Vinyl acetate comonomer

Ethylene/vinyl Acetate Copolymers (EVA). LDPE is easily internally plasticized by copolymerization with increasing amounts (2-20%) of vinyl acetate comonomer. 

Vinyl Acetate, Homo- and Copolymer Latexes Vinyl Acetate Comonomer (butyl acrylate, ethylene, vinyl ester of versatic add) Partially Hydrolyzed Polyvinyl Alcohol Sodium Bicarbonate Hydrogen Peroxide (35%) Sodium Formaldehyde Sulfoxylate Water 70.0-100.0 0.0-30.0 6.0 0.3 0.7 0.5 80.0... 

FIGURE 12.9 X-ray diffraction patterns of (a) commercial acrylic and (b) polyethylene terephthalate fibers. The acrylic fiber was a commercial sample containing 7% vinyl acetate comonomer. In both cases, the fiber axis is vertical. 

DuPont, in the late fifties, introduced ethylene vinyl acetate (EVA) copolymers as specialty low-crystallinity copolymers. EVA copolymers are produced by introducing vinyl acetate comonomer in the high-pressure process. 

Near-infrared diffuse reflectance spectra were measured by use of a rotating drawer for pellets of 12 kinds of ethylene-vinyl acetate copolymers with vinyl acetate comonomer varying in the 7-44 wt% range. An attempt was made to predict the melting points of these copolymers. The potential of near-infrared spectroscopy with that of Raman spectroscopy in the discrimination of copolymers and the prediction of their properties was given. 23 refs. 

Ethylene-vinyl acetate copolymers can be thought of as modified high pressure polyethylenes. Because of the free-radical polymerization process they have structural characteristics such as short-chain and long-chain branching in addition to the effects due to the incorporation of the vinyl acetate comonomer. Ethylene and vinyl acetate have a reactivity ratio which is close to 1 and as a result EVA copolymers contain vinyl acetate which is homogeneously distributed among the polymer chains. The major effect of the VA on polymer properties is to reduce... 

Poly(vinyl chloride-co-vinyl acetate) comonomer content (mol%)... 

A number of methods such as ultrasonics (137), radiation (138), and chemical techniques (139—141), including the use of polymer radicals, polymer ions, and organometaUic initiators, have been used to prepare acrylonitrile block copolymers (142). Block comonomers include styrene, methyl acrylate, methyl methacrylate, vinyl chloride, vinyl acetate, 4-vinylpyridine, acryUc acid, and -butyl isocyanate. 

Table 4. Copolymerization Parameters of Vinyl Acetate (M ) and Comonomers (M2)...

The nmr spectmm of PVAc iu carbon tetrachloride solution at 110°C shows absorptions at 4.86 5 (pentad) of the methine proton 1.78 5 (triad) of the methylene group and 1.98 5, 1.96 5, and 1.94 5, which are the resonances of the acetate methyls iu isotactic, heterotactic, and syndiotactic triads, respectively. Poly(vinyl acetate) produced by normal free-radical polymerization is completely atactic and noncrystalline. The nmr spectra of ethylene vinyl acetate copolymers have also been obtained (33). The ir spectra of the copolymers of vinyl acetate differ from that of the homopolymer depending on the identity of the comonomers and their proportion. 

Buffers are frequently added to emulsion recipes and serve two main purposes. The rate of hydrolysis of vinyl acetate and some comonomers is pH-sensitive. Hydrolysis of monomer produces acetic acid, which can affect the initiator, and acetaldehyde which as a chain-transfer agent may lower the molecular weight of the polymer undesirably. The rates of decomposition of some initiators are affected by pH and the buffer is added to stabilize those rates, since decomposition of the initiator frequently changes the pH in an unbuffered system. Vinyl acetate emulsion polymerization recipes are usually buffered to pH 4—5, eg, with phosphate or acetate, but buffering at neutral pH with bicarbonate also gives excellent results. The pH of most commercially available emulsions is 4—6. 

