Vinyl chloride acrylate ester copolymers

Polyvinylidene chloride (PVDC), a polymer formed from CH2=CCl2, is diiScult to formulate and is not used for any type of product by itself. It is usually manufactured as a copolymer with various monomers, including acrylonitrile, vinyl chloride, acrylic esters, or methacrylic esters. A unique property of PVDC copolymers is to prevent water and gases from diffusing through the film. In this way, PVDC copolymer films provide a vapor barrier, and are commonly used to wrap foods for storage. The commercial name Saran refers to both the PVDC homopolymer and its copolymers. Reference Spectrum 22 provides the IR and Raman spectra of a vinylidene... 

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 formation of coagulum is observed in all types of emulsion polymers (i) synthetic rubber latexes such as butadiene-styrene, acrylonitrile-butadiene, and butadiene-styrene-vinyl pyridine copolymers as well as polybutadiene, polychloroprene, and polyisoprene (ii) coatings latexes such as styrene-butadiene, acrylate ester, vinyl acetate, vinyl chloride, and ethylene copolymers (iii) plastisol resins such as polyvinyl chloride (iv) specialty latexes such as polyethylene, polytetrafluoroethylene, and other fluorinated polymers (v) inverse latexes of polyacrylamide and other water-soluble polymers prepared by inverse emulsion polymerization. There are no major latex classes produced by emulsion polymerization that are completely free of coagulum formation during or after polymerization. 

Styrene/butadiene polymer Styrene/methyl methacrylate copolymer Styrene/a-methyl styrene resin Tall oil rosin Tallow amide Terpene resin Tetrasodium pyrophosphate Trimethylolpropane Urea-formaldehyde resin Urea-formaldehyde resin, butylated Vinyl chloride/vinyl acetate copolymer Vinyl chloride/vinylidene chloride copolymer coatings, food-contact acrylate ester copolymer Sodium borate... 

Besides poly(vinyl acetate) emulsions, emulsions of vinyl acetate copolymers with ethylene, (meth)acrylates, vinyl chloride, maleic esters and vinyl laurate are of considerable importance as internally plasticized synthetic resin emulsions. 

The principal use of the peroxodisulfate salts is as initiators (qv) for olefin polymerisation in aqueous systems, particularly for the manufacture of polyacrylonitrile and its copolymers (see Acrylonitrile polymers). These salts are used in the emulsion polymerisation of vinyl chloride, styrene—butadiene, vinyl acetate, neoprene, and acryhc esters (see Acrylic ester polymers Styrene Vinyl polymers). 

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. 

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-... 

Copolymerization. Vinyl chloride can be copolymerized with a variety of monomers. Vinyl acetate, the most important commercial comonomer, is used to reduce crystallinity, winch aids fusion and allows lower processing temperatures. Copolymers are used in flooring and coatings. This copolymer sometimes contains maleic add or vinyl alcohol (hydrolyzed from the poly(vinyl acetate ) to improve the coating s adhesion to other materials, including metals, Copolymers with vinylidene chloride are used as barrier films and coatings. Copolymers of vinyl chlonde with acrylic esters in latex from are used as film formers in paint, nonwoven fabric binders, adhesives, and coatings. Copolymers with olefins improve thermal stability and melt flow, but at some loss of heat-deflection temperature,... 

ABA ABS ABS-PC ABS-PVC ACM ACS AES AMMA AN APET APP ASA BR BS CA CAB CAP CN CP CPE CPET CPP CPVC CR CTA DAM DAP DMT ECTFE EEA EMA EMAA EMAC EMPP EnBA EP EPM ESI EVA(C) EVOH FEP HDI HDPE HIPS HMDI IPI LDPE LLDPE MBS Acrylonitrile-butadiene-acrylate Acrylonitrile-butadiene-styrene copolymer Acrylonitrile-butadiene-styrene-polycarbonate alloy Acrylonitrile-butadiene-styrene-poly(vinyl chloride) alloy Acrylic acid ester rubber Acrylonitrile-chlorinated pe-styrene Acrylonitrile-ethylene-propylene-styrene Acrylonitrile-methyl methacrylate Acrylonitrile Amorphous polyethylene terephthalate Atactic polypropylene Acrylic-styrene-acrylonitrile Butadiene rubber Butadiene styrene rubber Cellulose acetate Cellulose acetate-butyrate Cellulose acetate-propionate Cellulose nitrate Cellulose propionate Chlorinated polyethylene Crystalline polyethylene terephthalate Cast polypropylene Chlorinated polyvinyl chloride Chloroprene rubber Cellulose triacetate Diallyl maleate Diallyl phthalate Terephthalic acid, dimethyl ester Ethylene-chlorotrifluoroethylene copolymer Ethylene-ethyl acrylate Ethylene-methyl acrylate Ethylene methacrylic acid Ethylene-methyl acrylate copolymer Elastomer modified polypropylene Ethylene normal butyl acrylate Epoxy resin, also ethylene-propylene Ethylene-propylene rubber Ethylene-styrene copolymers Polyethylene-vinyl acetate Polyethylene-vinyl alcohol copolymers Fluorinated ethylene-propylene copolymers Hexamethylene diisocyanate High-density polyethylene High-impact polystyrene Diisocyanato dicyclohexylmethane Isophorone diisocyanate Low-density polyethylene Linear low-density polyethylene Methacrylate-butadiene-styrene... 

