Modification of epoxy resins with functional silanes, polysiloxanes, silsesquioxanes, silica and silicates

Abstract Epoxy resins are very important and widely used thermosetting polymers that find many practical applications. Very often their properties can be effectively modified by an addition of reactive silanes, polysiloxanes, silsesquioxanes, silica, montmorillonite, and other fillers. This review considers the literature concerning: (a) synthesis of carbofunctional silanes (CFS), polysiloxanes (CFPS) and polyhedral silsesquioxanes (POSS); (b) properties of neat epoxy resins and their composites and nanocomposites, obtained by modifications with reactive silanes, silicon containing monomers and polymers, and silica based fillers, enabling improvement of their mechanical properties, thermal and flame resistance as well as providing corrosion and antimicrobial protection.

[1]  E. Kandare,et al.  Synthesis and characterization of a functional polyhedral oligomeric silsesquioxane and its flame retardancy in epoxy resin , 2009 .

[2]  He Zhang,et al.  Synthesis of organic silane microcapsules for self-healing corrosion resistant polymer coatings , 2012 .

[3]  R. Kambour,et al.  Limiting oxygen indices of silicone block polymer , 1981 .

[4]  R. Laine,et al.  Silsesquioxanes as Synthetic Platforms. 3. Photocurable, Liquid Epoxides as Inorganic/Organic Hybrid Precursors , 1996 .

[5]  Shih-hsuan Chiu,et al.  Study on mechanical properties and intermolecular interaction of silicone rubber/polyurethane/epoxy blends , 2003 .

[6]  Jiangxuan Song,et al.  Microstructure and thermal properties of silyl‐terminated polycaprolactone–polysiloxane modified epoxy resin composites , 2008 .

[7]  S. Devaraju,et al.  Octakis(dimethylsiloxypropylglycidylether)silsesquioxane (OG-POSS) reinforced 1,1-bis(3-methyl-4-hydroxymethyl)cyclohexane based polybenzoxazine nanocomposites , 2012, Journal of Polymer Research.

[8]  Craig L. Homrighausen,et al.  Synthesis and characterization of a silarylene–siloxane–diacetylene polymer and its conversion to a thermosetting plastic , 2002 .

[9]  Yi Xiao-su,et al.  Study on intercalation and exfoliation behavior of organoclays in epoxy resin , 2001 .

[10]  Liyi Shi,et al.  Epoxy Nanocomposites Containing Mercaptopropyl Polyhedral Oligomeric Silsesquioxane : Morphology, Thermal Properties, and Toughening Mechanism , 2008 .

[11]  M. Kitajima,et al.  Effect of phase structure on the adhesion properties of the dimethoxysilyl-terminated polypropylene oxide/epoxy resin system , 1999 .

[12]  S. Kuo,et al.  Thermal and dielectric properties and curing kinetics of nanomaterials formed from poss-epoxy and meta-phenylenediamine , 2004 .

[13]  R. Laine,et al.  Octa(aminophenyl)silsesquioxane as a nanoconstruction site. , 2001, Journal of the American Chemical Society.

[14]  J. Chruściel,et al.  Modification of Thermoplastics with Reactive Silanes and Siloxanes , 2012 .

[15]  M. Ochi,et al.  Effect on the toughness and adhesion properties of epoxy resin modified with silyl-crosslinked urethane microsphere , 2002 .

[16]  Chuanjian Zhou,et al.  The preparation of a new polysiloxane copolymer with glucosylthioureylene groups on the side chains , 2004 .

[17]  Zhanhu Guo,et al.  Rheological behaviors and electrical conductivity of epoxy resin nanocomposites suspended with in-situ stabilized carbon nanofibers , 2010 .

[18]  Yong Han,et al.  Reinforcing hydroxyapatite/thermosetting epoxy composite with 3-D carbon fiber fabric through RTM processing , 2004 .

[19]  J. Yang,et al.  Thermally and Mechanically Enhanced Epoxy Resin-Silica Hybrid Materials Containing Primary Amine-Modified Silica Nanoparticles , 2008 .

[20]  O. Danos,et al.  Preparation and evaluation of a new class of gene transfer reagents: poly(-alkylaminosiloxanes). , 2003, Journal of controlled release : official journal of the Controlled Release Society.

[21]  Y. Kawakami,et al.  Polysiloxanes with Periodically Distributed Isomeric Double-Decker Silsesquioxane in the Main Chain , 2009 .

[22]  Zengping Zhang,et al.  Epoxy/POSS organic–inorganic hybrids: Viscoelastic, mechanical properties and micromorphologies , 2007 .

[23]  D. K. Chattopadhyay,et al.  THERMAL AND MECHANICAL PROPERTIES OF EPOXY ACRYLATE/METHACRYLATES UV CURED COATINGS , 2005 .

[24]  M. Brook.  Silicon in Organic, Organometallic, and Polymer Chemistry , 1999 .

[25]  G. Riess,et al.  Non-aqueous PVAc dispersions prepared in a reactive epoxy functionalized PDMS liquid medium , 2007 .

[26]  J. Halbritter.  Remark on oxides as low-temperature nuclei of Nb-B1 and Nb-A15 compounds , 1987 .

[27]  Yu‐Chen Chang,et al.  Studies on the cure kinetics and networks properties of neat and polydimethylsioxane modified tetrafunctional epoxy resins , 2010 .

[28]  M. Ochi,et al.  Phase structure and thermomechanical properties of primary and tertiary amine‐cured epoxy/silica hybrids , 2001 .

