Dual Sulfide-Disulfide Crosslinked Networks with Rapid and Room Temperature Self-Healability.

Polymer-based crosslinked networks with intrinsic self-repairing ability have emerged due to their built-in ability to repair physical damages. Here, novel dual sulfide-disulfide crosslinked networks (s-ssPxNs) are reported exhibiting rapid and room temperature self-healability within seconds to minutes, with no extra healing agents and no change under any environmental conditions. The method to synthesize these self-healable networks utilizes a combination of well-known crosslinking chemistry: photoinduced thiol-ene click-type radical addition, generating lightly sulfide-crosslinked polysulfide-based networks with excess thiols, and their oxidation, creating dynamic disulfide crosslinkages to yield the dual s-ssPxNs. The resulting s-ssPxN networks show rapid self-healing within 30 s to 30 min at room temperature, as well as self-healing elasticity with reversible viscoelastic properties. These results, combined with tunable self-healing kinetics, demonstrate the versatility of the method as a new means to synthesize smart multifunctional polymeric materials.

[1]  Li Wang,et al.  Self-healing polymer materials constructed by macrocycle-based host-guest interactions. , 2015, Soft matter.

[2]  Jianjun Cheng,et al.  Hydrolyzable Polyureas Bearing Hindered Urea Bonds , 2014, Journal of the American Chemical Society.

[3]  Kyung-Nam Kim,et al.  Photo‐induced thiol‐ene polysulfide‐crosslinked materials with tunable thermal and mechanical properties , 2014 .

[4]  Guangji Li,et al.  An intermolecular quadruple hydrogen-bonding strategy to fabricate self-healing and highly deformable polyurethane hydrogels. , 2014, Journal of materials chemistry. B.

[5]  Zhibin Guan,et al.  Multivalent hydrogen bonding block copolymers self-assemble into strong and tough self-healing materials. , 2014, Chemical communications.

[6]  C. Sanchez,et al.  Nano-building block based-hybrid organic–inorganic copolymers with self-healing properties , 2014 .

[7]  H. Xia,et al.  Thermal-healable and shape memory metallosupramolecular poly(n-butyl acrylate-co-methyl methacrylate) materials , 2014 .

[8]  N. Sottos,et al.  Restoration of Large Damage Volumes in Polymers , 2014, Science.

[9]  Z. Zhao,et al.  An Internal Cure for Damaged Polymers , 2014, Science.

[10]  Yong J. Yuan,et al.  Room-Temperature Self-Healable and Remoldable Cross-linked Polymer Based on the Dynamic Exchange of Disulfide Bonds , 2014 .

[11]  S. Basak,et al.  Multi-stimuli responsive self-healing metallo-hydrogels: tuning of the gel recovery property. , 2014, Chemical communications.

[12]  Jianjun Cheng,et al.  Dynamic urea bond for the design of reversible and self-healing polymers , 2014, Nature Communications.

[13]  Renzo M. Paulus,et al.  Self‐Healing Materials via Reversible Crosslinking of Poly(ethylene oxide)‐Block‐Poly(furfuryl glycidyl ether) (PEO‐b‐PFGE) Block Copolymer Films , 2013 .

[14]  Zhibin Guan,et al.  Self-assembly of core–shell nanoparticles for self-healing materials , 2013 .

[15]  M. Rong,et al.  Intrinsic self-healing of covalent polymers through bond reconnection towards strength restoration , 2013 .

[16]  Josephine L. Harries,et al.  Healable supramolecular polymers , 2013 .

[17]  Mpf Mark Pepels,et al.  Self-healing systems based on disulfide–thiol exchange reactions , 2013 .

[18]  C. Chung,et al.  Repeatable self-healing of a microcapsule-type protective coating , 2013 .

[19]  Amy M. Peterson,et al.  The role of maleimide structure in the healing of furan-functionalized epoxy–amine thermosets , 2013 .

