Preparation and Characterization of Thermoresponsive Star Dendronized Polymers

Li Juan; Su Xin-yan; Li Wen; Liu Kun; Zhang A-fang

doi:10.11777/j.issn1000-3304.2017.16298

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Preparation and Characterization of Thermoresponsive Star Dendronized Polymers

Research Article | 更新时间：2021-05-18

- Preparation and Characterization of Thermoresponsive Star Dendronized Polymers
- Acta Polymerica Sinica Issue 2, Pages: 367-374(2017)
- 作者机构：
  
  上海大学材料科学与工程学院上海 200444
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2017.16298
  CLC：
- Published：20 February 2017，
  
  Received：25 September 2016，
  
  Revised：4 October 2016，
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Li Juan, Su Xin-yan, Li Wen, Liu Kun, Zhang A-fang. Preparation and Characterization of Thermoresponsive Star Dendronized Polymers. [J]. Acta Polymerica Sinica (2):367-374(2017)
DOI：

Li Juan, Su Xin-yan, Li Wen, Liu Kun, Zhang A-fang. Preparation and Characterization of Thermoresponsive Star Dendronized Polymers. [J]. Acta Polymerica Sinica (2):367-374(2017) DOI： 10.11777/j.issn1000-3304.2017.16298.

摘要

通过两步可逆-加成断裂链转移（RAFT）聚合反应制备了双嵌段树枝化共聚物PPDS

-PG1

，以此嵌段共聚物为臂，进一步以1

2-乙二硫醇为交联剂通过二硫键与巯基的交换反应实现核交联，采用“先臂后核”法设计制备了系列以烷氧醚树枝化聚合物为臂的温敏星形树枝化聚合物PPDS

-PG1

-SS.采用

H-NMR、GPC对目标星形树枝化聚合物的结构和分子量进行了分析表征；利用变温UV-Vis光谱和原子力显微镜等分别考察了目标星形树枝化聚合物水溶液的温敏行为及其分子形貌特征.结果表明，该类星形树枝化聚合物具有与母体树枝化聚合物类似的优异温敏行为（相转变温度~36℃），其单分子尺寸较大，且随着臂长的不同在底物上分别呈现出明显的星状或球状形貌.

Abstract

A series of star dendronized polymers PPDS

-PG1

-SS

constituted by cross-linked disulfide core and oligoethylene glycol (OEG)-based dendronized polymer arms

were designed and synthesized by the "arm first" approach for the first time. Due to the large difference between molar masses of dendronized macromonomer and conventional monomers

diblock copolymers used for core crosslinking were prepared by using the monomer bearing pyridyldisulfide side groups to form the first block. Therefore

the macro chain transfer agents (PPDS) were obtained by reversible addition-fragmentation chain transfer (RAFT) polymerization of monomer bearing pyridyldisulfide side groups. These terminally reactive macro chain transfer agents were subsequently used to further initiate polymerization of OEG-based dendritic monomer (MG1)

affording well-defined diblock copolymers. Finally

the objective star dendronized polymers were prepared based on thiol-disulfide exchange reaction by adding 1

2-ethanedithiol as cross-linkers. The structure and molecular weights of the resulting polymers were characterized by

H-NMR and GPC. UV-Vis spectroscopy and AFM were used to investigate the thermoresponsive behaviors and morphologies of the polymers

respectively. The results showed that star dendronized polymers were successfully prepared. Similar to their linear dendronized counterparts

these star polymers showed fast and sharp phase transitions with small hysteresis. Ascribed to the dendronized topology

these star dendronized polymers were directly visualized by AFM on mica to have star or spherical morphologies

dependent mainly on the chain length of the dendronized polymer arms. Therefore

we provide here the first example for convenient synthesis of thermoresponsive star dendronized polymers through core cross-linking of diblock dendronized polymers

which provide a platform to investigate the topological effects on stimuli-responsiveness of dendronized polymers. Due to the dynamic characteristics of thiol-disulfide exchange reaction

these star dendronized polymers have the potential to be reversibly transferred into linear counterparts. Overall

combination of the unique architecture and performance characteristics of star polymers with cylindrical morphology of oligoethylene glycol (OEG)-based thick dendronized polymers afforded not only novel star dendronized polymers

but also endowed the objective polymers with characteristic thermoresponsiveness for potential bioapplications.

关键词

温度敏感性烷氧醚树枝化聚合物星形聚合物

Keywords

ThermoresponsivenessOligoethylene glycolDendronized polymersStar polymers

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Institute of Polymer Science,Zhejiang University,Key Laboratory of Macromolec ule Synthesis and Functionalization,Ministry of Education

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