Scandium-Catalyzed Cyclocopolymerization of 1,5-Hexadiene with Styrene and Ethylene: Efficient Synthesis of Cyclopolyolefins Containing Syndiotactic Styrene–Styrene Sequences and Methylene-1,3-cyclopentane Units
Scandium-Catalyzed Cyclocopolymerization of 1,5-Hexadiene with Styrene and Ethylene: Efficient Synthesis of Cyclopolyolefins Containing Syndiotactic Styrene–Styrene Sequences and Methylene-1,3-cyclopentane Units
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DOI：
10.1021/ma201271r
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发表时间：
2011-07
期刊：
影响因子：
5.5
通讯作者：
Fangxu Guo;M. Nishiura;H. Koshino;Z. Hou
中科院分区：
文献类型：
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作者：
Fangxu Guo;M. Nishiura;H. Koshino;Z. Hou
研究了含不同辅助配体的钪二烷基半夹心配合物对1，5-己二烯（HD）的聚合及其与苯乙烯和乙烯的共聚反应。已观察到配体对催化活性和选择性的显著影响。不含THF的氨基苄基钪络合物具有空间要求高的配体，例如（C5Me4SiMe3）Sc（CH 2C 6 H4 NMe 2-o）2（4 e）与当量[Ph 3 C][B（C6 F5）4]结合，可作为HD与苯乙烯环聚合的优良催化剂，得到一类新的聚合物材料，包含亚甲基-1，3-环戊烷（MCP）单元、乙烯基四亚甲基（VTM）单元、和独特的间同立构苯乙烯-苯乙烯序列。通过使用该催化剂，HD，苯乙烯和乙烯的三元聚合也已首次实现，提供新的环聚合物材料含有五元环MCP单元，乙烯-乙烯嵌段，和间同立构苯乙烯-苯乙烯序列。The composition of the...
The polymerization of 1,5-hexadiene (HD) and its copolymerization with styrene and ethylene by a series of half-sandwich scandium dialkyl complexes bearing various auxiliary ligands have been examined. Significant ligand influence on the catalytic activity and selectivity has been observed. The THF-free aminobenzyl scandium complex with a sterically demanding ligand, such as (C5Me4SiMe3)Sc(CH2C6H4NMe2-o)2 (4e), in combination with an equivalent of [Ph3C][B(C6F5)4], serves as an excellent catalyst for the cyclocopolymerization of HD with styrene to afford a new family of polymer materials containing methylene-1,3-cyclopentane (MCP) units, vinyltetramethylene (VTM) units, and unique syndiotactic styrene–styrene sequences. By use of this catalyst, the terpolymerization of HD, styrene, and ethylene has also be achieved for the first time to afford novel cyclopolymer materials containing the five-member ring MCP units, ethylene–ethylene blocks, and syndiotactic styrene–styrene sequences. The composition of the...