[29]  Y. Chiu,et al.  Synthesis, characterization, and properties of novel organic/inorganic epoxy hybrids containing nitrogen/silicon via the sol–gel method , 2007 .

[30]  Chaobin He,et al.  Photocurable epoxy/cubic silsesquioxane hybrid materials for polythiourethane: Failure mechanism of adhesion under weathering , 2008 .

[31]  B. G. Soares,et al.  Synthesis and properties of epoxy resin modified with epoxy-terminated liquid polybutadiene , 2003 .

[32]  Lin Fan,et al.  Synthesis and characterization of imide ring and siloxane-containing cycloaliphatic epoxy resins , 2007 .

[33]  B. Bauer,et al.  Epoxy/SiO2 interpenetrating polymer networks , 1996 .

[34]  Rashmi,et al.  Dry sliding wear behaviour of organo-modified montmorillonite filled epoxy nanocomposites using Taguchi’s techniques , 2011 .

[35]  K. Strzelec,et al.  New polythiourethane hardeners for epoxy resins , 2005 .

[36]  Yasumasa Morita.  Curing of epoxy siloxane monomer with anhydride , 2005 .

[37]  E. Han,et al.  The influence of ultra-fine glass fibers on the mechanical and anticorrosion properties of epoxy coatings , 2011 .

[38]  S. Ryu,et al.  Effect of silane functionalization of montmorillonite on epoxy/montmorillonite nanocomposite , 2009 .

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

[40]  S. Fellahi,et al.  Toughening of epoxy resin using hydroxyl-terminated polyesters , 1999 .

[41]  D. Snihirova,et al.  Hybrid epoxy–silane coatings for improved corrosion protection of Mg alloy , 2013 .

[42]  Qiuyu Zhang,et al.  Preparation and mechanical properties researches of silane coupling reagent modified β-silicon carbide filled epoxy composites , 2009 .

[43]  C. Iojoiu,et al.  Synthesis and photocrosslinking of benzyl acrylate substituted polydimethylsiloxanes , 2000 .

[44]  P. Mather,et al.  Hybrid epoxy‐based thermosets based on polyhedral oligosilsesquioxane: Cure behavior and toughening mechanisms , 2003 .

[45]  Seon Jeong Kim,et al.  pH‐ and thermal characteristics of graft hydrogels based on chitosan and poly(dimethylsiloxane) , 2002 .

[46]  M. Montemor,et al.  Electrochemical study of modified bis-[triethoxysilylpropyl] tetrasulfide silane films applied on the AZ31 Mg alloy , 2007 .

[47]  Sviatlana V. Lamaka,et al.  Novel hybrid sol-gel coatings for corrosion protection of AZ31B magnesium alloy , 2008 .

[48]  M. Lavorgna,et al.  Molybdate doping of networks in epoxy–silica hybrids: Domain structuring and corrosion inhibition , 2006 .

[49]  A. I. Balabanovich,et al.  Pyrolysis of epoxy resins and fire behavior of epoxy resin composites flame‐retarded with 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide additives , 2007 .

[50]  Y. Kawakami,et al.  Precise Synthesis of Poly(silphenylenesiloxane)s with Epoxy Side Functional Groups by Tris(pentafluorophenyl)borane as a Catalyst , 2007 .

[51]  R. Laine,et al.  Tailoring the global properties of nanocomposites. Epoxy resins with very low coefficients of thermal expansion , 2006 .

[52]  U. Senthilkumar,et al.  Structure–gas separation property relationships of non-ionic and cationic amino-hydroxy functionalized poly (dimethylsiloxane) membranes , 2004 .

[53]  M. J. Umapathy,et al.  Development of Siloxane Based Tetraglycidyl Epoxy Nanocomposites for High Performance Applications—Study of the Mechanical, Thermal, Water Absorption and Flame Retardant Behaviour , 2011 .

[54]  Haitao Wang,et al.  Preparation and thermo‐mechanical properties of heat‐resistant epoxy/silica hybrid materials , 2008 .

[55]  D. Hui,et al.  Enhancement of mechanical properties of aluminium/epoxy composites with silane functionalization of aluminium powder , 2012 .

[56]  M. Alagar,et al.  Preparation and characterization of chain-extended bismaleimide modified polyurethane–epoxy matrices , 2003 .

[57]  Chunyi Tang,et al.  Syntheses of novel photosensitive polysiloxanes and their effects on properties of UV-cured epoxy methacrylate coatings , 2010 .

[58]  D. Hirt,et al.  Surface Characterization of Linear Low-Density Polyethylene Films Modified with Fluorinated Additives , 2003 .

[59]  W. Cook,et al.  Photopolymerization Kinetics and Dynamic Mechanical Properties of Silanes Hydrolyzed without Evolution of Byproducts. Tetrakis[(methacryloyloxy)ethoxy]silane−Diethylene Glycol Dimethacrylate , 2011 .

[60]  R. Laine,et al.  Organic/Inorganic Hybrid Epoxy Nanocomposites from Aminophenylsilsesquioxanes , 2004 .

[61]  G. Malucelli,et al.  Epoxy-Siloxane Hybrid Coatings by a Dual-Curing Process , 2009 .

[62]  Yasumasa Morita,et al.  Cationic copolymerization of epoxy siloxane monomer with liquid poly‐butadiene and its light emitting diode encapsulation , 2008 .

[63]  Bin Zhang,et al.  Preparation and anticorrosive performances of polysiloxane-modified epoxy coatings based on polyaminopropylmethylsiloxane-containing amine curing agent , 2011 .

