一种含假芪型偶氮生色团两亲性嵌段共聚物的合成与表征  

Synthesis and Characterization of a Novel Amphiphilic Azo Block Copolymer

作　　者：杨灿强[1] 朱煜[1] 王晓工[1] 

机构地区：[1]清华大学化工系高分子研究所教育部先进材料重点实验室,北京100O84,北京100084

出　　处：《高分子通报》2012年第5期70-75,共6页Polymer Bulletin

基　　金：国家自然科学基金项目(91027024)

摘　　要：利用原子转移自由基聚合(ATRP)合成了一种新型的含假芪型偶氮生色团的两亲性嵌段共聚物P(HEMA-b-6CNAzo)。首先,采用ATRP引发剂引发三甲基硅保护的羟乙基甲基丙烯酸酯(HEMA-TMS)聚合,得到大分子引发剂P(HEMA-TMS);接着进一步引发单体甲基丙烯酸6-(N-甲基苯胺基)己酯进行ATRP反应,得到前体聚合物P(HEMA-TMS-b-6MA)。最后,将前体聚合物与4-氰基苯胺的重氮盐进行重氮偶合反应,同时在强酸作用下使三甲基硅保护基团水解,得到目标聚合物P(HEMA-b-6CNAzo)。利用GPC、UV-Vis、1 H-NMR等手段对制备的聚合物进行了详细的表征。GPC结果表明,P(HEMA-TMS)与P(HEMA-TMS-b-6MA)均具有较窄的分子量分布。1 H-NMR分析结果表明,P(HEMA-TMS-b-P6MA)两嵌段的聚合度比为0.95∶1,重氮偶合反应转化率及三甲基硅基团的水解程度均接近100%。往浓度为0.2g/L的聚合物P(HEMA-b-6CNAzo)的THF溶液中,以1μL/s的速率滴加去离子水,该两亲性嵌段共聚物可自组装形成粒径为60～80nm的聚集体。A novel amphiphilic block copolymer functionalized with strong push-pull azobenzene moieties, P（HEMA-b-6CNAzo）, was synthesized by using ATRP. First, the macromolecular initiator P （HEMA-TMS） was prepared through ATRP reaction of monomer HEMA-TMS, which was hydroxylethyl-mathacrylate （HEMA） protected with trimethylsilane （TMS） groups. Then, the precursor diblock copolymer, P（HEMA-TMS-b-6MA）, containing aniline groups was prepared by a P （HEMA-TMS）-initiated ATRP of 6-（N-methylanilino）hexyl methacrylate. The amphiphilic azo block copolymer, P（HEMA-b-6CNAzo）, was obtained by azo-coupling reaction between P（HEMA-TMS-b- 6MA） and cliazonium salt of 4-aminobenzonitrile and the TMS groups were removed at the same time because of the acidic conditiond. The macro-initiator and block copolymers were characterized by GPC, 1H-NMR and UV-vis. GPC results showed that both P （HEMA-TMS） and P （HEMA-TMS-b-6MA） had narrow molecular weight distributions. 1H-NMR analysis indicated that the ratio of polymerization degree for HEMA andP6MA blocks is 0. 95. The conversion rate of azo-coupling reaction and hydrolysis Of TMS groups were close to 100%. By adding deionized water under a rate of 1μL/s to a THF solution of P （HEMA-b-6CNAzo） with the concentration of 0.2g/L, the amphiphilie block copolymers self-assembled to form colloidal spheres with sizes in range from 60 and to 80nm.

关 键 词：偶氮聚合物 嵌段共聚物 两亲性 合成 表征 

分 类 号：O631.3[理学—高分子化学]