Molecular thermodynamic model for swelling and volume phase transition behavior of random copolymer gels

doi:10.3969/j.issn.0438-1157.2013.01.029

CIESC Journal ›› 2013, Vol. 64 ›› Issue (1): 268-274.DOI: 10.3969/j.issn.0438-1157.2013.01.029

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Molecular thermodynamic model for swelling and volume phase transition behavior of random copolymer gels

ZHI Dongyan, LIAN Cheng, XU Shouhong, HUANG Yongmin, LIU Honglai

State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

Received:2012-04-22 Revised:2012-07-20 Online:2013-01-05 Published:2013-01-05
Supported by:
supported by the National Natural Science Foundation of China (21076071,20990224) and the Fundamental Research Funds for the Central Universities of China.

随机共聚高分子凝胶溶胀和体积相变行为的分子热力学模型

支东彦, 练成, 徐首红, 黄永民, 刘洪来

华东理工大学化学工程联合国家重点实验室,上海 200237

通讯作者: 徐首红
作者简介:支东彦(1985—),女,博士研究生。
基金资助:
国家自然科学基金项目(21076071,20990224);中央高校基本科研业务费项目。

Abstract

Abstract: Based on the lattice model of random polymer solution,a new molecular thermodynamic model for describing the swelling behavior of temperature and pH-sensitive random copolymer gels was developed.This model considers three contributions of chemical potential:mixing of different polymer and solvent,elasticity of polymer network,and ionic effect with Donnan equilibrium of ions distributed inside and outside gels and electrostatic interactions between the charges carried by polymer network and counter ions.Compared with other models,this model considers the composition of two polymers f.Two kinds of model parameters are included,which are the interaction energy parameters between polymer network and solvent ???,and a size parameter,which is the molecular weight of the network between two cross-linking points M_c.The results show that this model can describe the swelling behavior of temperature and pH-sensitive random copolymer gels by using fewer model parameters.

Key words: random copolymer gel, molecular thermodynamic model, swelling equilibrium, volume phase transition

摘要： 基于随机共聚高分子溶液的格子模型,建立了一个可以描述温度和pH双重响应的随机共聚高分子凝胶溶胀行为的分子热力学模型。该模型考虑了溶剂与不同高分子的混合、高分子网络的弹性以及包含小分子离子在凝胶内外分布的Donnan平衡和聚合物网络上的大分子离子及其反离子之间的静电相互作用的离子影响对化学势的贡献。与其他模型不同的是,该模型还考虑了高分子的组成f。该模型有两类可调的模型参数,一类是溶剂与不同高分子网络之间的相互作用能参数???,另一类是高分子网络自身的尺寸参数M_c。研究结果表明,该分子热力学模型只需较少的模型参数就可较好地描述温度和pH双重敏感的随机共聚高分子凝胶的溶胀行为。

关键词: 随机共聚高分子凝胶, 分子热力学模型, 溶胀平衡, 体积相变

CLC Number:

TQ013.1

ZHI Dongyan, LIAN Cheng, XU Shouhong, HUANG Yongmin, LIU Honglai. Molecular thermodynamic model for swelling and volume phase transition behavior of random copolymer gels[J]. CIESC Journal, 2013, 64(1): 268-274.

支东彦, 练成, 徐首红, 黄永民, 刘洪来. 随机共聚高分子凝胶溶胀和体积相变行为的分子热力学模型[J]. 化工学报, 2013, 64(1): 268-274.

