高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (11): 2545-2552.doi: 10.7503/cjcu20200387

• 高分子化学 • 上一篇    下一篇

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

石晓宇1,2, 王宋蒙1, 柳凌艳1(), 常卫星1, 李靖1   

  1. 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
  • 收稿日期:2020-06-23 出版日期:2020-11-10 发布日期:2020-11-06
  • 通讯作者: 柳凌艳 E-mail:liulingyan@nankai.edu.cn
  • 基金资助:
    天津市自然科学基金(17JCZDJC37300)

Controllable Synthesis of Amphiphilic Block Copolymer PMnEOS-b-PAA and co-Assembly Morphologies of PMDEOS-b-PAA/PS-b-PAA

SHI Xiaoyu1,2, WANG Songmeng1, LIU Lingyan1(), CHANG Weixing1, LI Jing1   

  1. 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
  • Received:2020-06-23 Online:2020-11-10 Published:2020-11-06
  • Contact: LIU Lingyan E-mail:liulingyan@nankai.edu.cn
  • Supported by:
    Supported by the Natural Science Foundation of Tianjin City, China(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

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.

Key words: Amphiphilic block copolymer, co-Assembly morphology, Assemble mechanism, pH-Responsiveness, thermo-Responsiveness

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