Influence of octakis-functionalized polyhedral oligomeric silsesquioxanes on the physical properties of their polymer nanocomposites

Abstract We synthesized the polyhedral oligomeric silsesquioxane (POSS) derivatives octakis[dimethyl(phenethyl)siloxy]silsesquioxane (OS-POSS), octakis[dimethyl(4-acetoxy phenethyl)siloxy]silsesquioxane (OA-POSS), and octakis[dimethyl(4-hydroxyphenethyl)siloxy] silsesquioxane (OP-POSS) through hydrosilylation with octakis(dimethylsiloxy)silsesquioxane (Q 8 M 8 H ). To investigate the influence of these octuply functionalized POSS derivatives in polymer nanocomposites, we blended OP-POSS, OA-POSS, and OP-POSS with the homopolymer poly(ethylene oxide) (PEO) and characterized its resulting intermolecular interactions (e.g., hydroxyl–ether and carbonyl–ethylene oxide) using FTIR spectroscopy. The thermal properties of these blend systems were investigated using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The crystallization kinetics in the miscible binary blends of the crystalline polymer and these inorganic nanoparticles were also determined through DSC and optical microscopy (OM) analyses. Herein, we emphasize the effects of the functional groups on POSS nanocomposites on the crystallization kinetics of PEO. We found that OP-POSS/PEO blend had the highest thermal stability and lowest crystallization rate because its hydrogen bonding interactions (between its hydroxyl and ether units) were stronger than those (between carbonyl and methylene groups) in OA-POSS/PEO.

[1]  S. Kuo,et al.  Phase Behavior and Hydrogen Bonding in Ternary Polymer Blends of Phenolic Resin/Poly(ethylene oxide)/Poly(ε-caprolactone) , 2002 .

[2]  S. Kuo,et al.  Low-dielectric, nanoporous polyimide films prepared from PEO–POSS nanoparticles , 2005 .

[3]  L. Schadler,et al.  Controlling the thermomechanical properties of polymer nanocomposites by tailoring the polymer–particle interface , 2006 .

[4]  S. Kuo,et al.  Miscibility and Hydrogen Bonding in Blends of Poly(vinylphenol-co-methyl methacrylate) with Poly(ethylene oxide) , 2001 .

[5]  D. G. Thomas,et al.  889. A study of the supercooling of drops of some molecular liquids , 1952 .

[6]  Sixun Zheng,et al.  Star-shaped poly(ɛ-caprolactone) with polyhedral oligomeric silsesquioxane core , 2006 .

[7]  N. Platé,et al.  Coherence of thermal transitions in poly(N-vinyl pyrrolidone)–poly(ethylene glycol) compatible blends 1. Interrelations among the temperatures of melting, maximum cold crystallization rate and glass transition , 2000 .

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

[9]  R. Landel,et al.  The Temperature Dependence of Relaxation Mechanisms in Amorphous Polymers and Other Glass-Forming Liquids , 1955 .

[10]  S. Kuo,et al.  Polyimide and polyhedral oligomeric silsesquioxane nanocomposites for low-dielectric applications , 2005 .

[11]  Toshio Nishi,et al.  Melting Point Depression and Kinetic Effects of Cooling on Crystallization in Poly(vinylidene fluoride)-Poly(methyl methacrylate) Mixtures , 1975 .

[12]  Hui Zhou,et al.  Interpolymer Complexation and Miscibility Enhancement by Hydrogen Bonding , 1999 .

[13]  Z. Zhong,et al.  Crystallization kinetics of crosslinkable polymer complexes of novolac resin and poly(ethylene oxide) , 1999 .

[14]  F. Maurer,et al.  Positron Lifetime Distributions and Free Volume Parameters of PEO/PMMA Blends Determined with the Maximum Entropy Method , 1997 .

[15]  S. Kuo,et al.  Synthesis and characterization of amorphous octakis-functionalized polyhedral oligomeric silsesquioxanes for polymer nanocomposites , 2008 .

