基于二硫键的聚氨酯网络:从可调多重形状记忆性能到同步修复（英文）
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摘要
随着智能化时代的迅速发展,具有多功能或多响应的智能材料受到高度关注.但如何将多个智能单元以协同模式结合到单一系统中仍是研究者面临的巨大挑战.本文设计合成了一种新型聚氨酯动态交联网络,该材料能够以独立的方式和协同作用模式呈现形状记忆效应和自修复效应.为了实现这一目标,本文选择了聚四氢呋喃作为软链段以确保聚合物链具有良好的运动性,同时将动态共价键二硫键引入聚氨酯的主链中以实现材料在温和条件下的自修复.此外,通过有效调节二硫键含量、交联度和网络结构,获得了较宽的玻璃化转变温度(T_g),使网络具有两重、三重甚至四重形状的记忆效应.在此基础上,利用该材料的形状回复和修复的外界刺激条件的高度吻合,同时实现了材料修复和回复,拓宽了材料的应用范围.
With the prompt development in intellectualization nowadays, the smart materials with multifunctionality or multi-responsiveness are highly expected. But it is a big challenge to integrate the different actuating units into a single system in a synergy pattern. Herein, we put forward a new strategy to develop the polyurethane networks which can present shape-memory effect and self-healing effect in independent way as well as simultaneous acting mode. To realize this goal, poly(tetremethylene ether) glycol was chosen as the soft segment to ensure the polymer chains a good mobility, and disulfide bond as the dynamic covalent bond was embedded in the backbone of polyurethane to endow it with desirable self-healing capacity under mild condition. Moreover, a rational control of the architecture of the networks by adjusting the content of disulfide bond and the degree of cross-linking, a broad glass transition temperature(T_g) was achieved, which enabled the network a versatile shape-memory effect, covering from dual-, triple-so far as to quadrupleshape memory effect. More importantly, the shape recovery and healing process can be realized simultaneously because of the highly matched actuating condition in this system.
With the prompt development in intellectualization nowadays, the smart materials with multifunctionality or multi-responsiveness are highly expected. But it is a big challenge to integrate the different actuating units into a single system in a synergy pattern. Herein, we put forward a new strategy to develop the polyurethane networks which can present shape-memory effect and self-healing effect in independent way as well as simultaneous acting mode. To realize this goal, poly(tetremethylene ether) glycol was chosen as the soft segment to ensure the polymer chains a good mobility, and disulfide bond as the dynamic covalent bond was embedded in the backbone of polyurethane to endow it with desirable self-healing capacity under mild condition. Moreover, a rational control of the architecture of the networks by adjusting the content of disulfide bond and the degree of cross-linking, a broad glass transition temperature(T_g) was achieved, which enabled the network a versatile shape-memory effect, covering from dual-, triple-so far as to quadrupleshape memory effect. More importantly, the shape recovery and healing process can be realized simultaneously because of the highly matched actuating condition in this system.
