Incorporation of titanium dioxide particles into polymer matrix using block copolymer micelles for fabrication of high refractive and transparent organic–inorganic hybrid materials

We report a novel strategy for incorporation of titanium dioxide (TiO₂) particles into poly(methyl methacrylate) (PMMA) to exploit high refractive and transparent organic–inorganic hybrid materials. Formation of TiO₂ particles of around 20 nm was conducted within hydrophilic core of block copolymer micelles of poly(methyl methacrylate‐block‐acrylic acid) (PMMA‐b‐PAA) in toluene via sol–gel process from titanium isopropoxide and hydrochloric acid. Subsequently, incorporation of TiO₂ particles into PMMA matrix was carried out by casting toluene solution of TiO₂ precursor‐loaded copolymer micelles, prepared from PMMA₃₅₀‐b‐PAA₉₃ and the precursor of mole ratio Ti⁴⁺/carboxyl 4.0, and PMMA. Hybrid films of TiO₂/PMMA exhibited high transparency to achieve transmission over 87% at 500 nm at 30 wt % of TiO₂ content. The refractive index of resulting hybrid films at 633 nm linearly increased with TiO₂ content to attain 1.579 at 30 wt % TiO₂, which was 0.1 higher than that of PMMA. Cross‐sectional transmission electron microscope images of TiO₂/PMMA hybrid films showed existence of TiO₂ clusters less than 100 nm, which were probably formed by aggregation or agglutination of TiO₂ particles during a drying process. It was also observed that decomposition temperature of the hybrid films elevated with increasing TiO₂ content. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Poly(methyl methacrylate)/Methacryl-POSS Nanocomposites with Excellent Thermal Properties

Poly(methyl methacrylate) (PMMA) nanocomposites containing (methacryloxy)propyl polyhedral oligomeric silsesquioxane (methacryl‐POSS) were prepared by bulk‐polymerization process. The structures of the products were characterized by FTIR, solid‐state NMR, TEM, XRD, DSC, TGA, XPS and UV‐Vis spectra. The hybrid materials were found to be largely homogeneous. DSC and TGA results indicate that the thermal properties of PMMA nanocomposites are significantly improved. The glass transition temperature (T_g) and thermal decomposition temperature (T_dec) of the nanocomposites increased by 58 and 110°C, respectively. The bulk hybrid material maintains excellent optical transparency in visible region.     

EXAFS Investigations on Nanocomposites Composed of Surface-Modified Zirconium and Zirconium/Titanium Mixed Metal Oxo Clusters and Organic Polymers

Summary.  The surface-modified oxometallate clusters Zr₆(OH)₄O₄(OMc)₁₂, Ti₄Zr₄O₆(OBu)₄ (OMc)₁₆, and Ti₂Zr₄O₄(OBu)₂(OMc)₁₄ (OMc = methacrylate) as well as their nanocomposites with polystyrene, poly(methacrylic acid) and poly(methyl methacrylate) were investigated by EXAFS. Studies on the nanocomposites revealed that the structure of the cluster core is retained in the hybrid materials. Received October 23, 2001. Accepted November 12, 2001     

PMMA-SiO<Subscript>2</Subscript> organic–inorganic hybrid films: determination of dielectric characteristics

Organic–inorganic hybrid thin films have been prepared by a modified sol–gel route using tetraethyl orthosilicate as the inorganic (silica) source, methyl methacrylate (MMA) as the organic source, and 3-trimetoxysilylpropyl methacrylate as the coupling agent. The films were prepared by spin coating on Si (100) p-type substrates and subsequently heat-treated at 90 °C. Fourier transform infrared results reveal a set of absorption bands associated with the formation of both PMMA and SiO₂ phases in the hybrid films. Capacitance–voltage (C–V) characterization was carried out on metal-insulator-metal (MIM) and metal-insulator-semiconductor (MIS) structures, with the hybrid films as the insulator layer to evaluate the electrical properties. We present a detailed comparative analysis of the dielectric constant obtained from C–V characterization in the frequency range of 1 kHz–1 MHz. For the PMMA-SiO₂ hybrid material the dielectric constant values obtained were around 9.5 at 1 MHz which is superior to the values reported for thermally grown SiO₂ and pure PMMA materials. The interface state density for PMMA-SiO₂ on Si was approximately 10¹⁰ cm⁻², which is comparable to the standard SiO₂/Si structures. Due to the electrical behavior and low processing temperatures this hybrid dielectric is a very promising candidate for flexible electronic devices and its subsequent implementation does not require complex equipment.     

