Double network(DN)hydrogels as one kind of tough gels have attracted extensive at-tention for their potential applications in biomedical and load-bearing fields.Herein,we import more functions like shape memory into t...Double network(DN)hydrogels as one kind of tough gels have attracted extensive at-tention for their potential applications in biomedical and load-bearing fields.Herein,we import more functions like shape memory into the conventional tough DN hydro-gel system.We synthesize the PEG-PDAC/P(AAm-co-AAc)DN hydrogels,of which the first network is a well-defined PEG(polyethylene glycol)network loaded with PDAC(poly(acryloyloxyethyltrimethyl ammonium chloride))strands,while the second network is formed by copolymerizing AAm(acrylamide)with AAc(acrylic acid)and cross-linker MBAA(N;N′-methylenebisacrylamide).The PEG-PDAC/P(AAm-co-AAc)DN gels exhibits high mechanical strength.The fracture stress and toughness of the DN gels reach up to 0.9 MPa and 3.8 MJ/m^3,respectively.Compared with the conventional double network hydrogels with neutral polymers as the soft and ductile second network,the PEG-PDAC/P(AAm-co-AAc)DN hydrogels use P(AAm-co-AAc),a weak polyelectrolyte,as the second network.The AAc units serve as the coordination points with Fe^3+ions and physically crosslink the second network,which realizes the shape memory property activated by the reducing ability of ascorbic acid.Our results indicate that the high mechanical strength and shape memory properties,probably the two most important characters related to the potential application of the hydrogels,can be introduced simultaneously into the DN hydrogels if the functional monomer has been integrated into the network of DN hydrogels smartly.展开更多
Poly（acrylamide-co-acrylic acid） nanocomposite physical （P（AAm-co-AAc）NCP） hydrogels have been prepared through the in situ free radical solution polymerization based on a ＂single network, dual cross-linkings＂...Poly（acrylamide-co-acrylic acid） nanocomposite physical （P（AAm-co-AAc）NCP） hydrogels have been prepared through the in situ free radical solution polymerization based on a ＂single network, dual cross-linkings＂ strategy. The P（AAm-co-AAc） NCP hydrogels are composed of nanobrushes of P（AAm-co-AAc） chains grafted on the surface of vinyl- hybrid silica nanoparticles （VSNPs）. In the hydrogel system, the VSNPs act as the ＂analogous chemical cross-linking points＂ once the hydrogen bonds formed between the P（AAm-co-AAc） chains of the nanobrushes, thus leading to the fabrication of high-strength P（AAm-co-AAc） NCP hydrogels. Compared with conventional thermosensitive P（AAm-co-AAc） hydrogels, the P（AAm-co-AAc） NCP hydrogels have a broader range of phase transition temperature, which can be adjusted by altering the monomer ratio, the VSNPs concentration, the addition of urea and N,N-dimethylacrylamide （DMAAm）. At the same time, the mechanical properties of the P（AAm-co-AAc） NCP hydrogels have been improved significantly by the introduction of VSNPs. Furthermore, both the phase transition and the tensile strength of the P（AAm-co-AAc） NCP hydrogels are largely influenced when Fe3＋ ions are introduced as the ionic crosslinkers into the hydrogel networks.展开更多
采用二步法,以锂藻土(Laponite)交联聚丙烯酰胺(PAM),N,N-亚甲基双丙烯酰胺(BIS)交联聚丙烯酸(PAA),通过自由基聚合制备了PAM/PAA双网络水凝胶。该水凝胶的拉伸强度可达137 k Pa,在酸性缓冲液中收缩,碱性缓冲液中溶胀,具有灵敏的pH响应...采用二步法,以锂藻土(Laponite)交联聚丙烯酰胺(PAM),N,N-亚甲基双丙烯酰胺(BIS)交联聚丙烯酸(PAA),通过自由基聚合制备了PAM/PAA双网络水凝胶。该水凝胶的拉伸强度可达137 k Pa,在酸性缓冲液中收缩,碱性缓冲液中溶胀,具有灵敏的pH响应性。通过调节丙烯酸(AA)单体的中和度和2种网络交联剂的用量及单体配比,可控制双网络水凝胶的拉伸性能和响应性能。结果表明,AA中和度为125%,m(AM)∶m(Laponite)=1∶0.6,m(AA)∶m(BIS)=1∶0.0002,m(AM)∶m(AA)=7∶1时,水凝胶的拉伸强度最佳,可达137 k Pa;该条件下制备的双网络水凝胶同时具有灵敏可逆的pH响应性,在pH=3的缓冲液中溶胀度达5.26,在pH=7的缓冲液中溶胀度可达16.98。展开更多
通过N-丙烯酰-1,2-乙二胺盐酸盐(ADE)的Michael加成反应制备阳离子超支化低聚物聚N-丙烯酰-1,2-乙二胺盐酸盐(HADE),以HADE为大分子单体,以丙烯酰胺(AAm)和丙烯酸(AAc)为单体,在无需外加有机交联剂的条件下制备具有高机械强度的两性聚...通过N-丙烯酰-1,2-乙二胺盐酸盐(ADE)的Michael加成反应制备阳离子超支化低聚物聚N-丙烯酰-1,2-乙二胺盐酸盐(HADE),以HADE为大分子单体,以丙烯酰胺(AAm)和丙烯酸(AAc)为单体,在无需外加有机交联剂的条件下制备具有高机械强度的两性聚电解质水凝胶(HAH凝胶).结果表明,HAH凝胶可以被压缩超过99%的形变而不断裂,压缩强度高达61.2 MPa;HAH凝胶的断裂伸长率和断裂强度分别达到1700%和70.2 k Pa.由于HADE末端伯胺基与强氧化引发剂通过氧化还原反应生成胺自由基和自身结构中的双键同时参与聚合反应,因而为凝胶网络形成提供了必要的化学交联作用.同时HADE结构中胺基正电荷与AAc的羧基负电荷之间的离子交联也为凝胶网络提供了物理交联作用.2种交联作用的协同作用是HAH凝胶具有良好机械性能的根本原因.展开更多
