采用ROMP的方法合成含有功能侧基的聚降冰片烯

【作者】 王赐明；

【导师】 鲁在君；

【作者基本信息】 山东大学 ， 高分子化学与物理， 2008， 硕士

【摘要】 活性开环易位聚合,由于其本身独特的聚合方式使其在合成具有优异的性能材料方面有着广泛的应用。在本文中我们合成了Grubbs催化剂[RuCl₂（=CHPh）（PPh₃）₂],并在它的催化下开环易位聚合了两种单体,分别是N-（4-羟基苯基）NA酰亚胺（HPNI）和含有苯并嗯嗪侧基的NA酰亚胺（NOB）。分别通过核磁和红外对聚合物的结构进行了表征。HPNI中含有酚羟基,本文采用叔丁基二甲基氯硅烷保护酚羟基,然后对其进行聚合,最后再对其酸解,最终得到含有酚羟基的聚降冰片烯。产物用GPC,¹H NMR,DSC,TGA进行了表征。这种聚合物除了本身的特性外还具有较高的反应活性,在聚合物分子结构设计方面有较广泛的应用。NOB是一种含有苯并噁嗪侧基的NA酰亚胺,除了含有具有较高开环易位活性的降冰片烯基外还含有苯并噁嗪侧基,苯并噁嗪是一种刚性基团,可以通过加热或者催化聚合形成类似酚醛树脂的交联结构。本文把苯并噁嗪基团和降冰片烯基通过化学方法结合起来,然后在自己合成的Grubbs催化剂的催化作用下开环易位聚合得到PNOB,加热固化PNOB得到具有较好热性能的苯并噁嗪树脂。并用GPC,¹HNMR,DSC,TGA等手段对其结构和性能进行了表征。结果表明PNOB的玻璃化转变温度达到148℃,固化PNOB后的苯并噁嗪树脂玻璃化转变温度达到265℃,二者均具有较好的热稳定性。更多还原

【Abstract】 The living-ROMP （ring open metathesis polymerization） has an important position in the synthesis of the materials of excellent property, for its special polymerization mode.In the paper we have finished the synthesis of the Grubbs Catalyst RuCl₂（=CHPh）（PPh₃）₂, the romp of two monomers, they are N-4-（hydroxylPhenyl） norbornenedicarboximid （HPNI）, and the norbornenedicarboximid of which side-group is benzoxazines （4-aza-4-（3-phenyl（2H,4H-benzo[2,4-3]1,3-oxazaper-hydroin-6yl））tricycle[5.2.1.0<2,6>]dec-8-ene-3,5dione）（NOB）. We also charactered them by ¹H NMR and IR.The phenol in HPNI was protected by tert-butyldimethylsilyl chloride, then the product was catalysed by Grubbs Catalyst to produce the polymer, which is decomposed by acid. Finally we received the polymer contain phenols. This kind of polymer has high reactivity except its own character, so there is a comprehensive application in the design of molecule structure. The polymer was charactered by GPC, ¹H NMR, DSC and TGA.NOB is a kind of norbornenedicarboximid which side-group is benzoxazines. Except the benzoxazines, it also has norbornene, which has high romp reactivity. Benzoxazines is a kind of rigid group. This kind of benzoxazines can form crosslinked structure like phenolic resin by heating or catalytic polymerization, which has a lot of special property. In this paper we combine the benzoxazines and norbone by chemical way, then romp this compound to receive PNOB by Grubbs catalyst, which is synthesized by ourselves. Finally cure PNOB to receive benzoxazine resin, which perform excellent thermal property. GPC, ¹H NMR, DSC, TGA are employed to character their structure and property. It shown that the Tg of PNOB was 148℃and benzoxazine resin was 265℃.They all perform excellent thermal stability.更多还原