不同体系的双网络水凝胶及其增强机理
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摘要
双网络水凝胶是由两种不同性质的聚合物形成的互穿网络,第一层为紧密交联的刚而脆聚电解质网络,第二层为松散交联的软而韧中性网络。双网络水凝胶具有极高的机械强度和韧性,甚至可以与橡胶相媲美。其中,刚而脆聚电解质网络为双网络水凝胶提供了"牺牲键",起到分散外界应力的作用;而软而韧的中性聚合物填补于刚性网络中,为双网络水凝胶提供了支架,保持水凝胶外形。基于上述机理,研究者设计合成了具有高强度、良好生物相容性、低摩擦和低磨损等特性的双网络水凝胶。着重讨论了不同体系双网络水凝胶的力学性能和增强机理,并展望了双网络水凝胶研究前景。
The double-network gels possess interpenetrating network structure,which is made up of two different kinds of polymers.The first network composed of rigid and brittle polyelectrolytes is tightly cross-linked,while the second network composed of soft and ductile neutral polymers is loosely cross-linked.The double-network gels manifest excellent mechanical properties as well as super high toughness comparable to rubbers.The rigid and brittle network constituted by polyelectrolytes serves as"sacrificial bonds",which disperse the external stress;meanwhile,this rigid network is filled with soft and ductile polymers which provide support for the double-network gel to maintain its shape.Based on the mechanism described above,some double-network gels exhibiting high strength,good biocompatibility,low friction resistance and low wear characteristics have been designed and fabricated.The mechanical properties and the reinforcing mechanisms of various double-network gels are introduced.Moreover,the research prospects of double-network gels are discussed.
The double-network gels possess interpenetrating network structure,which is made up of two different kinds of polymers.The first network composed of rigid and brittle polyelectrolytes is tightly cross-linked,while the second network composed of soft and ductile neutral polymers is loosely cross-linked.The double-network gels manifest excellent mechanical properties as well as super high toughness comparable to rubbers.The rigid and brittle network constituted by polyelectrolytes serves as"sacrificial bonds",which disperse the external stress;meanwhile,this rigid network is filled with soft and ductile polymers which provide support for the double-network gel to maintain its shape.Based on the mechanism described above,some double-network gels exhibiting high strength,good biocompatibility,low friction resistance and low wear characteristics have been designed and fabricated.The mechanical properties and the reinforcing mechanisms of various double-network gels are introduced.Moreover,the research prospects of double-network gels are discussed.
引文
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31 Liu X B,Gao Y,Bian L N,et al.Preparation and characterization of natural rubber/ultrafine full-vulcanized powdered styrene-butadiene rubber blends[J].Polym Bull,2014,71(8):2023
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33 Kitamura N,Yasuda K,Ogawa M,et al.Induction of spontaneous hyaline cartilage regeneration using a doublenetwork gel:The efficacy of a novel therapeutic strategy for an articular cartilage defect[J].Am J Sports Med,2011,39(6):1160
34 王华明,卢凌彬,曹阳.壳聚糖智能水凝胶在生物材料领域的应用[J].材料导报,2008,22(专辑Ⅹ):103
2 Yu L,Ding J D.Injectable hydrogels as unique biomedical materials[J].Chem Soc Rev,2008,37(8):1473
3 Haraguchi K,Takehisa T.Nanocomposite hydrogels:A unique organic-inorganic network structure with extraordinary mechanical,optical,and swelling/de-swelling properties[J].Adv Mater,2002,14(16):112
4 Gong J P,Katsuyama Y,Kurokawa T,et al.Double-network hydrogels with extremely high mechanical strength[J].Adv Mater,2003,15(14):1155
5 Nakayama A,Kakugo A,Gong J P,et al.High mechanical strength double-network hydrogel with bacterial cellulose[J].Adv Funct Mater,2004,14(11):1124
6 Hu J,Hiwatashi K,Kurokawa T,et al.Microgel-reinforced hydrogel films with high mechanical strength and their visible mesoscale fracture structure[J].Macromolecules,2011,44(19):7775
7 Yang W,Furukawa H,Gong J P.Highly extensible double-network gels with self-assembling anisotropic structure[J].Adv Mater,2008,20(23):4499
