Acta Chimica Sinica ›› 2014, Vol. 72 ›› Issue (5): 609-614.DOI: 10.6023/A14030211 Previous Articles     Next Articles



杜征臻a, 张静b, 张琰a, 郎美东a   

  1. a 华东理工大学材料科学与工程学院 超细材料制备与应用教育部重点实验室 上海市先进聚合物材料重点实验室 上海 200237;
    b 上海市纳米科技与产业发展促进中心 上海 200237
  • 投稿日期:2014-03-21 发布日期:2014-04-17
  • 通讯作者: 张琰,郎美东;
  • 基金资助:

    项目受国家自然科学基金(No. 21274039)、上海市自然科学基金(No. 12ZR1427300)和上海市教委重点学科建设(No. J50102)资助.

Synthesis and Properties of Thermo-sensitive Amphiphilic Pluronic-b-poly((ε-caprolactone)-co-(6-(benzyl-oxycarbonylmethyl)-ε-caprolactone))

Du Zhengzhena, Zhang Jingb, Zhang Yana, Lang Meidonga   

  1. a Shanghai Key Laboratory of Advanced Polymeric Materials, Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237;
    b Shanghai Nanotechnology Promotion Center, Shanghai 200237
  • Received:2014-03-21 Published:2014-04-17
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21274039), the Shanghai Municipal Natural Science Foundation (No. 12ZR1427300) and the Leading Academic Discipline Project of Shanghai Education Committee, China (No. J50102).

In this paper, a series of amphiphilic block copolymers Pluronic-b-poly(ε-caprolactone-co-benzyl-oxycarbonyl-methyl-ε-caprolactone) (Pluronic-b-P(CL-co-BCL)) were synthesized successfully via ring-opening polymerization (ROP) of ε-caprolactone (CL) and 6-(benzyl-oxycarbonylmethyl)-ε-caprolactone (BCL) using stannous octoate as the catalyst (weight ratio: 0.5‰) and PEO99-b-PPO69-b-PEO99 (Pluronic F127) as macroinitiator. 1H NMR, GPC and FT-IR were employed to determine the structure, composition, molecular weight and molecular weight distribution. The result of 1H NMR showed the content of BCL in the copolymers was less than the theoretical value, which may be attributed to the low reactivity of BCL due to the steric hindrance of Bn substituent on the δ position of CL. The number-average molecular weight by GPC was different from the value calculated by 1H NMR, it may be attributed to the hydrodynamic volume of the copolymers being different from that of the poly(styrene) as the GPC calibration in THF. The thermal properties of the copolymers were evaluated by TGA, DSC and XRD. The results indicated that the stability and the crystallinity of the copolymers could be adjusted by the content of the BCL. Due to the BCL units in the copolymers reduced the regularity of the PCL chain and intensively disrupted its crystallinity and the steric hindrance effect of BCL trammeled the movement of the PCL chain, the melting point (Tm) of CL segment in copolymer shifted down and the glass transition temperature (Tg) of copolymer increased with the increase of the content of BCL respectively. Emulsion/solvent evaporation technique was employed to prepare the polymeric micelle solution. The formation, size and morphologies of the micelles in aqueous solution were studied by fluorescence spectroscopy, TEM and DLS, the results demonstrated that the micelles were spherical spheres with narrow distribution, the copolymer had low critical micelles concentration (CMC) and depended on the content of BCL in the copolymer. Moreover, DLS results showed that the Pluronic-b-P(CL-co-BCL) had a reversible thermosensitivity due to the introduction of BCL.

Key words: functionalized caprolactone, thermo-sensitive, amphiphilic, Pluronic, emulsion/solvent evaporation technique