自破乳温敏性高分子表面活性剂的合成及其在乳液聚合中的应用

唐铖涛; 侯琳熙; 肖龙强

doi:10.11777/j.issn1000-3304.2023.23197

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自破乳温敏性高分子表面活性剂的合成及其在乳液聚合中的应用

研究论文 | 更新时间：2024-01-19

- 自破乳温敏性高分子表面活性剂的合成及其在乳液聚合中的应用
- Synthesis of Self-demulsification Thermosensitive Polymeric Surfactants and Their Application in Emulsion Polymerization
- 高分子学报 2024年55卷第2期页码：182-191
- 作者机构：
  
  福州大学石油化工学院福州 350100
- 作者简介：
  
  E-mail: xiaolq@fzu.edu.cn
- 基金信息：
  
  福建省自然科学基金(基金号 2023J01265┫与国家自然科学基金┣基金号 U21A20313)
- DOI：10.11777/j.issn1000-3304.2023.23197
  中图分类号：
- 纸质出版日期：2024-02-20，
  
  网络出版日期：2023-12-06，
  
  收稿日期：2023-07-25，
  
  录用日期：2023-10-10
- 稿件说明：
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唐铖涛, 侯琳熙, 肖龙强. 自破乳温敏性高分子表面活性剂的合成及其在乳液聚合中的应用. 高分子学报, 2024, 55(2), 182-191

Tang, C. T.; Hou, L. X.; Xiao, L. Q. Synthesis of self-demulsification thermosensitive polymeric surfactants and their application in emulsion polymerization. Acta Polymerica Sinica, 2024, 55(2), 182-191
唐铖涛, 侯琳熙, 肖龙强. 自破乳温敏性高分子表面活性剂的合成及其在乳液聚合中的应用. 高分子学报, 2024, 55(2), 182-191 DOI： 10.11777/j.issn1000-3304.2023.23197.

Tang, C. T.; Hou, L. X.; Xiao, L. Q. Synthesis of self-demulsification thermosensitive polymeric surfactants and their application in emulsion polymerization. Acta Polymerica Sinica, 2024, 55(2), 182-191 DOI： 10.11777/j.issn1000-3304.2023.23197.

摘要

提出了以温敏性表面活性剂作为乳化剂解决乳液聚合反应结束后破乳分离过程繁杂的问题. 通过原子转移自由基聚合(ATRP)合成了聚乙二醇-聚(

-异丙基丙烯酰胺) (PEG-

-PNIPAM)嵌段共聚物. 该共聚物在室温下表现为亲水性，而在35~80 ℃呈现两亲性. 表面张力和乳化性能等测试证实了其在上述温度区间可作为乳化剂应用于乳液聚合. 在乳液聚合反应完成后无需其他添加剂和方法，只需通过将反应体系降至室温即可实现破乳. 通过使用(PEG-

-PNIPAM)嵌段共聚物作为表面活性剂，可以利用温度控制乳化破乳的功能，极大简化了乳液聚合反应工艺，降低成本，实现绿色化生产.

Abstract

This study proposes utilizing thermosensitive surfactants

referred to as "environmentally responsive surfactants

" as emulsifiers for addressing the complexity of demulsification and separation processes after emulsion polymerization reactions. A series of polyethylene glycol-poly(

-isopropylacrylamide) (PEG-

-PNIPAM) block copolymers with various degrees of polymerization were synthesized

via

atom transfer radical polymerization (ATRP). The PNIPAM segments within the copolymers exhibit thermosensitive behavior

possessing a lower critical solution temperature (LCST) at 32 ℃

enabling the control of hydrogen bond formation and rupture with water molecules based on temperature variations. Consequently

the PEG-

-PNIPAM block copolymers display hydrophilic properties at room temperature and amphiphilic properties in the range from 35 ℃ to 80 ℃. Surface tension measurements at different concentrations confirmed the low critical micelle concentration (CMC) of the PEG-PNIPAM block copolymers

with a minimum value as low as 9.10×10

-3

g/L. Evaluations of particle size distribution and emulsification performance validated its applicability as an emulsifier in emulsion polymerization within the aforementioned temperature range. Microscopic observations of latex particles corroborated the precise occurrence of emulsion polymerization

displaying a relatively uniform particle size distribution in the resulting polymer. Upon completion of the emulsion polymerization reaction

the need for additional agents such as demulsifiers or physical methods like mechanical stirring was obviated. Merely lowering the reaction system to room temperature facilitated demulsification

yielding the desired polymer products. Further

rapid demulsification could be achieved by cooling the reaction system at lower temperatures (3‒8 ℃). Utilizing PEG-

-PNIPAM block copolymers as surfactants allowed the temperature-controlled emulsification and demulsification processes

significantly streamlining the emulsion polymerization process

reducing costs

and enabling environmentally friendly production practices.

关键词

温敏性表面活性剂乳液聚合嵌段共聚物自破乳

Keywords

Thermosensitive surfactantEmulsion polymerizationBlock copolymerSelf-demulsification

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