References 23

[1]	Flory P J.Principles of Polymer Chemistry[M].New York:Cornell University Press,1953:576-589
[2]	Marchetti M,Prager S,Cussler E L.Thermodynamic predictions of volume changes in temperature-sensitive gels(Ⅰ):Theory[J].Macromolecules,1990,23(6):1760-1765
[3]	Marchetti M,Prager S,Cussler E L.Thermodynamic predictions of volume changes in temperature-sensitive gels(Ⅱ):Experiments[J].Macromolecules,1990,23(14):3445-3450
[4]	Hino T,Prausnitz J M.Molecular thermodynamics for volume-change transitions in temperature-sensitive polymer gels[J].Polymer,1998,39(14):3279-3283
[5]	Oliveira É D,Silva A F S,Freitas R F S.Contributions to the thermodynamics of polymer hydrogel systems[J].Polymer,2004,45(4):1287-1293
[6]	Jung S C,Oh S Y,Bae Y C.Reentrant swelling behavior of thermosensitive N-isopropylacrylamide nano-sized gel particles[J].Polymer,2009,50(14):3370-3377
[7]	Tanaka T,Fillmore D,Sun S T,Nishio I.Phase transition in ionic gels[J].Phys. Rev. Lett.,1980,45(20):1636-1639
[8]	Ri[AKcˇD]ka J,Tanaka T.Swelling of ionic gels:quantitative performance of the Donnan theory[J].Macromolecules,1984,17(12):2916-2921
[9]	Hirotsu S,Hirokawa Y,Tanaka T.Volume-phase transitions of ionized N-isopropylacrylamide gels[J].J. Chem. Phys.,1987,87(2):1392-1395
[10]	Hooper H H,Baker J P,Blanch H W,Prausnitz J M. Swelling equilibria for positively ionized polyacrylamide hydrogels[J].Macromolecules,1990,23:1096-1104
[11]	Chan A W,Neufeld R J.Modeling the controllable pH-responsive swelling and pore size of networked alginate based biomaterials[J].Biomaterials,2009,30(30):6119-6129
[12]	Lu Danian(陆大年),Hu Ying(胡英).Molecular thermodynamic model for pH-sensitive hydrogels[J].Journal of Chemical Engineering of Chinese University(高校化学工程学报),1996,10(1):1-7
[13]	Shin B C,Jhon M S,Lee H B,Yuk S H.pH/temperature dependent phase transition of an interpenetrating polymer network:anomalous swelling behavior above lower critical solution temperature[J].Eur.Polym.J.,1998,34(11):1675-1681
[14]	Amin M C I M,Ahmad N,Halib N,Ahmad I.Synthesis and characterization of thermo- and pH-responsive bacterial cellulose/acrylic acid hydrogels for drug delivery[J].Carbohydr.Polym.,2012,88(2):465-473
[15]	Cha R,He Z B,Ni Y H.Preparation and characterization of thermal/pH-sensitive hydrogel from carboxylated nanocrystalline cellulose[J].Carbohydr.Polym.,2012,88(2):713-718
[16]	Zhi D Y,Huang Y M,Xu S H,Han X,Liu H L,Hu Y.Molecular thermodynamic model for swelling behavior and volume phase transition of multi-responsive hydrogels[J].Fluid Phase Equilib.,2011,312:106-115
[17]	Xin Q,Peng C J,Liu H L,Hu Y.A molecular thermodynamic model for random copolymer solutions[J].Fluid Phase Equilib.,2008,267(2):164-171
[18]	Xin Qin(辛琴),Xu Xiaochun(许笑春),Huang Yongmin(黄永民),Peng Changjun(彭昌军),Liu Honglai(刘洪来),Hu Ying(胡英).Molecular thermodynamic model of chain-like fluids based on lattice model[J].Science in China Series B(中国科学B),2008,38(11):947-956
[19]	Kovac J.Modified Gaussian model for rubber elasticity[J].Macromolecules,1978,11(2):362-365
[20]	Barr-Howell B D,Peppas N A.Importance of junction functionality in highly crosslinked polymers[J].Polym. Bull.,1985,13(2):91-96
[21]	Katchalsky A,Lifson S.The electrostatic free energy of polyelectrolyte solutions(Ⅰ):Randomly kinked macromolecules[J].J.Polym.Sci.,1955,XI(5):409-423
[22]	Huang Y M,Jin X Z,Liu H L,Hu Y.A molecular thermodynamic model for the swelling of thermo-sensitive hydrogels[J].Fluid Phase Equilib.,2008,263(1):96-101
[23]	Yoo M K,Sung Y K,Lee Y M,Cho C S.Effect of polyelectrolyte on the lower critical solution temperature of poly(N-isopropyl acrylamide)in the poly(NIPAAm-co-acrylic acid)hydrogel[J].Polymer,2000,41(15):5713-5719

Molecular thermodynamic model for swelling and volume phase transition behavior of random copolymer gels

随机共聚高分子凝胶溶胀和体积相变行为的分子热力学模型

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