Abstract
AbstractThe stability of the helical conformation in optically active poly(triphenylmethyl methacrylate) (PTrMA) was investigated by heating the polymer solutions at 100°C. The optical rotation slowly disappeared with time, and some preliminary experiments showed that this phenomenon is not due to a typical racemization process, as it is accompanied by a loss of triphenylmethyl (Tr) groups due to secondary reaction. Experimental results in the presence of methanol indicated that the decrease of optical activity occurs according to first‐order kinetics and qualitatively methyl triphenylmethyl ether was isolated from the final solution. In order to explain the above results, full characterization of copolymers obtained by interrupting the methanolysis at different conversions was performed. As a working hypothesis, it was assumed that the reaction starts at the end of the helices with a Tr‐oxygen bond fission and the reaction proceeds along the chain mainly with formation of block copolymers consisting of one block of PTrMA and one block of a probably random methacrylic acid anhydride/methacrylic acid copolymer.
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