Vinyl acetate copolymers with maleic esters

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. 

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... 

Polyquaternium-11 (quaternium-23—Gafquat) is a copolymer of vinyl pyrrolidone and dimethylaminoethyl melliacrylate quaternized with dimethyl sulfate. This polymer is related to the quaternized copolymer of PVP depicted in Table 7-2. One mousse product in retail sale contains both of these cationic polymers. Others contain one cationic polymer and either a neutral or an anionic resin such as polyvinyl pyrrolidone and vinyl acetate copolymer, or a resin such as the butyl ester of polyvinyl methyl ether, a maleic anydride copolymer. 

Graft copolymers between unsatnrated acids, especially acrylic acid and maleic anhydride (MA), and polyolefins (PE and PP) are widely used as surface modifiers and compatibilisers, sometimes in combination with bi-functional coupling agents [46], for talc, calcium carbonate and calcined clays. Such polymer coatings include polypropylene-maleic anhydride [47], polypropylene c/s-4-cyclohexene-l,2 dicarboxylic acid [48], polystearyl or polylauryl acrylate [49], polypropylene-acrylic acid, partially oxidised poly(butane diol) [50] and ethylene-vinyl acetate copolymers [51]. Acid-containing products can react with basic fillers. With most other types, they will simply adsorb on to the mineral surface, but they can form esters with some non-basic metal hydroxyls, notably silanols. 

Aqueous emulsions of polymeric compounds, e.g., homopolymers of vinyl acetate and vinyl propionate, vinyl acetate copoljmiers with ethylene or maleic esters polyacrylic esters, styrene copolymers. Uses paper, wood, also bonding to plastics. 

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 vinyl chloride with vinyl acetate and maleic anhydride are made more adhesive to metals through hydrolysis of the ester and anhydride units. 

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,... 

Several polymers were found to fit all or most of the above criteria and were used to prepare the carrier films. Many polymers have been used for this purpose, viz., ethyl cellulose, poly(y-benzyl glutamate), poly(vinyl acetate), cellulose acetate phthalate, and the copolymer of methyl vinyl ether with maleic anhydride. In addition to the base polymers, plasticizers were often needed to impart a suitable degree of flexibility. Plasticizers, which are found to be compatible with polymeric materials include, acetylated monoglycerides, esters of phthalic acid such as dibutyl tartarate, etc. An excipient was usually incorporated into the matrix of the carrier films. The excipients used were water-soluble materials, which are capable of creating channels in the polymer matrix and facilitate diffusion of the drug. PEGs of different molecular weights were used for this purpose. 

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. 

Neutral and acidic polymers such as polyvinyl pyrrolidone, copolymers of polyvinyl pyrrolidone with vinyl acetate, and copolymers of methyl vinyl ether with half esters of maleic anhydride, are all used in hair styling and hair setting products. 

The resins of styling or setting products are usually cationic (e.g., polyquatemium-11, a copolymer of vinyl pyrrolidone and dimethy-laminoethyl methacrylate quaternized with dimethyl sulfate, similar to the quatemized copolymer of PVP depicted in Table 7-2), anionic (e.g., butyl ester of polyvinyhnethyl ether and maleic anhydride), neutral (e.g., copolymer of polyvinyl pyrrolidone, vinyl acetate), or even polyvinyl pyrrolidone itself with polyacrylate thickeners. 

A number of copolymers are known where vinyl acetate is the major component. In coatings, vinyl acetate is often used in copolymers with alkyl acrylates (line 2-ethylhexyl acrylate) or with esters of maleic or fumaric acids. Such copolymers typically contain 50-20% by weight of the comonomer and are usually formed by emulsion polymerization in batch processes. They are used extensively as vehicles for emulsion paints. 

On the other hand, the joint polymerization of a series of electron-accepting and electron-donating monomers leads to alternating copolymers, mostly as a mixture with the head-to-head cycloaddition products. Electron-accepting maleic anhydride, fumaric ester, sulfur dioxide, or carbon dioxide in combination with electron-donating butadiene, isobutylene, vinyl ether, and p-dioxene or vinyl acetate belong to this series. 

