官能团化POSS及多臂星形聚酯的合成与表征

梁益玮; 刘鹏; 尹树杏; 刘景瑞; 张明祖; 何金林; 倪沛红

doi:10.11777/j.issn1000-3304.2019.19210

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官能团化POSS及多臂星形聚酯的合成与表征

论文 | 更新时间：2021-01-26

- 官能团化POSS及多臂星形聚酯的合成与表征
- Preparation and Characterization of Functionalized POSS Derivatives and Multi-arm Star-shaped Polyesters
- 高分子学报 2020年51卷第4期页码：366-376
- 作者机构：
  
  苏州大学材料与化学化工学部新型功能高分子材料国家地方联合工程实验室江苏省先进功能高分子材料设计及应用重点实验室苏州市大分子设计与精密合成重点实验室　苏州 215123
- 作者简介：
  
  E-mail: jlhe@suda.edu.cn He Jin-lin, E-mail: jlhe@suda.edu.cn
- 基金信息：
  
  国家自然科学基金面上项目(基金号 21774081)、江苏省自然科学基金面上项目(基金号 BK20171212)、江苏省高等学校大学生创新创业训练计划项目(项目号 201810285067Y)和江南大学合成与生物胶体教育部重点实验室开放课题基金(基金号 JDSJ2017-05)资助项目
- DOI：10.11777/j.issn1000-3304.2019.19210
  中图分类号：
- 纸质出版日期：2020-4，
  
  网络出版日期：2020-3-12，
  
  收稿日期：2019-12-16，
  
  修回日期：2020-1-9，
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梁益玮, 刘鹏, 尹树杏, 刘景瑞, 张明祖, 何金林, 倪沛红. 官能团化POSS及多臂星形聚酯的合成与表征[J]. 高分子学报, 2020,51(4):366-376.

Yi-wei Liang, Peng Liu, Shu-xing Yin, Jing-rui Liu, Ming-zu Zhang, Jin-lin He, Pei-hong Ni. Preparation and Characterization of Functionalized POSS Derivatives and Multi-arm Star-shaped Polyesters[J]. Acta Polymerica Sinica, 2020,51(4):366-376.
梁益玮, 刘鹏, 尹树杏, 刘景瑞, 张明祖, 何金林, 倪沛红. 官能团化POSS及多臂星形聚酯的合成与表征[J]. 高分子学报, 2020,51(4):366-376. DOI： 10.11777/j.issn1000-3304.2019.19210.

Yi-wei Liang, Peng Liu, Shu-xing Yin, Jing-rui Liu, Ming-zu Zhang, Jin-lin He, Pei-hong Ni. Preparation and Characterization of Functionalized POSS Derivatives and Multi-arm Star-shaped Polyesters[J]. Acta Polymerica Sinica, 2020,51(4):366-376. DOI： 10.11777/j.issn1000-3304.2019.19210.

摘要

利用八乙烯基多面体齐聚倍半硅氧烷(OVPOSS)与2-巯基乙醇、1-巯基甘油或半胱胺盐酸盐发生高效的“巯基-烯”点击化学反应，制备了表面分别含有8个或16个羟基以及8个氨基的3种POSS衍生物POSS-8OH、POSS-16OH和POSS-8NH

，采用核磁共振波谱(

H-

C-NMR)和傅里叶变换红外光谱(FTIR)详细表征了它们的化学结构. 随后，利用POSS-8OH和POSS-16OH中的羟基分别引发

-己内酯(

-CL)和2-乙氧基-2-氧代-1

2-二氧磷杂环戊烷(EOP)进行开环聚合，成功合成了疏水性八臂和十六臂星形聚己内酯(POSS-8PCL和POSS-16PCL)以及亲水性八臂星形聚磷酸酯(POSS-8PEEP). 利用FTIR、

H-NMR、

C-NMR、凝胶渗透色谱(GPC)和热失重分析(TGA)表征了星形聚酯的化学结构、分子量和分子量分布以及热稳定性.

Abstract

A set of functional POSS derivatives and star-shaped POSS-cored polyesters are presented. Three POSS derivatives POSS-8OH

POSS-16OH and POSS-8NH

are prepared by thiol-ene “click” reaction of octavinyl polyhedral oligomeric silsesquioxane (OVPOSS) with 2-mercapto-ethanol

1-thioglycerol and cysteamine hydrochloride. Their chemical structures are confirmed by

H-NMR

C-NMR

and FTIR analyses. Subsequently

POSS-8OH and POSS-16OH are used to initiate the ring-opening polymerization (ROP) of

-caprolactone (

-CL) and 2-ethoxy-2-oxo-1

2-dioxaphospholane (EOP)

resulting in hydrophobic 8-arm (POSS-8PCL) and 16-arm (POSS-16PCL) star-shaped poly(

-caprolactone)

as well as hydrophilic 8-arm star-shaped poly(ethyl ethylene phosphate) (POSS-8PEEP). Three star-shaped POSS-8PCL with different arm lengths are synthesized by changing the feed ratio of the monomer to initiator. As a demonstration

the chemical structure of POSS-8PCL-2 is confirmed by using FTIR

H-NMR and

C-NMR analyses. TGA test indicates that the initial decomposition temperature and decomposition mode are influenced by the molecular weights of POSS-8PCL. In order to compare the thermal stability of star-shaped PCL with a POSS core or an organic core

tripentaerythritol (TPE) is used to initiate the ROP reaction of

-CL to give eight-arm PCL (TPE-8PCL) with an organic core. TGA test demonstrates that inorganic POSS core has better support to maintain melt stability of 8-arm star-shaped PCL than organic TPE core. The chemical structure and molecular weight information of POSS-16PCL are characterized by FTIR

H-NMR and

C-NMR analyses

as well as GPC test. TGA analysis shows that the initial decomposition temperature is around 200 °C

the decomposition behavior also displays an apparent two-stage mode

and the residue derived from POSS segment is about 3.6% at 700 °C. Finally

POSS-8OH is used to initiate the ROP reaction of EOP to obtain POSS-8PEEP. The chemical structure and molecular weight information of POSS-8PEEP are confirmed by FTIR

H-NMR and GPC analyses. Furthermore

TGA analysis demonstrates that the thermal stability of POSS-8PEEP is weaker than star-shaped PCL and the initial decomposition temperature is decreased to about 100 °C. The decomposition of POSS-8PEEP shows a more apparent multi-stage mode and about 19.8% residue is left at 700 °C. This work reports a facile method for the preparation of functional POSS derivatives and star-shaped POSS-cored polymers.

关键词

星形聚合物聚己内酯聚磷酸酯点击化学多面体低聚倍半硅氧烷(POSS)

Keywords

Star-shaped polymerPoly(ε-caprolactone)PolyphosphoestersThiol-ene “click” reactionPolyhedral oligomeric silsesquioxane

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