高强度聚N-异丙基丙烯酰胺-黏土纳米复合水凝胶的制备及表征
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摘要
采用原位聚合方法制备出一种具有高强度、良好温度响应性的聚N-异丙基丙烯酰胺/黏土纳米复合水凝胶,并用红外光谱、扫描电镜、透射电镜对其结构进行了分析.测试结果表明,纳米黏土与聚合物分子链之间具有强的氢键作用,水凝胶具有均匀的多孔聚合物骨架,且黏土可均匀地分散在聚合物基体中.热力学测试结果表明,黏土的引入未对水凝胶热敏特性产生显著影响,即三种水凝胶均在35℃左右产生明显的相转变;同时,溶胀动力学测试结果表明,水凝胶样品在该温度下具有明显的去溶胀特性.机械性能测试结果表明,纳米黏土的加入,可显著提高水凝胶的机械性能.
A kind of novel high strength PNIPAM/Clay nanocomposite hydrogel with superior thermo-responsive nature was successfully prepared using in-situ polymerization method. The results of analysis on the structure of hydrogels using FT-IR spectra,scanning electronic microscopy,and transmittance electronic microscopy technologies indicated that the clay platelets were uniformly dispersed into the polymer matrix based on the hydrogen bond interactions among the clay platelets and polymer chains,which facilitated the formation of uniform internal interpenetrating porous network structure. The results of differential scanning calorimetry illustrated that the incorporation of clay into the polymer matrix would not significantly reduce the sensitiveness of thermo-responsive performance of hydrogels,and the study of swelling kinetics demonstrated that the clearly de-swelled behavior occurred when the hydrogels were immersed into the water at 35 ℃. The mechanical strength of hydrogels could be extensively enhanced from the incorporation of nano-clay platelets.
A kind of novel high strength PNIPAM/Clay nanocomposite hydrogel with superior thermo-responsive nature was successfully prepared using in-situ polymerization method. The results of analysis on the structure of hydrogels using FT-IR spectra,scanning electronic microscopy,and transmittance electronic microscopy technologies indicated that the clay platelets were uniformly dispersed into the polymer matrix based on the hydrogen bond interactions among the clay platelets and polymer chains,which facilitated the formation of uniform internal interpenetrating porous network structure. The results of differential scanning calorimetry illustrated that the incorporation of clay into the polymer matrix would not significantly reduce the sensitiveness of thermo-responsive performance of hydrogels,and the study of swelling kinetics demonstrated that the clearly de-swelled behavior occurred when the hydrogels were immersed into the water at 35 ℃. The mechanical strength of hydrogels could be extensively enhanced from the incorporation of nano-clay platelets.
引文
[1]LI Yulin,RODRIGUES J,TOMAS H.Injectable and biodegradable hydrogels:gelation.biodegradation and biomedical applications[J].Chemical Society Reviews,2012,41(6):2193-2221.
[2]SONG Ziyuan,HAN Zhiyuan,LYU Shixian,et al.Synthetic polypeptides:from polymer design to supramolecular assembly and biomedical application[J].Chemical Society Reviews,2017,46(21):6570-6599.
[3]HUANG Ting,XU Hongguang,JIAO Kexin,et al.A novel hydrogel with high mechanical strength:A macromolecular microsphere composite hydrogel[J].Advanced Materials,2007,19(12):1622-1626.
[4]WANG Jing,LIU Changsheng,LIU Yufei,et al.Double-Network interpenetrating bone cement via in situ hybridization protocol[J].Advanced Functional Materials,2010,20(22):3997-4011.
[5]张建合,杨亚江.亲水/疏水互穿网络水凝胶的合成及其pH敏感特性研究[J].信阳师范学院学报(自然科学版),1999,12(4):440-443.ZHANG Jianhe,YANG Yajiang.Studies on the synthesis and pH-sensitive of hydrophilic-hydrophobic interpenetrating polymer network[J].Journalof Xinyang Normal University(Natural Science Edition),1999,12(4):440-443.
[6]OKUMURA Y,ITO K.The polyrotaxanegel:A topological gel by figure-of-eight cross-links[J].Advanced Materials,2001,13(7):485-487.
[7]SUN J,ZHAO X H,ILLEPERUMA W R K,et al.Highly stretchable and tough hydrogels[J].Nature,2012,489(7414):133-136.
[8]SU Xing,CHEN Biqiong.Tough,resilient and pH-sensitive interpenetrating polyacrylamide/alginate/montmorillonite nanocomposite hydrogels[J].Carbohydrate Polymers,2018,197:497-507.
[9]ZHOU Chunhui,KEELING John.Fundamental and applied research on clay minerals:From climate and environment to nanotechnology[J].Applied Clay Science,2013,74:3-9.
[10]HUANG Biao,LIU Mingxian,ZHOU Changren.Chitosan composite hydrogels reinforced with natural clay nanotubes[J].Carbohydrate Polymers,2017,175:689-698.
[11]WANG Feng,YONG Xueyong,DENG Jianping,et al.Poly(N,N-dimethylacrylamide-octadecyl acrylate)clay hydrogels with high mechanical properties and shape memory ability[J].RSC Advances,2018,8(30):16773-16780.
[12]HARAGUCHI K,MURATA K,TAKEHISA T.Stimuli-Responsive nanocomposite Gels and Soft nanocomposites consisting of inorganic clays and copolymers with different chemical affinities[J].Macromolecules,2012,45(1):385-391.
