Control of chain ends of polyesters in polycondensation of AA and BB monomers by use of solid‐phase reagent

Abstract

ABSTRACTFor selective synthesis of linear polyester having a functional group at one end, polycondensation between 1,4‐butanediol (1a) and sebacoyl chloride (2a) and between 1,12‐dodecanediol (1b) and isophthaloyl chloride (2b) was conducted in the presence of oxime resin or oxime silica gel, followed by cleavage of the formed polyester from the solid‐phase support with aniline. Matrix‐assisted laser desorption ionization time‐of‐flight mass spectra and 1H NMR spectra of the cleaved polyester showed that the products contained not only polyester with anilide at one end (poly 1), but also polyester with anilides at both ends (poly 2). The product ratio of poly 1 to poly 2 (poly 1/poly 2) was dependent on monomers, monomer concentration, feed ratio of monomer to oxime moiety in the support, oxime content in the support, reaction solvent, and the nature of the support. Polyester with a high poly 1/poly 2 ratio of 81/21 and moderate molecular weight (Mn = 1430 g/mol) was obtained by polycondensation of 1b and 2b in the presence of oxime silica gel in dichloromethane. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 1379–1386