Nishikubo T, Kameyama A, Kawakami S
Department of Applied Chemistry, Faculty of Engineering, Kanagawa University, Rokkakubashi, Kanagawa-ku, Yokohama 221, Japan.
Macromolecules. 1998 Jul 28;31(15):4746-52. doi: 10.1021/ma980350u.
Poly(ester-alt-sulfide) (polymer 1) was synthesized by the alternating copolymerization of glycidyl phenyl ether (GPE) with gamma-thiobutyrolactone (TBL) catalyzed by either quaternary onium salts or crown ether complexes. The copolymerization proceeded to produce polymer 1 with good yields in neat or in various organic solvents at 30-120 degreesC, in which quaternary onium salts having Cl- as a counteranion such as tetrabutylammonium chloride (TBAC) had higher activity than quaternary onium salts such as tetrabutylammonium bromide having Br- as a counteranion. It was also found that the alternate copolymer (polymer 1) of GPE with TBL was obtained selectively under different feed ratios of GPE and TBL, although ring-opening homopolymerizations of GPE and TBL did not proceed. Copolymerizations of various oxiranes such as butyl glycidyl ether, styrene oxide, and 1,2-hexene oxide with TBL catalyzed by TBAC also proceeded, and the corresponding poly(ester-alt-sulfide)s (polymers 2, 3, and 4) were obtained under the same conditions as for the synthesis of polymer 1.
聚（酯-交替-硫化物）（聚合物1）是通过在季铵盐或冠醚配合物催化下，使缩水甘油基苯基醚（GPE）与γ-硫代丁内酯（TBL）交替共聚而合成的。该共聚反应在30至120℃的纯态或各种有机溶剂中进行，能够以良好的产率生成聚合物1，其中以Cl-作为抗衡阴离子的季铵盐（如四丁基氯化铵（TBAC））比以Br-作为抗衡阴离子的季铵盐（如四丁基溴化铵）具有更高的活性。还发现，尽管GPE和TBL的开环均聚反应未发生，但在GPE和TBL不同的进料比下可选择性地获得GPE与TBL的交替共聚物（聚合物1）。由TBAC催化的各种环氧乙烷（如丁基缩水甘油基醚、氧化苯乙烯和1,2-己烯氧化物）与TBL的共聚反应也能进行，并且在与聚合物1合成相同的条件下可得到相应的聚（酯-交替-硫化物）（聚合物2、3和4）。
