DuPont Neoprene
DuPont Neoprene
Introduction
This technical bulletin is intended to provide guidance in selecting the appropriate type of Neoprene for development of compounds for specific applications. In addition to providing recommendations for achieving certain physical properties, consideration is given to the selection of types of Neoprene best adapted to specific processing and storage conditions.
Neoprene Polychloroprene
The major monomer component in every type of Neoprene polychloroprene that is manufactured by DuPont, is chloroprene (2-chloro-1,3-butadiene). The monomer backbone structure of polychloroprene can be modified by copolymerizing chloroprene with sulfur, 2,3 dichloro-1,3-butadiene, or other monomers to yield a family of materials with a broad range of chemical and physical properties. By proper selection and formulation of these polymers, the compounder can achieve optimum performance for a given end-use.
WHV-100 Highly extended compounds W Excellent storage Best heat & set Needs accelerator
WHV Excellent for very highly extended compounds WRT Best low temperature
WB In blends for better Extrusion & calendering TW Better extrusion & calendering
Crystallization Resistance
Crystallization is a common phenomenon in polymer types that have high proportions of long chain molecules of significant regularity. Certain grades of Neoprene are designed to minimize chain regularity by addition of comonomers or polymerization at higher temperatures. DuPont Neoprene WRT and WD are designed for use in finished products that must remain flexible for long periods at low temperatures. The excellent crystallization resistance of these types helps counteract the increase in rate of crystallization-induced stiffening that is caused by ester plasticizers. Therefore, high levels of ester plasticizers can be tolerated for increased resistance to thermal stiffening. DuPont Neoprene GRT has the greatest resistance to crystallization of any of the G types. Raw polymer and stocks prepared from Neoprene GRT remain soft and flexible for long periods, particularly at low temperatures. Due to its excellent tack retention, Neoprene GRT is the preferred type of Neoprene for friction compounds and other applications requiring good building properties.
Compounding
Compounding of all types of Neoprene manufactured by DuPont is discussed in the technical bulletin A Guide to Grades, Compounding and Processing of Neoprene. Neoprene W types are available in a variety of viscosity grades, thus providing the compounder a wide choice in compound design. The high viscosity grades of both general purpose and crystallization-resistant W types can be highly extended with fillers and plasticizers. The resulting compounds will have workable compound viscosity and useful vulcanizate properties. Curing systems for Neoprene W types are available that not only provide processing safety and acceptable cure rate, but that also achieve desired vulcanizate properties such as optimum compression set resistance. Generally, the response of Neoprene G types to compounding ingredients is similar to that of Neoprene W types. However, G type compounds differ from W and T type compounds in several ways: Addition of chemical peptizers causes softening Mechanical shear causes softening Can be cured with metal oxides alone; organic accelerators are not required Less plasticizer is needed to prepare compounds in a workable viscosity range
DuPont Neoprene T types should be compounded similarly to W types with respect to filler and plasticizer loading, anti-degradant protection, and curing systems. However, for the same loading, a compound based on a T type will be slightly higher in viscosity, and vulcanizates will be slightly higher in modulus and hardness compared to those based on the corresponding W type. Additional plasticizer (usually an additional 34 parts) can be used to balance these properties, if desired.
