疏水缔合水凝胶性能及链缠结
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摘要
为研究凝胶体系的分子链缠结,通过胶束共聚合成不同单体含量组成的疏水缔合水凝胶(HA-gels).通过拉伸实验及溶胀实验分别测试HA-gels的力学性能及溶胀性能.通过力学及溶胀性能参数计算分子链缠结相关参数,进而利用MATLAB软件通过迭代法计算缠结分子质量.结果表明,HA-gels的力学强度与模量均随单体含量增加而增加,断裂伸长率相应下降.HA-gels的溶胀率随单体含量增加而降低,所有的HA-gels均呈现溶胀过冲现象.将HA-gels干燥后,干凝胶的溶胀率随单体含量增加而下降并出现溶胀过冲现象.HA-gels在水中的质量损失随单体含量增加而降低.适用于任意单体含量的HA-gels及干凝胶的缠结分子质量为M_(en)=15 606φ■.
In order to study the molecular chain entanglement of hydrogel system, hydrophobic association hydrogels(HA-gels) with different contents of monomers are synthesized by micellar copolymerization. The mechanical performance and swelling performance of HA-gels are tested by tensile test and swelling test respectively. The molecular chain entanglement parameters are calculated by the mechanical and swelling property parameters,and then the entanglement molecular mass is calculated by an iterative method using the MATLAB software. The results show that the mechanical strength and modulus increase and the elongation at break of HA-gels decreases with the increase of the monomer content. The swelling ratio of HA-gels decreases with the increase of the monomer content. All HA-gels present a swelling overshoot appearance. After HA-gels are dried, the swelling ratio of the xerogels decreases with the increase of monomer content and the swelling overshoot phenomenon can also occurs. The mass loss of hydrogels in water decreases with the increase of the monomer content. The entanglement molecular mass of HA-gels and xerogels for any monomer content is M_(en)=15 606φ_2~(-0.853).
In order to study the molecular chain entanglement of hydrogel system, hydrophobic association hydrogels(HA-gels) with different contents of monomers are synthesized by micellar copolymerization. The mechanical performance and swelling performance of HA-gels are tested by tensile test and swelling test respectively. The molecular chain entanglement parameters are calculated by the mechanical and swelling property parameters,and then the entanglement molecular mass is calculated by an iterative method using the MATLAB software. The results show that the mechanical strength and modulus increase and the elongation at break of HA-gels decreases with the increase of the monomer content. The swelling ratio of HA-gels decreases with the increase of the monomer content. All HA-gels present a swelling overshoot appearance. After HA-gels are dried, the swelling ratio of the xerogels decreases with the increase of monomer content and the swelling overshoot phenomenon can also occurs. The mass loss of hydrogels in water decreases with the increase of the monomer content. The entanglement molecular mass of HA-gels and xerogels for any monomer content is M_(en)=15 606φ_2~(-0.853).
引文
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[14]JIANG Guoqing, LIU Chang, LIU Xiaoli, et al. Network structure and compositional effects on tensile mechanical properties of hydrophobic association hydrogels with high mechanical strength [J]. Polymer, 2010, 51(6):1507-1515.
[15]HARAGUCHI K, TAKEHISA T, FAN S. Effects of clay content on the properties of nanocomposite hydrogels composed of poly(N-isopropylacrylamide) and clay [J]. Macromolecules, 2002, 35(27):10162-10171.
[16]FETTERS L J, LOHSE D J, RICHTER D, et al. Connection between polymer molecular weight, density, chain dimensions, and melt viscoelastic properties [J]. Macromolecules, 1994, 27(17):4639-4647.
[2]QIAN Zhiyuan, MCKENNA G B. Expanding the application of the van Gurp-Palmen plot: New insights into polymer melt rheology [J]. Polymer, 2018, 155:208-217.
[3]JIANG G Q, LIU C, LIU X L, et al. Construction and properties of hydrophobic association hydrogels with high mechanical strength and reforming capability [J]. Macromolecular Materials and Engineering, 2009, 294(12):815-820.
[4]YANG Meng, LIU Chang, LI Zhiying, et al. Temperature-responsive properties of poly(acrylic acid-co-acrylamide) hydrophobic association hydrogels with high mechanical strength [J]. Macromolecules, 2010, 43(24):10645-10651.
[5]LI Wenbo, AN Huiyong, TAN Ying, et al. Hydrophobically associated hydrogels based on acrylamide and anionic surface active monomer with high mechanical strength [J]. Soft Matter, 2012, 8(18):5078-5086.
[6]DUALEH A J, STEINER C A. Hydrophobic microphase formation in surfactant solutions containing an amphiphilic graft copolymer [J]. Macromolecules, 1990, 23(1):251-255.
[7]LIANG Zi, GAO Tingting, XU Jianan, et al. Mechanical properties and network structure of hydrophobic association hydrogels prepared from octylphenolpolyoxyethylene (7) acrylate and sodium dodecyl sulfate [J]. Chemical Research in Chinese Universities, 2015, 31(4):633-639.
[8]URUSHIHARA Y, NISHINO T. Surface properties of O-2-plasma-treated thermoplastic fluoroelastomers under mechanical stretching [J]. Polymer, 2009, 50(14):3245-3249.
[9]RAVI N, WAN K T, SWINDLE K, et al. Development of techniques to compare mechanical properties of reversible hydrogels with spherical, square columnar and ocular lens geometry [J]. Polymer, 2006, 47(11):4203-4209.
[10]LIU Chang, LIU Xiaoli, YU Jingfeng, et al. Network structure and mechanical properties of hydrophobic association hydrogels: surfactant effect I [J]. Journal of Applied Polymer Science, 2015, 132(1):41222-41229.
[11]ZHU Congcong, BETTINGER C J. Photoreconfigurable physically cross-linked triblock copolymer hydrogels: photodisintegration kinetics and structure-property relationships [J]. Macromolecules, 2015, 48(5):1563-1572.
[12]DIEZ-PE?A E, QUIJADA-GARRIDO I, BARRALES-RIENDA J M. Analysis of the swelling dynamics of cross-linked p(N-iPAAm-co-MAA) copolymers and their homopolymers under acidic medium. A kinetics interpretation of the overshooting effect [J]. Macromolecules, 2003, 36(7):2475-2483.
[13]JIANG Guoqing, LIU Chang, LIU Xiaoli, et al. Swelling behavior of hydrophobic association hydrogels with high mechanical strength [J]. Journal of Macromolecular Science, Part A: Pure and Applied Chemistry, 2010, 47(7):663-670.
[14]JIANG Guoqing, LIU Chang, LIU Xiaoli, et al. Network structure and compositional effects on tensile mechanical properties of hydrophobic association hydrogels with high mechanical strength [J]. Polymer, 2010, 51(6):1507-1515.
[15]HARAGUCHI K, TAKEHISA T, FAN S. Effects of clay content on the properties of nanocomposite hydrogels composed of poly(N-isopropylacrylamide) and clay [J]. Macromolecules, 2002, 35(27):10162-10171.
[16]FETTERS L J, LOHSE D J, RICHTER D, et al. Connection between polymer molecular weight, density, chain dimensions, and melt viscoelastic properties [J]. Macromolecules, 1994, 27(17):4639-4647.
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