Organic base‐catalyzed sol–gel route to prepare PMMA–silica hybrid materials

A series of sol–gel‐derived organic–inorganic hybrid materials that comprise organic poly(methyl methacrylate) (PMMA) and inorganic silica (SiO₂) was successfully prepared using aniline as an organic base catalyst to catalyze the sol–gel reactions of tetraethylorthosilicate (TEOS). Aniline was adopted not only as a catalyst but also as a dispersing agent during the preparation of the hybrid materials. The as‐prepared hybrid materials were then characterized using transmission electron microscopy, SEM/energy dispersive X‐ray spectroscopy and Fourier transform infrared spectroscopy. The characteristic temperatures (including T_d and T_g) of the hybrid materials slightly exceeded those of neat PMMA, as revealed from thermogravimetric analysis and differential scanning calorimetry evaluations. Studies of the protection against corrosion demonstrated that the hybrid coatings all improved the protection performance on cold‐rolled steel coupons relative to that of neat PMMA coatings, according to measurements of electrochemical corrosion parameters. Additionally, incorporating silica particles into the polymer may effectively reduce the gas permeability of the polymer membrane. Reducing the size of silica particles (at the same silica feeding) further improved the gas barrier property. Optical clarity studies indicated that introducing silica particles into the PMMA matrix may slightly reduce the optical clarity of the films/membranes, as determined by UV‐visible transmission spectroscopy. The contact angle of H₂O of the hybrid films increased with the amount of aniline. Copyright © 2006 Society of Chemical Industry Society of Chemical Industry     

Preparation and properties of organosoluble polyimide/silica hybrid materials by sol–gel process

Organosoluble polyimide/silica hybrid materials were prepared using the sol–gel process. The organosoluble polyimide was based on pyromellitic anhydride (PMDA) and 4,4′‐diamino‐3,3′‐dimethyldiphenylmethane (MMDA). The silica particle size in the hybrid is increased from 100–200 nm for the hybrid containing 5 wt % silica to 1–2 µm for the hybrid containing 20 wt % silica. The strength and the toughness of the hybrids are improved simultaneously when the silica content is below 10 wt %. As the silica content is increased, the glass transition temperature (T_g) of the hybrids is increased slightly. The thermal stability of the hybrids is improved obviously and their coefficients of thermal expansion are reduced. The hybrids are soluble in strong polar aprotic organic solvents when the silica content is below 5 wt %. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2977–2984, 1999     

Synthesis of polycarbonate‐silica nanocomposites from copolymerization of CO2 with allyl glycidyl ether,cyclohexene oxide,and sol‐gel

The copolymerization of carbon dioxide, allyl glycidyl ether, and cyclohexene oxide catalyzed by the system consisting of Y(CF₃CO₂)₃, Zn(Et)₂, and pyrogallol in the solvent of 1, 3‐dioxolane was performed in this study. The IR, ¹H NMR, and ¹³C‐NMR spectra, as well as the elemental analysis, indicated that the resulting copolymer was an alternating polycarbonate possessing more than 90% of carbonate units. The molecular weight could be as high as 1.5 × 10⁵, and the polydispersity index was 4.5. The resultant polycarbonate was found to effectively react with 3‐(trimethoxysilyl)propyl methacrylate via a free radical reaction to result in a precursor used in the sol‐gel process to synthesize a polycarbonate‐silica nanocomposite. The nanocomposites were characterized by SEM, ²⁹Si NMR, TGA, DSC, and UV–Vis. Silica particles with size less than 100 nm were found to disperse uniformly in the nanocomposites. It was also found that the thermal properties were dependent on the content of cyclohexene carbonate units. Both the thermal and mechanical properties of the resultant nanocomposites could be adjusted with silica content, while the transparency was comparable to the base copolymer even at high silica contents. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 750–757, 2005     

Preparation and properties of rigid‐rod polyimide/silica hybrid materials by sol–gel process