Uncured Compound Cure Rate Green Strength Processability E VG G E G G E G G VG VG G VG P G VG E VG Vulcanizate Compression Set Resistance Good Flex Good Tear Heat-Aging Resistance Low-Temperature Properties Property Rating: *Viscosity Rating: G E E VG P E E G P E E G E G G E E G G E E G G E E G G E E G G E E G G E E P P E E G G E E G G E VG E VG G G G G E VG VG G E VG VG E VG E E
VG
E = Excellent, VG = Very Good, G = Good, S = Satisfactory, P = Poor Hi = High, M = Medium, Lo = Low, VLo = Very Low
Family Characteristics
Type GW
Comonomer* Sulfur
Distinguishing Features Best tear and flex Best G type for heat-aging and compression set resistance Very slightly peptizable Contains thiuram
G Types
Raw Polymers Limited storage Peptizable to varying degrees Fast curing, but safe processing No accelerators necessary Vulcanizates Best tear strength Best flex Best resilience
GNA M1 M2
Sulfur
Good
4254 4759
Medium
GRT M1 M2
Sulfur/ACR
Good
3446 4052
Slow
Best tack Crystallization resistance Contains thiuram General purpose-low viscosity General purpose-std. viscosity General purpose-med. high viscosity General purpose-high viscosity Very slow crystallizing Slower curing than W High-viscosity WRT Contains high percentage of gel for processing Vulcanizate properties reduced Generally used in blends
W Types
W M1 W WHV 100 Raw Polymers Excellent storage stability Non-peptizable Vulcanizates Best compression set resistance Best heat-aging WHV WRT None None None None ACR Excellent Excellent Excellent Excellent Excellent 3442 4049 90105 106125 4151 Fast Fast Fast Fast Very Slow Very Slow Medium
WD WB
ACR None
Excellent Excellent
100120 4352
T Types
Raw Polymers Excellent storage stability Least verve Fast processing Vulcanizates Properties similar to W types
*Principal Monomer is chloroprene; ACR = 2,3-dichloro-1,3-butadiene; Gel = gel-forming comonomer **ML 1 + 4 at 100 C, DPE Test Method N200.5700
TW
Gel
Excellent
4252
Fast
Gel-containing for good processing Vulcanizate properties similar to W types Higher viscosity form of TW
TW 100
Gel
Excellent
8299
Fast
Neoprene G Types
General Characteristics
During emulsion polymerization of DuPont Neoprene G types, chloroprene monomer is copolymerized with sulfur to form a high molecular weight copolymer. The sulfur atoms are present in the polymer chain in clusters or as single atoms situated between the chloroprene (CD) segments. This is represented schematically below: (CD)n Sx (CD)m where Sx represents one or more sulfur atoms; m and n may be the same or different integers. After the polymerization is stopped, combinations of thiuram disulfides and dithiocarbamates are added to reduce the molecular weight to provide the desired Mooney viscosity. This polymerization process results in production of polymers having much broader molecular weight distributions than are found in Neoprene W or T types. In addition, raw polymer storage stability of G types is more limited than that of W or T types.
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Processing Characteristics DuPont Neoprene G types break down, or soften, under mechanical shear experienced during mixing and forming operations to a much greater extent than do the W or T types. Breakdown can be increased by the addition of chemical peptizers. This characteristic provides a means to facilitate a workable viscosity in highly loaded stocks while utilizing a minimum of plasticizer. Breakdown, i.e., peptization, also causes the G types to be tackier than other Neoprene types. DuPont Neoprene GW peptizes to a lesser extent than other G types. Compounds of Neoprene GW have higher viscosities, are less sticky, and have less building tack than similarly loaded compounds of other G types. In order to prevent scorch and minimize heat history, good temperature control should be maintained during mill or internal mixing, warming, extruding, and calendering operations. Use of refrigerated water is particularly helpful, especially during summer. Batch stock should be sheeted (9.5 mm thick or less), and should be cooled as quickly as possible with a water dip or spray, followed by air circulation to evaporate all traces of water. Sheets of freshly mixed stock should not be stacked until they have been cooled to temperatures of 32 C or below. With respect to G types, heat history should be kept to a minimum to guard against scorch. Even very slight scorching may introduce sufficient nerve into a stock so that mold flow and extrusion or calendaring will be adversely affected. Compounds of Neoprene G types have less nerve than those of W types (except Neoprene WB), and consequently shrink less and sheet out more smoothly on calendering. Extruded surfaces are smoother and better defined. With respect to these qualities, Neoprene G types approach, but do not quite equal, gel-containing polymers like T types, or blends containing 20% or more Neoprene WB. Peptization and Mechanical Breakdown Peptization is a process by which molecular weight of polymers is reduced by chemical action, mechanical work, or a combination of both. Peptization of an elastomer produces a workable compound viscosity at a high filler loading without a reduction Table 4 in vulcanizate hardness and strength. Neoprene GW is peptizable, but not to the same Grade of Neoprene GW GNA GRT W extent as other Neoprene G types because it Mooney Viscosity, contains fewer Sx structures where x is ML 1 + 4 at 100 C greater than 1. As shown in Table 4, peptization Original 43 39 35 40 reduces the viscosity of Neoprene GW by only Peptized* 33 8 10 41 510 Mooney units, even with chemical agents, *Samples peptized with 0.63 phr of Vanax 552 for 15 min at initial temperature of 70 C. while the viscosities of other Neoprene G types are reduced by up to 30 Mooney units. Compounds of Figure 2. Neoprene Peptization Rate Neoprene GW have a higher viscosity than similarly loaded compounds based on Neoprene GNA, or GRT and, therefore, are less sticky and have less building tack. Figure 2 illustrates the peptization rate of Neoprene GW versus other Neoprene types in a Brabender Plastograph. Note the final viscosity of Neoprene GW is intermediate between Neoprene W and the other Neoprene G types due to the limited breakdown of the polymer. In DuPont Neoprene GNA and GRT, a significant amount of uncleaved Sx (where x is greater than 1) units remain in the polymers after isolation. Thiuram disulfide remains in the polymer as well, and through mechanical work, the viscosities of these G grades will soften further.
