an ability to formulate water borne coatings and inks
carbon atoms and RandR are methyl or ethyl and X and y having excellent resistance to water;
have a sum in the range of 3 to 60, inclusive. Specific 55
ethyleneoxide adducts include the ethyleneoxide adducts of an ability to produce water borne coatings and inks which
3-methyl-1-nonyn-3-ol; 7,10-dimethyl-8-hexadecyne-7.10 may be applied to a variety of substrates with excellent
diol; 24.7.9-tetramethyl-5-decyne-4,7-diol; and 4.7- wetting of substrate surfaces including contaminated and
dimethyl-5-decyne-4,7-diol. Preferably, the ethyleneoxide low energy surfaces;
adducts range from 3 to 20 units. The patentees point out that an ability to provide a reduction in coating or printing
these ethyleneoxide adducts have outstanding wetting prop defects such as orange peel and flow/leveling deficiencies;
erty and that the presence of the acetylenic bond in the an ability to produce water borne coatings and inks which
hydrophobic chain increases water solubility and improves
surfactant properties. As the oxyethylene chain link have low volatile organic content thus making these surfac
increases, both detergency and amount of foamincrease, and 65 tants environmentally favorable; and
the wetting times decrease with increasing polyoxyethylene an ability to formulate coating and ink compositions
chain length. capable of high speed application.
5,650,543
3 4
DETAILED DESCRIPTION OF THE dynamic surface tension. Aqueous systems containing 0.14
NVENTION of active surfactant were evaluated. In preparing the ethoxy
The surfactants of this invention are ethoxylates of 2.5, lated acetylenic glycols, ethylene oxide was reacted with the
8, 11-tetramethyl-6-dodecyne-5,8-diol. These ethoxylates, surfactant base glycol. The moles EO represents the number
because of their ability to decrease the surface tension of 5 of moles ethylene oxide reacted permole of base glycol. The
aqueous systems, have wide utility in formulating coating results are as follows:
and ink formulations. The moles ethoxylate per mole of
acetylenic glycol range from 2-50, preferably 3-10 and
most preferably 4-7. When the moles ethoxylate ranges 10 Moles 0.1 wt % in Water Surface
below the lower end of the scale, and when the ethoxylate Surfactant Ethyleneoxide Tension, dynesicm
ranges above the upper end of the scale, properties of the Base Glycol Per Mole Glycol Equilibrium Dynamic
aqueous system may deteriorate.
The ethoxylates may be applied to a variety of substrates 104*
104
1.3
3.5
32
34
35.1
37.3
and these include metals, organic (e.g. oil) contaminated 15 104 10 43.1 46
surfaces, plastics, composites, wood, glass, ceramics and 104 30 48.2 50.2
other substrates that are printed or require a protective/ 124 is
124
4.
6
26.7
26.6
31.2
29.8
decorative coating. 124 10 29.6 32.7
The ethoxylates may be combined with other surface
active agents, e.g., dioctylsodium sulfosuccinate and 20 *104 is a designation for 24,79-tetramethyl-5-decyne-4,7-diol sold under the
ethoxylated alcohols, e.g., ethoxylated C-2 alkyl phenols trademark Surfynol.
**124 is a designation for 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol.
and higher (8-16) alkanols. Surfactant levels typically range
from 50-90 parts ethoxylated acetylenic glycol composition The above comparative studies confirms the superior
per 10-50 parts conventional surfactant. 25 wetting capabilities of the ethoxylated dodecynediol
Representative water based coating and ink formulations surfactants, particularly at a level of about 6 moles (5-7)
to which the ethoxylated acetylenic glycols may be added ethylene oxide over other high performance ethoxylated
are as follows:
acetylenic glycol based surfactants. In contrast to the
ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol, the
30
Typical Water Based Coating Formulation ethoxylated 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol sur
0 to 50 wt % Pigment Dispersant/Grind Resin
factants imparted much lower equilibrium and dynamic
O to 80 wt % Coloring Pigments/Extender surface tension at the lower ethoxylate levels.
Pigments/Anti-Corrosive
Pigments other pigment types 35 EXAMPLE 2
5 to 99.9 wt % Waterborne/Water Dispersible/
Water-soluble Resins
O to 30 wt % Slip Additives/Antimicrobials To determine the effectiveness of the surfactant properties
Processing Aids/TDefoamers with other surfactant compositions, the ethoxylated deriva
0 to 50 wt % Coalescing or Other Solvents
0.01 to 10 wt % Surfactant/Wetting Agent/Flow tives of 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol were
and Leveling Agents mixed with other conventional surfactants. These included
O to 50 wt % Pigment Dispersant/Grind Resin ethoxylated derivatives of nonyl phenol, acetylenic glycols
O to 80 wt % Coloring Pigments/Extender
Pigments other pigment types and diocytisodiumsulfosuccinate (DOSS). The results are
5 to 999 wit 9% Waterborne/Water Dispersible/ shown in Table 2.
Water-soluble Resins
O to 30 wt % Slip Additives/Antimicrobials 45
Processing Aids/Defoamers
0 to 50 wt % Coalescing or Other Solvents 0.1 wt % in Water;
0.01 to 10 wt % Surfactant/Wetting Agent/Flow Ratio Moles Surface Tension,
and Leveling Agents Surfactant Wt. Ethyleneoxide dyes/cm
50
Base Glycol Parts Per Mole Glycol Equilibrium Dynamic
The ethoxylated derivatives of this invention may be 1247CO-730 75/25 6 25.5 30.2
prepared in a manner similar to that used in producing the 124DOSS 75/25 6 24.9 27.7
corresponding ethoxylated tertiary acetylenic glycols which 124/Surfynol 420 90/10 6 24.4 27.3
124/CO-730 75/25 4. 25.4 30.7
are homologs and analogs to the derivatives described 124/DOSS 75/25 4. 25.5 31.7
herein. Typically these involve the reaction of an aliphatic 55
Nonyl phenol ethoxylate.
ketone with acetylene in the presence of potassium hydrox Surfynol 420 is a designation for the 1.3 mole ethoxylate of 24,79
ide followed by reaction with preselected molar levels of tetramethyl-5-decyne-4,7-diol.
ethylene oxide. The outstanding surface tension reduction
performance and other properties of the tetramethyldode The above results show that favorable surfactant proper
cynediol ethoxylates are illustrated in the following ties can be achieved by combining the ethoxylated deriva
examples. tive of 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol with con
EXAMPLE 1. ventional surfactants. The results appear to show some
synergism in that considerably lower equilibrium and
Comparative Evaluation of Surfactant Systems 65 dynamic surface tension results were obtained with the
A series of aqueous systems were prepared for determin admixture than were obtained obtained with the ethoxylated
ing the effect of various surfactants on equilibrium and derivative alone.
5,650,543
5 6
What is claimed is: wherein m and n are integers and the sum is from 2-50.
1. An ethoxylated acetylenic glycol composition the for
mula: 2. The composition of claim 1 wherein the sum of m plus
n is from 3-10.
CH3 CH3 CH CH 5
H3C-CH-CH2-CH-C-CEC-C-CH2-CH2-CH-CH3
3. The composition of claim 1 wherein the sum of m plus
n is from 4-7.
H--O-CH2-CH2O O-(-CH-CH-OH
