一种新型聚降冰片烯类无规共聚物的合成与表征

Synthesis and characterization of a novel norbornene based copolymer

降冰片烯衍生物的开环易位聚合具有反应条件温和、反应速率快及尺寸可控等优点,且因其独特的结构使得聚合物主链具有良好的热稳定性及耐酸碱性能。本文通过开环易位聚合法制备了降冰片烯基苯磺酰氯(NBSC)与5-降冰片烯-2,3-二羧酸二甲酯(DCNM)的新型二元无规共聚物。通过FT-IR、NMR表征了单体和共聚物的化学结构,并通过设计对比实验探究了最佳反应条件。GPC数据显示,当两单体配比1∶1,催化剂用量为单体总物质的量1/450,反应时间30 min,反应温度40℃时,共聚物的相对分子质量最大,分子量分布较窄,产率最高,此条件为最佳反应条件。DSC表明,DCNM单体均聚物的Tg为60℃,与NBSC共聚后,Tg升高至80℃左右。TGA数据显示共聚物质量分解5%时对应的温度为145℃,最大分解速率时的温度为245℃,证明该聚合物具有良好的热稳定性。综合考虑其各项性能,这种新型的聚合物有望用于燃料电池质子交换膜领域的研究。

Ring opening metathesis polymerization(ROMP)of norbornene derivatives have many advantages,including mild reaction conditions,high reaction rate and controllable size.Besides,polymer chains have good thermal stability and resistance to acid and alkali resistance because of its unique structure.Here we prepared a novel random copolymer with 4-(bicyclo [2.2.1]hept-5-en-2-yl)benzene-1-sulfonylchloride(NBSC)and dimethyl 8,9,10-rinorborn-5-ene-2,3-dicarboxylate(DCNM).And the structure of monomer and polymer were confirmed by NMR and FT-IR.Moreover,we studied the best reaction conditions viacontrast experiments.GPC showed the best reaction conditions were the monomers ratio was 1∶1,the catalyst was 1/450 of monomers'molar mass,the reaction time was 30 min and the temperature was 40℃,under which the relative molecular mass was the largest,the relative molecular mass distribution was narrow and the yield was the highest.DSC showed that the glass transition temperature of DCNM was 60℃,while that of polymer increased to 80℃.TGA showed that the temperature of 5% mass lost was 145℃and the temperature of the fastest loss of mass was 245℃,which implied the polymer had good thermal stability.From the point of comprehensive performance,the polymer were supposed to have the potential use in the field of proton exchange membrane for fuel cells.