引文
1 Lendlein A,Kelch S.Shape-memory polymers.Angew Chem Int Ed,2002,41:2034-2057
2 Behl M,Lendlein A.Shape-memory polymers.Mater Today,2007,10:20-28
3 Lendlein A,Langer R.Biodegradable,elastic shape-memory polymers for potential biomedical applications.Science,2002,296:1673-1676
4 Huang WM,Song CL,Fu YQ,et al.Shaping tissue with shape memory materials.Adv Drug Deliver Rev,2013,65:515-535
5 Pilate F,Toncheva A,Dubois P,et al.Shape-memory polymers for multiple applications in the materials world.Eur Polymer J,2016,80:268-294
6 Sun L,Huang WM,Wang CC,et al.Polymeric shape memory materials and actuators.Liquid Crysts,2013,41:277-289
7 Behl M,Razzaq MY,Lendlein A.Multifunctional shape-memory polymers.Adv Mater,2010,22:3388-3410
8 Yang Y,Urban MW.Self-healing polymeric materials.Chem Soc Rev,2013,42:7446-7467
9 Wool RP.Self-healing materials:a review.Soft Matter,2008,4:400
10 Wu DY,Meure S,Solomon D.Self-healing polymeric materials:a review of recent developments.Prog Polymer Sci,2008,33:479-522
11 Mauldin TC,Kessler MR.Self-healing polymers and composites.Int Mater Rev,2013,55:317-346
12 Syrett JA,Becer CR,Haddleton DM.Self-healing and self-mendable polymers.Polym Chem,2010,1:978-987
13 Jia R,Li L,Ai Y,et al.Self-healable wire-shaped supercapacitors with two twisted NiCo2O4coated polyvinyl alcohol hydrogel fibers.Sci China Mater,2018,61:254-262
14 Boyer C,Hoogenboom R.Multi-responsive polymers.Eur Polymer J,2015,69:438-440
15 Xie T.Recent advances in polymer shape memory.Polymer,2011,52:4985-5000
16 Zhan MQ,Yang KK,Wang YZ.Shape-memory poly(p-dioxanone)-poly(-caprolactone)/sepiolite nanocomposites with enhanced recovery stress.Chin Chem Lett,2015,26:1221-1224
17 Miaudet P,DerréA,Maugey M,et al.Shape and temperature memory of nanocomposites with broadened glass transition.Science,2007,318:1294-1296
18 Xie T.Tunable polymer multi-shape memory effect.Nature,2010,464:267-270
19 Luo Y,Guo Y,Gao X,et al.A general approach towards thermoplastic multishape-memory polymers via sequence structure design.Adv Mater,2013,25:743-748
20 Wen Z,Zhang T,Hui Y,et al.Elaborate fabrication of well-defined side-chain liquid crystalline polyurethane networks with tripleshape memory capacity.J Mater Chem A,2015,3:13435-13444
21 Cui J,del Campo A.Multivalent H-bonds for self-healing hydrogels.Chem Commun,2012,48:9302-9304
22 Wei M,Zhan M,Yu D,et al.Novel poly(tetramethylene ether)glycol and poly(ε-caprolactone)based dynamic network via quadruple hydrogen bonding with triple-shape effect and selfhealing capacity.ACS Appl Mater Interfaces,2015,7:2585-2596
23 Zhu D,Ye Q,Lu X,et al.Self-healing polymers with PEG oligomer side chains based on multiple H-bonding and adhesion properties.Polym Chem,2015,6:5086-5092
24 Hui Y,Wen ZB,Pilate F,et al.A facile strategy to fabricate highlystretchable self-healing poly(vinyl alcohol)hybrid hydrogels based on metal-ligand interactions and hydrogen bonding.Polym Chem,2016,7:7269-7277
25 Burattini S,Colquhoun HM,Fox JD,et al.A self-repairing,supramolecular polymer system:healability as a consequence of donor-acceptorπ-πstacking interactions.Chem Commun,2009,319:6717-6719
26 Zhong HY,Chen L,Ding XM,et al.Physio-and chemo-dual crosslinking toward thermoand photo-response of azobenzene-containing liquid crystalline polyester.Sci China Mater,2018,61:1225-1236
