含POSS侧基的非环二烯烃易位聚合及离子型杂化聚合物表征  

Synthesis of Ionic Hybrid Polymers with Polyhedral Oligomeric Silsesquioxane Pendant by Acyclic Diene Metathesis Polymerization and Characterization

作　　者：谢美然[1] 韩会景[1] 金瓯悦[1] 杜春霞[1] 

机构地区：[1]华东师范大学化学系,上海200241

出　　处：《化学学报》2013年第10期1441-1445,共5页Acta Chimica Sinica

基　　金：国家自然科学基金(No.21074036)资助~~

摘　　要：基于七异丁基-胺丙基-多面体低聚倍半硅氧烷(POSS-NH2)与溴丁烯或溴代十一烯反应,一步法合成了含POSS侧基的两种杂化二烯烃.以钌卡宾络合物为催化剂的非环二烯烃易位(ADMET)聚合,短链二烯烃未能发生,而长链二烯烃能顺利实现.将杂化二烯烃转变为离子型杂化二烯烃,其ADMET聚合活性较高,随着反应时间延长,聚合物分子量明显增大,分子量分布变窄,体现了逐步聚合的特征.核磁共振分析揭示了聚合物的不饱和结构和聚合反应的变化过程.主链不饱和的无定形聚合物,经氢化作用转变为饱和的离子型杂化聚乙烯,POSS基团精确地连接在聚乙烯骨架的侧位上,且POSS基团和聚乙烯骨架均表现出较强的结晶能力.这种离子型杂化聚乙烯具有球形的单分子或聚集形态,可直接构筑纳米尺度的聚合物材料.On the basis of nucleophilic substitution of aminopropyl heptaisobutyl-polyhedral oligomeric silsesquioxane （POSS-NH2） with 4-bromo-l-butene or 11-bromo-l-undecene, two types of a,co-diene monomers N,N＇-bis（butenyl）-amino- propyl-POSS （MI） and N,N＇-bis（10-undecenyl）-aminopropyl-POSS （M2） with POSS pendant were synthesized by one-step reaction, respectively. Acyclic diene metathesis （ADMET） polymerization has proven to be a versatile tool for the production of novel polymeric materials. Using tricyclohexylphosphine[1,3-bis（2,4,6-trimethylphenyl）-4,5-dihydroimidazol-2- ylidene]benzylidine ruthenium （IV） dichloride （second generation Grubbs catalyst, Ru-II） as the catalyst, ADMET polymerization behaviors of monomers M1 and M2 were investigated in toluene, and the results showed that no polymerization occurred for M1, which may be caused by the steric hindrance of the POSS units and the strong complexation between N of the monomer and Ru of Grubbs catalyst, while polymerization of M2 was well conducted to give the POSS-containing hybrid polymer P2 with moderate molecular weight （Mn） of 29.4 kDa and large polydispersed index （PDI） of 2.21 at the time point of 24 h. After ionization of N in M2 with methyl iodide, the methylated ionic a,co-diene monomer M3 was obtained. M3 displayed a good performance of ADMET polymerization catalyzed by Ru-II, and the corresponding polymers P3 （ad） have the Mn values of 37.1, 43.9, 86.4 and 108.2 kDa under different reaction time of 24, 48, 96 and 144 h, respectively, and also their PDIs become narrower from 1.94 to 1.63 as the reaction time prolonged. The unsaturated hybrid polymer P3d with the highest Mn was further hydrogenated by p-toluenesulfonhydrazidc and converted into the satu- rated hybrid polymer P4 with polyethylene backbone and POSS pendant at the precise position of main chain, and the hydrogenation degree was reasonably high with virtually little remaining unsaturation as monitored by IH NMR spectroscopy. P4 demonstrate

关 键 词：多面体低聚倍半硅氧烷 非环二烯烃易位聚合 离子型杂化聚合物 表征 形态 

分 类 号：O631.3[理学—高分子化学]