Synthesis and morphology of polyethylene‐block‐poly(methyl methacrylate) through the combination of metallocene catalysis with living radical polymerization

Polyethylene‐block‐poly(methyl methacrylate) (PE‐b‐PMMA) was successfully synthesized through the combination of metallocene catalysis with living radical polymerization. Terminally hydroxylated polyethylene, prepared by ethylene/allyl alcohol copolymerization with a specific zirconium metallocene/methylaluminoxane/triethylaluminum catalyst system, was treated with 2‐bromoisobutyryl bromide to produce terminally esterified polyethylene (PE‐Br). With the resulting PE‐Br as an initiator for transition‐metal‐mediated living radical polymerization, methyl methacrylate polymerization was subsequently performed with CuBr or RuCl₂(PPh₃)₃ as a catalyst. Then, PE‐b‐PMMA block copolymers of different poly(methyl methacrylate) (PMMA) contents were prepared. Transmission electron microscopy of the obtained block copolymers revealed unique morphological features that depended on the content of the PMMA segment. The block copolymer possessing 75 wt % PMMA contained 50–100‐nm spherical polyethylene lamellae uniformly dispersed in the PMMA matrix. Moreover, the PE‐b‐PMMA block copolymers effectively compatibilized homopolyethylene and homo‐PMMA at a nanometer level. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3965–3973, 2003     

Cross‐linking of poly(methyl methacrylate) by oxozirconate and oxotitanate clusters

Radical polymerization of methyl methacrylate with 0.5‐2 mol% of the (meth)acrylate‐substituted oxozirconium and oxotitanium clusters Zr₆(OH)₄O₄(OMc)₁₂ (OMc = methacrylate), Zr₄O₂(OMc)₁₂, Ti₆O₄(OEt)₈(OMc)₈ and Ti₄O₂(OPrⁱ)₆(OAcr)₆ (OAcr = acrylate) results in an efficient cross‐linking of the organic polymers. The obtained inorganic‐organic hybrid polymers exhibit a higher thermal stability due to inhibited depolymerization reactions. Contrary to undoped poly(methyl methacrylate), the cluster cross‐linked polymers are insoluble but swell in organic solvents. The solvent uptake upon swelling decreases with an increasing amount of polymerized cluster. The impedance spectra of PMMA doped with various proportions of Zr₄O₂(OMc)₁₂ show that the capacitance of the polymers decreases with an increasing proportion of the cluster. The polymer doped with 2 mol% of Zr₄O₂(OMc)₁₂ shows an increase in conductivity to 0.9·10⁻⁷ S·cm⁻¹ at 74°C.     

Improvement of the thermal stability of cluster‐crosslinked polystyrene and poly(methyl methacrylate) by optimization of the polymerization conditions

The polymerization conditions for polystyrene and poly(methyl methacrylate) crosslinked by 0.5 mol % of the cluster Zr₆O₄(OH)₄(methacrylate)₁₂ were optimized by applying a step polymerization procedure. The onset of thermal decomposition was thus increased up to about 50° for polystyrene and about 110° for poly(methyl methacrylate). The increase in thermal stability correlated with a higher char yield. The glass transition temperatures were also increased by about 15°. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6586–6591, 2005     

Red‐NIR Luminescent Hybrid Poly(methyl methacrylate) Containing Covalently Linked Octahedral Rhenium Metallic Clusters

The embedding of functional inorganic entities into polymer matrices has become an intense field of investigation in which the main challenges are to keep the added value of the inorganic entities while preventing their self‐aggregation within the organic matrix. We present a simple way to obtain a homogeneous highly red‐NIR luminescent hybrid copolymer that contains covalently bonded nanometric‐sized {Re₆} octahedral clusters. The [Re₆Seⁱ₈(OH)^a₆]^4? cluster complexes are primarily functionalized in two steps with tert‐butylpyridine (TBP) and methacrylic acid (MAC) to give neutral [Re₆Se₈(TBP)₄(MAC)₂] building blocks that are copolymerized with methyl methacrylate (MMA) either in solution or in bulk in the presence of azobisisobutyronitrile as an initiator. Several samples containing 0, 0.025, 0.05, and 0.1 wt % of functionalized {Re₆} clusters were prepared. As the {Re₆} cluster/MMA ratio is very low, the obtained copolymers keep the entire processability of pure poly(methyl methacrylate) (PMMA), as demonstrated by differential scanning calorimetry and thermogravimetric analysis. Voltammetric and luminescence studies also indicate that the intrinsic properties of the clusters are preserved within the polymer matrix. All the samples show a bright (emission quantum yield=0.07), broad, and structureless emission band, which extends from λ=600 nm to more than λ=950 nm, with the maximum wavelength centered around λ_em=710 nm either in solution or in the solid state. Moreover, the high stability of the incorporated inorganic phosphors prevents the material from photobleaching, and thus the luminescence properties are kept entirely even after nine months of ageing.     

