SYNTHESIS AND CHARACTERIZATION OF OPTICALLY ACTIVE POLY(PHENYLACETYLENE) WITH POLYLACTIDE SIDE CHAINS

ZHANG Chunhong; SU Guangdong; WANG Hailun; ZHANG Lili; SHEN Xiande; BAI Jianwei; SATOH Toshifumi; KAKUCHI Toyoji

doi:10.3724/SP.J.1105.2012.11177

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SYNTHESIS AND CHARACTERIZATION OF OPTICALLY ACTIVE POLY(PHENYLACETYLENE) WITH POLYLACTIDE SIDE CHAINS

Research Article | 更新时间：2021-03-19

- SYNTHESIS AND CHARACTERIZATION OF OPTICALLY ACTIVE POLY(PHENYLACETYLENE) WITH POLYLACTIDE SIDE CHAINS
- Acta Polymerica Sinica Issue 4, Pages: 365-373(2012)
- 作者机构：
  
  1. 哈尔滨工程大学材料科学与化学工程学院高分子材料研究中心,哈尔滨,150001
  2. 日本北海道大学工学研究院札幌 >,060-8628
- 作者简介：
- 基金信息：
- DOI：10.3724/SP.J.1105.2012.11177
  CLC：
- Published：20 April 2012，
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ZHANG Chunhong, SU Guangdong, WANG Hailun, ZHANG Lili, SHEN Xiande, BAI Jianwei, SATOH Toshifumi, KAKUCHI Toyoji. SYNTHESIS AND CHARACTERIZATION OF OPTICALLY ACTIVE POLY(PHENYLACETYLENE) WITH POLYLACTIDE SIDE CHAINS. [J]. Acta Polymerica Sinica (4):365-373(2012)
DOI：

ZHANG Chunhong, SU Guangdong, WANG Hailun, ZHANG Lili, SHEN Xiande, BAI Jianwei, SATOH Toshifumi, KAKUCHI Toyoji. SYNTHESIS AND CHARACTERIZATION OF OPTICALLY ACTIVE POLY(PHENYLACETYLENE) WITH POLYLACTIDE SIDE CHAINS. [J]. Acta Polymerica Sinica (4):365-373(2012) DOI： 10.3724/SP.J.1105.2012.11177.

摘要

通过4-溴苯甲醇和三甲基硅基乙炔的Sonagashira偶联反应与三甲基硅基的脱除反应

合成4-乙炔基苯甲醇.以4-乙炔基苯甲醇为引发剂

以有机氮杂环化合物DBU为催化剂

常温常压下进行丙交酯的活性开环聚合反应

采用1H-NMR和GPC对产物结构、分子量与分子量分布进行表征分析

结果表明

合成以了苯乙炔为端基的聚乳酸大分子单体PA-PLLA-3k、PA-PLLA-4k、PA-PDLA-3k和PA-PDLA-4k

实现了分子量的有效控制.以[Rh(nbd)Cl]2/Et3N为催化剂

实现了大分子单体的均聚

得到以聚乳酸为侧链的聚苯乙炔poly-(PA-PLLA)-3k

poly(PA-PLLA)-4k

poly(PA-PDLA)-3k和poly(PA-PDLA)-4k.采用GPC、GPC-MALLS和1H-NMR对聚苯乙炔进行表征分析

结果表明poly(PA-PLLA)和poly(PA-PDLA)均具有较高的分子量

分子链呈线形柔性链形态.CD和UV-Vis光谱分析表明poly(PA-PLLA)和poly(PA-PDLA)主链均形成了螺旋构象

而且Cotton效应的方向受大分子单体手性的影响

大分子单体的手性相同

聚苯乙炔主链Cotton效应的方向相同

大分子单体的手性相反

聚苯乙炔主链Cotton效应的方向相反;在不同溶剂中聚苯乙炔主链螺旋构象的规整程度不同;聚苯乙炔螺旋构象的稳定性随着温度的提高而降低.

Abstract

Sonagashira coupling reaction between 4-bromobenzyl alcohol and trimethylsilylacetylene was carried out and then the trimethylsilyl group was removed to give 4-ethynylbenzyl alcohol.Living ring-opening polymerization of lactide was performed under normal pressure and temperature by using DBU as a catalyst and 4-ethynylbenzyl alcohol as an initiator.1H-NMR spectra and GPC were employed to characterize the chemical structure of the products and analyze the molecular weight and polydispersity.The results indicated that polylactide macromonmers bearing 4-ethynylbenzyloxy end group(PA-PLLA-3k

PA-PLLA-4k

PA-PDLA-3k

and PA-PDLA-4k) were successfully synthesized

and the molecular weight of the macromonmers was controlled effectively.Homopolymerization of the macromonomers was carried out by using [Rh(nbd)Cl]2/Et3N as the catalyst to give poly(phenylacetylene)s with polylactide side chains (poly(PA-PLLA)-3k

poly-(PA-PLLA)-4k

poly(PA-PDLA)-3k and poly(PA-PDLA)-4k).The poly(phenylacetylene)s were characterized by GPC

GPC-MALLS and 1H-NMR.The results indicated that poly(PA-PLLA) and poly(PA-PDLA) possess linear flexible chain with high molecular weight.CD and UV-Vis spectra of the poly-(phenylacetylene)s showed that poly(PA-PLLA) and poly(PA-PDLA) main chains assuredly possess predominantly one-handed helical conformations

and the direction of Cotton effects was affected by the chirality of macromonomers.The direction of Cotton effects of the poly(phenylacetylene)s was the same when the chirality of macromonomers was the same

Cotton effects of the poly(phenylacetylene)s were reverse when the chirality of macromonomers was reverse.The intensity of Cotton effects was various in different solvents

this meant that the regularity of helical conformation of the poly(phenylacetylene) main chain was variable in different solvents.Moreover

the stability of helical conformation of poly(phenylacetylene) decreased with the increasing temperature.

关键词

丙交酯活性开环聚合聚乳酸大分子单体大分子单体的均聚聚苯乙炔螺旋构象

Keywords

LactideLiving ring-opening polymerizationPolylactide macromonomerHomopolymerization of macromonomerPoly(phenylacetylene)Helical conformation

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College of Chemical Engineering, Qingdao University of Science and Technology

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