[16]  Zhiyong Zhou,et al.  Isothermal crystallization kinetics of polypropylene/POSS composites , 2008 .

[17]  M. Avrami Kinetics of Phase Change. I General Theory , 1939 .

[18]  R. Colby,et al.  Concentration fluctuation induced dynamic heterogeneities in polymer blends , 1996 .

[19]  T. Nishi,et al.  Spherulitic Crystallization in Compatible Blends of Poly(vinylidene fluoride) and Poly(methyl methacrylate) , 1977 .

[20]  J. E. Mark Some interesting things about polysiloxanes. , 2004, Accounts of chemical research.

[21]  H. Beck Heterogeneous nucleating agents for crystallization of vinylidence chloride–vinyl chloride copolymers , 1975 .

[22]  G. Slonimsky,et al.  Effect of molecular weight on the crystallization and morphology of poly (ethylene oxide) fractions , 2007 .

[23]  Emmanuel P. Giannelis,et al.  Polymer Layered Silicate Nanocomposites , 1996 .

[24]  J. J. Iruin,et al.  An attempt to predict phenoxy resin miscibility using a group contribution method , 1991 .

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

[26]  J. Hoffman Regime III crystallization in melt-crystallized polymers: The variable cluster model of chain folding , 1983 .

[27]  D. Keum,et al.  Organic−Inorganic Polymer Hybrids Using Polyoxazoline Initiated by Functionalized Silsesquioxane , 2003 .

[28]  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 .

[29]  T. Mandal,et al.  Miscibility and spherulite growth kinetics in the poly(ethylene oxide)/poly(benzyl methacrylate) system , 2000 .

[30]  P. Mather,et al.  Mechanical Relaxation and Microstructure of Poly(norbornyl-POSS) Copolymers , 1999 .

[31]  S. Kuo,et al.  Hydrogen bonding interactions and miscibility between phenolic resin and octa(acetoxystyryl) polyhedral oligomeric silsesquioxane (AS‐POSS) nanocomposites , 2006 .

[32]  Y. Chujo,et al.  Liquid‐crystalline organic–inorganic hybrid polymers with functionalized silsesquioxanes , 2001 .

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

[34]  S. Kuo,et al.  Influence of PMMA-Chain-End Tethered Polyhedral Oligomeric Silsesquioxanes on the Miscibility and Specific Interaction with Phenolic Blends , 2006 .

[35]  Chih-Feng Huang,et al.  Miscibility, Specific Interactions, and Spherulite Growth Rates of Binary Poly(acetoxystyrene)/Poly(ethylene oxide) Blends , 2004 .

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

[37]  T. Kondo,et al.  Interchain Hydrogen Bonds in Blend Films of Poly(vinyl alcohol) and Its Derivatives with Poly(ethylene oxide) , 1999 .

[38]  N. Hannay,et al.  Treatise on solid state chemistry , 1973 .

[39]  S. Kuo,et al.  Solid State and Solution Self-Assembly of Helical Polypeptides Tethered to Polyhedral Oligomeric Silsesquioxanes , 2009 .

[40]  K. O'driscoll,et al.  Chain-length dependence of the glass transition temperature , 1991 .

[41]  S. Kuo,et al.  Effect of an Organically Modified Nanoclay on Low-Surface-Energy Materials of Polybenzoxazine , 2008 .

[42]  P. Painter,et al.  Specific interactions and miscibility of polymer blends , 1995 .

[43]  Jinghua Yin,et al.  Mixing enthalpy and phase behavior of PEO/PVAc blends , 1999 .

[44]  S. Kuo,et al.  Miscibility, specific interactions, and self‐assembly behavior of phenolic/polyhedral oligomeric silsesquioxane hybrids , 2004 .

[45]  S. Kuo,et al.  Miscibility and hydrogen-bonding behavior in organic/inorganic polymer hybrids containing octaphenol polyhedral oligomeric silsesquioxane. , 2008, The journal of physical chemistry. B.

