5-丁氧基亚甲基-2-降冰片烯的合成及其加成聚合反应

Synthesis and Addition Polymerization of 5-Butoxymethylenyl-2-norbornene

采用降冰片烯-5-甲醇和溴丁烷在氢化钠作用下合成了5-丁氧基亚甲基-2-降冰片烯,双-(β-酮萘胺)镍(Ⅱ)/B(C6F5)3催化体系使之聚合。考察了聚合时间对其均聚合的影响以及5-丁氧基亚甲基-2-降冰片烯和降冰片烯不同摩尔投料比对其共聚行为的影响。采用1HNMR、FTIR和TGA测试技术对所得的聚合物进行了结构表征和性能测试。结果表明,双-(β-酮萘胺)镍(Ⅱ)/B(C6F5)3催化体系对5-丁氧基亚甲基-2-降冰片烯均聚和共聚具有较高的催化活性。得到的均聚物和共聚物为加成型聚合物,料液中5-丁氧基亚甲基-2-降冰片烯的摩尔分数为10%～90%时,其在共聚物中的插入率为22.1%～76.9%,所得聚合物具有较好的热稳定性(Td>360℃),在THF和CHCl3等许多普通溶剂中有很好的溶解性能。

5-Butoxymethylenyl-2-norbornene（NBE-CH 2 OC 4 H 9） was synthesized.Polynorbornenes with functional groups were obtained by homo and copolymerizations of norbornene derivatives catalyzed by bis（β-ketonaphthylamino）Ni（Ⅱ）/B（C 6 F 5） 3 system.Influences on polymerizations by changing polymerization time and copolymerization monomer feed ratios was examined.The catalytic bis（β-ketonaphthylamino）Ni（Ⅱ）/B（C 6 F 5） 3 system exhibited higher catalysis activity.The obtained polymers were characterized by 1 H NMR,FTIR and TGA.Results indicated that the incorporation rate could reach 22.1%~76.9% ether units at a molar fraction of 10%~90% of the NBE-CH 2 OC 4 H 9 in the monomer feed ratios;the polymerizations are confirmed to be vinyl-addition mode.The polymer has a good thermal stability（T d 360 ℃） and is soluble in many common solvents,such as THF and CHCl 3.