27 Kakuta T,Takashima Y,Nakahata M,et al.Preorganized hydrogel:self-healing properties of supramolecular hydrogels formed by polymerization of host-guest-monomers that contain cyclodextrins and hydrophobic guest groups.Adv Mater,2013,25:2849-2853
28 Zhang M,Xu D,Yan X,et al.Self-healing supramolecular gels formed by crown ether based host-guest interactions.Angew Chem Int Ed,2012,51:7011-7015
29 Chen X,Dam MA,Ono K,et al.A thermally re-mendable crosslinked polymeric material.Science,2002,295:1698-1702
30 Li QT,Jiang MJ,Wu G,et al.Photothermal conversion triggered precisely targeted healing of epoxy resin based on thermoreversible Diels-Alder network and amino-functionalized carbon nanotubes.ACS Appl Mater Interfaces,2017,9:20797-20807
31 Zhang J,Niu Y,Huang C,et al.Self-healable and recyclable tripleshape PPDO-PTMEG co-network constructed through thermoreversible Diels-Alder reaction.Polym Chem,2012,3:1390-1393
32 Canadell J,Goossens H,Klumperman B.Self-healing materials based on disulfide links.Macromolecules,2011,44:2536-2541
33 Lafont U,van Zeijl H,van der Zwaag S.Influence of cross-linkers on the cohesive and adhesive self-healing ability of polysulfidebased thermosets.ACS Appl Mater Interfaces,2012,4:6280-6288
34 Yang WJ,Tao X,Zhao T,et al.Antifouling and antibacterial hydrogel coatings with self-healing properties based on a dynamic disulfide exchange reaction.Polym Chem,2015,6:7027-7035
35 An SY,Noh SM,Nam JH,et al.Dual sulfide-disulfide cross-linked networks with rapid and room temperature self-healability.Macromol Rapid Commun,2015,36:1255-1260
36 Xu Y,Chen D.A novel self-healing polyurethane based on disulfide bonds.Macromol Chem Phys,2016,217:1191-1196
37 Kim SM,Jeon H,Shin SH,et al.Superior toughness and fast selfhealing at room temperature engineered by transparent elastomers.Adv Mater,2018,30:1705145-1705152
38 Rekondo A,Martin R,Ruiz de Luzuriaga A,et al.Catalyst-free room-temperature self-healing elastomers based on aromatic disulfide metathesis.Mater Horiz,2014,1:237-240
39 Deng G,Tang C,Li F,et al.Covalent cross-linked polymer gels with reversible sol-gel transition and self-healing properties.Macromolecules,2010,43:1191-1194
40 Liu F,Li F,Deng G,et al.Rheological images of dynamic covalent polymer networks and mechanisms behind mechanical and selfhealing properties.Macromolecules,2012,45:1636-1645
41 Roberts MC,Hanson MC,Massey AP,et al.Dynamically restructuring hydrogel networks formed with reversible covalent cross-links.Adv Mater,2007,19:2503-2507
42 He L,Fullenkamp DE,Rivera JG,et al.p H responsive self-healing hydrogels formed by boronate-catechol complexation.Chem Commun,2011,47:7497-7499
43 Zhang Y,Yang B,Zhang X,et al.A magnetic self-healing hydrogel.Chem Commun,2012,48:9305-9307
44 Zhang Y,Tao L,Li S,et al.Synthesis of multiresponsive and dynamic chitosan-based hydrogels for controlled release of bioactive molecules.Biomacromolecules,2011,12:2894-2901
45 Rodriguez ED,Ounaies Z,Luo XF,Mather PT.Shape memory miscible blends for thermal mending.Proc of SPIE,2009,7289:728912
46 Luo X,Mather PT.Shape memory assisted self-healing coating.ACS Macro Lett,2013,2:152-156
47 Rodriguez ED,Luo X,Mather PT.Linear/network poly(ε-caprolactone)blends exhibiting shape memory assisted self-healing(SMASH).ACS Appl Mater Interfaces,2011,3:152-161
48 Du L,Xu ZY,Fan CJ,et al.A fascinating metallo-supramolecular polymer network with thermal/magnetic/light-responsive shapememory effects anchored by Fe3O4nanoparticles.Macromolecules,2018,51:705-715