Polyimide (PI) materials with a low coefficient of thermal expansion (CTE) while still retaining high strength and toughness are desirable in various applications. In this study a sol–gel process was used to incorporate silica into homopolyimides and copolyimides with highly rigid structures in an attempt to pursue this aim. A number of highly rigid monomers were used, including pyromellitic dianhydride (PMDA), p‐phenylene diamine (PPA), m‐phenylene diamine (MPA), benzidine, 2,4‐diaminotoluene, and o‐toluidine. No homopolyimide flexible films were obtained. However, it was possible to obtain flexible films from the copolyimides. Therefore, a copolyimide based on PPA, MPA, and PMDA (PPA/MPA = 2/1 mol) was then chosen as the matrix to prepare the PI/silica hybrids. Flexible films were obtained when the silica content was below 40 wt %. The hybrid films possessed low in‐plane CTEs ranging from 14.9 to 31.1 ppm with the decrease of the silica content. The copolyimide film was strengthened and toughened with the introduction of an appropriate amount of silica. The thermal stability and the Young's modulus of the hybrid films increased with the increase of the silica content. The silica particle size was assessed by scanning electron microscopy and was about 100 nm for the hybrids containing 10 and 20 wt % silica and 200–500 nm for the hybrids containing 30 and 40 wt % silica. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 794–800, 2001     

Formation and structure of polyacrylamide–silica nanocomposites by sol–gel process

The formation of nanocomposites by the sol–gel reaction of tetraethoxysilane (TEOS) in polyacrylamide (PAAm) is studied. The nanocomposites are prepared in aqueous solution. Fourier transform IR spectroscopy shows that substantial hydrogen bonding occurs in the nanocomposites. The fracture surfaces of the nanocomposites are observed by atomic force microscopy (AFM) as a function of the TEOS content. The AFM images reveal that the PAAm–silica nanocomposite exhibits particle–matrix morphology. It is also found that aggregate formation is more dominant than the particle growth with the TEOS contents. The solution of composite precursor is also applied to spin coating. Furthermore, during the calcination there is an observable change in the silica networks, and then a microinterconnected structure is generated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1817–1823, 2002     

Synthesis and characterization of acrylic rubber/silica hybrid composites prepared by sol‐gel technique

The organic–inorganic hybrid composites comprising acrylic rubber and silica were synthesized through sol–gel technique at ambient temperature. The composites were generated through the acid‐catalyzed hydrolysis and subsequent condensations of inorganic tetraethoxysilane (TEOS) in the organic acrylic rubber (ACM), solvated in tetrahydrofuran. The morphology of the hybrid materials was investigated by using the transmission electron microscope (TEM) and scanning electron microscope (SEM). Transmission electron micrographs revealed that the silica particles, uniformly distributed over the rubber matrix, are of nanometer scale (20–90 nm). The scanning electron micrographs demonstrated the existence of silica frameworks dispersed in the rubber matrix of the hybrid composites. The X‐ray silicon mapping also supported that observation. There was no evidence of chemical interaction between the rubber phase and the dispersed inorganic phase, as confirmed from the infrared spectroscopic analysis and solubility measurements. Dynamic mechanical analysis indicated mechanical reinforcements within the hybrid composites. The composites containing in situ silica, formed by sol–gel technique, demonstrated superior tensile strengths and tensile modulus values at 300% elongations with increasing proportions of tetraethoxysilane. However, the improvements in physical properties with similar proportions of precipitated silica were not significant. Maximum tensile strength and tensile modulus were obtained when the rubber phase in the hybrid composites was cured with ammonium benzoate and hexamethylenediamine carbamate system, as compared with benzoyl peroxide cured system. Thermal stability of the hybrid composites was not improved appreciably with respect to the virgin rubber specimen. Residue analysis from thermogravimetric study together with infrared spectroscopic analysis indicated the presence of unhydrolyzed tetraethoxysilane in the hybrid composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2579–2589, 2004     

Thermal and optical properties of PMMA–titania hybrid materials prepared by sol‐gel approach with HEMA as coupling agent

A series of sol‐gel derived organic–inorganic hybrid materials consisting of organic poly(methyl methacrylate) (PMMA) and inorganic titania (TiO₂) were successfully synthesized by using 2‐hydroxyethyl methacrylate (HEMA) as coupling agent. In this work, HEMA is first copolymerized with methyl methacrylate monomer at specific feeding ratios by using benzoyl peroxide (BPO) as initiator. Subsequently, the as‐prepared copolymer (i.e., sol‐gel precursor) is then cohydrolyzed with various contents of titanium butoxide to afford chemical bondings to the forming titania networks to give a series of hybrid materials. Transparent organic–inorganic hybrid materials with different contents of titania are always achieved. Effects of the material composition on the thermal stability, optical properties, and morphology of neat copolymer and a series of hybrid materials, in the form of both coating and free‐standing film, are also studied by differential scanning calorimetry, thermogravimetric analysis, UV–Vis transmission spectra, refractometer, and atomic force microscopy, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 400–405, 2004     