Ethylhexyl acrylate manufacture represented about 15 percent of domestic consumption of the alcohol. The acrylate is the longest chain acrylate ester produced by esterification of acrylic acid. The monomer is used in acrylic copolymers for pressure sensitive adhesives, PVC impact modifiers, and as a comonomer with vinyl acetate and vinyl chloride in latexes for paints and textiles. Growth over the next 5 years is estimated at 6 percent per year. 

To survey as completely as possible the grafting behavior of EVA copolymers toward various vinyl compounds, our investigations covered the grafting of vinyl acetate, vinylidene chloride, and acrylic and meth-acrylic esters. As polymerization processes, at first we preferred suspension polymerization to exclude the influence of solvents by terminating or transfer reactions during polymerization. Grafting by emulsion polymerization, in which the EVA copolymer was dissolved in the monomer before polymerization, was difficult because coagulate was formed as polymerization proceeded. 

Vinyl lacquers are used mainly where a high degree of chemical resistance is required these lacquers are based on vinyl chlorides and vinyl acetates. Acrylic lacquers are based on methyl methacrylate and methyl acrylate polymers and copolymers. Other esters of acrylic and methacrylic acid also may be used to make nonconvertible film formers. Judicious selection of these acrylic acid or methacrylic acid esters allows one to produce film formers with specifically designed properties such as hardness, flexibility, gloss, durability, heat, and chemical resistance. Acrylic lacquers, however, are not noted for their water resistance. The principal uses of acrylic-type lacquers are fluorescent and metallic paints, car refinish applications, clear lacquers and sealers for metals, and protective coatings for aircraft components and for vacuum-deposited metals, as well as uses in pigmented coatings for cabinets and appliances. 

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... 

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. 

The vinyl radical is designated chemically as CH2= CH- therefore, the term "vinyl resins" could be applied to substituted ethylenes and their many copolymers. Among these can be included polyethylene, polystyrene, polyvinyl chloride, polyvinyl acetate, acrylic esters, methacrylic esters and even some of... 

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. 

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. 

In addition to ABS, with polybutadiene as the elastifying component, there is another forerunner among the polymer products formulated for low-temperature impact resistance, PVC-U. Elastifying ligands include EVAC, EVAC/VC graft polymer, PAEA C (polyacrylic acid ester/vinyl chloride copolymer), ACE (acrylic ester/MMA graft polymer) as well as the chlorinated low-pressure polyethylene PE-C in use for over 35 years. All of the polymer blends listed here are suitable for outdoor applications since they contain no unsaturated components. Polybutadiene-modified products are better suited to interior applications, for example MBS, a methylmethacrylate/butadiene/styrene graft polymer [55]. 

Acrylates/hydroxyesters acrylates copolymer Acrylates/PVP copolymer t-Butylacrylate/ethylacrylate/methacrylic acid copolymer Isobutylene/MA copolymer Methacrylic acid copolymer Octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer Polymethacrylamidopropyl trimonium chloride Polyquaternium-29 PVM/MA copolymer, ethyl ester PVP PVP/d i methylam i noethyl methacrylate copolymer Sodium p-styrenesulfonate VA/butyl maleate/isobornyl acrylate copolymer Vinyl acetate/crotonic acid copolymer Vinyl... 

Alcryn Chlorinated olefin/EVAl/acrylate ester blends PVC/ethylene-carbon monoxide-vinyl chloride copolymer TP elastomers E. I. du Pont de Nemours... 

Saran The names Saran and Saran Wrap are tradenames for vinylidene chloride copolymer produced by Dow Chemical Co. They represent a series of vinylidene chloride copolymers with vinyl chloride or acrylonitrile. The vinyl chloride copolymers are best known. Other copolymers with vinyl acetate, allyl esters, unsaturated ethers, acrylates, methacrylates, and styrene have appeared but have not achieved significant commercial interest. 

Copolymers of acrylonitrile and lower acrylates have also been used as thickeners. The proportion of the acrylate in the copolymer was 60-90% by weight the preferred acrylates were the methyl through butyl esters. These authors also tested an extensive list of known and novel thickeners as comparative examples. The latter included nitrile rubber and vinyl acetate-vinyl chloride, methyl methacrylate-butadiene-styrene (MBS), and acrylonitrile-butadiene-styrene (ABS) copolymers. The copolymers of this invention were claimed to provide better stability, higher viscosity, less stringing, and better impact strength than do the thickeners of the prior art. The claims of this patent do not cover the disclosed copolymers. Polyvinyl ethers are another class of cyanoacrylate thickeners which have been disclosed but not claimed. ... 

ACM (copolymer of acrylic ester with a vulcanizable monomer, e.g. 2-chlorovinyl ether) grafted on vinyl chloride chain ACM- -VC... 

Additionally to the procedures described earlier, improvements for thermostabilization is copolymerisation of vinyl chloride with suitable monomers. A great number of monomers were investigated to optimize the properties of resins. But only vinyl acetate, vinylidene chloride, ethylene, propylene, acrylonitrile, acrylic acid esters, and maleic acid esters, respectively, are of interest commercially [305,436,437]. The copolymerization was carried out in emulsion, suspension, and solution in connection with water- or oil-soluble initiators, as mentioned elsewhere. Another possibility for modifying PVC is grafting of VC on suitable polymers [305,438], blends of PVC with butadiene/styrene and butadiene/ methacryl acid esters copolymers [433], and polymer-analogous reactions on the macromolecule [439,440] (e.g., chlorination of PVC). 

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