2 Behl M,Lendlein A.Shape-memory polymers.Mater Today,2007,10:20-28
3 Lendlein A,Langer R.Biodegradable,elastic shape-memory polymers for potential biomedical applications.Science,2002,296:1673-1676
4 Huang WM,Song CL,Fu YQ,et al.Shaping tissue with shape memory materials.Adv Drug Deliver Rev,2013,65:515-535
5 Pilate F,Toncheva A,Dubois P,et al.Shape-memory polymers for multiple applications in the materials world.Eur Polymer J,2016,80:268-294
6 Sun L,Huang WM,Wang CC,et al.Polymeric shape memory materials and actuators.Liquid Crysts,2013,41:277-289
7 Behl M,Razzaq MY,Lendlein A.Multifunctional shape-memory polymers.Adv Mater,2010,22:3388-3410
8 Yang Y,Urban MW.Self-healing polymeric materials.Chem Soc Rev,2013,42:7446-7467
9 Wool RP.Self-healing materials:a review.Soft Matter,2008,4:400
10 Wu DY,Meure S,Solomon D.Self-healing polymeric materials:a review of recent developments.Prog Polymer Sci,2008,33:479-522
11 Mauldin TC,Kessler MR.Self-healing polymers and composites.Int Mater Rev,2013,55:317-346
12 Syrett JA,Becer CR,Haddleton DM.Self-healing and self-mendable polymers.Polym Chem,2010,1:978-987
13 Jia R,Li L,Ai Y,et al.Self-healable wire-shaped supercapacitors with two twisted NiCo2O4coated polyvinyl alcohol hydrogel fibers.Sci China Mater,2018,61:254-262
14 Boyer C,Hoogenboom R.Multi-responsive polymers.Eur Polymer J,2015,69:438-440
15 Xie T.Recent advances in polymer shape memory.Polymer,2011,52:4985-5000
16 Zhan MQ,Yang KK,Wang YZ.Shape-memory poly(p-dioxanone)-poly(-caprolactone)/sepiolite nanocomposites with enhanced recovery stress.Chin Chem Lett,2015,26:1221-1224
17 Miaudet P,DerréA,Maugey M,et al.Shape and temperature memory of nanocomposites with broadened glass transition.Science,2007,318:1294-1296
18 Xie T.Tunable polymer multi-shape memory effect.Nature,2010,464:267-270
19 Luo Y,Guo Y,Gao X,et al.A general approach towards thermoplastic multishape-memory polymers via sequence structure design.Adv Mater,2013,25:743-748
20 Wen Z,Zhang T,Hui Y,et al.Elaborate fabrication of well-defined side-chain liquid crystalline polyurethane networks with tripleshape memory capacity.J Mater Chem A,2015,3:13435-13444
21 Cui J,del Campo A.Multivalent H-bonds for self-healing hydrogels.Chem Commun,2012,48:9302-9304
22 Wei M,Zhan M,Yu D,et al.Novel poly(tetramethylene ether)glycol and poly(ε-caprolactone)based dynamic network via quadruple hydrogen bonding with triple-shape effect and selfhealing capacity.ACS Appl Mater Interfaces,2015,7:2585-2596
23 Zhu D,Ye Q,Lu X,et al.Self-healing polymers with PEG oligomer side chains based on multiple H-bonding and adhesion properties.Polym Chem,2015,6:5086-5092
24 Hui Y,Wen ZB,Pilate F,et al.A facile strategy to fabricate highlystretchable self-healing poly(vinyl alcohol)hybrid hydrogels based on metal-ligand interactions and hydrogen bonding.Polym Chem,2016,7:7269-7277
25 Burattini S,Colquhoun HM,Fox JD,et al.A self-repairing,supramolecular polymer system:healability as a consequence of donor-acceptorπ-πstacking interactions.Chem Commun,2009,319:6717-6719
26 Zhong HY,Chen L,Ding XM,et al.Physio-and chemo-dual crosslinking toward thermoand photo-response of azobenzene-containing liquid crystalline polyester.Sci China Mater,2018,61:1225-1236
