高等学校化学学报 ›› 2001, Vol. 22 ›› Issue (S1): 273.

• 研究论文 • 上一篇    下一篇

梳形接枝共聚物的合成(Ⅱ)——载体化钌卡宾络合物催化降冰片烯基聚苯乙烯的开环岐化聚合

李弘, 张文芳, 何炳林   

  1. 吸附与分离功能高分子材料国家重点实验室, 南开大学高分子化学研究所, 天津 300071
  • 收稿日期:2001-08-14 出版日期:2001-12-31 发布日期:2001-12-31
  • 通讯作者: 李弘(1940年出生),男,教授,博士生导师,从事催化聚合及功能高分子研究.e-mail:hongli@sun.nankai.edu.cn E-mail:hongli@sun.nankai.edu.cn
  • 基金资助:

    国家自然科学基金资助研究项目(项目批准号:29874018)资助.

Synthesis of Comb Graft Copolymers (Ⅱ)

LI Hong, ZHANG Wen-Fang, HE Bing-Lin   

  1. The Stale Key Laboratory of Functional Polymeric Maieriah for Adsorption and Separation, institute of Polymer Chemistry, Nankai University, Tianjin 300071, China
  • Received:2001-08-14 Online:2001-12-31 Published:2001-12-31
  • Contact: hongli@sun.nankai.edu.cn E-mail:hongli@sun.nankai.edu.cn

摘要:

由石油化工副产C5馏份提取双环戊二烯(DCPD)、以聚合物负载三氟化硼为催化剂进行DCPD与烯丙基氯(AC)的Diels-Alder反应合成5-氯甲基-2-降冰片烯(NBCH2Cl),经锂代反应后用以引发苯乙烯的活性阴离子聚合合成了降冰片烯(NB)基聚苯乙烯(PS)大分子环烯单体NB-PS,在聚合物负载钌卡宾络合物[RuCl2(PPh3)2(=C=CHtBu)]催化(引发)作用下进行大分子单体NB-PS的开环歧化聚合(ROMP)合成了梳形接枝共聚物PNB-g-PS.实验结果表明所合成聚合物负载硼、钌络合物催化剂的性能均明显优于对应非负载体.讨论了上述催化剂的聚合物载体效应的机理及温度、溶剂等对活性阴离子聚合反应的影响.

关键词: 活性阴离子聚合, 开环歧化聚合, 大分子单体, 高分子催化剂, 钌,

Abstract:

Diels-Alder reaction of cyclopentadiene, refined from the by-product C5 fraction in petrochemical industry, and allyl chloride (AC) was carried out by a polymer supported BF3 catalyst to synthesize 5-chloromethyl-2-norbornene (NBCH2Cl). The latter was lithiated and used as an initiator for lhe living anionic polymerization of styrene. A norbornyl-PS macromonomer (NB-PS) was synthesized.Under the catalysis (initiation) of a polymer supported ruthenium carbene complex the macromonomer undergoes ring, opening metathesis polymerization (ROMP) and a comb-shaped graft copolymer was synthesized. The catalytic behaviour of the polymer supported boron trifluoride and ruthenium carbene catalysts is superior to that of their corresponding unsupported counterparts. The mechanism of effect of the polymer supports in increasing catalyst stability and lifetime of the labile propagation active species of metal carbene was discussed.

Key words: living anionic polymerization, ring opening metathesis polymerization, macromonomer, polymer supported catalysts, ruthenium, boron

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