Peptization of Neoprene
When to Use G Types Compounders choose DuPont Neoprene G types for use in applications where building tack is important in fabricating the final product and in situations where the end-use involves severe flexing or other dynamic stresses, and minimum compression set is not required. Neoprene G types are used when a compound requires high loadings with a minimum of plasticizer. Because G types break down or soften when subjected to shear during mixing, workable viscosities can be achieved in this type of compound. When organic accelerators are not appropriate for use, such as in some compounds requiring FDA approval, G types may be cured with metal oxides alone. Neoprene G types, and particularly DuPont Neoprene GRT, are preferred when good friction characteristics are desired. DuPont Neoprene GW is recommended for end uses when a good balance of dynamic and aging properties is desired.
DuPont Neoprene GW
Description Neoprene GW is a sulfur-modified polychloroprene stabilized with a thiuram disulfide. The crystallization rate of Neoprene GW is slightly faster than that of Neoprene GRT. Processing and Performance Features Limited Polymer Breakdown Neoprene GW breaks down to a lesser degree than other G types. Compounds based on Neoprene GW will, therefore, exhibit a higher viscosity than similarly loaded compounds based on Neoprene GNA or GRT. Because of the higher compound viscosity, stocks based on Neoprene GW are slightly less sticky and have slightly less building tack than stocks based on other G types. Compounds of Neoprene GW have approximately the same viscosity as similarly loaded compounds of Neoprene W. Vulcanizates Resistant to Flexing, Dynamic Stress, Heat-Aging, and Compression Set Properly compounded vulcanizates of Neoprene GW have high resilience, and excellent flex cracking resistance, and the best tear strength of any vulcanized Neoprene type. Vulcanizates of Neoprene GW retain their properties after heat-aging better than vulcanizates of other G types. Compression set resistance is significantly improved over that of other G types, although it is not as good as that of thiourea-cured W types.
DuPont Neoprene W family vulcanizates have good resistance to heat aging and compression setsubstantially better than vulcanizates of Neoprene GNA or GRT. If properly compounded with nonstaining compounding ingredients, they can be used in applications where staining of finishes cannot be tolerated. When to Use W Types Neoprene W types are chosen primarily where service conditions call for Neoprene types with the best available heat and compression set resistance. Even when these properties are not the primary consideration, Neoprene W types are frequently used because of their combination of excellent storage stability, uniform processability, broad compounding latitude, and all-around good vulcanizate properties.
DuPont Neoprene WB
Description Neoprene WB is a nonstaining polychloroprene that contains a high percentage of gel polymer for superior processibility.
Processing and Performance Features Outstanding Processing Characteristics DuPont Neoprene WB contains a high percentage of gel polymer. The presence of gel improves processability and Neoprene WB exhibits better processing characteristics than any other type of Neoprene. Compounds based on Neoprene WB are firm and have very low nerve. They are fast-extruding, yielding smooth extrudates with good collapse resistance, sharp die definition, and low die swell. They also calender well, yielding smooth sheets with low shrinkage. Reduced Vulcanizate Strength Vulcanizates of Neoprene WB exhibit good resistance to heat aging and compression set that is typical of the Neoprene W types. However, because of higher gel content, vulcanizates of Neoprene WB generally exhibit somewhat lower tensile strength, elongation, tear strength, and resistance to flex cut growth than vulcanizates of Neoprene W. For this reason, Neoprene WB is most often used in blends with other types of Neoprene to improve processing at minimum sacrifice in vulcanizate strength.
