活性负离子聚合法制备POSS基七臂星形聚合物及其表征

晏雪生; 徐俊; 何金林; 张明祖; 戴礼兴; 倪沛红

doi:10.11777/j.issn1000-3304.2017.16128

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活性负离子聚合法制备POSS基七臂星形聚合物及其表征

研究论文 | 更新时间：2021-03-19

- 活性负离子聚合法制备POSS基七臂星形聚合物及其表征
- Preparation and Characterization of POSS-based Seven-arm Star-shaped Polymers via Living Anionic Polymerization
- 高分子学报 2017年第3期页码：454-463
- 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苏州市大分子设计与精密合成重点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 215123
- 作者简介：
  
  E-mail: jlhe@suda.edu.cnJin-lin He,E-mail: jlhe@suda.edu.cn
- 基金信息：
  
  国家自然科学基金(21304061);北京分子科学国家实验室开放课题基金(20140152);江苏高校优势学科建设工程(PAPD);高等学校博士学科点专项科研基金(20133201120007);中国博士后科学基金(2013M531396);江苏省自然科学基金(BK20130286);江苏省高校自然科学研究面上项目(13KJB150034)
- DOI：10.11777/j.issn1000-3304.2017.16128
  中图分类号：
- 纸质出版日期：2017-3，
  
  收稿日期：2016-4-12，
  
  修回日期：2016-5-5，
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晏雪生, 徐俊, 何金林, 张明祖, 戴礼兴, 倪沛红. 活性负离子聚合法制备POSS基七臂星形聚合物及其表征[J]. 高分子学报, 2017,(3):454-463.

Yan Xue-sheng, Xu Jun, He Jin-lin, Zhang Ming-zu, Dai Li-xing, Ni Pei-hong. Preparation and Characterization of POSS-based Seven-arm Star-shaped Polymers via Living Anionic Polymerization[J]. Acta Polymerica Sinica, 2017,(3):454-463.
晏雪生, 徐俊, 何金林, 张明祖, 戴礼兴, 倪沛红. 活性负离子聚合法制备POSS基七臂星形聚合物及其表征[J]. 高分子学报, 2017,(3):454-463. DOI： 10.11777/j.issn1000-3304.2017.16128.

Yan Xue-sheng, Xu Jun, He Jin-lin, Zhang Ming-zu, Dai Li-xing, Ni Pei-hong. Preparation and Characterization of POSS-based Seven-arm Star-shaped Polymers via Living Anionic Polymerization[J]. Acta Polymerica Sinica, 2017,(3):454-463. DOI： 10.11777/j.issn1000-3304.2017.16128.

摘要

首先利用高真空活性负离子聚合方法制备聚异戊二烯锂（PI-Li）和（聚苯乙烯-

-聚异戊二烯）锂（PS-PI-Li）活性链，再与单羟基七乙烯基多面体齐聚倍半硅氧烷（VPOSS-OH）发生加成反应，一步法制备2种含羟基的七臂星形聚合物.用分级沉淀法去除低加成产物，即可得到纯的七臂星形聚合物7PI-POSS-OH和7（PS-PI）-POSS-OH，利用凝胶渗透色谱（GPC）、核磁共振波谱（

H-，

C-NMR）、红外光谱（FTIR）和基质辅助激光解吸电离飞行时间质谱（MALDI-TOF MS）表征了聚合物的化学结构、分子量及分子量分布，并通过热失重分析（TGA）测试了聚合物的热分解温度.

Abstract

The preparation of star-shaped polymers using incorporation of living anionic polymerization with polyhedral oligomeric silsesquioxane (POSS) is rarely reported. In this study

two types of POSS-cored star-shaped polymers were obtained by one-step addition reaction. Firstly

the living (polyisopryl)lithium (PI-Li) and living polystyrene-block-polyisoprene block copolymer chain (PS-PI-Li) were synthesized by high-vacuum living anionic polymerization. Meanwhile

a POSS derivative with one hydroxyl and seven vinyl groups (VPOSS-OH) was prepared by the addition of triflic acid to commercial octavinyl POSS with eight vinyl groups (V

). Subsequently

the mono-hydroxyl functionalized seven-arm star polymers were prepared by directly adding living PI-Li or PS-PI-Li to VPOSS-OH in benzene. The purified star-shaped polyisoprene 7PI-POSS-OH and star-block copolymer 7(PS-PI)-POSS-OH were obtained after fractionation precipitation

and then characterized by nuclear magnetic resonance (

H- and

C-NMR)

gel permeation chromatography (GPC)

Fourier transform infrared spectroscopy (FTIR) and matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectroscopy

respectively. By changing the feed ratio of the monomer to initiator

the polymers with different degree of polymerizations were synthesized. The compositions of the polymers were calculated by comparison of the integrals of the characteristic signals from

H-NMR spectra. GPC analysis indicated that the trace of the crude products showed an apparent shift to smaller retention time compared with that of the base PI or PS-PI. The fractionated samples had symmetric peaks and relatively narrow polydispersity. MALDI-TOF MS tests demonstrated that the base PS gave a single molecular weight distribution

and the observed molecular weight was in good agreement with the calculated value. The similar result was also found for the base PS-PI. However

the MALDI-TOF MS spectra were not obtained for the fractionated star-shaped polymers

possibly because of their high molecular weights. TGA analysis showed that the thermal decomposition temperature of 7PI-POSS-OH and 7(PS-PI)-POSS-OH was higher than the base PI and the block copolymer PS-PI. In addition

it was also found that about 6% of residue left at 600℃

which may be due to the incorporation of POSS segment. The process reported here may serve as an alternative approach to produce functional star-shaped polymers by changing the structure of the initiators and the monomers.

关键词

高真空活性负离子聚合多面体齐聚倍半硅氧烷POSS星形聚合物

Keywords

Living anionic polymerizationPolyhedral oligomeric silsesquioxanePOSSStar-shaped polymer

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