Zhang Zhen, Hadjichristidis Nikos
School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China.
Physical Sciences and Engineering Division, KAUST Catalysis Center, Polymer Synthesis Laboratory, King Abdullah University of Science and Technology (KAUST), Thuwal 23955, Saudi Arabia.
ACS Macro Lett. 2018 Jul 17;7(7):886-891. doi: 10.1021/acsmacrolett.8b00329. Epub 2018 Jul 5.
A series of aggregation-induced emission (AIE) active core crosslinked miktoarm star copolymers, having multi polyethylene (PE) and poly(methacrylic acid) (PMAA) arms, were synthesized and their thermal/pH responsive properties were studied. The procedure involves (a) the synthesis of PE-Br by polyhomologation of dimethylsulfoxonium methylide with triethylborane as initiator, followed by oxidation-hydrolysis/esterification reactions and of poly(-butyl methacrylate) (PBMA-Br) by atom transfer radical polymerization (ATRP) of -butyl methacrylate, (b) the synthesis of (PE)-(PBMA)-P(TPE-2St) by ATRP of a double styrene-functionalized tetraphenylethene (TPE-2St) with PE-Br and PBMA-Br macroinitiators, and (c) the hydrolysis of (PE)-(PBMA)-P(TPE-2St) to afford the amphiphilic miktoarm star copolymers (PE)-(PMMA)-P(TPE-2St). Due to their spherical core-shell structure (temperature-responsive) and the presence of hydrophilic PMAA (pH-responsive) and TPE-2St (AIE), these miktoarm star copolymers are AIE materials with temperature/pH-dual responsivity. In addition, thanks to the coexistence of hydrophilic and hydrophobic arms, these materials promote stable water-in-oil emulsions.
合成了一系列具有多个聚乙烯(PE)和聚(甲基丙烯酸)(PMAA)臂的聚集诱导发光(AIE)活性核交联杂臂星形共聚物,并研究了它们的热/pH响应特性。该过程包括:(a)以三乙基硼烷为引发剂,通过二甲基亚砜甲基化物的多聚同系化反应合成PE-Br,随后进行氧化水解/酯化反应;通过甲基丙烯酸丁酯的原子转移自由基聚合(ATRP)合成聚(甲基丙烯酸丁酯)(PBMA-Br);(b)通过双苯乙烯官能化的四苯乙烯(TPE-2St)与PE-Br和PBMA-Br大分子引发剂进行ATRP反应合成(PE)-(PBMA)-P(TPE-2St);(c)将(PE)-(PBMA)-P(TPE-2St)水解,得到两亲性杂臂星形共聚物(PE)-(PMMA)-P(TPE-2St)。由于其球形核壳结构(温度响应性)以及亲水性PMAA(pH响应性)和TPE-2St(AIE)的存在,这些杂臂星形共聚物是具有温度/pH双响应性的AIE材料。此外,由于亲水臂和疏水臂的共存,这些材料促进了稳定的油包水乳液的形成。