Vinyl carboxylic acids, copolymerization with

Copolymerization with Vinyl Carboxylic Acids. The acids usually suggested for this method include maleic and fumaric acids and their half esters, crotonic, itaconic, methacrylic, and acrylic acid. The latter three appear to be most generally preferred. On occasion, the amides of these acids are suggested for achieving the same end result (24). Suggested specifically for butadiene-styrene latexes are these acids at about 0.05-10 wt. % based on total monomer. The latex should be adjusted to pH 8-11 (28, 29). For copolymerization with vinyl acetate (2) and acrylic monomers (18) identical acid monomers are suggested. Use of such latexes is claimed to give F/T stable emulsion floor polishes (25) and paints (16). 

Vinyl acetate is polymerized in aqueous emulsion and used widely in surface coating and in adhesives. Copolymerized with vinyl esters of branched carboxylic acids and small quantities of acrylic acid, it gives paint latices of excellent performance characteristics. G. C. Vegter found that a coagulum-free latex of very low residual monomer content can be produced from a mixture of an anionic and a nonionic emulsifier according to a specific operating procedure. The freeze/thaw stability of polymeric latices has been investigated by H. Naidus and R. Hanzes. 

Chemical reactions with alkyd resins can take place via their hydroxyl or carboxyl groups as well as via the double bonds of the unsaturated fatty acids. Isocyanates, epoxy resins, or colophony, for example, may be reacted with the hydroxyl groups. The carboxyl groups can be reacted with polyamidoamines (reaction products formed from dimerized linoleic acid and ethylenediamine) to form thixotropic resins, or can react with hydroxy-functional silicone precondensates. The double bonds of the unsaturated fatty acids permit copolymerization with vinyl compounds [e.g., styrene or (meth)acrylic acid derivatives]. 

Kaita Sh, Matsushita K, Tobita M, Maruyama Y, Wakatsuki Y (2006) Cyclopentadienyl nickel and palladium complexes/activator system for the vinyl-type copolymerization of norbomene with norbomene carboxylic acid esters control of polymer solubility and glass transition temperature. Macromol Rapid Commun 27 1752-1756... 

Although the peroxyester-monosaccharide or peroxyester-monosac-charide-carboxylic acid ester catalyst system is useful in the bulk and suspension polymerization of vinyl chloride, the redox system may also be used in the copolymerization of vinyl chloride with vinylidene chloride, vinyl acetate, and other monomers which undergo copolymerization with vinyl chloride. 

Vinyl groups of 1,4-DVB microgels have been converted to carboxylic acid groups by ozone [291]. After modification the microgels could be dissolved in methanol. About 83 % of the vinyl groups could be converted. A simpler way to prepare microgels with carboxyl acid groups at their surface is the copolymerization of DVB with methacrylic acid in an aqueous emulsion [292]. 

Copolymerization of vinyl chloride with metal salts of unsaturated carboxylic acids has been investigated more closely. By radical copolymerization in methanol solution of vinyl chloride and lead acrylate small amounts of lead acrylate can be inserted into the copolymer chains. However, only about one-third to one-half of the lead salt originally present in the monomer mixture is incorporated in the chains. Moreover, the thermal stability of the resulting polymer shows only a relatively small improvement over that of homopolymeric vinyl chloride (1) (see Figure 4). Although the rate of dehydrochlorination is distinctly lowered with increasing lead content in the polymers, there is no induction period at the onset of thermal treatment. Therefore, one cannot speak of true stabilization in this case. 

Vinyl chloride can be copolymerized with a series of monomers Vinylidene chloride, trans-dichloroethylene, vinylesters of aliphatic carboxylic acid (C2-C18), acrylic acid esters, methacrylic and/or maleic acid as well as fumaric acid with mono-functional aliphatic saturated alcohols (Cj-C18), mono-functional aliphatic unsaturated alcohols (C8—C18), vinyl ethers from mono-functional aliphatic saturated alcohols (C i-Cis), propylene, butadiene, maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid (total < 8 %) and N-cyclohexylmaleinimide (< 7 %). 

Emulsion Copolymerization of Vinyl Esters of Branched Carboxylic Acids with Vinyl Acetate... 

According to literature data vinyl esters of saturated aliphatic carboxylic acid copolymerize randomly with each other (I), the monomers being incorporated into the copolymer in about the same ratio at which they are present in the monomer mixture. This means that for practical purposes the relative reactivity ratios ri and r > can be taken to be equal and unity. 

To address these shortcomings the carboxylic acid was replaced with weaker phenol for a better shelf life and dry etch stability and the vinyl ether functionality was separated from the acidic functionality employing a three component design. A water soluble phenolic copolymer was prepared by radical copolymerization of 4-acetoxystyrene and sodium styrenesulfonate, followed by deacetylation with ammonium hydroxide. A water soluble bis(vinyl ether)... 

In preparing cation exchange membranes having carboxylic acid groups, acrylic acid, methacrylic acid and their esters, etc., are copolymerized with divinylbenzene and, optionally, other vinyl monomers. The copolymer membranes are then immersed in hydroxide solution, or the ester groups of the membranes are hydrolyzed. 

The synthesis of vinyl esters of the higher monocarboxylic acids is troublesome and costly. The preparation may involve transvinylation with vinyl acetate and the higher carboxylic acid with a costly mercuric salt as a catalyst. In this procedure, the equilibrium situation is unfavorable and yields of product usually are low. Alternatively, a similar catalyst may be used for the addition of acetylene to the carboxylic acid. This procedure requires pressure equipment not usually available in a synthesis laboratory. The allyl esters, on the other hand are readily prepared by conventional esterification procedures. Therefore, they are of potential interest as plasticizers which might copolymerize with resins such as vinyl acetate that normally give rise to hard resins. Unfortunately, allyl esters of more ordinary carboxylic acids homopolymerize sluggishly. Their ability to enter into copolymer systems also seems to be marginal. 

All vinyl polymers are addition polymers. To differentiate the, the homopolymers have been classified by the substituents attached to one carbon atom of the double bone. If the substituent is hydrogen, alkyl or aryl, the homopolymers are listed under polyolefins. Olefin homopolymers with other substituents are described under polyvinyl compounds, except where the substituent is a nitrile, a carboxylic acid, or a carboxylic acid ester or amide. The monomers in the latter cases being derivatives of acrylic acid, the derived polymers are listed under acrylics. Under olefin copolymers are listed products which are produced by copolymerization of two or more monomers. 

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