RAFT Polymerization of N-[3-(Trimethoxysilyl)-propyl]acrylamide and Its Versatile Use in Silica Hybrid Materials.

Reversible addition-fragmentation chain transfer (RAFT) polymerization and characterization of an alkoxysilane acrylamide monomer using a trithiocarbonate chain transfer agent are described. Poly(N-[3-(trimethoxysilyl)propyl]acrylamide) (PTMSPAA) homopolymers are obtained with good control over the polymerization. A linear increase in the molecular weight is observed whereas the polydispersity values do not exceed 1.2 regardless of the monomer conversion. Moreover, PTMSPAA is used as a macro-RAFT agent to polymerize N-isopropylacrylamide (NIPAM). By varying the degree of polymerization of NIPAM within the block copolymer, different sizes of thermoresponsive particles are obtained. These particles are stabilized by the condensation of the alkoxysilane moieties of the polymers. Furthermore, a co-network of silica and PTMSPAA is prepared using the sol-gel process. After drying, transparent mesoporous hybrids are obtained with a surface area of up to 400 m(2) g(-1).

[1]  S. Perrier,et al.  Preparation of complex multiblock copolymers via aqueous RAFT polymerization at room temperature , 2015 .

[2]  Weikun Li,et al.  Synthesis and Self-Assembly of Amphiphilic Hybrid Nano Building Blocks via Self-Collapse of Polymer Single Chains , 2014 .

[3]  Julian R. Jones,et al.  Chemical characterisation and fabrication of chitosan-silica hybrid scaffolds with 3-glycidoxypropyl trimethoxysilane. , 2014, Journal of materials chemistry. B.

[4]  D. Portehault,et al.  Molecular Engineering of Functional Inorganic and Hybrid Materials , 2014 .

[5]  Thomas Maschmeyer,et al.  Rapid and quantitative one-pot synthesis of sequence-controlled polymers by radical polymerization , 2013, Nature Communications.

[6]  Yi Shi,et al.  Thermo-responsive organic–inorganic hybrid vesicles with tunable membrane permeability , 2012 .

[7]  Graeme Moad,et al.  RAFT Agent Design and Synthesis , 2012 .

[8]  C. R. Becer,et al.  "Clicking" on/with polymers: a rapidly expanding field for the straightforward preparation of novel macromolecular architectures. , 2012, Chemical Society reviews.

[9]  Mariana Beija,et al.  RAFT/MADIX polymers for the preparation of polymer/inorganic nanohybrids , 2011 .

[10]  Molly M. Stevens,et al.  Silica‐Gelatin Hybrids with Tailorable Degradation and Mechanical Properties for Tissue Regeneration , 2010 .

[11]  Andreas Walther,et al.  Water-soluble organo-silica hybrid nanotubes templated by cylindrical polymer brushes. , 2010, Journal of the American Chemical Society.

[12]  E. Bourgeat‐Lami,et al.  Micellar Behavior of Well-Defined Polystyrene-Based Block Copolymers with Triethoxysilyl Reactive Groups and Their Hydrolysis-Condensation , 2010 .

[13]  Lei Gao,et al.  Functional sandwich-like organic/inorganic nanoplates from gelable triblock terpolymers , 2009 .

[14]  Ke Zhang,et al.  ATRP of 3-(triethoxysilyl)propyl methacrylate and preparation of “stable” gelable block copolymers , 2008 .

[15]  M. Maskos,et al.  Functionalization of Crosslinked Vesicles by Co‐Self‐Assembly of a Gelable Diblock Copolymer and Mercaptosilane , 2008 .

[16]  Jiayin Yuan,et al.  Water-soluble organo-silica hybrid nanowires. , 2008, Nature materials.

[17]  R. Zhuo,et al.  Synthesis and applications of shell cross-linked thermoresponsive hybrid micelles based on poly(N-isopropylacrylamide-co-3-(trimethoxysilyl)propyl methacrylate)-b-poly(methyl methacrylate). , 2008, Langmuir : the ACS journal of surfaces and colloids.

[18]  Lei Gao,et al.  Organic-Inorganic Hybrid Materials by Self-Gelation of Block Copolymer Assembly and Nanoobjects with Controlled Shapes Thereof , 2007 .

[19]  Hui Zhu,et al.  Gelation Inside Block Copolymer Aggregates and Organic/Inorganic Nanohybrids , 2006 .

[20]  Shi-zhong Luo,et al.  Fabrication of Hybrid Nanoparticles with Thermoresponsive Coronas via a Self-Assembling Approach , 2005 .

[21]  F. D’Agosto,et al.  Block Copolymers of γ-Methacryloxypropyltrimethoxysilane and Methyl Methacrylate by RAFT Polymerization. A New Class of Polymeric Precursors for the Sol−Gel Process , 2005 .

[22]  Jianzhong Du,et al.  Atom-Transfer Radical Polymerization of a Reactive Monomer: 3-(Trimethoxysilyl)propyl Methacrylate , 2004 .

[23]  N. Ayres,et al.  Facile, controlled, room-temperature RAFT polymerization of N-isopropylacrylamide. , 2004, Biomacromolecules.

[24]  Bruce M. Novak,et al.  Hybrid nanocomposite materials―between inorganic glasses and organic polymers , 1993 .

[25]  C. Brinker,et al.  Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing , 1990 .

[26]  E. Teller,et al.  ADSORPTION OF GASES IN MULTIMOLECULAR LAYERS , 1938 .

[27]  Martina H. Stenzel,et al.  Complex polymer architectures via RAFT polymerization: From fundamental process to extending the scope using click chemistry and nature's building blocks , 2012 .

[28]  H. G. Schild.  Poly(N-isopropylacrylamide): experiment, theory and application , 1992 .