Alternating Copolymerization of Cyclohexene Oxide with Carbon Dioxide Catalyzed by (salalen)CrCl Complexes
Alternating Copolymerization of Cyclohexene Oxide with Carbon Dioxide Catalyzed by (salalen)CrCl Complexes
复制标题
DOI：
10.1021/ma9012626
复制
发表时间：
2009-09-22
期刊：
影响因子：
5.5
通讯作者：
Nozaki, Kyoko
中科院分区：
文献类型：
--
作者：
Nakano, Koji;Nakamura, Mitsuru;Nozaki, Kyoko
用salalen的还原类似物salalen-H-2N，N '-二亚丙基-1，2-乙二胺（salen-H-2N，N'-dispersiblidene-1，2-ethylenediamine）与铬的配合物催化环氧环己烷与二氧化碳的共聚反应。虽然单独使用（salalen）CrCl络合物而不使用添加剂对共聚没有效果，但（salalcn）CrCl络合物和鎓盐的混合物以相对高的催化活性催化共聚。特别地，本催化剂体系在所报道的那些催化剂体系中在大气CO2压力下显示出最高的催化活性。一般来说，所得共聚物由几乎完全交替的结构组成。通过MALDI-TOF质谱对共聚物进行结构分析，发现氯离子引发了共聚反应。此外，发现伴随的水作为链转移试剂和双官能引发剂起作用。
Copolymerization of cyclohexene oxide with carbon dioxide was investigated by using chromium complexes with salalen ligands which are reduced analogues of salen ones (salen-H-2 N,N'-disalicylidene-1,2-ethylenediamine). Although the use of (salalen)CrCl complexes alone without additives was not effective for the copolymerization, a mixture of (salalcn)CrCl complexes and onium salts catalyzed the copolymerization with relatively high catalytic activity. Particularly, the present catalyst system showed the highest catalytic activity under atmospheric pressure of CO2 among those ever reported. In general, the obtained copolymers consisted of almost perfectly alternating structure. Structural analysis of the copolymers by MALDI-TOF mass spectrometry revealed that chloride initiated the copolymerization. In addition, concomitant water was found to work as a chain transfer reagent and a bifunctional initiator.