载体化络合催化开环歧化聚合合成梳形接枝共聚物研究

由环戊二烯（CPD）及烯丙基氯（AC）经聚合物支载三氟化硼催化的Diels-Alder反应合成了5-氯甲基-2-降冰片烯（NB-CH2Cl)，锂代后用以引发甲基丙烯酸甲酯（MMA）及苯乙烯（S）的活性阴离子聚合，合成了带聚合物取代基的降冰片烯大分子单体NB-PMMA及NB-PS。在聚合物支载钌卡宾络合物催化作用下进行所合成大分子单体的开环歧化聚合反应（ROMP），合成了二种接枝于开环歧化聚降冰片烯（PNB）主链的梳形接技共聚物PNB-g-PMMA及PNB-g-PS。实验结果表明所研制聚合物支载硼、钌络合物催化性能明显优于对应非支载活性种。

SYNTHESIS OF COMB-SHAPED GRAFT COPOLYMERS VIA RING OPENING METATHESIS POLYMERIZATION CATALYZED BY SUPPORTED RUTHENIUM CARBENE COMPLEX

chloromethyl-2-norbornene (NBCH2Cl) was synthesized via Diels-Alder reaction of cyclopentadinene and allyl chloride using polymer supported boron trifluoride as the catalyst, and was then lithiated and used to initiate the living anionic polymerization of methyl methacrylate and styrene to prepare norbornyl macromonomer NBPMMA and NBPS. Two comb-shaped graft copolymers, i.e., PNBgPMMA and PNBgPS were synthesized via ring opening metathesis polymerization of the synthesized macromonomers under the eatalysis of ruthenium carbene complex RuCl2(PPh3)2(=C=CHtBu) and its polymer-supported counterpart. Experimental results showed that the behaviour of both polymer supported boron and ruthenium catalysts are superior to their unsupported correspondents.