Copolymers wet and adhere well to nonporous surfaces, such as plastics and metals. They form soft, flexible films, in contrast to the tough, horny films formed by homopolymers, and are more water-resistant. As the ratio of comonomer to vinyl acetate increases, the variety of plastics to which the copolymer adheres also increases. Comonomers containing functional groups often adhere to specific surfaces for example, carboxyl containing polymers adhere well to metals. 

When more than routine water resistance is required, a copolymer vinyl acetate emulsion can be used. The plasticizing comonomer in the polymer particles increases their intrinsic coalescing ability thus, they can coalesce more readily than homopolymer particles to a film that has a higher resistance to water. This resistance to water does not extend to the organic solvents, however, which are better resisted by homopolymer films. The soft copolymers have lower solubility parameters than homopolymers and are more readily attacked by solvents of low polarity, eg, hydrocarbons. 

A variety of trichloroethylene copolymers have been reported, none with apparent commercial significance. The alternating copolymer with vinyl acetate has been patented as an adhesive (11) and as a flame retardant (12,13). Copolymerization with 1,3-butadiene and its homologues has been reported (14—16). Other comonomers include acrylonitrile (17), isobutyl vinyl ether (18), maleic anhydride (19), and styrene (20). 

In order to improve the physical properties of HDPE and LDPE, copolymers of ethylene and small amounts of other monomers such as higher olefins, ethyl acrylate, maleic anhydride, vinyl acetate, or acryUc acid are added to the polyethylene. Eor example, linear low density polyethylene (LLDPE), although linear, has a significant number of branches introduced by using comonomers such as 1-butene or 1-octene. The linearity provides strength, whereas branching provides toughness. 

A further class of ethylene-vinyl acetate copolymer exists where the vinyl acetate content is of the order of 3 mole %. These materials are best considered as a modification of low-density polyethylene, where the low-cost comonomer introduces additional irregularity into the structure, reducing crystallinity and increasing flexibility, softness and, in the case of film, surface gloss. They have extensive clearance as non-toxic materials. 

In addition to homopolymers of varying molecular and particle structure, copolymers are also available commercially in which vinyl chloride is the principal monomer. Comonomers used eommercially include vinyl acetate, vinylidene chloride, propylene, acrylonitrile, vinyl isobutyl ether, and maleic, fumaric and acrylic esters. Of these the first three only are of importance to the plastics industry. The main function of introducing comonomer is to reduce the regularity of the polymer structure and thus lower the interchain forces. The polymers may therefore be proeessed at much lower temperatures and are useful in the manufacture of gramophone records and flooring compositions. 

Poly(vinyl acetate) is too soft and shows excessive cold flow for use in moulded plastics. This is no doubt associated with the fact that the glass transition temperature of 28°C is little above the usual ambient temperatures and in fact in many places at various times the glass temperature may be the lower. It has a density of 1.19 g/cm and a refractive index of 1.47. Commercial polymers are atactic and, since they do not crystallise, transparent (if free from emulsifier). They are successfully used in emulsion paints, as adhesives for textiles, paper and wood, as a sizing material and as a permanent starch . A number of grades are supplied by manufacturers which differ in molecular weight and in the nature of comonomers (e.g. vinyl maleate) which are commonly used (see Section 14.4.4)... 

Grassie and coworkers [136,137] carried out a comparative study of the thermal degradation of vinyl chloride-vinyl acetate copolymers covering the entire composition range. They observed that <10% of vinyl acetate produced a marked decrease in stability as compared with PVC. Thereafter, there was a progressive decrease in stability as the amount of comonomer was increased with a minimum at 40-50% vinyl acetate. Stability progressively increased with further increase in... 

Graft copolymerization of acrylonitrile with various vinyl comonomers such as methyl acrylate, ethyl acrylate, vinyl acetate, and styrene onto cellulose derivatives using ceric ion was studied [24]. The results showed that... 

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