Curing and Vulcanizate Properties Despite the gel content of DuPont Neoprene T types, the mechanical properties of Neoprene T vulcanizates do not differ substantially from those of vulcanizates of the W types. Neoprene T types also provide good resistance to heat aging and compression set that is also a characteristic of DuPont Neoprene W types. If properly compounded with nonstaining compounding ingredients, T types can be used in applications where staining of finishes cannot be tolerated. When to Use T Types Neoprene T types are typically used in calendering and extrusion applications. They are frequently used in the production of extruded profiles requiring low die swell, little distortion, and high green strength. They are useful when properties similar to those of Neoprene W types are needed, coupled with superior processing characteristics. DuPontNeoprene TW is an excellent base polymer for extruded products, providing high extrusion speed, low die swell, excellent definition, and very good collapse resistance. In calendered goods, Neoprene TW produces smooth sheeting with low nerve and shrinkage. Neoprene TW-100 offers these same benefits in a higher viscosity range suitable for more heavily loaded compounds.
Handling Precautions
DuPont is not aware of any unusual health hazards associated with any Neoprene solid polymer. However, for all the solid polymers, routine industrial hygiene practices are recommended during handling and processing to avoid such conditions as dust buildup or static charges. For additional information consult Guide for Safe Handling and FDA Status of Neoprene Solid Polymers, and observe the precautions described. Compounding ingredients used with Neoprene to prepare finished products may present hazards in handling and use. Before proceeding with any compounding work, consult and follow label directions and handling precautions from suppliers of all ingredients. Also, see comments on specific compounding ingredients in the safe handling bulletin.
Information on European Union Dangerous Preparations Directive 1999/45/EC related to Colophony Skin Sensitization
Colophony is classified as a skin contact sensitizer under European Union Dangerous Preparations Directive 1999/45/EC effective July 30, 2002. This Directive requires labeling of products that contain colophony at levels equal to or greater than 0.1% (refer to the Directives for specific details). Solid (dry type) Neoprene adhesive grade products manufactured by DuPont contain about 4% colophony (CAS No. 8050-09-7). Toxicological tests have demonstrated that dry Neoprene is not a skin sensitizer. Because of this testing, dry Neoprene polymer is not subject to mandatory labeling under the above Directive despite the presence of colophony. However, when these Neoprene adhesive grade products are dissolved in organic solvents, colophony may still be present at concentrations up to 0.8% depending on the solids content of the solutions. In the absence of data showing the adhesive is not a skin sensitizer, the adhesive could be subject to the above EU regulation. We recommend that manufacturers and marketers of adhesive solutions containing DuPont Neoprene (dry type) adhesive grade products determine whether the colophony level is above 0.1%. If the manufactured preparation has a colophony content of less than 0.1% it will not be subject to mandatory labeling (provided no other constituents necessitate mandatory labeling). Manufactured preparations that contain higher colophony contents will require the labeling and/or container notices described in the Directive.
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The information set forth herein is furnished free of charge and is based on technical data that DuPont believes to be reliable and falls within the normal range of properties. It is intended for use by persons having technical skill, at their own discretion and risk. This data should not be used to establish specification limits nor used alone as the basis of design. Handling precaution information is given with the understanding that those using it will satisfy themselves that their particular conditions of use present no health or safety hazards. Since conditions of product use and disposal are outside our control, we make no warranties, express or implied, and assume no liability in connection with any use of this information. As with any product, evaluation under end-use conditions prior to specification is essential. Nothing herein is to be taken as a license to operate or a recommendation to infringe on patents. Caution: Do not use in medical applications involving permanent implantation in the human body. For other medical applications, discuss with your DuPont customer service representative and read Medical Caution Statement H-50103-3. Copyright 2010 DuPont. The DuPont Oval Logo, DuPont, and The miracles of science are trademarks or registered trademarks of E.I. du Pont de Nemours and Company or its affiliates. All rights reserved. Vanax is a registered trademark of R.T. Vanderbilt. (01/04) Reference No. NPE-H68563-00-K0910
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