VINYL ACETATE COPOLYMER

Low-density Medium-density High-density Ultra high-molecular-weight Glass-fiber- reinforced, high-density Ethylene-vinyl acetate copolymer... 

Under conditions of extreme acidity or alkalinity, acryhc ester polymers can be made to hydroly2e to poly(acryhc acid) or an acid salt and the corresponding alcohol. However, acryhc polymers and copolymers have a greater resistance to both acidic and alkaline hydrolysis than competitive poly(vinyl acetate) and vinyl acetate copolymers. Even poly(methyl acrylate), the most readily hydroly2ed polymer of the series, is more resistant to alkah than poly(vinyl acetate) (57). Butyl acrylate copolymers are more hydrolytically stable than ethyl acrylate copolymers (58). 

This type of adhesive is generally useful in the temperature range where the material is either leathery or mbbery, ie, between the glass-transition temperature and the melt temperature. Hot-melt adhesives are based on thermoplastic polymers that may be compounded or uncompounded ethylene—vinyl acetate copolymers, paraffin waxes, polypropylene, phenoxy resins, styrene—butadiene copolymers, ethylene—ethyl acrylate copolymers, and low, and low density polypropylene are used in the compounded state polyesters, polyamides, and polyurethanes are used in the mosdy uncompounded state. 

Ethylene vinyl acetate copolymer (EVA) forms a soft, tacky film with good water-vapor barrier but very poor gas-barrier properties. It is widely used as a low temperature initiation and broad-range, heat-sealing medium. The film also serves for lamination to other substrates for heat-sealing purposes. 

Hydrocarbon resins (qv) are prepared by copolymerization of vinyltoluene, styrene, and a-methylstyrene in the presence of a Eriedel-Crafts catalyst (AlCl ). These resins are compatible with wax and ethylene—vinyl acetate copolymer (197). 

Polyvinylpyrrohdinone/vinyl acetate copolymer (PVP/VA) was developed as an improved, less hygroscopic version of PVP. The monomer ratios control the stiffness and the resistance to humidity however, too high a vinyl acetate monomer content requires another solvent in addition to water to completely solubilize it. 

The alcohols, proprietary denatured ethyl alcohol and isopropyl alcohol, are commonly used for E-type inks. Many E-type inks benefit from the addition of small amounts of ethyl acetate, MEK, or normal propyl acetate to the solvent blends. Aromatic hydrocarbon solvents are used for M-type inks. Polystyrene resins are used to reduce the cost of top lacquers. T-type inks are also reduced with aromatic hydrocarbons. Acryflc resins are used to achieve specific properties for V-type inks. Vehicles containing vinyl chloride and vinyl acetate copolymer resins make up the vinyl ink category. Ketones are commonly used solvents for these inks. 

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. 

Gross-Linking. A variety of PE resins, after their synthesis, can be modified by cross-linking with peroxides, hydrolysis of silane-grafted polymers, ionic bonding of chain carboxyl groups (ionomers), chlorination, graft copolymerization, hydrolysis of vinyl acetate copolymers, and other reactions. 

The adhesives (qv) used to form tube seams and bag bottoms include unborated dextrin, borated dextrin, casein, latex—casein, latex, poly(vinyl acetate), vinyl acetate copolymers, and hot-melt materials (10,27). Dextrin and casein adhesives are more commonly used in the production of grocery sacks vinyl acetate-type adhesives are commonly used in ah paper multiwah bags. The hot-melt adhesives are typicahy used to tack the phes of the multiwah bag together and to form the seam and bottom joints when polymer film phes or coated paper phes are used in bag constmction. 

The seam closure on a folding carton is typicahy made using a latex, poly(vinyl acetate), vinyl acetate copolymer, or hot-melt adhesive (27). The choice of adhesive depends on a number of factors, including the nature of any coating used on the package and the production speeds required. 

Vinyl acetate is another monomer used in latex manufacture for architectural coatings. When copolymerized with butyl acrylate, it provides a good balance of cost and performance. The interior flat latex paint market in North America is almost completely dominated by vinyl acetate—acryHc copolymers. Vinyl acetate copolymers are typicaHy more hydrophilic than aH-acryHc polymers and do not have the same ultraviolet light resistance as acryHcs as a result. 

Organic peroxides are used in the polymer industry as thermal sources of free radicals. They are used primarily to initiate the polymerisation and copolymerisation of vinyl and diene monomers, eg, ethylene, vinyl chloride, styrene, acryUc acid and esters, methacrylic acid and esters, vinyl acetate, acrylonitrile, and butadiene (see Initiators). They ate also used to cute or cross-link resins, eg, unsaturated polyester—styrene blends, thermoplastics such as polyethylene, elastomers such as ethylene—propylene copolymers and terpolymers and ethylene—vinyl acetate copolymer, and mbbets such as siUcone mbbet and styrene-butadiene mbbet. 

