Synthesis of Amphiphilic Polymer Brushes with Mixed Side Chains and Their Emulsifying Function

Ye-chao Yan; Hua-hua Huang; Wen Zhu; Li-xin Liu; Ke Zhang; Yong-ming Chen

doi:10.11777/j.issn1000-3304.2017.17111

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Synthesis of Amphiphilic Polymer Brushes with Mixed Side Chains and Their Emulsifying Function

Research Article | 更新时间：2021-01-27

- Synthesis of Amphiphilic Polymer Brushes with Mixed Side Chains and Their Emulsifying Function
- Acta Polymerica Sinica Issue 9, Pages: 1531-1537(2017)
- 作者机构：
  
  1.中山大学材料科学与工程学院聚合物复合材料及功能材料教育部重点实验室广州 510275
  2.高分子物理与化学国家重点实验室中国科学院化学研究所北京 100190
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2017.17111
  CLC：
- Published：20 September 2017，
  
  Received：27 April 2017，
  
  Revised：16 May 2017，
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Ye-chao Yan, Hua-hua Huang, Wen Zhu, Li-xin Liu, Ke Zhang, Yong-ming Chen. Synthesis of Amphiphilic Polymer Brushes with Mixed Side Chains and Their Emulsifying Function. [J]. Acta Polymerica Sinica (9):1531-1537(2017)
DOI：

Ye-chao Yan, Hua-hua Huang, Wen Zhu, Li-xin Liu, Ke Zhang, Yong-ming Chen. Synthesis of Amphiphilic Polymer Brushes with Mixed Side Chains and Their Emulsifying Function. [J]. Acta Polymerica Sinica (9):1531-1537(2017) DOI： 10.11777/j.issn1000-3304.2017.17111.

摘要

报道了一种随机高密度接枝亲水、疏水聚合物侧链的刷形两亲性聚合物.首先，结合可逆加成-断裂链转移（RAFT）聚合和后修饰方法，得到含叠氮侧基的聚甲基丙烯酸缩水甘油酯（PGMA-N

）作为主链；再分别合成端炔基聚苯乙烯（PS）和端炔基聚环氧乙烷（PEO），然后通过铜催化的叠氮-炔环加成反应，将疏水性PS和亲水性PEO同时高效的接到PGMA主链上，制得两亲性杂侧链的聚合物刷.由凝胶渗透色谱（SEC）分析得知，在主链叠氮基团与两侧链总炔基的摩尔投料比为1：1的条件下，PS和PEO的接枝效率很高，都大于90%.通过调节主链长度和2种侧链的投料比，获得不同组成的聚合物刷.通过等质量的甲苯/水混合体系，考察两亲性聚合物刷的乳化能力，发现主链聚合度为100，PS：PEO比例为70：30的聚合物刷表现出最佳的乳化性能.

Abstract

A series of amphiphilic polymer brushes with a high grafting density as a new polymeric surfactant are developed. A great deal of research on amphiphilic block polymers has been reported to apply as the surfactants

but the research on polymer brush is still scarce. Nevertheless

amphiphilic polymer brushes would be good surfactants due to their rich surface properties and various morphologies. Therefor

a series of polymer brushes with mixed hydrophilic and hydrophobic side chains were designed and synthesized

via

a grafting-onto approach. Firstly

a polymeric backbone of poly(glycidyl methacrylate) (PGMA) with pendent azide groups was prepared by reversible addition-fragmentation chain transfer (RAFT) mediated radical polymerization followed by post-modification. Two PGMA polymers with degrees of polymerization (DP) of 100 and 390 were obtained by tuning the ratio of the monomer to initiate. Then

an alkynyl-terminated polystyrene (PS

DP=44) as a hydrophobic side chain was prepared

via

RAFT polymerization using an alkynyl-containing chain transfer agent

and an alkynyl-terminated poly(ethylene oxide) (PEO

DP=113) as a hydrophilic side chain was obtained by a nucleophilic substitution reaction of PEO with propargyl bromide. Finally

the two types of side chains were simultaneously coupled onto the PGMA backbone by a copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction

to yield the PGMA-

-(PS

-PEO

113

) polymer brush. The results from size exclusion chromatography (SEC) indicated that the grafting ratios of both PS

and PEO

113

were above 90%

with a molar feeding ratio of azide to alkynyl group at 1:1 at 50℃ in dimethyl formamide. A series of polymer brushes with different compositions were obtained by tuning the DP of the backbone and the feeding ratio of the two side chains. All samples have narrow molecular weight distributions (

1.20). The emulsifying ability of these amphiphilic polymer brushes in a toluene/water system was characterized. To stabilize toluene/water emulsion

the required amount of PGMA

100

-(PS

-PEO

113

) decreased with an increase in the content of PS

side chain. A stable emulsion can be formed using PGMA

100

-[(PS

)

-(PEO

113

)

] at a concentration of as low as 0.002 wt% versus the weight of toluene. In addition

the polymer brush with a long backbone of PGMA

390

was not beneficial to emulsion stability. In comparison with the other polymer brushes

the polymer brush with a short backbone of PGMA

100

and a molar ratio of the side chains PS

:PEO

113

of 70:30 was found to exhibit the most efficient emulsifying ability.

关键词

聚合物刷耦合法点击反应乳化性能

Keywords

Polymer brushGrafting-ontoClick chemistryEmulsifying function

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State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences

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