8 Nakajima T,Furukawa H,Tanaka Y,et al.Effect of void structure on the toughness of double network hydrogels[J].Polym Sci Part B Polym Phys,2011,49(17):1246
9 Gong J P.Why are double network hydrogels so tough?[J].Soft Matter,2010,6(12):2583
10 Tsukeshiba H,Huang M,Na Y H,et al.Effect of polymer entanglement on the toughening of double network hydrogels[J].Phys Chem B,2005,109(34):16304
11 Na Y H,Tanaka Y,Kawauchi Y,et al.Necking phenomenon of double-network gels[J].Macromolecules,2006,39(14):4641
12 Huang M,Furukawa H,Tanaka Y,et al.Importance of entanglement between first and second components in highstrength double network gels[J].Macromolecules,2007,40(18):6658
13 Tanaka Y,Kuwabara R,Na Y H,et al.Determination of fracture energy of high strength double network hydrogels[J].Phys Chem B,2005,109(23):11559
14 Nakajima T,Furukawa H,Tanaka Y,et al.True chemical structure of double network hydrogels[J].Macromolecules,2009,42(6):2184
15 Na Y H,Kurokawa T,Katsuyama Y,et al.Structural characteristics of double network gels with extremely high mechanical strength[J].Macromolecules,2004,37(14):5370
16 Nakajima T,Kurokawa T,Furukawa H,et al.Super tough gels with a double network structure[J].J Chin Polym Sci,2009,27(1):1
17 Wu Z L,Kurokawa T,Gong J P.Novel developed systems and techniques based on double-network principle[J].Bull Chem Soc Jpn,2011,84(12):1295
18 Hestrin S,Schramm M.Synthesis of cellulose by Acetobacter xylinum.2.Preparation of freeze-dried cells capable of polymerizing glucose to cellulose[J].Biochemist J,1954,58(2):345
19 Olsson R T,Azizi Samir M A S,Salazar-Alvarez G.Making flexible magnetic aerogels and stiff magnetic nanopaper using cellulose nanofibrils as templates[J].Nat Nanotechnol,2010,5(8):584
20 Takai M,Tsuta Y,Watanabe S.Biosynthesis of cellulose by acetobacter xylinum.I.Characterizations of bacterial cellulose[J].Polym J,1975,7:137
21 左瑞霖,梁国正,常鹏善,等.热致型液晶增韧热固性树脂的研究进展[J].材料导报,2003,17(5):17
22 Wang Q G,Justin L,Mynar Masaru Y.High-water-content mouldable hydrogels by mixing clay and a dendritic molecular binder[J].Nature,2010,463(7279):339
23 Haque M A,Kamita G,Kurokawa T,et al.Unidirectional alignment of lamellar bilayer in hydrogel:One-dimensional swelling,anisotropic modulus,and stress/strain tunable structural color[J].Adv Mater,2010,22(45):5110
24 Haque M A,Kurokawa T,Kamita G,et al.Rapid and reversible tuning of structural color of a hydrogel over the entire visible spectrum by mechanical stimulation[J].Chem Mater,2011,23(23):5200
25 Sun T L,Wu Z L,Gong J P.Self-assembled structures of a semi-rigid polyanion in aqueous solutions and hydrogels[J].Sci Chin Chem,2012,55(5):735
26 Dobashi T,Furusawa K,Kita E,et al.DNA liquid-crystalline gel as adsorbent of carcinogenic agent[J].Langmuir,2007,23(3):1303
27 Vandenberg E J,Diveley W R,Filar L J,et al.The synthesis and solution properties of some rigid-chain,water-soluble polymers:Poly[N,N′-(sulfo-phenylene)phthalamide]s and poly[N,N′-(sulfo-p-phenylene)pyromellitimide][J].J Polym Sci Part A Polym Chem,1989,27(11):3745
28 Sarkar N,Kershner L D.Rigid rod water-soluble polymers[J].J Appl Polym Sci,1996,62(2):393
29 Viale S,Best A S,Mendes E,et al.Formation of aqueous molecular nematic liquid crystal phase in poly(p-sulfophenylene sulfoterephthalamide)[J].Chem Commun,2004,14(12):1596
30 鲁德平,管蓉,刘剑洪.微孔发泡高分子材料[J].高分子材料科学与工程,2002,18(4):30
31 Liu X B,Gao Y,Bian L N,et al.Preparation and characterization of natural rubber/ultrafine full-vulcanized powdered styrene-butadiene rubber blends[J].Polym Bull,2014,71(8):2023
32 Jeong Y S,Zhao X H,Widusha R K,et al.Highly stretchable and tough hydrogels[J].Nature,2012,489(7414):133
33 Kitamura N,Yasuda K,Ogawa M,et al.Induction of spontaneous hyaline cartilage regeneration using a doublenetwork gel:The efficacy of a novel therapeutic strategy for an articular cartilage defect[J].Am J Sports Med,2011,39(6):1160
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