UV-photopolymerisation of poly(methyl methacrylate)-based inorganic-organic hybrid coatings and bulk samples reinforced with methacrylate-modified zirconium oxocluster

Abstract In this work, we developed and optimised a synthetic route which enables to produce by spray-coating hard, transparent and stable inorganic–organic hybrid coatings for a wide variety of different substrates (e.g. stone, stainless steel, polymethylmethacrylate, polyethylene, wood, anodized aluminum). Chemically and thermally stable acrylate-based hybrid materials embedding the zirconium oxocluster Zr4O2(OMc)12, OMc (CH2 C(CH3)C(O)O) were prepared and UV-cured. The coatings of different compositions on different substrates were characterized by numerous analytical and spectroscopic methods such as FT-IR spectroscopy, Angle Resolved-XPS (AR-XPS), Secondary Ion Mass Spectrometry (SIMS), X-ray Absorption Spectroscopy (XAS), Environmental Scanning Electron Microscopy (ESEM) and Energy Dispersive X-ray analysis (EDX). Bulk samples were also prepared for additional characterizations. The bulk samples were analysed by FT-IR, whereas the cross-linking degree was qualitatively evaluated by swelling experiments. As far as the mechanical properties are concerned, the shear storage modulus (G′) and loss modulus (G″) were measured by Dynamical Mechanical Thermal Analysis (DMTA) technique. Moreover, the best conditions for the curing and cross-linking processes of the hybrid materials were studied up to 200 °C by using Differential Scanning Calorimetry (DSC). The thermal stability of the hybrid samples was evaluated by Thermogravimetric Analysis (TGA).

[1]  N. Binsted,et al.  A rapid, exact curved-wave theory for EXAFS calculations , 1984 .

[2]  Ulrich S. Schubert,et al.  Can the Clusters Zr6O4(OH)4(OOCR)12 and [Zr6O4(OH)4(OOCR)12]2 Be Converted into Each Other? , 2006 .

[3]  U. Schubert,et al.  Control of the ratio of functional and non-functional ligands in clusters of the type Zr6O4(OH)4(carboxylate)12 for their use as building blocks for inorganic–organic hybrid polymers , 2004 .

[4]  U. Schubert.  Organofunctional Metal Oxide Clusters as Building Blocks for Inorganic-Organic Hybrid Materials , 2004 .

[5]  K. G. Sharp.  Inorganic/Organic Hybrid Materials , 1998 .

[6]  J. Fouassier,et al.  Radiation curing in polymer science and technology , 1993 .

[7]  U. Schubert.  Polymers Reinforced by Covalently Bonded Inorganic Clusters , 2001 .

[8]  A. Terauchi,et al.  Phase structure and mechanical and adhesion properties of epoxy/silica hybrids , 2001 .

[9]  H. Bertagnolli,et al.  XAFS Spectroscopy of Liquid and Amorphous Systems: Presentation and Verification of a Newly Developed Program Package , 1992 .

[10]  U. Schubert,et al.  Ring-opening metathesis polymerizations with norbornene carboxylate-substituted metal oxo clusters , 2006 .

[11]  Pedro Gómez-Romero,et al.  Functional Hybrid Materials , 2004 .

[12]  U. Schubert,et al.  ω-Mercapto-functionalized hafnium- and zirconium-oxoclusters as nanosized building blocks for inorganic–organic hybrid materials: synthesis, characterization and photothiol-ene polymerization , 2007 .

[13]  U. Schubert,et al.  Methacrylate‐Substituted Titanium‐Yttrium Mixed‐Metal Oxo Clusters , 2004 .

[14]  C. Sanchez,et al.  Molecular design of alkoxide precursors for the synthesis of hybrid organic-inorganic gels , 1992 .

[15]  U. Schubert,et al.  Dielectric investigation of inorganic–organic hybrid film based on zirconium oxocluster-crosslinked PMMA , 2003 .

[16]  Ulrich S. Schubert,et al.  Mono-, Di-, and Trimetallic Methacrylate-substituted Metal Oxide Clusters Derived from Hafnium Butoxide , 2003 .

[17]  A. Priola,et al.  Hybrid Organic‐Inorganic Nanostructured Acrylic Films Based on Methacylate Modified Zirconium Oxocluster , 2007 .

[18]  V. Di Noto,et al.  Metal Oxoclusters as Molecular Building Blocks for the Development of Nanostructured Inorganic–Organic Hybrid Thin Films , 2006 .

[19]  D. A. Shirley,et al.  High-Resolution X-Ray Photoemission Spectrum of the Valence Bands of Gold , 1972 .

[20]  G. Rossetto,et al.  Corrosion protection and mechanical performance of SiO2 films deposited via PECVD on OT59 brass , 2005 .

[21]  U. Schubert,et al.  Mechanical Properties of Organic-Inorganic Hybrid Materials Determined by Indentation Techniques , 2007 .

[22]  P. Fratzl,et al.  Inorganic-organic hybrid polymers by polymerization of methacrylate- or acrylate-substituted oxotitanium clusters with methyl methacrylate or methacrylic acid , 2002 .

[23]  U. Schubert,et al.  Part 2: Inorganic−Organic Hybrid Polymers by Polymerization of Methacrylate-Substituted Oxotitanium Clusters with Methyl Methacrylate: Thermomechanical and Morphological Properties , 2002 .

[24]  M. Holland,et al.  Changes in the Zr environment in zirconia–silica xerogels with composition and heat treatment as revealed by Zr K-edge XANES and EXAFS , 2000 .

[25]  U. Schubert,et al.  Swelling behavior and thermal stability of poly(methylmethacrylate) crosslinked by the oxozirconium cluster Zr4O2(methacrylate)12 , 2001 .