[64]  M. Honkanen,et al.  Thermal, mechanical and dielectric properties of nanostructured epoxy-polyhedral oligomeric silsesquioxane composites , 2008, IEEE Transactions on Dielectrics and Electrical Insulation.

[65]  Ying‐Ling Liu,et al.  Flame‐retardant epoxy resins: An approach from organic–inorganic hybrid nanocomposites , 2001 .

[66]  Chih-Yuan Hsu,et al.  Poly(methylmethacrylate)-silica nanocomposites films from surface-functionalized silica nanoparticles , 2005 .

[67]  Nilhan Kayaman‐Apohan,et al.  The novel use of organo alkoxy silane for the synthesis of organic-inorganic hybrid coatings , 2006 .

[68]  Lei Wang,et al.  Organic-inorganic poly(hydroxyether of bisphenol A) copolymers with double-decker silsesquioxane in the main chains , 2011 .

[69]  J. Crivello,et al.  Novel Epoxynorbornane Monomers. 1. Synthesis and Characterization , 1996 .

[70]  Zengping Zhang,et al.  Preparation and Dielectric Properties of POSS-NH2/Cyanate Ester Resin Organic-Inorganic Hybrids , 2011 .

[71]  Ho-Cheol Kim,et al.  On exfoliation of montmorillonite in epoxy , 2001 .

[72]  H. Galina,et al.  Epoxy resins modified with reactive low molecular weight siloxanes , 2012 .

[73]  M. Selvaraj,et al.  Studies on the evaluation of the performance of organic coatings used for the prevention of corrosion of steel rebars in concrete structures , 2009 .

[74]  J. Pascault,et al.  General Concepts about Epoxy Polymers , 2010 .

[75]  H. Inoue,et al.  Preparation and curing behavior of siloxane‐containing epoxy resins , 1992 .

[76]  W. Kern,et al.  Epoxy silicone based matrix materials for two-photon patterning of optical waveguides , 2011 .

[77]  J. Lichtenhan,et al.  Functionalized polyhedral oligosilsesquioxane (POSS) macromers: new graftable POSS hydride, POSS α-olefin, POSS epoxy, and POSS chlorosilane macromers and POSS–siloxane triblocks , 1999 .

[78]  L. Matějka,et al.  Structure evolution in epoxy–silica hybrids: sol–gel process , 1998 .

[79]  B. Novak,et al.  "Inverse" organic-inorganic composite materials. 3. High glass content "nonshrinking" sol-gel composites via poly(silicic acid esters) , 1993 .

[80]  B. Marciniec.  Functionalised (Poly)silsesquioxanes and Silicon-Containing Dendrimers , 2009 .

[81]  Guoyue Xu,et al.  The epoxy-siloxane/Al composite coatings with low infrared emissivity for high temperature applications , 2010 .

[82]  Xiao-jie Li,et al.  Preparation of epoxy-silica-acrylate hybrid coatings , 2008 .

[83]  Sharif Ahmad,et al.  Synthesis, characterization and development of high performance siloxane-modified epoxy paints , 2005 .

[84]  G. Hsiue,et al.  A New Class of Organic−Inorganic Sol−Gel Materials for Second-Order Nonlinear Optics , 1997 .

[85]  Hsieh-Chih Tsai,et al.  Morphology, thermal and mechanical properties of the polyhedral oligomeric silsesquioxane side‐chain epoxy hybrid material , 2010 .

[86]  Songqi Ma,et al.  MODIFICATION OF EPOXY RESINS WITH POLYETHER-G-POLYSILOXANES , 2010 .

[87]  Andre Lee,et al.  Thermal and viscoelastic property of epoxy-clay and hybrid inorganic-organic epoxy nanocomposites , 1999 .

[88]  E. Sudoł,et al.  Polymer latexes: Preparation, characterization, and applications , 1992 .

[89]  A. Afzal,et al.  The effect of SiO2 filler content and its organic compatibility on thermal stability of epoxy resin , 2012, Journal of Thermal Analysis and Calorimetry.

[90]  S. A. Kumar,et al.  Studies on novel silicone/phosphorus/sulphur containing nano-hybrid epoxy anticorrosive and antifouling coatings , 2010 .

[91]  B. Wetzel,et al.  Sliding wear behavior of epoxy containing nano-Al2O3 particles with different pretreatments , 2004 .

[92]  Yuhui Lin,et al.  Surface study of ladderlike polyepoxysiloxanes , 2000 .

[93]  A. Afzal,et al.  Thermally and mechanically superior hybrid epoxy-silica polymer films via sol-gel method , 2010 .

[94]  J. Higgins,et al.  Non-aqueous polymer dispersions ― investigation of anchor blocks in the adsorbed diblock copolymer poly(styrene-b-[ethylene-co-propylene]) by small angle neutron scattering , 1988 .

[95]  W. Hanoosh,et al.  Polydimethyl Siloxane Toughened Epoxy Resins: Tensile Strength and Dynamic Mechanical Analysis , 2009 .

[96]  Gregory R. Yandek,et al.  Synthesis of Aromatic Polyhedral Oligomeric SilSesquioxane (POSS) Dianilines for Use in High-Temperature Polyimides , 2012, Silicon.

[97]  R. Laine,et al.  Toughening of Cubic Silsesquioxane Epoxy Nanocomposites Using Core−Shell Rubber Particles: A Three-Component Hybrid System , 2004 .

