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两亲性嵌段共聚物PMnEOS-b-PAA的可控合成及与PS-b-PAA共组装体的形貌
引用本文:石晓宇,王宋蒙,柳凌艳,常卫星,李靖. 两亲性嵌段共聚物PMnEOS-b-PAA的可控合成及与PS-b-PAA共组装体的形貌[J]. 高等学校化学学报, 2020, 41(11): 2545. DOI: 10.7503/cjcu20200387
作者姓名:石晓宇  王宋蒙  柳凌艳  常卫星  李靖
作者单位:1.南开大学化学学院, 元素有机化学国家重点实验室, 2. 南开大学功能高分子教育部重点实验室, 天津 300071;3.天津化学化工协同创新中心, 天津 300071
基金项目:天津市自然科学基金(17JCZDJC37300)
摘    要:在苯乙烯单体的对位引入具有亲水性链段的乙二醇单元, 利用可逆加成断裂链转移聚合方法(RAFT), 可控合成了几种新的两亲性嵌段共聚物聚(4-乙烯基苄基乙二醇单甲醚)-b-聚丙烯酸(PMnEOS-b-PAA, n=1~3), 对其温敏和pH敏性质进行了初步研究. 同时, 研究了PMnEOS-b-PAA分别在亲水性环境下(四氢呋喃/水)和亲脂性环境下(四氢呋喃/甲苯)自组装体的形貌. 将聚对二乙二醇单甲醚苯乙烯-b-聚丙烯酸与聚苯乙烯-b-聚丙烯酸按质量比1:1[m(PMDEOS-b-PAA)/m(PS-b-PAA)=1:1]共混进行共组装, 在四氢呋喃/甲苯体积比为2∶1的混合溶剂中, 发现了一类新型具有均匀分布内部孔道且表面光滑的球形组装体. 进一步研究了该组装体的可重复性和组装机理, 为其后期应用于工业上的负载催化、 小分子识别与释放提供了一种新的策略.

关 键 词:两亲性嵌段共聚物  组装形貌  组装机理  pH响应  温度响应  
收稿时间:2020-06-23

Controllable Synthesis of Amphiphilic Block Copolymer PMnEOS-b-PAA and co-Assembly Morphologies of PMDEOS-b-PAA/PS-b-PAA
SHI Xiaoyu,WANG Songmeng,LIU Lingyan,CHANG Weixing,LI Jing. Controllable Synthesis of Amphiphilic Block Copolymer PMnEOS-b-PAA and co-Assembly Morphologies of PMDEOS-b-PAA/PS-b-PAA[J]. Chemical Research In Chinese Universities, 2020, 41(11): 2545. DOI: 10.7503/cjcu20200387
Authors:SHI Xiaoyu  WANG Songmeng  LIU Lingyan  CHANG Weixing  LI Jing
Affiliation:1.State Key Laboratory of Elemento?Organic Chemistry,College of Chemistry;2.Key Laboratory of Functional Polymer Materials of the Ministry of Education,Nankai University,Tianjin 300071,China
Abstract:The co-assembly of polymers has attracted increasing attention due to the ability of generating diverse assembly morphology. This paper describes the synthesis and self-assembly of several novel amphiphilic block copolymers(PMnEOS-b-PAA, n=1—3) as well as co-assembly of PMDEOS-b-PAA with typical polystyrene-b-polyacrylic acid(PS-b-PAA). Namely, these block copolymers were fabricated by reversible addition fragmentation chain transfer(RAFT) polymerization of functionalized styrene bearing different glycol units on the para-position and acrylic acid, and characterized by 1H nuclear magnetic resonance spectrum(1H NMR). The thermo-responsive and pH-responsive properties of these block copolymers were then investigated, and they showed good thermo- and pH- responsiveness. Furthermore, as a comparison, the self-assembly actions of these block copolymers were also examined in tetrahydrofuran(THF)/H2O and THF/toluene(PhMe), respectively. It was found that the different block copolymers with different glycol units displayed various morphologies, especially in two different solvent systems. More interestingly, the co-assembly action of PMDEOS-b-PAA/PS-b-PAA(mass ratio 1∶1) in a mixture of THF-PhMe(volume ratio 2∶1) was detaily studied and a new spherical nanoparticle with uniformly distributed internal channel and smooth surface was found. Also, thisco-assembly morphology could be well repeated. The corresponding self- and co-assembly mechanisms were also proposed. This novel co-assembly mode would have potential application for further supporting catalysts, small molecules recognition and release in industry.
Keywords:Amphiphilic block copolymer  co-Assembly morphology  Assemble mechanism  pH-Responsiveness  thermo-Responsiveness  
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