[13]XU Wen,ZENG Qinghua,YU Aibing.Young’s modulus of effective clay clusters in polymer nanocomposites[J].Polymer,2012,53(17):3735-3740.
[14]JEON S,HAUSER A W,HAYWARD R C.Shape-Morphing materials from Stimuli-Responsive hydrogel hybrids[J].Accounts of Chemical Research,2017,50(2):161-169.
[15]柳晓艳,周艺峰,聂王焰,等.磁性pH响应型纤维素水凝胶的制备及载药研究[J].安徽大学学报(自然科学版),2015,39(6):73-79.LIU Xiaoyan,ZHOU Yifeng,NIE Wangyan,et al.Synthesis of the magnetic and p H-responsive hydrogel based oncellulose and study as a drug carrier[J].Journal of Anhui University(Natural Science Edition),2015,39(6):73-79.
[16]ZHENG Wenjiang,AN Ning,YANG Jianhai,et al.Tough Al-alginate/Poly(N-isopropylacrylamide)Hydrogel with Tunable LCST for Soft Robotics[J].ACS Applied Materials&Interfaces,2015,7(3):1758-1764.
[17]FENG Xianqi,ZHANG Gongzheng,ZHUO Shuyun,et al.Dual responsive shape memory polymer/clay nanocomposites[J].Composites Science and Technology,2016,129:53-60.
[2]SONG Ziyuan,HAN Zhiyuan,LYU Shixian,et al.Synthetic polypeptides:from polymer design to supramolecular assembly and biomedical application[J].Chemical Society Reviews,2017,46(21):6570-6599.
[3]HUANG Ting,XU Hongguang,JIAO Kexin,et al.A novel hydrogel with high mechanical strength:A macromolecular microsphere composite hydrogel[J].Advanced Materials,2007,19(12):1622-1626.
[4]WANG Jing,LIU Changsheng,LIU Yufei,et al.Double-Network interpenetrating bone cement via in situ hybridization protocol[J].Advanced Functional Materials,2010,20(22):3997-4011.
[5]张建合,杨亚江.亲水/疏水互穿网络水凝胶的合成及其pH敏感特性研究[J].信阳师范学院学报(自然科学版),1999,12(4):440-443.ZHANG Jianhe,YANG Yajiang.Studies on the synthesis and pH-sensitive of hydrophilic-hydrophobic interpenetrating polymer network[J].Journalof Xinyang Normal University(Natural Science Edition),1999,12(4):440-443.
[6]OKUMURA Y,ITO K.The polyrotaxanegel:A topological gel by figure-of-eight cross-links[J].Advanced Materials,2001,13(7):485-487.
[7]SUN J,ZHAO X H,ILLEPERUMA W R K,et al.Highly stretchable and tough hydrogels[J].Nature,2012,489(7414):133-136.
[8]SU Xing,CHEN Biqiong.Tough,resilient and pH-sensitive interpenetrating polyacrylamide/alginate/montmorillonite nanocomposite hydrogels[J].Carbohydrate Polymers,2018,197:497-507.
[9]ZHOU Chunhui,KEELING John.Fundamental and applied research on clay minerals:From climate and environment to nanotechnology[J].Applied Clay Science,2013,74:3-9.
[10]HUANG Biao,LIU Mingxian,ZHOU Changren.Chitosan composite hydrogels reinforced with natural clay nanotubes[J].Carbohydrate Polymers,2017,175:689-698.
[11]WANG Feng,YONG Xueyong,DENG Jianping,et al.Poly(N,N-dimethylacrylamide-octadecyl acrylate)clay hydrogels with high mechanical properties and shape memory ability[J].RSC Advances,2018,8(30):16773-16780.
[12]HARAGUCHI K,MURATA K,TAKEHISA T.Stimuli-Responsive nanocomposite Gels and Soft nanocomposites consisting of inorganic clays and copolymers with different chemical affinities[J].Macromolecules,2012,45(1):385-391.
[13]XU Wen,ZENG Qinghua,YU Aibing.Young’s modulus of effective clay clusters in polymer nanocomposites[J].Polymer,2012,53(17):3735-3740.
[14]JEON S,HAUSER A W,HAYWARD R C.Shape-Morphing materials from Stimuli-Responsive hydrogel hybrids[J].Accounts of Chemical Research,2017,50(2):161-169.
[15]柳晓艳,周艺峰,聂王焰,等.磁性pH响应型纤维素水凝胶的制备及载药研究[J].安徽大学学报(自然科学版),2015,39(6):73-79.LIU Xiaoyan,ZHOU Yifeng,NIE Wangyan,et al.Synthesis of the magnetic and p H-responsive hydrogel based oncellulose and study as a drug carrier[J].Journal of Anhui University(Natural Science Edition),2015,39(6):73-79.
[16]ZHENG Wenjiang,AN Ning,YANG Jianhai,et al.Tough Al-alginate/Poly(N-isopropylacrylamide)Hydrogel with Tunable LCST for Soft Robotics[J].ACS Applied Materials&Interfaces,2015,7(3):1758-1764.
[17]FENG Xianqi,ZHANG Gongzheng,ZHUO Shuyun,et al.Dual responsive shape memory polymer/clay nanocomposites[J].Composites Science and Technology,2016,129:53-60.