[98]  Ying‐Ling Liu,et al.  Preparation, thermal properties, and flame retardance of epoxy–silica hybrid resins , 2003 .

[99]  M. Huskić,et al.  Preparation and properties of organic–inorganic hybrids based on poly(methyl methacrylate) and sol–gel polymerized 3-glycidyloxypropyltrimethoxysilane , 2009 .

[100]  J. Chruściel,et al.  Carbofunctional silanes and polysiloxanes. Part I. Applications of carbofunctional silanes , 2008 .

[101]  G. Hsiue,et al.  Chemical modification of dicyclopentadiene-based epoxy resins to improve compatibility and thermal properties , 2001 .

[102]  R. Laine.  Nanobuilding blocks based on the [OSiO1.5]x (x= 6, 8, 10) octasilsesquioxanes , 2005 .

[103]  R. Laine,et al.  Silsesquioxane barrier materials , 2007 .

[104]  Lee,et al.  Viscoelastic Responses of Polyhedral Oligosilsesquioxane Reinforced Epoxy Systems. , 1998, Macromolecules.

[105]  S. Jäger,et al.  Über oligomere Siliciumverbindungen mit funktionellen Gruppen. 12. Mitt. Über Herstellung von oligomeren siliciumorganischen Diolen und Diaminen und ihre Umsetzungen mit organischen Diisocyanaten , 1962 .

[106]  E. Koumoulos,et al.  Evaluation of corrosion resistance of magnesium alloy ZK10 coated with hybrid organic–inorganic film including containers , 2012 .

[107]  Chaobin He,et al.  Preparation, morphology and thermal/mechanical properties of epoxy/nanoclay composite , 2006 .

[108]  Walter Noll,et al.  Chemistry and technology of silicones , 1968 .

[109]  A. Yee,et al.  Organic/inorganic hybrid composites from cubic silsesquioxanes. , 2001, Journal of the American Chemical Society.

[110]  Ying‐Ling Liu,et al.  Epoxy/polyhedral oligomeric silsesquioxane nanocomposites from octakis(glycidyldimethylsiloxy)octasilsesquioxane and small‐molecule curing agents , 2006 .

[111]  Qifang Li,et al.  Alkoxysilane functionalized polycaprolactone/polysiloxane modified epoxy resin through sol–gel process , 2008 .

[112]  Zengping Zhang,et al.  The effect of POSS on the thermal properties of epoxy , 2007 .

[113]  J. Chruściel,et al.  Carbofunctional silanes and polysiloxanes. Part II. Preparation and applications of carbofunctional polysiloxanes , 2008 .

[114]  Xianting Zeng,et al.  Two-part epoxy-siloxane hybrid corrosion protection coatings for carbon steel , 2009 .

[115]  C. Pittman,et al.  Polyhedral Oligomeric Silsesquioxane (POSS) Polymers and Copolymers: A Review , 2001 .

[116]  W. Liaw,et al.  Preparation and properties of poly(imide siloxane) segmented copolymer/silica hybrid nanocomposites , 2007 .

[117]  G. Sauvet,et al.  Biocidal polymers active by contact. V. Synthesis of polysiloxanes with biocidal activity , 2000 .

[118]  B. Hausnerova,et al.  Preparation and characterization of an epoxy resin modified by a combination of MDI-based polyurethane and montmorillonite , 2011 .

[119]  Q. Xie,et al.  Thermal and mechanical properties of poly(urethane-imide)/epoxy/silica hybrids , 2010 .

[120]  Shengyu Feng,et al.  Viscosity–molecular weight relationship for aminopropyl‐terminated poly(dimethylsiloxane) , 2001 .

[121]  Chih-Yuan Hsu,et al.  A novel approach of chemical functionalization on nano-scaled silica particles , 2003 .

[122]  A. Gu,et al.  Novel modification of bismaleimide–triazine resin by reactive hyperbranched polysiloxane , 2010 .

[123]  R. Laine,et al.  Organic/Inorganic Imide Nanocomposites from Aminophenylsilsesquioxanes , 2003 .

[124]  Krzysztof Pielichowski,et al.  Polyhedral Oligomeric Silsesquioxanes (POSS)-Containing Nanohybrid Polymers , 2006 .

[125]  D. A. Russell,et al.  Optical Biosensing of Nitrate Ions Using a Sol–Gel Immobilized Nitrate Reductase , 1997 .

[126]  L. Mascia,et al.  Curing and morphology of epoxy resin-silica hybrids , 1998 .

[127]  L. Matějka,et al.  Electrical and thermomechanical properties of epoxy-POSS nanocomposites , 2011 .

[128]  R. Laine,et al.  Silsesquioxanes as synthetic platforms. II. Epoxy-functionalized inorganic-organic hybrid species , 1996 .

[129]  Xiaofei Ma,et al.  Synthesis and characterization of epoxy resin modified with nano-SiO2 and γ -glycidoxypropyltrimethoxy silane , 2007 .

[130]  K. E. J. Barrett,et al.  Dispersion polymerization in organic media , 1974 .

[131]  J. Hutchinson,et al.  Homopolymerization effects in polymer layered silicate nanocomposites based upon epoxy resin: Implications for exfoliation , 2009 .

[132]  Y. Liu,et al.  Preparation and characterization of epoxy resin modified with alkoxysilane- functionalized poly(urethane-imide) by the sol–gel process , 2011 .

[133]  R. Buchheit,et al.  Alkoxysilane oligomer modified epoxide primers , 2012 .