[20]  J. M. Elliott,et al.  Molecular recognition between functionalized gold nanoparticles and healable, supramolecular polymer blends – a route to property enhancement , 2013 .

[21]  D. Shchukin,et al.  Container-based multifunctional self-healing polymer coatings , 2013 .

[22]  M. Urban,et al.  Facile UV-healable polyethylenimine–copper (C2H5N–Cu) supramolecular polymer networks , 2013 .

[23]  Hyuntaek Oh,et al.  Autonomous self-healing of poly(acrylic acid) hydrogels induced by the migration of ferric ions , 2013 .

[24]  M. Rong,et al.  Alkoxyamine with reduced homolysis temperature and its application in repeated autonomous self-healing of stiff polymers , 2013 .

[25]  Andrew P. Janisse,et al.  Highly Tunable Thiol–Ene Networks via Dual Thiol Addition , 2013 .

[26]  A. Szilágyi,et al.  Reversible disulphide formation in polymer networks: A versatile functional group from synthesis to applications , 2013 .

[27]  Feihe Huang,et al.  A self-healing supramolecular polymer gel with stimuli-responsiveness constructed by crown ether based molecular recognition , 2013 .

[28]  Ying‐Ling Liu,et al.  Self-healing polymers based on thermally reversible Diels–Alder chemistry , 2013 .

[29]  Stijn Billiet,et al.  Chemistry of crosslinking processes for self-healing polymers. , 2013, Macromolecular rapid communications.

[30]  Henrik Birkedal,et al.  Self-healing mussel-inspired multi-pH-responsive hydrogels. , 2013, Biomacromolecules.

[31]  Jinying Yuan,et al.  Redox-switchable supramolecular polymers for responsive self-healing nanofibers in water , 2013 .

[32]  Aaron M. Kushner,et al.  Self-healing supramolecular block copolymers. , 2012, Angewandte Chemie.

[33]  Krzysztof Matyjaszewski,et al.  Self‐Healing of Covalently Cross‐Linked Polymers by Reshuffling Thiuram Disulfide Moieties in Air under Visible Light , 2012, Advanced materials.

[34]  Yoshifumi Amamoto,et al.  Self-healing of chemical gels cross-linked by diarylbibenzofuranone-based trigger-free dynamic covalent bonds at room temperature. , 2012, Angewandte Chemie.

[35]  Krzysztof Matyjaszewski,et al.  Self-Healing Polymer Films Based on Thiol-Disulfide Exchange Reactions and Self-Healing Kinetics Measured Using Atomic Force Microscopy , 2012 .

[36]  Ming Qiu Zhang,et al.  Self-Healing of Polymers via Synchronous Covalent Bond Fission/Radical Recombination , 2011 .

[37]  C. R. Becer,et al.  Self-healing and self-mendable polymers , 2010 .

[38]  Wayne Hayes,et al.  Healable polymeric materials: a tutorial review. , 2010, Chemical Society reviews.

[39]  C. Bowman,et al.  Thiol-click chemistry: a multifaceted toolbox for small molecule and polymer synthesis. , 2010, Chemical Society reviews.

[40]  Christopher N Bowman,et al.  Thiol-ene click chemistry. , 2010, Angewandte Chemie.

[41]  David M. Haddleton,et al.  Self-healing polymers prepared via living radical polymerisation , 2010 .

[42]  P. Braun,et al.  Coaxial Electrospinning of Self‐Healing Coatings , 2010, Advanced materials.

[43]  N. K. Singha,et al.  "Click chemistry" in tailor-made polymethacrylates bearing reactive furfuryl functionality: a new class of self-healing polymeric material. , 2009, ACS applied materials & interfaces.

[44]  Samuel R. Mendes,et al.  Catalytic oxidation of thiols to disulfides using iodine and CeCl3·7H2O in graphite , 2007 .

[45]  S. Nutt,et al.  A Thermally Re-mendable Cross-Linked Polymeric Material , 2002, Science.