高等学校化学学报 ›› 2005, Vol. 26 ›› Issue (12): 2381.

• 研究论文 • 上一篇    下一篇

双亲嵌段共聚物PSt-b-PAA在甲苯中的自聚集行为

汤誌忠,高保娇,何三雄   

  1. 中北大学化工系,太原030051
  • 收稿日期:2005-01-11 出版日期:1905-03-14 发布日期:1905-03-14
  • 通讯作者: 高保娇(1946年出生),女,教授,博士生导师,主要从事功能高分子材料研究.E-mail:gaobaojiao@126.com
  • 基金资助:

    山西省自然基金项目(批准号:20040402)资助.

Self-aggregation Behavior of Amphiphilic Block Copolymer PSt-b-PAA in Toluene

TANG Zhi-Zhong, GAO  Bao-Jiao*, HE  San-Xiong   

  1. Department of Chemical Engineering,  North University of China,  Taiyuan 030051, China
  • Received:2005-01-11 Online:1905-03-14 Published:1905-03-14
  • Contact: GAO Bao-Jiao;E-mail:gaobaojiao@126.com

摘要:

以α-溴乙苯为引发剂,溴化亚铜为催化剂,2,2′-联吡啶为配体,用原子转移自由基聚合(ATRP)法合成了结构一定的嵌段共聚物聚苯乙烯-b-聚丙烯酸丁酯(PSt-b-PBA).经水解制备了双亲性嵌段共聚物聚苯乙烯-b-聚丙烯酸(PSt-b-PAA);采用单溶剂溶解法配制了PSt-b-PAA在甲苯中的反胶束溶液;以极性荧光化合物N-1-萘乙二胺盐酸盐(NEAH)为极性微区探针,用荧光光谱法并配合透射电镜观察探索了双亲嵌段共聚物PSt-b-PAA在甲苯溶液中的自聚集行为,考察了双亲性嵌段共聚物浓度、链结构及温度等因素对反胶束化行为的影响规律.结果表明,亲水链PAA短而亲油链PSt长的双亲嵌段共聚物PSt-b-PAA,用单溶剂溶解法可使其在甲苯中发生自聚集,形成以亲水段为核,疏水段为壳的星状反胶束结构;反胶束为10~20nm的球形聚集态结构;PSt-b-PAA的自聚集行为及临界胶束浓度与分子链的微结构和温度等因素相关,且随着共聚物浓度的增大,小胶束会逐渐结合形成大的纺垂状聚集体.

关键词: 自聚集;反胶束;极性荧光探针;苯乙烯-丙烯酸双亲嵌段共聚物, 自聚集, 反胶束, 极性荧光探针, 苯乙烯-丙烯酸双亲嵌段共聚物

Abstract:

The block copolymer of PSt-b-PBA with well-defined structure was synthesized via atom transfer radical polymerization(ATRP) by using 1-phenylethyl bromide(1-PEBr) as the initiator, cuprous bromide as the catalyst, 2,2′-bipyridine(bpy) as the ligand and xylene as the solvent. The block copolymer PSt-b-PBA was characterized and the living polymerization was validated by GPC, FTIR, and 1H NMR. Then the amphiphilic block copolymer of PSt-b-PAA was prepared by alkaline hydrolysis of PSt-b-PBA. The reversed micellization behavior of PSt-b-PAA in toluene was investigated by fluorescence probe technique with  polar fluorescence compound N-(1-naphthyl)ethylenediamine dihydrochloride(NEAH) as a polar fluorescence probe and by the observation of TEM. It was found that NEAH as a polar fluorescence compound can clearly reveal the reversed micellization behavior of PSt-b-PAA in toluene. The results show that the reversed micelles which have hydrophilic core and hydrophobic shell can formed spontaneously through self-aggregation of PSt-b-PAA macromolecules in toluene, the aggregates have the morphology of sphere, and the self-aggregation behavior of PSt-b-PAA depends apparently on the microstructure of the macromolecules and the temperature. The longer the PAA block is, the lower the critical micelle concentration is; the higher the temperature is, the lower the critical micelle concentration is.

Key words: Self-aggregation; Reversed micelle; Polar fluorescence probe; Amphiphilic block copolymer of styrene-acrylic acid, Self-aggregation, Reversed micelle, Polar fluorescence probe, Amphiphilic block copolymer of styrene-acrylic acid

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