One-pot Preparation of Block Copolymer Nanoparticles byPolymerization-induced Self-assembly

Zhi-peng Su; Meng-ting Tan; Yan-ling Cao; Yan Shi; Zhi-feng Fu

doi:10.11777/j.issn1000-3304.2019.19026

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One-pot Preparation of Block Copolymer Nanoparticles byPolymerization-induced Self-assembly

Research Article | 更新时间：2021-01-26

- One-pot Preparation of Block Copolymer Nanoparticles byPolymerization-induced Self-assembly
- Acta Polymerica Sinica Vol. 50, Issue 8, Pages: 808-815(2019)
- 作者机构：
  
  化工资源有效利用国家重点实验室北京化工大学　北京 100029
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2019.19026
  CLC：
- Published：2019-8，
  
  Published Online：19 April 2019，
  
  Received：31 January 2019，
  
  Revised：11 March 2019，
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Zhi-peng Su, Meng-ting Tan, Yan-ling Cao, Yan Shi, Zhi-feng Fu. One-pot Preparation of Block Copolymer Nanoparticles byPolymerization-induced Self-assembly. [J]. Acta Polymerica Sinica 50(8):808-815(2019)
DOI：

Zhi-peng Su, Meng-ting Tan, Yan-ling Cao, Yan Shi, Zhi-feng Fu. One-pot Preparation of Block Copolymer Nanoparticles byPolymerization-induced Self-assembly. [J]. Acta Polymerica Sinica 50(8):808-815(2019) DOI： 10.11777/j.issn1000-3304.2019.19026.

摘要

采用“一锅法”合成了聚4-乙烯基吡啶-

-聚(4-乙烯基吡啶-

-苯乙烯) (P4VP-

-P(4VP-

-St))两亲性共聚物纳米粒子. 采用可逆加成-断裂链转移(RAFT)聚合制备了结构明确的P4VP三硫代碳酸酯(P4VP-TTC)；以P4VP-TTC为大分子链转移剂在醇/水混合溶剂中进行St和4VP的RAFT分散共聚合反应，得到了球状、蠕虫状和囊泡状的共聚物胶束；考察了亲溶剂链段和疏溶剂链段的聚合度之比、P(4VP-

-St)嵌段中共聚单体4VP的用量、溶剂组成对嵌段共聚物纳米粒子形貌、尺寸及形貌发展过程的影响. 与相同条件下St的分散聚合相比，亲溶剂单体4VP和St的分散共聚能有效调控嵌段共聚物纳米粒子的形貌和尺寸，更易发展出囊泡胶束. 利用透射电子显微镜(TEM)、凝胶渗透色谱(GPC)、动态光散射(DLS)和核磁共振氢谱(

H-NMR)表征了共聚物的组成和纳米粒子结构.

Abstract

Polymeric vesicles have important applications in biomedicine

nuclear magnetic imaging

nanoreactors

and catalyst fields. Amphiphiic block copolymer nanoparticles with different morphologies (such as vesicles and spheres)

sizes and surface chemical properties have been successfully prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization-induced self-assembly (PISA). Generally

it is difficult for researchers to obtain pure vesicles with different sizes. In this study

we report an efficient approach to produce block copolymers vesicles by PISA. A one-pot

facile method for the synthesis of nano-objects composed of amphiphilic poly(4-vinylpyridine)-

-poly(4-vinylpyridine-

-styrene) block copolymer

P4VP-

-P(4VP-

-St)

is introduced by P4VP trithiocarbonate macro-RAFT agent mediated dispersion copolymerization of 4VP and St in ethanol/water mixture. It is found that the morphology of P4VP-

-P(4VP-

-St) diblock copolymer nano-objects like spherical micelles

worms

and vesicles can be easily tuned either by changing the degree of polymerization of the random P(4VP-

-St) block

the amount of 4VP comonomer

solvent composition and the ratio of the degree of polymerization of PSt and P4VP segments. Among them

by adding a small amount of 4VP comonomer during the dispersion RAFT polymerization of St

the final morphology of the block copolymer can be greatly affected

pure vesicle can be formed and the size can be adjusted more effectively. Compared with the dispersion RAFT polymerization of St

the advantage of the dispersion RAFT copolymerization by utilizing residual solvophilic monomer to tune the block copolymer morphology is demonstrated. It is believed to be a novel

convenient and efficient protocol for the control of the morphology and size of the block copolymer nano-objects fabricated by PISA. The polymerization shows characteristic features of " living”/controlled radical polymerization and the experimental results are confirmed by gel permeation chromatography (GPC)

dynamic light scattering (DLS)

transmission electron microscopy (TEM) and

H-NMR. Due to diverse potential applications of polymer vesicles

the results of this study are of great importance for the theoretical design and application of PISA strategies.

关键词

聚合诱导自组装分散聚合可逆加成-断裂链转移聚合嵌段共聚物纳米粒子

Keywords

Polymerization-induced self-assemblyDispersion polymerizationReversible addition-fragmentation chain transfer polymerizationBlock copolymer nanoparticles

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Institute of Nanochemistry and Nanobiology, Shanghai University

State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University

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