Important copolymers of styrene are SBR (styrene butadiene rubbers), ABS, a copolymer with butadiene and acrylonitrile, and various copolymers with methacylic and acrylic esters, such as styrene-methyl methacrylate and styrene-methyl acrylate copolymers. Additionally, copolymers formed with one or more of the following monomers also exist ethylene, a-methyl styrene, vinyl acetate, maleic anhydride, and acrylonitrile. 

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). 

Free-radical copolymerization of alkyl vinyl ethers has been carried out with the following typical monomers acrylic acid (bulk and emulsion) [39,40], acrylonitrile (emulsion) [26,27], acrylic esters (emulsion) [41], methyl methacrylate (bulk) [42], maleic anhydride (solution) [43], vinyl acetate (bulk and emulsion) [27,44,45], and vinyl chloride (emulsion) [26, 37,46]. The properties of these and other copolymers are described in a technical bulletin by General Aniline Film Corporation [38]. 

Maleate esters such as dimethyl maleate, diethyl maleate and dibutyl maleate are extensively used in the production of latex emulsion polymers, thermoplastic and thermosetting plastics. Dimethyl maleate has found use in applications where improvement in hardness and toughness of polymer films are desired. This includes, in particular, the improvement of anti-blocking properties of copolymers of vinyl acetate with dimethyl maleate. It is also used as an internal modifier to increase the glass transition temperature of styrene or vinyl chloride polymer. The intermediate in esterification of maleic acid with methanol, monomethyl maleate provides plastsizing effect, as well as promotion of improved polymer adhesion due to the carboxylic group. It can be copolymerized with a variety of vinyl and acrylic monomers to provide coatings with improved stiffness and adhesion and reduced tackiness or tendency to block. Monoesters of maleates are used to provide carboxylic acid functionality in emulsions and water-soluble polymers. 

Several vinyl monomers are used to prepare thermoplastics that are useful in certain adhesive applications. The most important vinyl resins for adhesives are polyvinyl acetate, polyvinyl acetals (butyral and formal), and polyvinyl alkyl ethers. PVC and copolymers of both vinyl chloride and vinyl acetate with other monomers, such as maleic acid esters, alkyl acrylates, maleic anhydride, and ethylene, are also used to produce solvent-based adhesives. ... 

Blends of NBR with Polyvinyl Acetate PVAC) and its Copolymers Stollfuss investigated blends of NBR with polyvinyl acetate (PVAC) and its copolymers. The object was to obtain better low-temperature flexibility, compression set behaviour, and ageing resistance than that possible with NBR/PVC blends. Although the solubility parameters are similar in the two cases and the formation of a homogeneous phase was expected, only two-phase systems were found, except in the case of a vinyl acetate/maleic acid ester copolymer. All the mechanical properties, and also the resistance to ozone, were inferior to those of the NBR/PVC blends. Only the resistance to ageing was improved. 

Among such oxidations, note that liquid-phase oxidations of solid paraffins in the presence of heterogeneous and colloidal forms of manganese are accompanied by a substantial increase (compared with homogeneous catalysis) in acid yield [3]. The effectiveness of n-paraffin oxidations by Co(III) macrocomplexes is high, but the selectivity is low the ratio between fatty acids, esters, ketones and alcohols is 3 3 3 1. Liquid-phase oxidations of paraffins proceed in the presence of Cu(II) and Mn(II) complexes boimd with copolymers of vinyl ether, P-pinene and maleic anhydride (Amberlite IRS-50) [130]. Oxidations of both linear and cyclic olefins have been studied more intensively. Oxidations of linear olefins proceed by a free-radical mechanism the accumulation of epoxides, ROOH, RCHO, ketones and RCOOH in the course of the reaction testifies to the chain character of these reactions. The main requirement for these processes is selectivity non-catalytic oxidation of propylene (at 423 K) results in the formation of more than 20 products. Acrylic acid is obtained by oxidation of propylene (in water at 338 K) in the presence of catalyst by two steps at first to acrolein, then to the acid with a selectivity up to 91%. Oxidation of ethylene by oxygen at 383 K in acetic acid in... 

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