基金supported by the National Natural Science Foundation of China (No.51273189)the National Science and Technology Major Project of the Ministry of Science and Technology of China (No.2016ZX05016),the National Science and Technology Major Project of the Ministry of Science and Technology of China (No.2016ZX05046)
文摘Double network(DN)hydrogels as one kind of tough gels have attracted extensive at-tention for their potential applications in biomedical and load-bearing fields.Herein,we import more functions like shape memory into the conventional tough DN hydro-gel system.We synthesize the PEG-PDAC/P(AAm-co-AAc)DN hydrogels,of which the first network is a well-defined PEG(polyethylene glycol)network loaded with PDAC(poly(acryloyloxyethyltrimethyl ammonium chloride))strands,while the second network is formed by copolymerizing AAm(acrylamide)with AAc(acrylic acid)and cross-linker MBAA(N;N′-methylenebisacrylamide).The PEG-PDAC/P(AAm-co-AAc)DN gels exhibits high mechanical strength.The fracture stress and toughness of the DN gels reach up to 0.9 MPa and 3.8 MJ/m^3,respectively.Compared with the conventional double network hydrogels with neutral polymers as the soft and ductile second network,the PEG-PDAC/P(AAm-co-AAc)DN hydrogels use P(AAm-co-AAc),a weak polyelectrolyte,as the second network.The AAc units serve as the coordination points with Fe^3+ions and physically crosslink the second network,which realizes the shape memory property activated by the reducing ability of ascorbic acid.Our results indicate that the high mechanical strength and shape memory properties,probably the two most important characters related to the potential application of the hydrogels,can be introduced simultaneously into the DN hydrogels if the functional monomer has been integrated into the network of DN hydrogels smartly.
基金financially supported by the National Nature Science Foundation of China(No.21474058)State Key Laboratory for Modification of Chemical Fibers and Polymer Materials,Donghua University(No.LK1404)Tsinghua University Scientific Research Project(No.2014Z22069)
文摘Poly（acrylamide-co-acrylic acid） nanocomposite physical （P（AAm-co-AAc）NCP） hydrogels have been prepared through the in situ free radical solution polymerization based on a ＂single network, dual cross-linkings＂ strategy. The P（AAm-co-AAc） NCP hydrogels are composed of nanobrushes of P（AAm-co-AAc） chains grafted on the surface of vinyl- hybrid silica nanoparticles （VSNPs）. In the hydrogel system, the VSNPs act as the ＂analogous chemical cross-linking points＂ once the hydrogen bonds formed between the P（AAm-co-AAc） chains of the nanobrushes, thus leading to the fabrication of high-strength P（AAm-co-AAc） NCP hydrogels. Compared with conventional thermosensitive P（AAm-co-AAc） hydrogels, the P（AAm-co-AAc） NCP hydrogels have a broader range of phase transition temperature, which can be adjusted by altering the monomer ratio, the VSNPs concentration, the addition of urea and N,N-dimethylacrylamide （DMAAm）. At the same time, the mechanical properties of the P（AAm-co-AAc） NCP hydrogels have been improved significantly by the introduction of VSNPs. Furthermore, both the phase transition and the tensile strength of the P（AAm-co-AAc） NCP hydrogels are largely influenced when Fe3＋ ions are introduced as the ionic crosslinkers into the hydrogel networks.
文摘采用二步法,以锂藻土(Laponite)交联聚丙烯酰胺(PAM),N,N-亚甲基双丙烯酰胺(BIS)交联聚丙烯酸(PAA),通过自由基聚合制备了PAM/PAA双网络水凝胶。该水凝胶的拉伸强度可达137 k Pa,在酸性缓冲液中收缩,碱性缓冲液中溶胀,具有灵敏的pH响应性。通过调节丙烯酸(AA)单体的中和度和2种网络交联剂的用量及单体配比,可控制双网络水凝胶的拉伸性能和响应性能。结果表明,AA中和度为125%,m(AM)∶m(Laponite)=1∶0.6,m(AA)∶m(BIS)=1∶0.0002,m(AM)∶m(AA)=7∶1时,水凝胶的拉伸强度最佳,可达137 k Pa;该条件下制备的双网络水凝胶同时具有灵敏可逆的pH响应性,在pH=3的缓冲液中溶胀度达5.26,在pH=7的缓冲液中溶胀度可达16.98。
文摘通过N-丙烯酰-1,2-乙二胺盐酸盐(ADE)的Michael加成反应制备阳离子超支化低聚物聚N-丙烯酰-1,2-乙二胺盐酸盐(HADE),以HADE为大分子单体,以丙烯酰胺(AAm)和丙烯酸(AAc)为单体,在无需外加有机交联剂的条件下制备具有高机械强度的两性聚电解质水凝胶(HAH凝胶).结果表明,HAH凝胶可以被压缩超过99%的形变而不断裂,压缩强度高达61.2 MPa;HAH凝胶的断裂伸长率和断裂强度分别达到1700%和70.2 k Pa.由于HADE末端伯胺基与强氧化引发剂通过氧化还原反应生成胺自由基和自身结构中的双键同时参与聚合反应,因而为凝胶网络形成提供了必要的化学交联作用.同时HADE结构中胺基正电荷与AAc的羧基负电荷之间的离子交联也为凝胶网络提供了物理交联作用.2种交联作用的协同作用是HAH凝胶具有良好机械性能的根本原因.