[134]  Rudolph D. Deanin,et al.  Comparison of epoxy resins for applications in light‐emitting diodes , 2004 .

[135]  Juan Li,et al.  Synthesis and characterization of epoxy resin modified with γ-thiopropyl triethoxy silane , 2009 .

[136]  P. Latha,et al.  Room temperature curing of CTBN-toughened epoxy adhesive with elevated temperature service capability , 1990 .

[137]  C. Chiang,et al.  Synthesis, characterization and thermal properties of novel epoxy/expandable graphite composites , 2010 .

[138]  J. Speier,et al.  Syntheses of (3-aminoalkyl) silicon compounds , 1971 .

[139]  R. Laine,et al.  Organic/inorganic hybrid composites from cubic silsesquioxanes. Epoxy resins of octa(dimethylsiloxyethylcyclohexylepoxide) silsesquioxane , 2003 .

[140]  M. Kitajima,et al.  Effect of modified silicone elastomer particles on the toughening of epoxy resin , 1998 .

[141]  Richard M. Laine,et al.  Hydrosilylation of Allyl Alcohol with [HSiMe2OSiO1.5]8: Octa(3-hydroxypropyldimethylsiloxy)octasilsesquioxane and Its Octamethacrylate Derivative as Potential Precursors to Hybrid Nanocomposites , 2000 .

[142]  Yasumasa Morita,et al.  Thermally initiated cationic polymerization and properties of epoxy siloxane , 2006 .

[143]  B. Marciniec,et al.  Modification of (Poly)Siloxanes via Hydrosilylation Catalyzed by Rhodium Complex in Ionic Liquids , 2006 .

[144]  A. Yee,et al.  Toughening mechanisms in elastomer-modified epoxies , 1986 .

[145]  S. Bose,et al.  Recent advances in graphene based polymer composites , 2010 .

[146]  A. Atkinson,et al.  Formation of silica/epoxy hybrid network polymers , 2003 .

[147]  G. Sauvet,et al.  Amphiphilic block and statistical siloxane copolymers with antimicrobial activity , 2003 .

[148]  Yu‐hui Lin,et al.  Synthesis and characterization of ladder-like copolymethyl-epoxysilsesquioxane , 2000 .

[149]  M. Alagar,et al.  MODIFICATION OF SILICONIZED EPOXY RESIN USING MULTIFUNCTIONAL SILANES , 2004 .

[150]  I. Yilgor,et al.  1,3-bis(γ-aminopropyl)tetramethyldisiloxane modified epoxy resins: curing and characterization , 1998 .

[151]  P. Cardiano.  Hydrophobic Properties of New Epoxy-Silica Hybrids , 2008 .

[152]  M. Macoveanu,et al.  Epoxy urethane acrylate , 2000 .

[153]  A. Hasnat,et al.  Synthesis, characterization, and performance evaluation of hard, anticorrosive coating materials derived from diglycidyl ether of bisphenol A acrylates and methacrylates , 2005 .

[154]  V. Cádiz,et al.  Preparation, thermal properties and flame retardancy of phosphorus-and silicon-containing epoxy resins , 2008 .

[155]  L. Mascia,et al.  Network density control in epoxy–silica hybrids by selective silane functionalization of precursors , 2005 .

[156]  A. N. Khramov,et al.  Sol gel coatings with phosphonate functionalities for surface modification of magnesium alloys , 2006 .

[157]  A. I. Balabanovich,et al.  Pyrolysis and fire behaviour of epoxy systems containing a novel 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-(DOPO)-based diamino hardener , 2008 .

[158]  D. W. Schaefer,et al.  Chemistry of mixtures of bis-[trimethoxysilylpropyl]amine and vinyltriacetoxysilane: an NMR analysis , 2009 .

[159]  S. Rai,et al.  Studies on Physicomechanical properties of Fly Ash-filled Hydroxyl-terminated Polyurethane-toughened Epoxy Composites , 2010 .

[160]  M. Döring,et al.  A Novel DOPO‐Based Diamine as Hardener and Flame Retardant for Epoxy Resin Systems , 2008 .

[161]  Ying‐Ling Liu,et al.  Synthesis, characterization, thermal, and flame retardant properties of phosphate-based epoxy resins , 1997 .

[162]  M. Soucek,et al.  Synthesis of telechelic methacrylic siloxanes with cycloaliphatic substituents groups for UV-curable applications , 2008 .

[163]  J. Yeh,et al.  Siloxane-modified epoxy resin–clay nanocomposite coatings with advanced anticorrosive properties prepared by a solution dispersion approach , 2006 .

[164]  Hisao Oikawa,et al.  Synthesis and Characterization of Organosoluble Aromatic Polyimides Containing POSS in Main Chain Derived from Double-Decker-Shaped Silsesquioxane , 2007 .

[165]  L. Matějka,et al.  Epoxy Networks Reinforced with Polyhedral Oligomeric Silsesquioxanes (POSS). Thermomechanical Properties , 2004 .

[166]  Chaobin He,et al.  Preparation and thermomechanical properties of epoxy resins modified by octafunctional cubic silsesquioxane epoxides , 2004 .

[167]  R. Laine,et al.  Organic–Inorganic Nanocomposites with Completely Defined Interfacial Interactions , 2001 .

[168]  M. Soucek,et al.  Protective space coatings: a ceramer approach for nanoscale materials , 2003 .

[169]  C. Burger,et al.  Polysiloxanes and Polymers Containing Siloxane Groups , 1996 .