Fig. 10. Preparation and morphology of toughened PVC (a) secondary PVC grain (50—250 flm) (b) modified PVC with coherent primary grain (ca 1 -lm) (220). CPE = chlorinated polyethylene EVA = ethylene—vinyl acetate copolymers ABS = acrylonitrile—butadiene—styrene MBS = methyl...

Pubhcations on curing polymers with TAIC include TEE—propylene copolymer (135), TEE—propylene—perfluoroaHyl ether (136), ethylene—chlorotrifluoroethylene copolymers (137), polyethylene (138), ethylene—vinyl acetate copolymers (139), polybutadienes (140), PVC (141), polyamide (142), polyester (143), poly(ethylene terephthalate) (144), sdoxane elastomers (145), maleimide polymers (146), and polyimide esters (147). 

Substituted amides (not of the alkanolamide variety) are sold to diverse low volume markets. They have some utility ki polymers such as polyethylene, ethylene-vinyl acetate copolymers, acryUc polymers, PVC, polyamides, and polyesters. They have been found effective as pharmaceutical processkig aids, defoamers (qv), antimicrobials, pesticides, kisect repellents, dispersion stabilizers, and corrosion inhibitors. 

Rosin, modified rosins, and derivatives are used in hot-melt adhesives. They are based primarily on ethylene—vinyl acetate copolymers. The rosin derivative is used in approximately a 1 1 1 concentration with the polymer and a wax. The resin provides specific adhesion to the substrates and reduces the viscosity at elevated temperatures, allowing the adhesive to be appHed as a molten material. 

Materials are also blended with VDC copolymers to improve toughness (211—214). VinyHdene chloride copolymer blended with ethylene—vinyl acetate copolymers improves toughness and lowers heat-seal temperatures (215,216). Adhesion of a VDC copolymer coating to polyester can be achieved by blending the copolymer with a linear polyester resin (217). 

Vinyl acetate [108-05-4] (VAc), CH2=CHOOCCH2, the ethenyl ester of acetic acid, is primarily use for the manufacture of poly(vinyl acetate) [9003-20-7] (PVAc) and vinyl acetate copolymers. Poly(vinyl acetate) homo- and copolymers are found as components in coatings, paints and sealants, binders (adhesives, nonwovens, constmction products, and carpet-backing), and miscellaneous uses such as chewing gum and tablet coatings. AppHcations have grown over the years in a number of areas (1 4). 

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. 

In poly(vinyl acetate) copolymer emulsions, the properties are significantly affected by the composition of the aqueous phase and by the stabilizers and buffers used iu the preparation of these materials, along with the process conditions (eg, monomer concentrations, pH, agitation, and temperature). The emulsions are milk-white Hquids containing ca 55 wt % PVAc, the balance being water and small quantities of wetting agents or protective coUoids. 

The low vinyl acetate ethylene—vinyl acetate copolymers, ie, those containing 10—40 wt % vinyl acetate, are made by processes similar to those used to make low density polyethylene for which pressures are usually > 103 MPa (15,000 psi). A medium, ie, 45 wt % vinyl acetate copolymer with mbber-like properties is made by solution polymerisation in /-butyl alcohol at 34.5 MPa (5000 psi). The 70—95 wt % vinyl acetate emulsion copolymers are made in emulsion processes under ethylene pressures of 2.07—10.4 MPa (300—1500 psi). 

Poly(ethyl methacrylate) (PEMA) yields truly compatible blends with poly(vinyl acetate) up to 20% PEMA concentration (133). Synergistic improvement in material properties was observed. Poly(ethylene oxide) forms compatible homogeneous blends with poly(vinyl acetate) (134). The T of the blends and the crystaUizabiUty of the PEO depend on the composition. The miscibility window of poly(vinyl acetate) and its copolymers with alkyl acrylates can be broadened through the incorporation of acryUc acid as a third component (135). A description of compatible and incompatible blends of poly(vinyl acetate) and other copolymers has been compiled (136). Blends of poly(vinyl acetate) copolymers with urethanes can provide improved heat resistance to the product providing reduced creep rates in adhesives used for vinyl laminating (137). 

Growth in PVAc consumption is illustrated in Eigure 3. The emulsions continue to dominate the adhesives and paint markets. It also shows the distribution of PVAc and copolymer usage by market. The companies Hsted in Table 10 are among the principal suppHers of poly(vinyl acetate)s and vinyl acetate copolymers, but there are numerous other suppHers. Many other companies produce these polymers and consume them internally in the formulation of products. 

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