Preparation of new types of linear polymers by the polyrecombination reaction

Abstract

AbstractIn an extension of previously reported studies of the use of the polyrecombination reaction to synthesize high molecular weight compounds, it has been shown for the first time that this method yields linear polymers without any significant formation of threedimensional structures. Such polymers may be synthesized from compounds containing a methylene group in the α‐position to the benzene ring, carboxyalkyl or carboxyphenyl groups. On treatment of diphenylmethane with tert‐butyl peroxide, a linear polymer of molecular weight 10,000‐900,000 (depending on the quantity of peroxide used) was obtained. Linear polymers in the form of benzene‐soluble powders were also obtained from benzyl benzoate (molecular weight 400,000), methyl phenylacetate, etc. The composition and structure of the polymers obtained were confirmed by chemical analysis and infrared spectroscopy. The relation between the molecular weight of the polymer and the amount of peroxide consumed in the reaction was also established. If groups capable of serving as branching centers in the polymer (e.g., methyl groups in ditolylmethane) are present in the starting compounds, three‐dimensional products are formed along with the linear polymers.