Mechanical Properties of Organic-Inorganic Hybrid Materials Determined by Indentation Techniques

Summary. The mechanical properties of hybrid materials consisting of polystyrene (PS), which was cross-linked with different proportions of the multifunctional cluster Zr₆O₄(OH)₄(methacrylate)₁₂ (Zr6) were investigated. With the help of (micro)indentation and scratch testing, the influence of the Zr6 clusters on mechanical properties, such as hardness, stiffness, creep, craze initiation, and scratch resistance was shown. There was only a slight increase in hardness and in indentation modulus with higher cluster loadings. While this observation was in agreement with the compression behaviour of the materials, the tensile properties showed a much stronger dependence on the Zr6 content. With increasing cluster loading, an increase of craze initiation stress, as determined by ball indentation experiments, was found. Performing scratch testing with constant load, a reduction of pile-up and a stronger recovery were observed for the hybrid materials compared to the neat PS. Scratch tests with a constant increase of load showed an increase of the critical load for crack opening during scratching.     

Organic–inorganic hybrid materials. V. Dynamics and degradation of poly(methyl methacrylate) silica hybrids

Poly(methyl methacrylate)–silica hybrid materials (PMMA–SiO₂) were prepared by in situ polycondensation of alkoxysilane in the presence of trialkoxysilane‐functional PMMA. Infrared, differential scanning calorimetry, ²⁹Si and ¹³C nuclear magnetic resonance spectroscopy, and thermogravimetric analysis were used to study the PMMA–SiO₂ hybrids. The effects of the content and kind of the alkoxysilane on the dynamics and stability of the PMMA–SiO₂ hybrids were investigated in this study.The dynamics of SiO₂within hybrids were investigated with ²⁹Si–¹H cross‐polarization. The spin‐diffusion path length was on a nanometer scale estimated with the spin–lattice relaxation time in the rotating frame (T). The apparent activation energies for the degradation of the hybrids under air and nitrogen were evaluated by the van Krevelen method. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1972–1980, 2000     

Copolymers of methyl methacrylate and fluoroalkyl methacrylates: Effects of fluoroalkyl groups on the thermal and optical properties of the copolymers

Fluoroalkyl methacrylates, 2,2,2‐trifluoroethyl methacrylate ( 1 ), hexafluoroisopropyl methacrylate ( 2 ), 1,1,1,3,3,3‐hexafluoro‐2‐methyl‐2‐propyl methacrylate ( 3 ), and perfluoro t‐butyl methacrylate ( 4 ) were synthesized. Homopolymers and copolymers of these fluoroalkyl methacrylates with methyl methacrylate (MMA) were prepared and characterized. With the exception of the copolymers of MMA and 2,2,2‐trifluoroethyl methacrylate ( 1 ), the glass transition temperatures (T_gs) of the copolymers were found to deviate positively from the Gordon‐Taylor equation. The positive deviation from the Gordon‐Taylor equation could be accounted for by the dipole–dipole intrachain interaction between the methyl ester group and the fluoroalkyl ester group of the monomer units. These T_g values of the copolymers were found to fit with the Schneider equation. The fitting parameters in the Schneider equation were calculated, and R² values, the coefficients of determination, were almost 1.0. The refractive indices of the copolymers, measured at 532, 633, and 839 nm wavelengths, were lower than that of PMMA and showed a linear relationship with monomer composition in the copolymers. 2 and MMA have a tendency to polymerize in an alternating uniform monomer composition, resulting in less light scattering. This result suggests that the copolymer prepared with an equal molar ratio of 2 and MMA may have useful properties with applications in optical devices. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4748–4755, 2008     

Crystallization of titania ultra-fine particles from peroxotitanic acid in aqueous solution in the present of polymer and incorporation into poly(methyl methacylate) via dispersion in organic solvent