[170]  J. Baselga,et al.  Water absorption in polyaminosiloxane-epoxy thermosetting polymers , 2003 .

[171]  Prashant Gupta,et al.  Development of Siliconized Epoxy Resins and Their Application as Anticorrosive Coatings , 2011 .

[172]  G. Kickelbick,et al.  Concepts for the incorporation of inorganic building blocks into organic polymers on a nanoscale , 2003 .

[173]  Y. Xiu,et al.  Preparation, thermal and mechanical properties of POSS epoxy hybrid composites , 2007 .

[174]  M. Soucek,et al.  A new class of silicone resins for coatings , 2007 .

[175]  M. Pinteala,et al.  Functional Polysiloxanes. 3. Reaction of 1,3-Bis(3-Glycidoxypropyl)-1,1,3,3-Tetramethyldisiloxane with Amino Compounds , 1995 .

[176]  N. Chikhi,et al.  Modification of epoxy resin using reactive liquid (ATBN) rubber , 2002 .

[177]  S. H. Anastasiadis,et al.  Polyolefin/layered silicate nanocomposites with functional compatibilizers , 2011 .

[178]  Qing Li,et al.  Novel composite films prepared by sol–gel technology for the corrosion protection of AZ91D magnesium alloy , 2009 .

[179]  M. Soucek,et al.  Mechanical and Film Properties of Telechelic Methacrylic Polysiloxanes with Cycloaliphatic Substituents Groups for UV-Curable Applications , 2010 .

[180]  Lihua He,et al.  Morphology of epoxy resin modified with silyl‐crosslinked urethane elastomer , 2005 .

[181]  K. Moon,et al.  Glass transition and relaxation behavior of epoxy nanocomposites , 2004 .

[182]  Yen Wei,et al.  A fast convenient method to prepare hybrid sol-gel materials with low volume-shrinkages , 1996 .

[183]  R. Laine,et al.  Silsesquioxanes as synthetic platforms. Thermally curable and photocurable inorganic/organic hybrids , 1996 .

[184]  Jun-gang Gao,et al.  Curing kinetics, thermal, mechanical, and dielectric properties based on o-cresol formaldehyde epoxy resin with polyhedral oligomeric (N-aminoethyl-γ-amino propyl)silsesquioxane , 2011 .

[185]  Yaru Nie,et al.  Effect of carbon nanofiber (CNF) silanization on the properties of CNF/epoxy nanocomposites , 2011 .

[186]  P. Innocenzi,et al.  New Synthetic Route to (3-Glycidoxypropyl)trimethoxysilane-Based Hybrid Organic−Inorganic Materials , 1999 .

[187]  K. Zeng,et al.  Poly(ethylene imine) hybrids containing polyhedral oligomeric silsesquioxanes: Preparation, structure and properties , 2008 .

[188]  N. Leventis,et al.  Cross-linking Amine-Modified Silica Aerogels with Epoxies: Mechanically Strong Lightweight Porous Materials , 2005 .

[189]  T. Yoko,et al.  Hybrid Organic-Inorganic Sol-Gel Materials Based on Epoxy-Amine Systems , 2005 .

[190]  R. Nascimento,et al.  Modification of epoxy resin: a comparison of different types of elastomer , 2005 .

[191]  R. C. Ponterio,et al.  Epoxy-silica polymers as stone conservation materials , 2005 .

[192]  R. Laine,et al.  A Polyimide Nanocomposite from Octa(aminophenyl)silsesquioxane , 2003 .

[193]  I. Yilgor,et al.  Polysiloxane containing copolymers: A survey of recent developments , 1988 .

[194]  A. Slawin,et al.  Hydrocarbonylation reactions using alkylphosphine-containing dendrimers based on a polyhedral oligosilsesquioxane core , 2002 .

[195]  Yasumasa Morita.  Cationic polymerization of hydrogenated bisphenol‐A glycidyl ether with cycloaliphatic epoxy resin and its thermal discoloration , 2005 .

[196]  C. Ma,et al.  Thermal degradation and flammability of P/Si polysilsesquioxane epoxy nanocomposites , 2009 .

[197]  G. Wilkes,et al.  Silicone/amine resin hybrid materials as abrasion resistant coatings , 2001 .

[198]  S. Gido,et al.  Polymers and Copolymers Containing Covalently Bonded Polyhedral Oligomeric Silsesquioxanes Moieties , 2011 .

[199]  M Kagami,et al.  Fabrication of large-core, high-Δ optical waveguides in polymers. , 1995, Applied optics.

[200]  F. Babonneau,et al.  Unsupported SiO2-based organic–inorganicmembranes , 1997 .

[201]  A. Gu,et al.  Novel modification of cyanate ester by epoxidized polysiloxane , 2007 .

[202]  L. Barral,et al.  Epoxy/POSS organic–inorganic hybrids: ATR-FTIR and DSC studies , 2008 .

[203]  Thomas J. Pinnavaia,et al.  Interfacial Effects on the Reinforcement Properties of Polymer−Organoclay Nanocomposites , 1996 .

[204]  Masayuki Tobita,et al.  Development of an anisotropic conductive adhesive film (ACAF) from epoxy resins , 1995 .

[205]  J. Pernak,et al.  Hydrosilylation of functionalised olefins catalysed by rhodium siloxide complexes in ionic liquids , 2009 .

[206]  C. Chan,et al.  Novel nanocomposite of epoxy resin by introduced reactive and nanoporous material , 2007 .

