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Synthesis of Aliphatic Polyesters via Ring‐Opening Polymerization of Macrocyclic Oligoesters
Author(s) -
Nakayama Yuushou,
Sakaguchi Keisuke,
Tanaka Ryo,
Cai Zhengguo,
Shiono Takeshi
Publication year - 2015
Publication title -
macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 1022-1360
DOI - 10.1002/masy.201400019
Subject(s) - polymerization , condensation polymer , polyester , polymer chemistry , oligomer , ring opening polymerization , dimer , chemistry , dicarboxylic acid , polymer , materials science , organic chemistry
Summary To synthesize high molecular weight aliphatic polyesters, ring‐opening polymerization (ROP) of macrocyclic oligoesters made from several dicarboxylic acids and diols was investigated. Macrocyclic oligoesters used for the ROP were synthesized in ca. 50% yield via polycondensation of dicarboxylic acids (small excess) and diols under dilute condition in toluene, followed by washing with aq. NaHCO 3 to remove linear oligomers. The obtained products were the mixtures of macrocyclic oligoesters with various ring size (dimer to heptamer). The polymerization of the macrocyclic oligoesters made from succinic acid and 1,4‐butanediol using rare earth catalysts such as Nd(BH 3 )(thf) 3 and Nd(O i Pr) 3 was found to give high molecular weight polymers in good yields. Cyclic dimer of butylene succinate ((BS) 2 ) was isolated from the mixture of the cyclic oligomers by column chromatography, and was similarly polymerized by the rare earth catalysts. Bulk polymerization of (BS) 2 by Nd(BH 3 )(thf) 3 yielded poly(butylene succinate) with M n up to 38 000. Cyclic oligomers of trimethylene oxalate were not polymerized under the similar conditions applied in this study.