High‐Tg,heat resistant epoxy–silica hybrids with a low content of silica generated by nonaqueous sol–gel process

The epoxy‐silica hybrids showing high T_g and thermal stability are prepared by the non‐aqueous sol–gel process initiated with borontriflouride monoethylamine. Tetramethoxysilane (TMOS) is used as a precursor of silica and 3‐glycidyloxypropyl trimethoxysilane as a coupling agent to strengthen the interphase interaction with an epoxy matrix. The basic factors governing the nonaqueous sol–gel process are studied in order to reveal the formation–structure–properties relationships and to optimize the hybrid composition as well as conditions of the nonaqueous synthesis. The formation of the hybrid, its structure, thermomechanical properties and thermal stability are followed by chemorheology experiments, NMR, DMA and TGA. The most efficient reinforcement of the epoxy network is achieved by the combination of both alkoxysilanes, showing synergy effects. The hybrids with a low content (～10 wt %) of the in situ generated silica exhibit dramatic increase in T_g and the high modulus, 335 MPa, up to the temperature 300°C. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40899.     

Synthesis and characterization of nanocomposite of polyimide–silica hybrid from nonaqueous sol–gel process

Polyimide–silica (PI–SiO₂) hybrids with a nanostructure was obtained using the nonaqueous sol–gel process by polycondensation of phenyltriethoxysilane in a polyamic acid solution. Self‐catalyzed hydrolysis of phenyl‐substituted akoxysilane and modification on the polyimide structure are applied and result in highly compatible PI–SiO₂ hybrids. Transparent PI–SiO₂ with a high silica content of about 45% was thus obtained. The prepared PI–SiO₂ films were characterized by infrared spectrometry, ²⁹Si‐NMR, thermogravimetric analysis, differential scanning calorimetry, and scanning electron microscopy. These characterizations showed the silica influence on the properties of the hybrid. The thermal expansion coefficient of the PI–SiO₂ and the temperature correlation were also established for probing the potential for application. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1609–1618, 2000     

Structure–property behavior of UV‐curable polyepoxy–acrylate hybrid materials prepared via sol–gel process

UV‐curable, hard, transparent organic/inorganic hybrid material with an improved mechanical property was prepared by the sol–gel process, based on a commonly used epoxy acrylate (EA) oligomeric resin. Systematic experiments were carried out to study the effect of the inorganic content, the acid content, and the content of a silane coupling agent on the property behavior of the hybrid materials. The structure of the hybrids were characterized by IR spectra and SEM observation. Results from thermogravimetric analysis (TGA) and mechanical measurement show that the properties of the hybrids differ with the changes of these variables. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1654–1659, 2003     

Properties and preparation of thermoplastic polyurethane/silica hybrid using sol–gel process

A thermoplastic polyurethane elastomer/silica hybrid (TPU/SiO₂) was prepared using the sol–gel process. This work was undertaken to investigate the thermal and physical properties of this type of hybrid by employing different catalyst systems during sol–gel processing. Two types of catalyst systems including acetic acid (HOAc) and hydrochloric acid (HCl) were used to prepare sol particles. The mixing of the sol solution and TPU solution was then carried out to form a TPU/silica hybrid. Fourier transform IR spectra and dynamic mechanical properties were recorded to depict the enhanced interfacial interaction. Thermogravimetric analysis was used to determine the actual silica content forming in the hybrid and to evaluate the heat resistance of the hybrid. Mechanical properties such as the tensile strength and cutting strength were investigated at various concentrations of in situ silica. The tensile strength increased at all concentrations of silica. In contrast, the cutting strength decreased, probably because of a reduction of the energy dissipation from silica as physical crosslinks. The HOAc catalyzed system showed better optical properties than the HCl catalyzed system. The fracture surface was revealed through scanning electron microscopy to observe the degree of dispersion of SiO₂, which in turn confirmed the results for the optical and mechanical properties. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1316–1325, 2005     

Organic‐acid‐catalyzed sol–gel route for preparing poly(methyl methacrylate)–silica hybrid materials