[207]  A. Yee,et al.  Toughening mechanisms in elastomer-modified epoxies , 1989 .

[208]  M. J. O'brien,et al.  Amino Disiloxanes for CO2 Capture , 2011 .

[209]  Q. Xie,et al.  Synthesis and properties of poly(urethane‐imide) diacid/epoxy composites cured with an aziridine system , 2009 .

[210]  Thomas J. Pinnavaia,et al.  Hybrid Organic−Inorganic Nanocomposites: Exfoliation of Magadiite Nanolayers in an Elastomeric Epoxy Polymer , 1998 .

[211]  J. Crivello.  The discovery and development of onium salt cationic photoinitiators , 1999 .

[212]  Kiyohito Koyama,et al.  Viscoelastic and Mechanical Properties of Epoxy/Multifunctional Polyhedral Oligomeric Silsesquioxane Nanocomposites and Epoxy/Ladderlike Polyphenylsilsesquioxane Blends , 2001 .

[213]  Jiangxuan Song,et al.  Properties of alkoxysilane functionalized polycaprolactone/polydimethylsiloxane‐modified epoxy resin composites: Effect of curing temperature and compositions , 2009 .

[214]  E. Yıldız,et al.  Novel amine terminated elastomeric oligomers and their effects on properties of epoxy resins as a toughener , 2010 .

[215]  Tai‐Shung Chung,et al.  Surface free energy of ladderlike polyepoxysiloxane-diamine reaction systems , 2000 .

[216]  G. Hsiue,et al.  Synthesis, characterization, thermal and flame‐retardant properties of silicon‐based epoxy resins , 1999 .

[217]  J. Matisons,et al.  Polyhedral Oligomeric Silsesquioxanes: From Early and Strategic Development through to Materials Application , 2011 .

[218]  C. Su,et al.  Preparation, characterization and thermal properties of organic–inorganic composites involving epoxy and polyhedral oligomeric silsesquioxane (POSS) , 2010 .

[219]  J. Yeh,et al.  Preparation and anticorrosive properties of hybrid coatings based on epoxy-silica hybrid materials , 2009 .

[220]  Rongjie Yang,et al.  Pyrolysis and fire behaviour of epoxy resin composites based on a phosphorus-containing polyhedral oligomeric silsesquioxane (DOPO-POSS) , 2011 .

[221]  Dong-Kwon Kim,et al.  Preparation of Water-Repellent Glass by Sol-Gel Process Using Perfluoroalkylsilane and Tetraethoxysilane. , 2001, Journal of colloid and interface science.

[222]  M. Ochi,et al.  Thermomechanical properties and phase structure of epoxy/silica nano‐hybrid materials constructed from a linear silicone oligomer , 2005 .

[223]  Study on Excitation Voltage Effects of the Thermal Excitation Resonant Pressure Sensor , 2009 .

[224]  Hailiang Zhang,et al.  Preparation and characterization of epoxy-silica hybrid materials by the sol-gel process , 2005 .

[225]  Jin-Yeol Kim,et al.  Reliability and thermodynamic studies of an anisotropic conductive adhesive film (ACAF) prepared from epoxy/rubber resins , 2004 .

[226]  Thomas J. Pinnavaia,et al.  Mechanism of Clay Tactoid Exfoliation in Epoxy-Clay Nanocomposites , 1995 .

[227]  R. Narayan,et al.  Hydroxyl Terminated Hydrophilic Silanes , 2012, Silicon.

[228]  S. Ahmad,et al.  Synthesis, formulation, and characterization of siloxane‐modified epoxy‐based anticorrosive paints , 2006 .

[229]  M. Alagar,et al.  Mechanical, thermal and morphological behavior of bismaleimide modified polyurethane‐epoxy IPN matrices , 2003 .

[230]  Qian Ma,et al.  Nanostructured nanofibers based on PBT and POSS: Effect of POSS on the alignment and macromolecular orientation of the nanofibers , 2013 .

[231]  I. Jerman,et al.  Influence of amino functionalised POSS additive on the corrosion properties of (3-glycidoxypropyl)trimethoxysilane coatings on AA 2024 alloy , 2011 .

[232]  P. Cardiano,et al.  Epoxy-silica polymers as restoration materials. Part II , 2003 .

[233]  M. Cazacu,et al.  Ionic organic/inorganic materials. II. New linear and crosslinked poly(ethylene oxide)‐based ionomers by quaternization with chloroalkyl‐functionalized siloxanes , 2004 .

[234]  J. Baselga,et al.  Preparation of cycloaliphatic epoxy hybrids with non-conventional amine-curing agents , 2011 .

[235]  A. Afzal,et al.  A comprehensive study of the bicontinuous epoxy–silica hybrid polymers: I. Synthesis, characterization and glass transition , 2011 .

[236]  G. Pulla,et al.  Hydrophilic fumed silica/clay nanocomposites: Effect of silica/clay on performance , 2011 .

[237]  Chow Wen Shyang,et al.  Flexural and Morphological Properties of Epoxy/Glass Fibre/Silane- Treated Organo-montmorillonite Composites , 2010 .

[238]  Jiangbo Wang,et al.  Nonisothermal degradation kinetics for epoxy resin systems containing polymethylphenylsilsesquioxane , 2012 .

[239]  Y. Chiu,et al.  Thermal stability and degradation kinetics of novel organic/inorganic epoxy hybrid containing nitrogen/silicon/phosphorus by sol–gel method , 2007 .

[240]  M. Šlouf,et al.  A view from inside onto the surface of self-assembled nanocomposite coatings , 2008 .

