Acrylic polymers oxidative degradation

Poly(acrylic acid) and Poly(methacrylic acid). Poly(acryHc acid) (8) (PAA) may be prepared by polymerization of the monomer with conventional free-radical initiators using the monomer either undiluted (36) (with cross-linker for superadsorber appHcations) or in aqueous solution. Photochemical polymerization (sensitized by benzoin) of methyl acrylate in ethanol solution at —78° C provides a syndiotactic form (37) that can be hydrolyzed to syndiotactic PAA. From academic studies, alkaline hydrolysis of the methyl ester requires a lower time than acid hydrolysis of the polymeric ester, and can lead to oxidative degradation of the polymer (38). Po1y(meth acrylic acid) (PMAA) (9) is prepared only by the direct polymerization of the acid monomer it is not readily obtained by the hydrolysis of methyl methacrylate. 

Acrylate polymers also have fully saturated polymer backbones free of any heteroatoms in the main chain. This makes the polymers highly resistant to oxidation, photo-degradation and chemical attack. The acrylate groups are esters, which could be hydrolyzed under severe conditions. However, the hydrophobic nature of most acrylic polymers minimizes the risk for hydrolysis and, even if this reaction happened to some extent, the polymer backbone would still be intact. Other desirable acrylate properties include the following ... 

Rubbers, often based on poly diene rubbers or else copolymers of dienes like 1,3-butadiene, were the first successful toughening additives, and they are effective partly because they have a low modulus, 100 to 500 times lower than that of most thermoplastic polymers. Unfortunately polydienes introduce chemical double bonds which are susceptible to UV, thermal and oxidative degradation. Hydrogenation removes some of them. Acrylic compounds and ethylene copolymers are also popular impact modifiers, and they do not necessarily introduce double bonds. 

UV irradiation of poly(ethylene oxide) (Fig. 6.2) and poly(acrylic acid) (Fig. 6.3) dissolved in H2O2 (30wt%) causes a rapid oxidative degradation of both polymers [1342]. Increasing the poly (ethylene oxide) concentration in H2O2 accelerates its photodecomposition (Fig. 8.4) [1342]. Similar results have been obtained for the photolysis of H2O2 in the presence of trimethacrylic acid and poly(methacrylic acid) [201]. 

Because the polymer degrades before melting, polyacrylonitrile is commonly formed into fibers via a wet spinning process. The precursor is actually a copolymer of acrylonitrile and other monomer(s) which are added to control the oxidation rate and lower the glass transition temperature of the material. Common copolymers include vinyl acetate, methyl acrylate, methyl methacrylate, acrylic acid, itaconic acid, and methacrylic acid [1,2]. 

The desizing of water-soluble size polymers can be summarised as follows. Batchwise or continuous methods can be used in both cases an adequate supply of hot water is needed during the washing-off. Hot water and detergent are needed to remove polyfvinyl alcohol) or carboxymethylcellulose. The addition of alkali may be beneficial with carboxymethylcellulose. Alkali is essential with modified starches and acrylic acid copolymers. Polyfvinyl alcohol) can be degraded effectively by alkaline oxidation. 

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