Multi-Functional Hyperbranched Poly(vinylene sulfide)s Constructed via Spontaneous Thiol–Yne Click Polymerization

Multifunctional hyperbranched polymers have found wide applications in diverse areas. However, the preparation of these polymers is generally under harsh polymerization conditions with limited reactions. In this work, we prepared multifunctional hyperbranched poly(vinylene sulfide)s (hb-PVSs) by our established efficient and spontaneous thiol–yne click polymerization for the first time. A series of hb-PVSs with high molecular weights (Mw up to 63100) were obtained in high yields (up to 86%) from the polymerizations of monomers 1 and 2 with equivalent molar ratio in THF at 20 °C for 2 h. All the hb-PVSs are regioregular, soluble, and thermally stable. Thanks to the unreacted ethynyl groups on their peripheries, the hb-PVSs could be facilely functionalized by consecutive thiol–yne click reactions. Moreover, the solid films of hb-PVSs exhibit higher refractive index (RI) values (n > 1.64) than those of traditional optical plastics. The TPE-containing hb-PVS shows unique aggregation-enhanced emission characte...

[1]  D. Wiersma,et al.  The first thiol–yne click chemistry approach for the preparation of liquid crystalline elastomers , 2015 .

[2]  Lei Tao,et al.  Polymeric AIE-based nanoprobes for biomedical applications: recent advances and perspectives. , 2015, Nanoscale.

[3]  Zhen Li,et al.  Functional hyperbranched polymers with advanced optical, electrical and magnetic properties. , 2015, Chemical Society reviews.

[4]  Yongfeng Zhou,et al.  Hyperbranched polymer vesicles: from self-assembly, characterization, mechanisms, and properties to applications. , 2015, Chemical Society reviews.

[5]  Yaochen Zheng,et al.  Hyperbranched polymers: advances from synthesis to applications. , 2015, Chemical Society reviews.

[6]  Yuguang Ma,et al.  Progress in small-molecule luminescent materials for organic light-emitting diodes , 2015, Science China Chemistry.

[7]  B. Tang,et al.  Regioselective Metal‐Free Click Polymerization of Azides and Alkynes , 2015 .

[8]  W. Yuan,et al.  Aggregation-induced emission of non-conjugated poly(amido amine)s: Discovering, luminescent mechanism understanding and bioapplication , 2015, Chinese Journal of Polymer Science.

[9]  Fengxia Sun,et al.  Synthesis of hyperbranched polymers and their applications in analytical chemistry , 2015 .

[10]  T. Aida,et al.  Revisiting thiol‐yne chemistry: Selective and efficient monoaddition for block and graft copolymer formation , 2015 .

[11]  H. Zou,et al.  Preparation of monolithic polymer columns with homogeneous structure via photoinitiated thiol-yne click polymerization and their application in separation of small molecules. , 2014, Analytical chemistry.

[12]  A. Lowe.  Thiol-yne ‘click’/coupling chemistry and recent applications in polymer and materials synthesis and modification , 2014 .

[13]  S. Perrier,et al.  Synthesis of Polystyrene-Based Hyperbranched Polymers by Thiol–Yne Chemistry: A Detailed Investigation , 2014 .

[14]  Ben Zhong Tang,et al.  Aggregation‐Induced Emission: The Whole Is More Brilliant than the Parts , 2014, Advanced materials.

[15]  C. Hawker,et al.  High refractive index polyvinylsulfide materials prepared by selective radical mono-addition thiol–yne chemistry , 2014 .

[16]  B. Tang,et al.  Catalyst-Free Thiol−Yne Click Polymerization: A Powerful and Facile Tool for Preparation of Functional Poly(vinylene sulfide)s , 2014 .

[17]  Ian D. Williams,et al.  Polycyclotrimerization of Dinitriles: A New Polymerization Route for the Construction of Soluble Nitrogen-Rich Polytriazines with Hyperbranched Structures and Functional Properties , 2013 .

[18]  C. Hawker,et al.  Radical thiol-yne chemistry on diphenylacetylene: selective and quantitative addition enabling the synthesis of hyperbranched poly(vinyl sulfide)s. , 2013, Macromolecular rapid communications.

[19]  J. Qin,et al.  Second-order nonlinear optical hyperbranched polymer containing isolation chromophore moieties derived from both “H”-type and star-type chromophores , 2013, Chinese Journal of Polymer Science.

[20]  B. Tang,et al.  Thiol-yne click polymerization , 2013 .

[21]  D. Ding,et al.  Bioprobes based on AIE fluorogens. , 2013, Accounts of chemical research.

[22]  B. Tang,et al.  Hyperbranched Poly(aroxycarbonyltriazole)s: Metal-Free Click Polymerization, Light Refraction, Aggregation-Induced Emission, Explosive Detection, and Fluorescent Patterning , 2013 .

