温敏型微球表面接枝交联复合凝胶的制备及性能

doi:10.7503/cjcu20150912

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (5): 996.doi: 10.7503/cjcu20150912

温敏型微球表面接枝交联复合凝胶的制备及性能

徐甜甜^1,², 徐昆², 周超¹, 谭颖², 路璀阁², 王丕新²()

1. 长春工业大学化学工程学院, 长春 130012
2. 中国科学院长春应用化学研究所生态环境高分子材料实验室, 长春 130022

收稿日期:2015-11-26 出版日期:2016-05-10 发布日期:2016-03-18
作者简介:联系人简介: 王丕新, 男, 博士, 研究员, 博士生导师, 主要从事智能凝胶、油田化学品、天然高分子改性及应用等研究. E-mail:pxwang@ciac.ac.cn
基金资助:
中国科学院科技服务网络计划项目(批准号: KFJ-EW-STS-048)、吉林省科技发展计划项目(批准号: 20140204083GX, 20140204064SF)、长春市科技发展计划项目(批准号: 14KG050)和中国科学院科技合作专项资金资助项目(批准号: 2014SYHZ0021)资助

Preparation and Performance of Composite Hydrogel Crosslinked by Surface Grafting Method of Thermo-sensitive Microsphere^†

XU Tiantian^1,², XU Kun², ZHOU Chao^1,^*, TAN Ying², LU Cuige², WANG Pixin^2,^*()

1. College of Chemical Engineering, Changchun University of Technology, Changchun 130012, China
2. Key Laboratory of Polymer Ecomaterials, Chinese Academy of Sciences, Changchun Institute of Applied Chemistry, Changchun 130022, China

Received:2015-11-26 Online:2016-05-10 Published:2016-03-18
Contact: ZHOU Chao,WANG Pixin E-mail:pxwang@ciac.ac.cn

摘要/Abstract

摘要：

为改善高分子微球复合凝胶响应速率慢及韧性差的缺陷, 采用非交联温敏型疏水单体组装的高分子微球作为交联剂, 在不外加交联剂的条件下制备微球表面接枝交联聚丙烯酰胺复合凝胶. 由于微球内部无化学交联结构, 因此可通过自身可逆性结构及形态改变对复合凝胶机械性能和刺激响应特性进行调控. 复合凝胶具有良好的韧性, 断裂伸长率和断裂强度分别可达2400%和80 kPa, 且凝胶机械强度可通过温度进行调控. 由于温敏型微球交联点的存在, 采用非敏感型聚丙烯酰胺为基质的复合凝胶对温度具有良好的响应性, 其响应速率较传统聚N-异丙基丙烯酰胺有机凝胶提升5~10倍.

关键词: 温敏性, 响应速率, 高分子微球, 韧性, 水凝胶

Abstract:

To improve slow response rate and poor toughness of microsphere composite hydrogel(MCH), the MCH gels were prepared by grafting polyacrylamide chains onto the surface of thermo-sensitive polymer microspheres in the absence of crosslinking agent. Herein, polymer microspheres without chemical cross-linking structure were obtained by assembly of amphiphilic thermo-sensitive graft copolymer and employed as cross-linking junctions. MCH gels own excellent toughness(strain at break: 2800%, fracture energy: 80 kPa) and can adjust the mechanical properties according to temperature stimuli. Moreover, the results of investigation suggest that MCH gels exhibit thermo-sensitive property and their response rate are 5 to 10 times faster than the traditional poly(N-isopropyl acrylamide) organic gel.

Key words: Thermo-sensitive, Response rate, Polymer microsphere, Toughness, Hydrogel

中图分类号:

O633

TrendMD:

徐甜甜, 徐昆, 周超, 谭颖, 路璀阁, 王丕新. 温敏型微球表面接枝交联复合凝胶的制备及性能. 高等学校化学学报, 2016, 37(5): 996.

XU Tiantian, XU Kun, ZHOU Chao, TAN Ying, LU Cuige, WANG Pixin. Preparation and Performance of Composite Hydrogel Crosslinked by Surface Grafting Method of Thermo-sensitive Microsphere^†. Chem. J. Chinese Universities, 2016, 37(5): 996.

图/表 13

Scheme 1 Synthetic mechanism of microspheres

Fig.1 TEM images of microspheres at 25 ℃(A) and 45 ℃(B)

Fig.2 Particle size distribution of microspheres at 25 ℃(a) and 45 ℃(b)

Fig.3 IR spectrum of microspheres

Fig.4 Deformation of MCH gels at 25 ℃

Fig.5 IR spectrum of MCH gels

Fig.6 Angular frequency dependence of storage modulus G'(solid symbol) and loss modulus G″(open symbol) at 20 ℃

Fig.7 Effective network chain density varying microspheres content at 20 ℃

Fig.8 Stress-strain curves of MCH gels with different contents of microspheres at 25 ℃Mass fraction of microsphere(%): a. 15; b. 20;c. 25; d. 30; e. 35.

Fig.9 Temperature dependence of storage modulus G'(solid symbol) and loss modulus G″(open symbol) of MCH gels

Fig.10 Temperature dependence of storage modulus ΔG' of MCH gels

Fig.11 Stress-strain curves of MCH gels(30%) at 25 ℃(a) and 45 ℃(b)

Fig.12 Shrinking dynamic curves of hydrogels(A) Deionized water; (B) V(acetone)∶V(water)=1∶1.

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温敏型微球表面接枝交联复合凝胶的制备及性能

Preparation and Performance of Composite Hydrogel Crosslinked by Surface Grafting Method of Thermo-sensitive Microsphere^†

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温敏型微球表面接枝交联复合凝胶的制备及性能

Preparation and Performance of Composite Hydrogel Crosslinked by Surface Grafting Method of Thermo-sensitive Microsphere†

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Preparation and Performance of Composite Hydrogel Crosslinked by Surface Grafting Method of Thermo-sensitive Microsphere^†