Catalyst-Transfer Condensation Polymerization for the Synthesis of Well-Defined Polythiophene with Hydrophilic Side Chain and of Diblock Copolythiophene with Hydrophilic and Hydrophobic Side Chains
Catalyst-Transfer Condensation Polymerization for the Synthesis of Well-Defined Polythiophene with Hydrophilic Side Chain and of Diblock Copolythiophene with Hydrophilic and Hydrophobic Side Chains
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DOI：
10.1177/0954008307081212
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发表时间：
2007-10
影响因子：
2.1
通讯作者：
T. Yokozawa;I. Adachi;Ryo Miyakoshi;A. Yokoyama
中科院分区：
文献类型：
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作者：
T. Yokozawa;I. Adachi;Ryo Miyakoshi;A. Yokoyama
研究了Ni催化剂催化2-溴-5-氯镁-3-[2-（2-甲氧基-氧乙氧基）乙氧基]甲基噻吩(2)的链生长缩聚反应，并通过这种聚合方法合成了聚2与聚（3-己基噻吩）的嵌段共聚物。2的聚合依赖于Ni催化剂的配体，以1,2-双（二苯基膦）乙烷（dppe）为配体得到的聚2的多分散性最低。聚合物中2和Mn的转化率以及2与Ni催化剂的投料比与聚合物中Mn的投料比之间的线性关系表明，该聚合通过催化剂-转移缩聚机理以链式生长聚合方式进行。然后通过改变两种单体的聚合顺序和催化剂，以四种方式进行了2和2-溴-5-氯镁-3-己基噻吩(1)的嵌段共聚。结果表明，先将1与Ni(dppe)Cl2或Ni(dppp)Cl2 （dppp = 1,2-二苯膦丙烷）聚合，再将2进行后聚合，在不形成均聚物的情况下得到嵌段共聚物。在两种催化剂中，Ni(dppe)Cl2导致嵌段共聚物的聚分散性较窄。
Chain-growth condensation polymerization of 2-bromo-5-chloromagnesio-3-[2-(2-metho-xyethoxy)ethoxy]methylthiophene (2) with Ni catalysts was studied, and the block copolymer of poly2 and poly(3-hexylthiophene) was synthesized by this polymerization method. The polymerization of 2 depended on the ligands of the Ni catalyst, and poly2 with the lowest polydispersity was obtained when 1,2-bis(diphenylphosphino)ethane (dppe) was used as the ligand. The linear relationships between the conversion of 2 and Mn of the polymer and between the feed ratio of 2 to the Ni catalyst and Mn of the polymer indicate that this polymerization proceeds in a chain-growth polymerization manner via a catalyst-transfer condensation polymerization mechanism. The block copolymerization of 2 and 2-bromo-5-chloromagnesio-3-hexylthiophene (1) was then carried out in four ways by changing the order of polymerization of the two monomers and the catalysts. It turned out that the block copolymer was obtained without the formation of the homopolymers by the polymerization of 1 with Ni(dppe)Cl2 or Ni(dppp)Cl2 (dppp = 1,2-bis(diphenylphosphino)propane), followed by the postpolymerization of 2. Of the two catalysts, Ni(dppe)Cl2 resulted in narrower polydispersity of the block copolymer.