Copolymers ethylene with vinyl ester

We can also incorporate branches by copolymerizing ethylene with vinyl esters and vinyl acids. In addition to their ester or acid side groups, these copolymers also contain the long and short chain branches, which are characteristic of low density polyethylene. 

The high pressure polymerization of ethylene can be slightly modified for the copolymerization of ethylene with vinyl- and acrylic-type monomers such as vinyl acetate, vinyl chloride, acrylonitrile, or acrylic esters. Some of these copolymers of ethylene and vinyl acetate or maleic anhydride are already available and have found various applications in plastics, coatings, and adhesives. Copolymers of ethylene and vinyl chloride and of ethylene and acrylonitrile appear particularly interesting because of the low cost of monomers and the properties of the copolymers. Although their synthesis has been disclosed in a number of patents their larger scale production is still in a state of development. 

Yoshimura et al. [1989] give a lengthy description of their invention, which was primarily aimed at producing film (Table 11.9) particularly suited for shrink wrapping, with many examples and extensive sets of results. The film is made from the following three groups of polymers (i) LDPE and a copolymer of ethylene, either with vinyl ester monomer, or with an unsaturated aliphatic monocarboxylic acid or its aliphatic ester (EVAc being the most desirable copolymer) (ii) one of the... 

Polymers with pendant cyclic carbonate functionality were synthesized via the free radical copolymerization of vinyl ethylene carbonate (4-ethenyl-l,3-dioxolane-2-one, VEC) with other imsaturated monomers. Both solution and emulsion free radical processes were used. In solution copolymerizations, it was found that VEC copolymerizes completely with vinyl ester monomers over a wide compositional range. Conversions of monomer to polymer are quantitative with complete incorporation of VEC into the copolymers. Cyclic carbonate functional latex polymers were prepared by the emulsion copolymerization of VEC with vinyl acetate and butyl acrylate. VEC incorporation was quantitative and did not affect the stability of the latex. When copolymerized with acrylic monomers, however, VEC is not completely incorporated into the copolymer. Sufficient levels can be incorporated to provide adequate cyclic carbonate functionality for subsequent reaction and crosslinking. The unincorporated VEC can be removed using a thin film evaporator. The Tg of VEC copolymers can be modeled over the compositional range studied using either linear or Fox models with extrapolated values of the Tg of VEC homopolymer. 

Vinyl acetate copolymers are used worldwide in polymer dispersions. Copolymers with dibutyl maleate are particularly elastic, while copolymers with vinyl esters of Versatic Acid have particularly good weather resistance for shade formulations. Copolymers with acrylate esters and vinyl acetate-ethylene-vinyl chloride terpoly-mers with a good cost - performance ratio are also important. 

Vinyl acetate is relatively inexpensive and is readily copolymerized with vinyl chloride, ethylene, acrylates and methacrylates. The monomer is a colourless, flammable liquid with an initial pleasant odour, which on exposure becomes irritating. One of the major disadvantages of vinyl acetate-based copolymers is their poor hydrolytic and UV stability. This was shown to improve when copolymerized with vinyl esters of versatic acid [18]. Copolymers of vinyl acetate with the vinyl esters of versatic acid have been used in Europe for the last quarter-century. In the US similar monomers were introduced in the past five years, two of which are illustrated in Table 6.1, namely, vinyl pivalate and vinyl neo-decanoate. More details of the copolymerization of these monomers with vinyl acetate is given in Chapter 16. 

Many synthetic latices exist (7,8) (see Elastomers, synthetic). They contain butadiene and styrene copolymers (elastomeric), styrene—butadiene copolymers (resinous), butadiene and acrylonitrile copolymers, butadiene with styrene and acrylonitrile, chloroprene copolymers, methacrylate and acrylate ester copolymers, vinyl acetate copolymers, vinyl and vinyUdene chloride copolymers, ethylene copolymers, fluorinated copolymers, acrylamide copolymers, styrene—acrolein copolymers, and pyrrole and pyrrole copolymers. Many of these latices also have carboxylated versions. 

The properties of ethylene-vinyl acetate copolymers vary widely with their ester content. At the lowest levels of vinyl acetate, they have physical properties that are similar to those of low density polyethylene. As the comonomer content increases, the material becomes less crystalline and more elastic. Copolymers made with the highest comonomer levels contain no measurable crystallinity. The resulting products are tough, flexible, and clear. The ester... 

Emulsion paints are based on aqueous synthetic resin dispersions, which afford a lacquer-like paint film. The resin dispersions which are commonly used by the paint industry contain water as the carrier phase. A large number of such dispersions are available, based on different resins such as poly(vinyl acetate), which may be employed as a copolymer with vinyl chloride, maleic dibutyl ester, ethylene, acrylic acid esters, polyacrylic resin, and copolymers of the latter with various monomers, as well as styrene-butadiene or poly(vinyl propionate). These disper-... 

Copolymers of isobutene with styrene (< 10 %) and isoprene (< 3 %) may be used for the manufacture of food contact materials. The following polymerizates and polymer mixes can be added to these polymerizates polyethylene, polypropylene, styrene-acrylonitrile mixed polymers, mixed polymers of ethylene, propylene, butylene, vinyl esters and unsaturated aliphatic acids as well as salts and esters and polybutene-1. 

