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| 以聚乳酸为侧链的光学活性聚苯乙炔的合成与表征 | |
| 引用本文： | 张春红,苏广东,王海伦,张丽丽,沈贤德,白建伟,佐藤敏文,覚知豊次.以聚乳酸为侧链的光学活性聚苯乙炔的合成与表征[J].高分子学报,2012(4):365-373. |
| 作者姓名： | 张春红 苏广东 王海伦 张丽丽 沈贤德 白建伟 佐藤敏文 覚知豊次 |
| 作者单位： | 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;哈尔滨工程大学材料科学与化学上程学院超轻材料与表面技术教育部重点实验室 哈尔滨150001 2. 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 3. 日本北海道大学工学研究院 札幌060-8628 |
| 基金项目： | 中央高校基本科研业务费专项资金，黑龙江省自然科学基金 |
| 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... |
| 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 |
SYNTHESIS AND CHARACTERIZATION OF OPTICALLY ACTIVE POLY(PHENYLACETYLENE) WITH POLYLACTIDE SIDE CHAINS |
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| Chun-hong Zhang , Guang-dong Su , Hai-lun Wang , Li-li Zhang , Xian-de Shen , Jian-wei Bai , Toshifumi Satoh , Toyoji Kakuchi.SYNTHESIS AND CHARACTERIZATION OF OPTICALLY ACTIVE POLY(PHENYLACETYLENE) WITH POLYLACTIDE SIDE CHAINS[J].Acta Polymerica Sinica,2012(4):365-373. | |
| Authors: | Chun-hong Zhang Guang-dong Su Hai-lun Wang Li-li Zhang Xian-de Shen Jian-wei Bai Toshifumi Satoh Toyoji Kakuchi |
| Institution: | Chun-hong Zhang1,2,Guang-dong Su1,Hai-lun Wang1,Li-li Zhang1,Xian-de Shen1,Jian-wei Bai1,Toshifumi Satoh3,Toyoji Kakuchi3(1 Polymer Materials Research Center,College of Materials Science and Chemical Engineering,Harbin Engineering University,Harbin 150001)(2 Key Laboratory of Superlight Materials and Surface Technology(College of Materials Science and Chemical Engineering,Harbin Engineering University),Ministry of Education,Harbin 150001)(3 Graduate School of Engineering,Hokkaido University,Sapporo 060-8628,Japan) |
| 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. |
| Keywords: | Lactide Living ring-opening polymerization Polylactide macromonomer Homopolymerization of macromonomer Poly(phenylacetylene) Helical conformation |
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