[241]  B. S. Reddy,et al.  Synthesis and characterization of polyimide containing PEG/PDMS amphiphilic conetworks by hydrosilylation: Correlation between structure and properties , 2007 .

[242]  Jihui Wang,et al.  Synthesis and characterization of novel ultraviolet‐curing polyurethane acrylate/epoxy acrylate/SiO2 hybrid materials via sol–gel reaction , 2013 .

[243]  M. Cazacu,et al.  Poly(siloxaneimide)s 2. Polycondensation of some imidic diacid chlorides with aminoalkylsiloxanes , 2002 .

[244]  B. Novak,et al.  "Inverse" organic-inorganic composite materials. 2. Free-radical routes into nonshrinking sol-gel composites , 1991 .

[245]  J. Cano,et al.  Selection of a precursor of a monofunctional polyhedral oligomeric silsesquioxane reacted with aromatic diamines , 2004 .

[246]  Danqing Zhu,et al.  Corrosion Protection Properties of Organofunctional Silanes—An Overview , 2005 .

[247]  Roberto J. J. Williams,et al.  Synthesis of oligomeric silsesquioxanes functionalized with (β-carboxyl)ester groups and their use as modifiers of epoxy networks , 2007 .

[248]  Todd M. Osman,et al.  The commercialization of nanomaterials: Today and tomorrow , 2006 .

[249]  Congju Li,et al.  A novel approach to interpenetrating networks of epoxy resin and polydimethylsiloxane , 2007 .

[250]  L. Matějka.  Reinforcement of crosslinked rubbery epoxies by in-situ formed silica , 2000 .

[251]  R. Davidson,et al.  The photopolymerization of acrylates and methacrylates containing silicon , 1992 .

[252]  W. Cook,et al.  Hybrid UV-cured organic–inorganic IPNs , 2012 .

[253]  S. García-Garabal,et al.  Thermodegradation kinetics of a hybrid inorganic–organic epoxy system , 2005 .

[254]  Wen‐Chang Chen,et al.  Synthesis and characterization of organic–inorganic hybrid thin films from poly(acrylic) and monodispersed colloidal silica , 2003 .

[255]  M. Abad,et al.  Epoxy Networks Containing Large Mass Fractions of a Monofunctional Polyhedral Oligomeric Silsesquioxane (POSS) , 2003 .

[256]  J. Baselga,et al.  Reactive compatibilization of epoxy/polyorganosiloxane blends , 2003 .

[257]  G. McKenna,et al.  Thermal Pressure Coefficient of a Polyhedral Oligomeric Silsesquioxane (POSS)-Reinforced Epoxy Resin , 2010 .

[258]  M. Soucek,et al.  Synthesis of Amine and Epoxide Telechelic Siloxanes , 2008 .

[259]  Sixun Zheng,et al.  Inorganic–organic nanocomposites of polybenzoxazine with octa(propylglycidyl ether) polyhedral oligomeric silsesquioxane , 2006 .

[260]  R. Corriu,et al.  Ceramics and Nanostructures from Molecular Precursors. , 2000, Angewandte Chemie.

[261]  C. Kaynak,et al.  Modification of Epoxy by a Liquid Elastomer and Solid Rubber Particles , 2004 .

[262]  T. Hayakawa,et al.  Hydrosilylation Polymerization of Double-Decker-Shaped Silsesquioxane Having Hydrosilane with Diynes , 2006 .

[263]  S. Rai,et al.  Tensile, Flexural, Density and Void Content Studies on Granite Powder Filled Hydroxyl Terminated Polyurethane Toughened Epoxy Composite , 2008 .

[264]  L. Matějka,et al.  Formation and structure of the epoxy-silica hybrids , 1999 .

[265]  A. N. Khramov,et al.  Nanostructured sol–gel derived conversion coatings based on epoxy- and amino-silanes , 2003 .

[266]  P. D. Lickiss,et al.  Recent developments in the chemistry of cubic polyhedral oligosilsesquioxanes. , 2010, Chemical reviews.

[267]  Rongjie Yang,et al.  Novel flame retardancy effects of DOPO-POSS on epoxy resins , 2011 .

[268]  Joseph Green,et al.  A Review of Phosphorus-Containing Flame Retardants , 1992 .

[269]  Mi-Chang Chang,et al.  Highly porous interlayer dielectric for interconnect capacitance reduction , 1995, 1995 Symposium on VLSI Technology. Digest of Technical Papers.

[270]  M. Grunlan,et al.  Synthesis of 1,9-bis[glycidyloxypropyl]penta( 1'H, 1'H, 2'H, 2'H-perfluoroalkylmethylsiloxane)s and copolymerization with piperazine , 2004 .

[271]  A. A. Prabu,et al.  Thermal and Morphological Properties of Silicone‐Polyurethane‐Epoxy Intercrosslinked Matrix Materials , 2005 .

[272]  B. Hausnerova,et al.  Preparation and property evaluation of nanocomposites based on polyurethane‐modified epoxy/montmorillonite systems , 2010 .

[273]  J. Jang,et al.  Corrosion protection of epoxy-coated steel using different silane coupling agents , 1999 .

[274]  J. Macan,et al.  Study of cure kinetics of epoxy-silica organic–inorganic hybrid materials , 2004 .

[275]  L. Matějka,et al.  Epoxy Networks Reinforced with Polyhedral Oligomeric Silsesquioxanes (POSS). Structure and Morphology , 2004 .