[46]  Hongyao Xu,et al.  Preparations, Thermal Properties, and Tg Increase Mechanism of Inorganic/Organic Hybrid Polymers Based on Polyhedral Oligomeric Silsesquioxanes , 2002 .

[47]  S. Kuo,et al.  Synthesis, thermal properties, and specific interactions of high Tg increase in poly(2,6-dimethyl-1,4-phenylene oxide)-block-polystyrene copolymers , 2005 .

[48]  S. Kuo,et al.  Thermal and surface properties of phenolic nanocomposites containing octaphenol polyhedral oligomeric silsesquioxane , 2006 .

[49]  Zhigang Wang,et al.  Crystallization kinetics in mixtures of poly(ε-caprolactone) and poly(styrene-co-acrylonitrile) , 1997 .

[50]  T. Russell,et al.  Kinetics of crystallization in semicrystalline/amorphous polymer mixtures , 1986 .

[51]  Isao Noda,et al.  Two-dimensional correlation spectroscopy , 2002 .

[52]  R. Laine,et al.  Synthesis and Characterization of Liquid Crystalline Silsesquioxanes , 2001 .

[53]  G. Camino,et al.  Polypropylene–polyhedral oligomeric silsesquioxanes (POSS) nanocomposites , 2005 .

[54]  S. Kuo,et al.  Glass transition temperatures of poly(hydroxystyrene-co-vinylpyrrolidone-co-isobutylstyryl polyhedral oligosilsesquioxanes) , 2002 .

[55]  S. Kuo,et al.  Effect of hydrogen bonding strength on the microstructure and crystallization behavior of crystalline polymer blends , 2003 .

[56]  Emmanuel P. Giannelis,et al.  Compatibilizing Poly(vinylidene fluoride)/Nylon-6 Blends with Nanoclay , 2007 .

[57]  S. Kuo,et al.  Crystallization kinetics and morphology of binary phenolic/poly(?-caprolactone) blends , 2004 .

[58]  S. Kuo,et al.  Self-Assembled Fernlike Microstructures of Polyhedral Oligomeric Silsesquioxane/Gold Nanoparticle Hybrids , 2009 .

[59]  Sandra J. Tomczak,et al.  Developments in nanoscience: polyhedral oligomeric silsesquioxane (POSS)-polymers , 2004 .

[60]  Patrick T. Mather,et al.  Amphiphilic Telechelics Incorporating Polyhedral Oligosilsesquioxane: 1. Synthesis and Characterization , 2002 .

[61]  S. Kuo,et al.  Synthesis of the Organic/Inorganic Hybrid Star Polymers and Their Inclusion Complexes with Cyclodextrins , 2005 .

[62]  P. Mather,et al.  Vertex Group Effects in Entangled Polystyrene−Polyhedral Oligosilsesquioxane (POSS) Copolymers , 2009 .

[63]  P. D. Lickiss,et al.  Chapter 1 – Fully Condensed Polyhedral Oligosilsesquioxanes (POSS): From Synthesis to Application , 2008 .

[64]  S. Wunder,et al.  Oligomeric Poly(ethylene oxide)-Functionalized Silsesquioxanes: Interfacial Effects on Tg, Tm, and ΔHm , 2002 .

[65]  R. Farris,et al.  Novel polyolefin nanocomposites: Synthesis and characterizations of metallocene-catalyzed polyolefin polyhedral oligomeric silsesquioxane copolymers , 2001 .

[66]  B. S. Butola,et al.  Polymeric Nanocomposites—Polyhedral Oligomeric Silsesquioxanes (POSS) as Hybrid Nanofiller , 2004 .

[67]  S. Kuo,et al.  Surface modification of gold nanoparticles with polyhedral oligomeric silsesquioxane and incorporation within polymer matrices , 2009 .

[68]  Isao Noda,et al.  Two-dimensional infrared spectroscopy , 1989 .