Liu Zhanqing, Luo Yanling, Zhang Kaipu
Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry & Materials Science, Shaanxi Normal University, Xi'an, P. R. China.
J Biomater Sci Polym Ed. 2008;19(11):1503-20. doi: 10.1163/156856208786140373.
A highly pH-sensitive hybrid hydrogel with semi-interpenetrating networks (semi-IPN)composed of co-polymer networks of acrylamide-methacrylic acid (P(AAm-co-MAA)) and polyaniline (PANI)/carboxyl-functionalized multi-walled carbon nanotubes (MWNTs-COOH) was designed and synthesized by a cross-linking co-polymerization route in the presence of N,N-methylene bisacrylamide (BIS) and ammonium persulfate (APS). The structural and morphological characterization and mechanical properties of the gels were investigated using a Equinx55 FT-IR spectrometer, an environmental scanning electron microscope and a dynamical viscoelasticity analyzer, respectively. Swelling capability of the hybrid hydrogels was examined under the conditions of various pH buffer solutions (1.35, 6.95 and 12.86) at a temperature of 27 degrees C. P(AAm-co-MAA) co-polymer hydrogels were discussed as a control sample at the same time. The experimental results indicated that the prepared P(AAm-co-MAA) co-polymer hydrogels showed a high equilibrium swelling ratio in distilled water, pH-responsive characteristics and excellent strain recoverability. After having incorporated the polyelectrolyte PANI and MWNTs-COOH into the above-mentioned network, the P(AAm-co-MAA)/PANI/MWNTs-COOH semi-IPN hybrid hydrogels obtained possessed an even higher sensitivity to pH environments, good swelling reversibility, higher ultimate compressive strength and good strain recoverable ability. Swelling experimentations in buffer solutions of different pH revealed that the semi-IPN hybrid hydrogels possessed higher tensile strengths at a lower pH than at a higher pH value. All the excellent properties may primarily be attributed to the formation and weakening or disappearance of a repulsive force based on hydrogen bonds, as well as appearance of attractive forces of pole-pole interactions between PANI chains at different pH values.
通过在N,N-亚甲基双丙烯酰胺(BIS)和过硫酸铵(APS)存在下的交联共聚路线,设计并合成了一种具有半互穿网络(semi-IPN)的高pH敏感性杂化水凝胶,该网络由丙烯酰胺-甲基丙烯酸共聚物网络(P(AAm-co-MAA))和聚苯胺(PANI)/羧基功能化多壁碳纳米管(MWNTs-COOH)组成。分别使用Equinx55傅里叶变换红外光谱仪、环境扫描电子显微镜和动态粘弹性分析仪对凝胶的结构、形态特征和力学性能进行了研究。在27℃的温度下,在各种pH缓冲溶液(1.35、6.95和12.86)条件下检测了杂化水凝胶的溶胀能力。同时讨论了P(AAm-co-MAA)共聚物水凝胶作为对照样品。实验结果表明,制备的P(AAm-co-MAA)共聚物水凝胶在蒸馏水中表现出高平衡溶胀率、pH响应特性和优异的应变恢复能力。在将聚电解质PANI和MWNTs-COOH引入上述网络后,得到的P(AAm-co-MAA)/PANI/MWNTs-COOH半互穿网络杂化水凝胶对pH环境具有更高的敏感性、良好的溶胀可逆性、更高的极限抗压强度和良好的应变恢复能力。在不同pH缓冲溶液中的溶胀实验表明,半互穿网络杂化水凝胶在较低pH值下比在较高pH值下具有更高的拉伸强度。所有这些优异性能主要归因于基于氢键的排斥力的形成和减弱或消失,以及不同pH值下PANI链之间极-极相互作用吸引力的出现。