Department of Material and Life Chemistry, Kanagawa University, Rokkakubashi, Kanagawa-ku, Yokohama 221-8686, Japan.
Macromol Rapid Commun. 2011 Jun 1;32(11):801-6. doi: 10.1002/marc.201100037. Epub 2011 Apr 20.
(t)Bu(3) PPd(Ph)Br (1)-catalyzed Suzuki-Miyaura coupling polymerization of 2-(4-hexyl-5-iodo-2-thienyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2) was investigated. Monomer 2 was polymerized with 1 at 0 °C in the presence of CsF and 18-crown-6 in THF containing a small amount of water to yield P3HT with a narrow molecular weight distribution and almost perfect head-to-tail regioregularity. The M(n) values increased up to 11,400 g · mol(-1) in proportion to the feed ratio of 2 to 1. The MALDI-TOF mass spectra showed that P3HT with moderate molecular weight uniformly had a phenyl group at one end and a hydrogen atom at the other, indicating involvement of a catalyst-transfer mechanism. Successive 1-catalyzed polymerization of fluorene monomer 3 and then 2 yielded a well-defined block copolymer of polyfluorene and P3HT.
(t)Bu(3) PPd(Ph)Br（1）催化的 2-(4-己基-5-碘-2-噻吩基)-4,4,5,5-四甲基-1,3,2-二氧杂环戊硼烷（2）的 Suzuki-Miyaura 偶联聚合反应进行了研究。单体 2 在 0°C 下，在 CsF 和 18-冠-6 的存在下，在含有少量水的 THF 中聚合 1，得到具有窄分子量分布和几乎完美的头-尾区域规整性的 P3HT。M(n)值与 2 与 1 的进料比成比例增加至 11400g·mol(-1)。MALDI-TOF 质谱表明，具有中等分子量的 P3HT 均匀地在一端具有苯基，在另一端具有氢原子，表明涉及催化剂转移机制。连续的 1 催化芴单体 3 的聚合，然后聚合 2，得到了聚芴和 P3HT 的定义明确的嵌段共聚物。