[23]  Y. Ju,et al.  Metal-free click approach for facile production of main chain poly(bile acid)s , 2013 .

[24]  B. Tang,et al.  Metal-free click polymerizations of activated azide and alkynes , 2013 .

[25]  B. Tang,et al.  Self-healing hyperbranched poly(aroyltriazole)s , 2013, Scientific Reports.

[26]  B. Tang,et al.  Tetraphenylethene: a versatile AIE building block for the construction of efficient luminescent materials for organic light-emitting diodes , 2012 .

[27]  B. Tang,et al.  Ethynyl-Capped Hyperbranched Conjugated Polytriazole: Click Polymerization, Clickable Modification, and Aggregation-Enhanced Emission , 2012 .

[28]  Kazuo Tanaka,et al.  Advanced luminescent materials based on organoboron polymers. , 2012, Macromolecular rapid communications.

[29]  Chao Gao,et al.  Fast and scalable production of hyperbranched polythioether-ynes by a combination of thiol-halogen click-like coupling and thiol-yne click polymerization , 2012 .

[30]  Jiashing Yu,et al.  Reactive polymer coatings: a general route to thiol-ene and thiol-yne click reactions. , 2012, Macromolecular rapid communications.

[31]  M. Meier,et al.  A novel polymerization approach via thiol‐yne addition , 2012 .

[32]  Jia-rui Xu,et al.  Recent advances in organic mechanofluorochromic materials. , 2012, Chemical Society reviews.

[33]  R. Haag,et al.  Multifunctional dendritic polymers in nanomedicine: opportunities and challenges. , 2012, Chemical Society reviews.

[34]  Ana M. Costero,et al.  Optical chemosensors and reagents to detect explosives. , 2012, Chemical Society reviews.

[35]  Ben Zhong Tang,et al.  Aggregation-induced emission. , 2011, Chemical Society reviews.

[36]  M. Taşdelen,et al.  Diels–Alder “click” reactions: recent applications in polymer and material science , 2011 .

[37]  Chain‐Shu Hsu,et al.  Synthesis and electroluminescence properties of white-light single polyfluorenes with high-molecular weight by click reaction , 2011 .

[38]  Jiechao Ge,et al.  New sensing mechanisms for design of fluorescent chemosensors emerging in recent years. , 2011, Chemical Society reviews.

[39]  K. Neoh,et al.  Poly(vinylidene fluoride) Graft Copolymer Membranes with “Clickable” Surfaces and Their Functionalization , 2011 .

[40]  He Tian,et al.  Recent progress on polymer-based fluorescent and colorimetric chemosensors. , 2011, Chemical Society reviews.

[41]  B. Tang,et al.  Hyperbranched polytriazoles with high molecular compressibility: aggregation-induced emission and superamplified explosive detection , 2011 .

[42]  N. Marchetti,et al.  An insight into the radical thiol/yne coupling: the emergence of arylalkyne-tagged sugars for the direct photoinduced glycosylation of cysteine-containing peptides. , 2011, The Journal of organic chemistry.

[43]  B. Tang,et al.  Thiol−Yne Click Polymerization: Regio- and Stereoselective Synthesis of Sulfur-Rich Acetylenic Polymers with Controllable Chain Conformations and Tunable Optical Properties , 2011 .

[44]  Jae Wook Lee,et al.  Synthesis and Photovoltaic Properties of Side‐Chain Liquid‐Crystal Click Polymers for Dye‐Sensitized Solar‐Cells Application , 2010 .

[45]  K. Anseth,et al.  Synthesis of cyclic, multivalent Arg-Gly-Asp using sequential thiol-ene/thiol-yne photoreactions. , 2010, Chemical communications.

[46]  C. Bowman,et al.  Synthesis, Thiol−Yne “Click” Photopolymerization, and Physical Properties of Networks Derived from Novel Multifunctional Alkynes , 2010 .

[47]  R. Hoogenboom.  Thiol-yne chemistry: a powerful tool for creating highly functional materials. , 2010, Angewandte Chemie.

[48]  J. Lam,et al.  Metal‐Free Alkyne Polyhydrothiolation: Synthesis of Functional Poly(vinylenesulfide)s with High Stereoregularity by Regioselective Thioclick Polymerization , 2010 .

[49]  C. Bowman,et al.  Reaction Rates and Mechanisms for Radical, Photoinitated Addition of Thiols to Alkynes, and Implications for Thiol−Yne Photopolymerizations and Click Reactions , 2010 .

[50]  Ben Zhong Tang,et al.  Fluorescent bio/chemosensors based on silole and tetraphenylethene luminogens with aggregation-induced emission feature , 2010 .