We report a novel strategy for incorporation of titanium dioxide (TiO₂) particles, which were crystallized from peroxotitanic acid in the presence of hydrophilic polymer by hydrothermal treatment in aqueous solution, into poly(methyl methacrylate) (PMMA) via dispersion into chloroform. Dispersion of TiO₂ particles into chloroform was achieved by solvent change from water to chloroform in aid of amphiphilic polymer dispersant, poly(N-vinyl pyrrolidone) (PVP), poly(N-vinyl pyrrolidone-co-methyl methacrylate) (PVP-co-PMMA), poly(N-vinyl pyrrolidone-block-methyl methacrylate) (PVP-b-PMMA) through azeotropical removal of water. Incorporation of TiO₂ particles into PMMA was carried out by a casting process of a mixture of TiO₂ particles dispersed with PVP₁₅₄-b-PMMA₁₅₆ in chloroform and PMMA on a glass substrate. Resultant hybrid film containing TiO₂ less than 10 wt.% showed high transparency in visible region attributable to homogeneous dispersion into PMMA matrix. The refractive index of the hybrid films increased with TiO₂ content and agreed with the calculated values.     

Radiation‐induced fabrication of polymer nanoporous materials from microphase‐separated structure of diblock copolymers as a template

Polymer nanoporous materials with periodic cylindrical holes were fabricated from microphase‐separated structure of diblock copolymers consisting of a radiation‐crosslinking polymer and a radiation‐degrading polymer through simultaneous crosslinking and degradation by γ‐irradiation. A polybutadiene‐block‐poly(methyl methacrylate) (PB‐b‐PMMA) diblock copolymer film that self‐assembles into hexagonally packed poly(methyl methacrylate) cylinders in polybutadiene matrix was irradiated with γ‐rays. Solubility test, IR spectroscopy, and TEM and SEM observations for this copolymer film in comparison with a polystyrene‐block‐poly(methyl methacrylate) diblock copolymer film revealed that poly(methyl methacrylate) domains were removed by γ‐irradiation and succeeding solvent washing to form cylindrical holes within polybutadiene matrix, which was rigidified by radiation crosslinking. Thus, it was demonstrated that nanoporous materials can be prepared by γ‐irradiation, maintaining the original structure of PB‐b‐PMMA diblock copolymer film. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5916–5922, 2007     

Synthesis and characterization of stereoregular poly(methyl methacrylate)–silica hybrid utilizing stereocomplex formation

Stereoregular poly(methyl methacrylate) (PMMA)–silica nanocomposites were prepared using stereocomplex formation between i-PMMA and s-PMMA by an in situ method. The methodology adopted here is the simultaneous formation of organic gel and inorganic gel, the so-called interpenetrating polymer network (IPN) formation. The gelation of i- and s-PMMA were performed by stereocomplex formation with the associated segments forming the crosslinking points in the presence of tetramethoxysilane (TMOS). The effects of the i/s-ratio, PMMA concentration, molecular weight, and solvent nature on the hybrid materials formation were addressed. The presence of the stereocomplex in the silica matrix was confirmed by DSC and solvent extraction methods. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 785–794, 2004     

High Refractive Index Films Prepared from Titanium Chloride and Methyl Methacrylate via a Non-Aqueous Sol–Gel Route

Poly(methylmethacrylate)/silica/titania films were prepared via a nonaqueous sol–gel route at ambient temperature, followed by spin-coating and multistep baking. The acrylic monomers used were methyl methacrylate (MMA) and 3-(trimethoxysilyl)propyl methacrylate (MSMA). Silicic acid and titanium(IV) chloride were used as the precursors of the inorganic component. FTIR results indicated the successful bonding between TiO₂ and SiO₂. TEM images suggested the silica/titania particles were well dispersed in the Poly(methyl methacrylate) (PMMA) matrix with the particles size smaller than 40 nm in our study. The refractive index and extinction coefficient were also studied. The refractive index of the hybrid increased with increasing the titania content, and the hybrid films showed high optical transparency in visible region.     

Mechanical Properties of Organic-Inorganic Hybrid Materials Determined by Indentation Techniques

The mechanical properties of hybrid materials consisting of polystyrene (PS), which was cross-linked with different proportions of the multifunctional cluster Zr₆O₄(OH)₄(methacrylate)₁₂ (Zr6) were investigated. With the help of (micro)indentation and scratch testing, the influence of the Zr6 clusters on mechanical properties, such as hardness, stiffness, creep, craze initiation, and scratch resistance was shown. There was only a slight increase in hardness and in indentation modulus with higher cluster loadings. While this observation was in agreement with the compression behaviour of the materials, the tensile properties showed a much stronger dependence on the Zr6 content. With increasing cluster loading, an increase of craze initiation stress, as determined by ball indentation experiments, was found. Performing scratch testing with constant load, a reduction of pile-up and a stronger recovery were observed for the hybrid materials compared to the neat PS. Scratch tests with a constant increase of load showed an increase of the critical load for crack opening during scratching.     