[26]  Chen,et al.  X-ray-absorption studies of zirconia polymorphs. I. Characteristic local structures. , 1993, Physical review. B, Condensed matter.

[27]  M. Ding,et al.  Preparation and properties of polyimide films codoped with barium and titanium oxides , 2002 .

[28]  U. Schubert,et al.  Mechanical Properties of an Inorganic−Organic Hybrid Polymer Cross-linked by the Cluster Zr4O2(methacrylate)12 , 2001 .

[29]  J. Rehr,et al.  Near-edge x-ray-absorption fine structure of Pb: A comparison of theory and experiment. , 1993, Physical review. B, Condensed matter.

[30]  U. Schubert.  Organically modified transition metal alkoxides: chemical problems and structural issues on the way to materials syntheses. , 2007, Accounts of chemical research.

[31]  U. Schubert,et al.  Methacrylate‐Substituted Mixed‐Metal Clusters Derived from Zigzag Chains of [ZrO8]/[ZrO7] and [TiO6] Polyhedra , 2001 .

[32]  U. Schubert,et al.  Improvement of the thermal stability of cluster‐crosslinked polystyrene and poly(methyl methacrylate) by optimization of the polymerization conditions , 2005 .

[33]  R. Thouvenot,et al.  New Hybrid Covalent Networks Based on Polyoxometalates: Part 1. Hybrid Networks Based on Poly(ethyl methacrylate) Chains Covalently Cross-linked by Heteropolyanions: Synthesis and Swelling Properties , 2000 .

[34]  U. Schubert,et al.  Inorganic Clusters in Organic Polymers and the Use of Polyfunctional Inorganic Compounds as Polymerization Initiators , 2001 .

[35]  U. Schubert,et al.  Mechanical, thermomechanical, and thermal properties of polystyrene crosslinked with a multifunctional zirconium oxo cluster , 2007 .

[36]  M. Popall,et al.  Applications of hybrid organic–inorganic nanocomposites , 2005 .

[37]  Valérie Cabuil,et al.  Designed Hybrid Organic−Inorganic Nanocomposites from Functional Nanobuilding Blocks , 2001 .

[38]  U. Schubert,et al.  A New Type of Methacrylate-Substituted Oxozirconium Clusters: [Zr3O(OR)5(OMc)5]2 and [Zr3O(OR)3(OMc)7]2 , 2001 .

[39]  L. Fambri,et al.  Inorganic−Organic Clusters of Zirconium as Initiators of Hydroxyethyl Methacrylate Polymerization , 2002 .

[40]  U. Schubert,et al.  Tuning the properties of nanostructured inorganic–organic hybrid polymers obtained from metal oxide clusters as building blocks , 2007 .

[41]  W. Stickle,et al.  Handbook of X-Ray Photoelectron Spectroscopy , 1992 .

[42]  G. Guella,et al.  Gels from Modified Zirconium N-Butoxide: A Pyrolysis Study by Coupled Thermogravimetry, Gas Chromatographic, and Mass Spectrometric Analyses , 1998 .

[43]  Jacqueline I. Kroschwitz,et al.  Encyclopedia of Polymer Science and Technology , 1970 .

[44]  U. Schubert,et al.  Inorganic-organic Hybrid Materials from poly(methylmethacrylate) crosslinked by an organically Modified oxozirconium cluster. Synthesis and characterization , 2002 .

[45]  U. Schubert,et al.  Cluster-Crosslinked Inorganic-Organic Hybrid Polymers: Influence of the Cluster Type on the Materials Properties , 2002 .

[46]  S. Gurman,et al.  Amplitude reduction in EXAFS. , 1999, Journal of synchrotron radiation.

[47]  U. Schubert,et al.  Crosslinking vs. filler effect of carboxylate-substituted zirconium oxo clusters on the thermal stability of polystyrene , 2007 .

[48]  U. Schubert,et al.  Zirconium and hafnium oxoclusters as molecular building blocks for highly dispersed ZrO2 or HfO2 nanoparticles in silica thin films , 2005 .

[49]  U. Schubert,et al.  Magnetic behaviour of a hybrid polymer obtained from ethyl acrylate and the magnetic cluster Mn12O12(acrylate)16 , 2004 .

[50]  G. Kickelbick,et al.  Hybrid materials : synthesis, characterization, and applications , 2007 .

[51]  M. Seah,et al.  Practical Surface Analysis , 1992 .

[52]  E. Stern,et al.  Number of relevant independent points in x-ray-absorption fine-structure spectra. , 1993, Physical review. B, Condensed matter.

[53]  L. Fedrizzi,et al.  Inorganic–organic hybrid materials with zirconium oxoclusters as protective coatings on aluminium alloys , 2008 .

[54]  U. Schubert,et al.  Small-angle X-ray scattering investigation of the cluster distribution in inorganic–organic hybrid polymers prepared from organically substituted metal oxide clusters , 2004 .

[55]  R. Mcgreevy,et al.  X-ray diffraction, neutron scattering and EXAFS spectroscopy of monoclinic zirconia: analysis by Rietveld refinement and reverse Monte Carlo simulations , 2002 .

[56]  A. Priola,et al.  Thiol-ene Hybrid Organic/Inorganic Nanostructured Coatings Based on Thiol-Functionalized Zirconium Oxoclusters , 2007 .

[57]  S. Russo,et al.  Comprehensive polymer science: the synthesis, characterization, reactions & applic ations of polymers , 1989 .

[58]  J. Saja,et al.  Dynamic mechanical analysis of injection-moulded discs of polypropylene and untreated and silane-treated talc-filled polypropylene composites , 1999 .

[59]  C. Sanchez.  Advanced functional nanomaterials – From nanoscale objects to nanostructured inorganic and hybrid materials , 2005 .