[51]  S. Perrier,et al.  Hyperbranched polymers by thiol-yne chemistry: from small molecules to functional polymers. , 2009, Journal of the American Chemical Society.

[52]  Jingang Liu,et al.  High refractive index polymers: fundamental research and practical applications , 2009 .

[53]  Albena Lederer,et al.  Hyperbranched and highly branched polymer architectures--synthetic strategies and major characterization aspects. , 2009, Chemical reviews.

[54]  Ben Zhong Tang,et al.  Acetylenic polymers: syntheses, structures, and functions. , 2009, Chemical reviews.

[55]  B. Liu,et al.  Fluorescent Single-Molecular Core−Shell Nanospheres of Hyperbranched Conjugated Polyelectrolyte for Live-Cell Imaging , 2009 .

[56]  Ben Zhong Tang,et al.  Aggregation-induced emission: phenomenon, mechanism and applications. , 2009, Chemical communications.

[57]  J. Lam,et al.  Metal‐Free Click Polymerization: Synthesis and Photonic Properties of Poly(aroyltriazole)s , 2009 .

[58]  Cheng-Liang Liu,et al.  Synthesis and Memory Device Characteristics of New Sulfur Donor Containing Polyimides , 2009 .

[59]  L. Tang,et al.  Polytriazoles with Aggregation-Induced Emission Characteristics: Synthesis by Click Polymerization and Application as Explosive Chemosensors , 2009 .

[60]  C. Bowman,et al.  Thiol−Yne Photopolymerizations: Novel Mechanism, Kinetics, and Step-Growth Formation of Highly Cross-Linked Networks , 2008, Macromolecules.

[61]  Yongqiang Dong,et al.  Hyperbranched Polytriazoles: Click Polymerization, Regioisomeric Structure, Light Emission, and Fluorescent Patterning , 2008 .

[62]  S. W. Thomas,et al.  Chemical sensors based on amplifying fluorescent conjugated polymers. , 2007, Chemical reviews.

[63]  Ben Zhong Tang,et al.  Click polymerization : facile synthesis of functional poly(aroyltriazole)s by metal-free, regioselective 1,3-dipolar polycycloaddition , 2007 .

[64]  T. Long,et al.  Highly Branched Poly(ether ester)s via Cyclization-Free Melt Condensation of A2 Oligomers and B3 Monomers , 2006 .

[65]  Ben Zhong Tang,et al.  Construction of Hyperbranched Poly(alkenephenylene)s by Diyne Polycyclotrimerization: Single-Component Catalyst, Glycogen-like Macromolecular Structure, Facile Thermal Curing, and Strong Thermolysis Resistance , 2004 .

[66]  D. Yan,et al.  Hyperbranched polymers: from synthesis to applications , 2004 .

[67]  Mitsutoshi Jikei,et al.  Hyperbranched polymers: a promising new class of materials , 2001 .

[68]  Zainuddin Muchtar,et al.  HYPERBRANCHED NANOMOLECULES: REGULAR POLYSTYRENE DENDRIGRAFTS , 2001 .

[69]  M. G. Finn,et al.  Click Chemistry: Diverse Chemical Function from a Few Good Reactions. , 2001, Angewandte Chemie.

[70]  T. Emrick,et al.  An A2 + B3 approach to hyperbranched aliphatic polyethers containing chain end epoxy substituents , 1999 .

[71]  M. Kakimoto,et al.  Synthesis of hyperbranched aromatic polyamide from aromatic diamines and trimesic acid , 1999 .

[72]  Jean M. J. Fréchet,et al.  One-pot synthesis of hyperbranched polyethers , 1992 .

[73]  Alessandro Gandini,et al.  The furan/maleimide Diels–Alder reaction: A versatile click–unclick tool in macromolecular synthesis , 2013 .

[74]  C. Bowman,et al.  Thiol-X chemistries in polymer and materials science , 2013 .

[75]  J. Naciri,et al.  Hydrodynamic shaping, polymerization, and subsequent modification of thiol click fibers. , 2013, ACS applied materials & interfaces.

[76]  Zhiqian Guo,et al.  Recent Application Progress on Aggregation-Induced Emission , 2012 .

[77]  Ben Zhong Tang,et al.  Luminogenic polymers with aggregation-induced emission characteristics , 2012 .

[78]  B. Tang,et al.  Azide-alkyne click polymerization: An update , 2011, Chinese Journal of Polymer Science.

[79]  A. Müller,et al.  Hyperbranched (Meth)acrylates in Solution, Melt, and Grafted From Surfaces. , 2003, Topics in current chemistry.

[80]  H S Kwok,et al.  Aggregation-induced emission of 1-methyl-1,2,3,4,5-pentaphenylsilole. , 2001, Chemical communications.