紫外光照亲水性聚碳酸酯的合成及性能  

Synthesis and Properties of Hydrophilic Poly(propylene carbonate)under UV Irradiation

作　　者：于伶伶 程瑞华[1] 童钰涛 刘柏平[1,2] Ling-ling Yu;Rui-hua Cheng;Yu-tao Tong;Bo-ping Liu(State Key Laboratory of Chemical Engineering,East China University of Science and Technology,Shanghai 200237;College of Materials and Energy,South China Agricultural University,Guangzhou 510642)

机构地区：[1]华东理工大学化学工程联合国家重点实验室,上海200237 [2]华南农业大学材料与能源学院,广州510642

出　　处：《高分子学报》2019年第11期1202-1207,共6页Acta Polymerica Sinica

基　　金：上海市浦江人才计划(项目号16PJD016)资助项目

摘　　要：采用2-{[(2-硝基苯基)甲氧基]甲基}环氧乙烷(单体a)与二氧化碳(CO2)、环氧丙烷(PO)在SalenCo(Ⅲ)Cl/双(三苯基正膦基)氯化铵(PPNCl)催化下三元共聚,紫外(UV)光照脱除保护基,成功合成羟基官能化聚碳酸酯(PPC-OH).采用红外光谱、核磁共振、凝胶渗透色谱、接触角测量仪等对产物表征,结果表明:单体a成功引入聚碳酸酯骨架;SalenCo(Ⅲ)Cl催化剂表现出高催化活性、高选择性以及对第三单体良好的耐受性,聚合物碳酸酯单元含量>98%,首尾相连结构>99%,分子量分布极窄,CO2和环氧化物完美交替共聚.通过UV光照成功脱除羟基保护基生成PPC-OH,主链骨架无降解;单体a加入量至6%时,PPC-OH羟基含量增加至19.4%,水接触角由78.3°减小至57.6°,亲水性得到明显改善.To improve the hydrophilic properties of poly(propylene carbonate)(PPC), hydroxyl-functionalized PPC(PPC-OH) were prepared by two steps. First, PPC containing o-nitrobenzyl(ONB) protecting groups(PPCONB) were synthesized by terpolymerization reactions of 2-{[(2-nitrophenyl)methoxy]-methyl}oxirane(monomer a), propylene oxide(PO), and CO2 over SalenCo(Ⅲ)Cl/bis(triphenylphosphine)iminium chloride(PPNCl) catalyst system. 1 H-NMR result showed that the PPC-ONB was a random copolymer with monomer a randomly inserted.Then PPC-OH were obtained with the removal of o-nitrobenzyl(ONB) protecting groups under ultraviolet(UV)irradiation. PPC-ONB were synthesized with various feed ratios of the monomer a and different reaction time.Based on the analysis of 1 H-NMR, 13 C-NMR, gel permeation chromatography(GPC), and differential scanning calorimeter(DSC), SalenCo(Ⅲ)Cl catalyst performed high reactivity and high selectivity(> 94%). The polycarbonate exhibited excellent regioselectivity and perfect alternating copolymerization of CO2 and PO with the carbonate linkages up to 98%, and the head-to-tail linkage(HT) up to 99%. With the increase of the feed ratios of the monomer a, the polymer ratio of the monomer a increased to 19.4% without sacrificing the reactive activity,while the molecular weight(Mn) decreased slightly owing to the better reactivity of monomer a. The glass transition temperatures(Tg) were in the range of 35.7-38.9 ℃. The kinetics of deprotection by UV irradiation proved that the ONB protecting groups could be carried out efficiently within minutes. And the characterization of polymer by 1 H-NMR, Fourier transform infrared spectrometer(FTIR) and GPC showed that the ONB protecting groups were removed and the ―OH was observed. Meanwhile, no degradation of polymer backbone occurred.The contact angle(CA) measurement of PPC-ONB and PPC-OH displayed a difference in hydrophilia. The hydrophilia of PPC-OH has been greatly improved compared with PPC-ONB due to the increase in polarity, and the CA of PPC-OH decreased

关 键 词：羟基官能化聚碳酸酯 二氧化碳 亲水性 三元共聚 SalenCo(Ⅲ)Cl催化剂 

分 类 号：TQ323.41[化学工程—合成树脂塑料工业]