官能团化POSS及多臂星形聚酯的合成与表征  

Preparation and Characterization of Functionalized POSS Derivatives and Multi-arm Star-shaped Polyesters

作　　者：梁益玮 刘鹏 尹树杏 刘景瑞 张明祖 何金林 倪沛红 Yi-wei Liang;Peng Liu;Shu-xing Yin;Jing-rui Liu;Ming-zu Zhang;Jin-lin He;Pei-hong Ni(College of Chemistry,Chemical Engineering and Materials Science,State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials,Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application,Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis,Soochow University,Suzhou 215123)

机构地区：[1]苏州大学材料与化学化工学部新型功能高分子材料国家地方联合工程实验室江苏省先进功能高分子材料设计及应用重点实验室苏州市大分子设计与精密合成重点实验室,苏州215123

出　　处：《高分子学报》2020年第4期366-376,I0003,共12页Acta Polymerica Sinica

基　　金：国家自然科学基金面上项目(基金号21774081);江苏省自然科学基金面上项目(基金号BK20171212);江苏省高等学校大学生创新创业训练计划项目(项目号201810285067Y);江南大学合成与生物胶体教育部重点实验室开放课题基金(基金号JDSJ2017-05)资助项目.

摘　　要：利用八乙烯基多面体齐聚倍半硅氧烷(OVPOSS)与2-巯基乙醇、1-巯基甘油或半胱胺盐酸盐发生高效的"巯基-烯"点击化学反应,制备了表面分别含有8个或16个羟基以及8个氨基的3种POSS衍生物POSS-8OH、POSS-16OH和POSS-8NH2,采用核磁共振波谱(1H-, 13C-NMR)和傅里叶变换红外光谱(FTIR)详细表征了它们的化学结构.随后,利用POSS-8OH和POSS-16OH中的羟基分别引发ε-己内酯(ε-CL)和2-乙氧基-2-氧代-1,3,2-二氧磷杂环戊烷(EOP)进行开环聚合,成功合成了疏水性八臂和十六臂星形聚己内酯(POSS-8PCL和POSS-16PCL)以及亲水性八臂星形聚磷酸酯(POSS-8PEEP).利用FTIR、1H-NMR、13CNMR、凝胶渗透色谱(GPC)和热失重分析(TGA)表征了星形聚酯的化学结构、分子量和分子量分布以及热稳定性.A set of functional POSS derivatives and star-shaped POSS-cored polyesters are presented. Three POSS derivatives POSS-8OH, POSS-16OH and POSS-8NH2 are prepared by thiol-ene "click" reaction of octavinyl polyhedral oligomeric silsesquioxane(OVPOSS) with 2-mercapto-ethanol, 1-thioglycerol and cysteamine hydrochloride. Their chemical structures are confirmed by 1H-NMR, 13C-NMR, and FTIR analyses. Subsequently,POSS-8OH and POSS-16OH are used to initiate the ring-opening polymerization(ROP) of ε-caprolactone(ε-CL)and 2-ethoxy-2-oxo-1,3,2-dioxaphospholane(EOP), resulting in hydrophobic 8-arm(POSS-8PCL) and 16-arm(POSS-16PCL) star-shaped poly(ε-caprolactone), as well as hydrophilic 8-arm star-shaped poly(ethyl ethylene phosphate)(POSS-8PEEP). Three star-shaped POSS-8PCL with different arm lengths are synthesized by changing the feed ratio of the monomer to initiator. As a demonstration, the chemical structure of POSS-8PCL-2 is confirmed by using FTIR, 1H-NMR and 13C-NMR analyses. TGA test indicates that the initial decomposition temperature and decomposition mode are influenced by the molecular weights of POSS-8PCL. In order to compare the thermal stability of star-shaped PCL with a POSS core or an organic core, tripentaerythritol(TPE) is used to initiate the ROP reaction of ε-CL to give eight-arm PCL(TPE-8PCL) with an organic core. TGA test demonstrates that inorganic POSS core has better support to maintain melt stability of 8-arm star-shaped PCL than organic TPE core. The chemical structure and molecular weight information of POSS-16PCL are characterized by FTIR, 1H-NMR and 13C-NMR analyses, as well as GPC test. TGA analysis shows that the initial decomposition temperature is around 200 ℃, the decomposition behavior also displays an apparent two-stage mode, and the residue derived from POSS segment is about 3.6% at 700 ℃. Finally, POSS-8OH is used to initiate the ROP reaction of EOP to obtain POSS-8PEEP. The chemical structure and molecular weight information of POSS-8PEEP are confirmed by FTIR, 1H-NMR and GP

关 键 词：星形聚合物 聚己内酯 聚磷酸酯 点击化学 多面体低聚倍半硅氧烷(POSS) 

分 类 号：TQ323.4[化学工程—合成树脂塑料工业]