Molecular mobility in hybrid materials: A study of the 3(Trimethoxysilyl) propyl methacrylate-methyl methacrylate system

Hybrid glasses based on 3(Trimethoxysilyl) propyl methacrylate (TMSM) and methyl methacrylate (MMA) were successfully prepared by sol-gel process. The molecular mobility of hybrid materials was studied by mean of high resolution dynamic mechanical spectrometry technique. The results of hybrid materials were compared with those of polymethylmethacrylate (PMMA) prepared in the same conditions and interpreted in term of local or large-scale molecular motion.     

Optical properties of core/shell typed PMMA/CdS nanoparticles prepared by in situ and ex situ surfactant-free emulsion polymerization

Core/shell poly(methyl methacrylate)/cadmium sulfide (PMMA/CdS) nanoparticles were prepared by surfactant-free emulsion copolymerization with 2-(dimethylamino)ethyl methacrylate (DMAEMA) auxiliary monomer. According to the addition time of Cd²⁺ ions, the synthesis of the hybrid nanoparticles was conducted in in situ and ex situ techniques. The core/shell PMMA/CdS nanoparticles synthesized by the post-addition (ex situ) of Cd²⁺ ions showed a wide size distribution and interference fringes in the photoluminescence (PL) spectrum. However, these results were improved when the PMMA/CdS nanoparticles were synthesized in the presence of Cd²⁺ ions (in situ method). The in situ method made it possible to obtain monodisperse hybrid nanoparticles and fairly narrow band-gap emission.     

Synthesis and radiation degradation of vinyl polymers with fluorine: Search for improved lithographic resists

Homopolymers of methyl α-fluoroacrylate (MFA), trifluoroethyl methacrylate (TFEM), and hexafluoroisopropyl methacrylate (HFIM) were prepared, as were their methyl methacrylate (MMA) copolymers. Copolymers of vinylidene fluoride (VDF) and chlorotrifluoroethylene (CTFE) with MMA were also prepared. The radiation susceptibilities of these polymers were measured by the ⁶⁰Co γ-irradiation method, in which molecular weights were measured by membrane osmometry and gel permeation chromatography (GPC). All the copolymers degraded by predominant chain scission except poly(methyl α-fluoroacrylate), (PMFA), which crosslinks even at low doses (ca. 1 Mrad). The G_s - G_x and G_s values of the chain scissioning polymers and copolymers are higher than those of poly(methyl methacrylate) PMMA reference. The high susceptibility of PMFA homopolymer to crosslinking is in contrast to that of poly(methyl α-chloroacrylate), as we reported earlier. This effect is interpreted as resulting from extensive hydrogen fluoride and polyenlyl radical formation, which leads to facile crosslinking. However, incorporation of the MFA monomer unit causes the (22/78) MFA/MMA copolymer to degrade with a larger value of G_s that PMMA. Apparently a second-order process leads to crosslinking in PMFA and this is retarded in the copolymer. In the hehomopolymers of HFIM and TFEM and in the HFIM-MMA and TFEM-MMA copolymers the HFIM and TFEM components facilitate degradation with negligible crosslinking. The increased degradation susceptibility of VDF and CTFE copolymers with MMA over that of PMMA is attributed to processes at the VDF or CTFE components present in smaller concentrations (3-5 mole %) than the threshold levels (25-50% necessary for significant crosslinking).     

Ternary interpenetrating networks of polyurethane-poly(methyl methacrylate)-silica: Preparation by the sol–gel process and characterization of films

Novel organic/inorganic interpenetrating networks composed of polyurethane (PU), poly(methyl methacrylate) (PMMA) and silica generated from tetraethoxysilane (TEOS), were prepared by in situ bulk polymerization. Optically transparent films were successfully synthesized using 3-(trimethoxysilyl)propyl methacrylate (TMSPM) and isocyanatopropyl triethoxysilane (IPTES) as dual coupling agents. An experimental protocol was established to minimize undesirable side-reactions. According to infrared spectroscopic analysis and thermogravimetric studies of the hybrid materials, the degree of silica condensation was unfavorably affected by the presence of the organic components. Consequently, storage modulus (E′) at 25 °C, and hardness of the films decreased with increasing silica content.