Poly chain cleavage

The preceding results on polycarbonate are at variance with the ultrasonic degradation of poly(vinyl pyrollidone) prepared with peroxide linkages where the rate of chain cleavage was determined to be 5000 times faster at the — 0 — 0 — than the — C —C— bonds [164]. 

Thus, while these two polymers differ greatly in their rate of hydrolytic chain cleavage, gel permeation chromatography (GPC) analysis of a 1 1 blend of PCL and poly(glycolic acid-co-lactic acid) in pH 7.4 buffer showed that both components of the blend were subject to the same rate of chain cleavage (65). 

Alkyl and aryl derivatives of poly(dichlorophosphazene) are not efficiently synthesized by nucleophilic reaction of LXXXIV with metal alkyls or aryls. The halogen substitution reaction occurs but is accompanied by polymer chain cleavage. Use of poly(difluorophosphazene) or introduction of aryl and alkyl groups at the monomer stage offer some improvement, but neither method is fully satisfactory. The best route to alkyl and aryl derivatives is polymerization of A-(trimethylsilyl)-/).P-dialkyl-.P-halophosphoranimines at moderate temperatures (25-60°C) in the presence of a Lewis acid [Allcock et al., 1996, 2000, 2001a,b Neilson and Wisian-Neilson, 1988]. The reaction proceeds as a cationic chain polymerization ... 

The poly (amino acid)s with aromatic side chains behave somewhat differently. In poly(phenylalanine) the a-carbon radical is the major radical species observed, but radicals formed by hydrogen atom addition to the ring are also found. Benzyl radicals formed by side-chain cleavage are present, but only in very low yield. In poly (tyrosine) the only radical species observed is the tyrosyl phenoxyl radical formed by loss of the hydroxyl hydrogen. There is no evidence for formation of significant concentrations of a-carbon radicals. Thus, the nature of the substituents can strongly influence the radiation sensitivity of the backbone chain. 

The high specificity of elimination of alkyl side branches from poly (olefin) s is attributed to (1) enhanced scission of C-C bonds at tertiary carbon atoms, reflecting their lower bond energies, and (2) a cage effect which produces geminate recombination of many of the main-chain cleavages, whereas the mobility of fragments of low molar mass enables them to escape. 

Random chain cleavage followed by chain unzipping is characterized by high monomer yields and a slow decrease in the molecular weight of the polymer, for example, exhibited by PMMA, poly(a-methyl styrene), polystyrene polytetrafluoroethylene. 

Random chain cleavage followed by further chain scission is characterized by very low monomer yields among the degradation products and a rapid drop in molecular weight, for example, exhibited by PE, PP, poly(methyl acrylate), and polychlorotrifluoroethylene. 

The equilibrium 20 is important not only in the synthesis of linear polysiloxanes but also in their applications. The effects of water vapor on inducing chain cleavage at high temperature are not only reduced molecular weights but also a dramatic increase in the rates of chemically induced stress relaxation at 250 °C in cross-linked poly(dimethylsiloxane) networks under load (70). Slow hydrolytic bond cleavage in cross-linked networks is seen even in studies of stress relaxation in air at room temperature, and appreciable rates of stress relaxation in the loaded networks are measured at temperatures as low as 70 (7i). The stress relaxation is greatly accelerated... 

Pitt, G.G. Gu, Z.W. Modification of the rates of chain cleavage of poly(e-caprolactone) and related polyesters in the solid state. J. Controlled Release 1987, 283 (4), 283-291. 

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