27 Kakuta T,Takashima Y,Nakahata M,et al.Preorganized hydrogel:self-healing properties of supramolecular hydrogels formed by polymerization of host-guest-monomers that contain cyclodextrins and hydrophobic guest groups.Adv Mater,2013,25:2849-2853
28 Zhang M,Xu D,Yan X,et al.Self-healing supramolecular gels formed by crown ether based host-guest interactions.Angew Chem Int Ed,2012,51:7011-7015
29 Chen X,Dam MA,Ono K,et al.A thermally re-mendable crosslinked polymeric material.Science,2002,295:1698-1702
30 Li QT,Jiang MJ,Wu G,et al.Photothermal conversion triggered precisely targeted healing of epoxy resin based on thermoreversible Diels-Alder network and amino-functionalized carbon nanotubes.ACS Appl Mater Interfaces,2017,9:20797-20807
31 Zhang J,Niu Y,Huang C,et al.Self-healable and recyclable tripleshape PPDO-PTMEG co-network constructed through thermoreversible Diels-Alder reaction.Polym Chem,2012,3:1390-1393
32 Canadell J,Goossens H,Klumperman B.Self-healing materials based on disulfide links.Macromolecules,2011,44:2536-2541
33 Lafont U,van Zeijl H,van der Zwaag S.Influence of cross-linkers on the cohesive and adhesive self-healing ability of polysulfidebased thermosets.ACS Appl Mater Interfaces,2012,4:6280-6288
34 Yang WJ,Tao X,Zhao T,et al.Antifouling and antibacterial hydrogel coatings with self-healing properties based on a dynamic disulfide exchange reaction.Polym Chem,2015,6:7027-7035
35 An SY,Noh SM,Nam JH,et al.Dual sulfide-disulfide cross-linked networks with rapid and room temperature self-healability.Macromol Rapid Commun,2015,36:1255-1260
36 Xu Y,Chen D.A novel self-healing polyurethane based on disulfide bonds.Macromol Chem Phys,2016,217:1191-1196
37 Kim SM,Jeon H,Shin SH,et al.Superior toughness and fast selfhealing at room temperature engineered by transparent elastomers.Adv Mater,2018,30:1705145-1705152
38 Rekondo A,Martin R,Ruiz de Luzuriaga A,et al.Catalyst-free room-temperature self-healing elastomers based on aromatic disulfide metathesis.Mater Horiz,2014,1:237-240
39 Deng G,Tang C,Li F,et al.Covalent cross-linked polymer gels with reversible sol-gel transition and self-healing properties.Macromolecules,2010,43:1191-1194
40 Liu F,Li F,Deng G,et al.Rheological images of dynamic covalent polymer networks and mechanisms behind mechanical and selfhealing properties.Macromolecules,2012,45:1636-1645
41 Roberts MC,Hanson MC,Massey AP,et al.Dynamically restructuring hydrogel networks formed with reversible covalent cross-links.Adv Mater,2007,19:2503-2507
42 He L,Fullenkamp DE,Rivera JG,et al.p H responsive self-healing hydrogels formed by boronate-catechol complexation.Chem Commun,2011,47:7497-7499
43 Zhang Y,Yang B,Zhang X,et al.A magnetic self-healing hydrogel.Chem Commun,2012,48:9305-9307
44 Zhang Y,Tao L,Li S,et al.Synthesis of multiresponsive and dynamic chitosan-based hydrogels for controlled release of bioactive molecules.Biomacromolecules,2011,12:2894-2901
45 Rodriguez ED,Ounaies Z,Luo XF,Mather PT.Shape memory miscible blends for thermal mending.Proc of SPIE,2009,7289:728912
46 Luo X,Mather PT.Shape memory assisted self-healing coating.ACS Macro Lett,2013,2:152-156
47 Rodriguez ED,Luo X,Mather PT.Linear/network poly(ε-caprolactone)blends exhibiting shape memory assisted self-healing(SMASH).ACS Appl Mater Interfaces,2011,3:152-161
48 Du L,Xu ZY,Fan CJ,et al.A fascinating metallo-supramolecular polymer network with thermal/magnetic/light-responsive shapememory effects anchored by Fe3O4nanoparticles.Macromolecules,2018,51:705-715