Cure site monomers

Tetrafluoroethylene, perfluoromethyl vinyl ether cure site monomer... 

Two kinds of monomers are present in acryUc elastomers backbone monomers and cure-site monomers. Backbone monomers are acryUc esters that constitute the majority of the polymer chain (up to 99%), and determine the physical and chemical properties of the polymer and the performance of the vulcanizates. Cure-site monomers simultaneously present a double bond available for polymerization with acrylates and a moiety reactive with specific compounds in order to faciUtate the vulcanization process. 

Cure-Site Monomers. A large variety of cure-site monomers has been proposed, but only a few have achieved commercial significance. Two of the most important classes are labile chlorine containing monomers and epoxy/carboxyl containing monomers. 

More recendy, Du Pont Co. has commercialized a new family of copolymers of just ethylene and methyl acrylate, where the cure-site monomer has been removed from the polymer backbone. 

Commercial Forms. Eour different base polymers of VAMAC ethylene—acryhc elastomer are commercially available (Table 1). Until 1990, existing grades of ethylene—acryhc elastomers were based on a single-gum polymer. VAMAC G, defined as a terpolymer of 55% methyl acrylate, ethylene, and a cure-site monomer (5). In 1991, a higher methyl acrylate terpolymer, VAMAC LS, was introduced. The composition of this polymer was specifically chosen because it significantly increases the oil resistance of the polymer while minimizing losses in low temperature fiexibihty (6). 

E is ethylene MA, methyl acrylate and CS, proprietary cure-site monomer. 

Fig. 3. The percent volume swell in benzene after seven days at 21°C compared with the wt % of fluorine on standard recommended compounds. A, copolymers of vinyUdene fluoride—hexafluoropropylene B, terpolymers of vinyUdene fluoride—hexafluoropropylene—tetrafluoroethylene C, terpolymers of vinyhdene fluoride—hexafluoropropylene—tetrafluoroethylene-cure site monomer D, copolymer of tetrafluoroethylene—perfluoro(methyl vinyl ether)-cure...

Interpenetrating networks have been made by co-curing polychloroprene with copolymers of 1-chloro-1,3-butadiene [627-22-5]. The 1-chloro-1,3-butadiene serves as a cure site monomer, providing a cure site similar to that already in polychloroprene. The butadiene copolymer with 1-chloro-1,3-butadiene (44) and an octyl acrylate copolymer (45) improved the low temperature brittieness of polychloroprene. The acrylate also improved oil resistance and heat resistance. 

Interestingly, later grades of Vamac to become available did not employ the cure site monomer, using instead a peroxide-curing system. Some of these copolymers also contained higher levels of methyl acrylate (up to 69%) to enhance the oil resistance. 

Substituted and unsubstituted bi- or multi-cyclic mono-, di- or multi-olefins, i.e. containing condensed rings at least one of which contains a double bond. Norbomene is homopolymerised commercially whilst, as previously mentioned, ethylidenenorbomene and dicyclopentadiene are used as the cure site monomer in EPDM rubbers. 

In attempts to further improve the stability of fluorine-containing elastomers Du Pont developed a polymer with no C—H groups. This material is a terpolymer of tetrafluoroethylene, perfluoro(methyl vinyl ether) and, in small amounts, a cure site monomer of undisclosed composition. Marketed as Kalrez in 1975 the polymer withstands air oxidation up to 290-315°C and has an extremely low volume swell in a wide range of solvents, properties unmatched by any other commercial fluoroelastomer. This rubber is, however, very expensive, about 20 times the cost of the FKM rubbers and quoted at 1500/kg in 1990, and production is only of the order of 1 t.p.a. In 1992 Du Pont offered a material costing about 75% as much as Kalrez and marketed as Zalak. Structurally, it differs mainly from Kalrez in the choice of cure-site monomer. 

Because of processing problems 2-chloroethyl vinyl ether has now been replaced with other cure site monomers. These include vinyl and allyl chloracetates and allyl glycidyl ether. 

Although the above chemical structure is used as an example, acrylates are a class of materials rather than one single type. These polymers are formed by the copolymerisation of an acrylic ester and a cure site monomer, ethyl acrylate and chloroethyl vinyl ether respectively being illustrated above. 

The cure site monomer directly controls which cure systems can be used to vulcanise the rubber. Since the cure behaviour is determined by the cure site monomer, and this can differ between suppliers, and presumably grades, it is advisable to read the manufacturers recommendation when deciding on the choice of cure system to use. 

Some terpolymers contain an additional cure site monomer, for example, bromotetrafluorobutene, to permit crosslinking with peroxides. Peroxide curing gives vulcanisates more resistance to amine stabilisers in motor oils, more resistance to methanol containing motor fluids. Resistance to acids, aqueous media and steam is also improved. Compression set and heat resistance are slightly inferior to bisphenol A cure systems. 

The simplest diene that satisfies this requirement is 1,4-hexadiene, and indeed it has been adopted as the cure site monomer in commercial ethylene-propylene-diene rubber. Because 1,4-hexadiene exists in both trans and cis configurations, significant amounts of work have been devoted to find ways to control the selectivity of the catalysts for one of the isomers over the other. 

This structure is similar to that of the copolymer TFE and ethylene, except that the random onentation of the methyl group from nonstereospeciftc free radical copo-lymenzation of propylene affords a noncrystalline structure [35] The relatively low fluorine content (54%) of these elastomers compared with VDF-based elas tomers (66-69 5%) makes them significantly less resistant to swelling by hydrocarbons Because of strict alternation, these elastomers have a relatively high glass transition temperature ( 2 °CJ and consequently limited low temperature properties Furthermore, they must be polymerized with a cure site monomer or receive a postpolymerization treatment to adequately activate them for vulcanization [36] To counteract the limited cure response, low-temperature flexibility, and hydrocarbon resistance, these polymers have also been modified with substantial amounts (ca 35 wt %) of VDF [37, 38] This provides some improvements but inevitably decreases the resistance to bases and polar solvents... 

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