构型异构聚(降冰片烯羧酸甲酯)的合成及性能  

Syntheses and Properties of Configurationally Isomeric Poly(norbornene methyl carboxylate)s

作　　者：武成 黄华超 杨平峰 魏海兵 WU Cheng;HUANG Huachao;YANG Pingfeng;WEI Haibing(School of Chemistry and Chemical Engineering,Hefei University of Technology,Hefei,Anhui 230009,China)

机构地区：[1]合肥工业大学化学与化工学院,安徽合肥230009

出　　处：《塑料》2023年第5期94-98,共5页Plastics

摘　　要：以外型和内型为主的5-降冰片烯-2-羧酸异构体混合物为原料,通过Fischer酯化并结合柱色谱分离的方法,得到了单一构型的5-降冰片烯-2-羧酸甲酯exo-MeNB和endo-MeNB,并利用^(1)H和^(13)C-NMR证明单体结构。以这2种单体为原料,通过Grubbs二代催化剂引发开环易位聚合,得到了构型异构的降冰片烯羧酸甲酯聚合物(P(exo-MeNB)和P(endo-MeNB)),并且,通过GPC、^(1)H-NMR、FTIR表征了聚合物的分子量和结构。另外,还研究了构型异构对聚合物热力学性能的影响。研究结果表明,2种聚合物热分解温度均大于400℃,均具有较好的热稳定性;二者的玻璃化转变温度(T_(g))存在较大差异,P(endo-MeNB)的T_(g)为85℃,而P(exo-MeNB)仅为56℃;除此以外,P(endo-MeNB)储能模量达到1049 MPa,P(exo-MeNB)仅为802 MPa。Two configurational isomers,exo-methyl 5-norbornene-2-carboxylate(exo-MeNB)and endo-methyl 5-norbornene-2-carboxylate(endo-MeNB)were prepared from exo-5-norbornenecarboxylic acid and isomeric mixture of 5-norbornenecarboxylic acid by Fischer esterification and column chromatography purification,the monomer structure was confirmed by ^(1)H and ^(13)C-NMR.Used these two isomers as monomers,two configurationally isomeric polymers,P(exo-MeNB)and P(endo-MeNB)were synthesized by ring-opening metathesis polymerization initiated by Grubbs II catalyst,and their molecular weights and chemical structures were characterization by GPC,^(1)H-NMR and FIIR.In addition,the isomeric effects on the properties of the polymers were investigated.The thermal decomposition temperature of the polymers exceeded 400℃,both had good thermal stabilities.The glass transition temperature(T_(g))of P(endo-MeNB)was 85℃,which was 29℃higher than that of P(exo-MeNB)(56℃).Moreover,the storage modulus of P(endo-MeNB)was 1049 MPa,the corresponding P(exo-MeNB)was only 802 MPa.

关 键 词：5-降冰片烯-2-羧酸甲酯 构型异构体 开环易位聚合 聚降冰片烯羧酸酯 构型异构聚合物 

分 类 号：TQ323.4[化学工程—合成树脂塑料工业]