PVC can be blended with numerous other polymers to give it better processability and impact resistance. For the manufacture of food contact materials the following polymerizates and/or polymer mixtures from polymers manufactured from the above mentioned starting materials can be used Chlorinated polyolefins blends of styrene and graft copolymers and mixtures of polystyrene with polymerisate blends butadiene-acrylonitrile-copolymer blends (hard rubber) blends of ethylene and propylene, butylene, vinyl ester, and unsaturated aliphatic acids as well as salts and esters plasticizerfrec blends of methacrylic acid esters and acrylic acid esters with monofunctional saturated alcohols (Ci-C18) as well as blends of the esters of methacrylic acid butadiene and styrene as well as polymer blends of acrylic acid butyl ester and vinylpyrrolidone polyurethane manufactured from 1,6-hexamethylene diisocyanate, 1.4-butandiol and aliphatic polyesters from adipic acid and glycols. 

Internal plasticizers are synthesized by copolymerization of suitable monomers. Polymeric non-extractable plasticizers, mostly copolymers having substantially lower glass transition temperatures due to the presence of plasticizing ( soft ) segments such as poly(ethylene-co-vinyl acetate) with approximately 45 % vinylacetate content, ethylene-vinyl acetate-carbon monooxide terpolymer, or chlorinated PE, are available for rather special applications in medicinal articles (Meier, 1990). In this case, the performance of the internally plasticized polymers is the principal advantage. However, copolymerization may account for worse mechanical properties. A combination with external plasticizers may provide an optimal balance of properties. For example, food contact products made from poly(vinylidene chloride) should have at most a citrate or sebacate ester based plasticizers content of 5 % and at most 10 % polymeric plasticizers. 

Poly(vinyl alcohol) is utilized as a component of starch-based adhesives.11121114 Other patents report the use of partially oxidized starch,1115 dextrins,1116 dextrins and urea,1117 borax,1118 boric acid,1119 and vinyl methyl ether-maleic acid copolymers.1120 Other patents indicate the use of poly (vinyl alcohol) with partially hydrolyzed poly(vinyl acetate),1121 nonhy-drolyzed poly(vinyl acetate),1122 and poly(vinyl chloride).1123 A few patents have reported such poly acrylic additives as poly (acrylic acid)1124 and its salts,1125 poly(acrylamide),1126 1127 A-methylacrylamide or poly(A-acryl-amide),1128 and polyethyleneimine.1129 Polystyrene has also been used,1130 as well as more complex copolymers such as a maleic acid monobutyl ester-methyl vinyl ether copolymer, together with dextrin and polyacrylamide),1131 carboxylated ethyl acrylate-styrene zinc salt copolymer,1132 ethylene-methyl acrylate-vinyl acetate copolymer,1133 vinyl acetate-vinyl pyr-rolidone copolymer,1134 and ethylene-vinyl acetate copolymer.1135 Some adhesives are compounded with SBR latex1136 1138 and phenol-formaldehyde resins.1139... 

Acetic acid, ethylene ester polymer with ethane CoTran-ethylene/vinyl acetate copolymer EVA EVA copolymer EVM poly (ethylene-co-vinyl acetate) VA/ethylene copolymer vinyl acetate/ethylene copolymer. 

Klabunde and Ittel reported the use of nickel complexes containing the phosphorus—oxygen chelating ligands to homo- and copolymerize ethylene with a variety of functional olefins.Negative results were obtained with both vinyl acetate and methyl methacrylate, but copolymers could be obtained if monomers with at least two methylene spacers between the olefin and polar group, lihe functionalities successfully tolerated include ester, trimethyl-silyl-protected acids, ketones, fluoro groups, and 2° amides. 

Useful film-forming resin adhesives include polyvinyl esters and ethers and their copolymers and interpolymers with ethylene and vinyl monomers, acrylic resins and their copolymers, polyvinyl alcohol, water dispersion of polyolefin resins, polystyrene copolymers such as polystyrene butadiene, polyamide resins, natural rubber dispersions, and natural and modified carbohydrates (starch or carboxycellulose). Particularly preferred for use are aqueous dispersions of polyvinyl acetate and vinyl acetate-ethylene copolymers. 

Poly(vinyl ester) dispersions are quantitatively more important than solid resins. Homopolymer and copolymer dispersions are used for binders in emulsion (dispersion) paints, plastic-bonded plasters, and water-thinnable adhesives. Poly(vinyl acetate) dispersions are less important than vinyl acetate copolymer dispersions. The most important comonomers of vinyl acetate are vinyl laurate, dibutyl maleate, Versatic Acid esters (VeoVa, Shell), ethylene, vinyl chloride, and butyl acrylate. Poly(vinyl propionate) and copolymers of vinyl propionate with butyl acrylate, styrene, or vinyl chloride are also marketed and used as dispersions. 

Poly(vinyl acetate) dispersions form lightfast, dry, hard, brittle films. Plasticizers therefore have to be used (external plasticization), which are, however, volatile and lead to embrittlement of the films after a relatively short time. Internally plasticized dispersions of copolymers of vinyl acetate with vinyl laurate, butyl maleate, Versatic Acid esters, or ethylene form permanently flexible, nonaging films that are not, however, always sufficiently resistant to hydrolysis. Terpolymer (vinyl acetate-ethylene-vinyl chloride) dispersions form films that are more resistant to hydrolysis than homopolymer and copolymer dispersions. The films also have a higher mechanical strength and lower flammability. The glass transition temperature of the terpolymer can be varied within wide limits and properties can be matched to requirements by using a suitable choice of comonomers. The same is true of vinyl propionate copolymer dispersions. 

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