In this study, a series of organic–inorganic hybrid sol–gel materials consisting of a poly(methyl methacrylate) (PMMA) matrix and dispersed silica (SiO₂) particles were successfully prepared through an organic‐acid‐catalyzed sol–gel route with N‐methyl‐2‐pyrrolidone as the mixing solvent. The as‐synthesized PMMA–SiO₂ nanocomposites were subsequently characterized with Fourier transform infrared spectroscopy and transmission electron microscopy. The solid phase of organic camphor sulfonic acid was employed to catalyze the hydrolysis and condensation (i.e., sol–gel reactions) of tetraethyl orthosilicate in the PMMA matrix. The formation of the hybrid membranes was beneficial for the physical properties at low SiO₂ loadings, especially for enhanced mechanical strength and gas barrier properties, in comparison with the neat PMMA. The effects of material composition on the thermal stability, thermal conductivity, mechanical strength, molecular permeability, optical clarity, and surface morphology of the as‐prepared hybrid PMMA–SiO₂ nanocomposites in the form of membranes were investigated with thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, gas permeability analysis, ultraviolet–visible transmission spectroscopy, and atomic force microscopy, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Co‐poly(vinyl chloride‐vinyl acetate‐vinyl alcohol)‐silica nanocomposites from sol–gel process: Morphological,mechanical, and thermal investigations

Organic–inorganic nanocomposites consisting of co‐poly(vinyl chloride‐vinyl acetate‐vinyl alcohol) and silica were prepared via sol–gel process. Two types of hybrids were prepared, one in which interactions between hydroxyl group present in the copolymer chain and silanol groups of silica network were developed. In the second set, extensive chemical bonding between the phases was achieved through the reaction of hydroxyl groups on the copolymer chains with 3‐isocyanatopropyltriethoxysilane (ICTS). Hydrolysis and condensation of tetraethoxysilane and pendant ethoxy groups on the chain yielded inorganic network structure. Mechanical and thermal behaviors of the hybrid films were studied. Increase in Young's modulus, tensile strength, and toughness was observed up to 2.5 wt % silica content relative to the neat copolymer. The system in which ICTS was employed as binding agent, the tensile strength and toughness of hybrid films increased significantly as compared to the pure copolymer. Thermogravimetric analysis showed that these nanocomposite materials were stable up to 250°C. The glass transition temperature increases up to 2.5 wt % addition of silica in both the systems. Field emission scanning electron microscope results revealed uniform distribution of silica in the copolymer matrix. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Writing–erasing properties and characterizations of hybrid materials based on disperse red by sol–gel process

We investigated the synthesis and writing–erasing properties of three different hybrid materials (SGDR1, SGDR13 and SGDR19) based on disperse red by the sol–gel process. The sol–gel process was undergone using tetraethyl orthosilicate (TEOS) as a precursor. Optical properties of three hybrid materials are compared as structurally similar materials (SGDR1, SGDR13 and SGDR19). The diffraction efficiency, reversible photoinduced process and writing–erasing properties of hybrid materials were measured as a function of time. The diffraction efficiencies of SGDR1, SGDR13, and SGDR19 films were observed up to a level of 0.65%, 0.24%, and 0.99%, respectively. AFM view of the surface relief grating on the SGDR19 film showed a depth of 15 nm and a surface distance of 2.50 μm.     

Water absorption characteristics of hybrid materials incorporating tetrabutyl titanate with acrylic polymer via sol–gel process

The sol–gel process was used to prepare organic/inorganic hybrids utilizing a terpolymer of n‐butyl methacrylate, methyl methacrylate, and methacrylic acid as an organic phase and titanium tetrabutoxide as a precursor of the inorganic phase. Such hybrid materials may be of interest as primers for corrosion protection of metal substrates. In the absence of electrochemical influence, which is usually provided by anticorrosive pigments in current protective coatings, the barrier mechanism becomes one of the basic elements for protecting metals against atmospheric corrosion. In that context, we report the water uptake characteristics of hybrid films with titania content up to 16.3 wt %. The slow hydrolysis of butoxy, acetate, and carboxylate ligands, which becomes more and more obvious with an increase in titanium oxide cluster content, is found to produce a chemically driven force for water uptake in hybrids. The 4.6 wt % TiO₂ hybrid results in the best balance of properties with a far lower diffusion coefficient and nearly the same amount of water absorbed at saturation compared to the polymer matrix. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 92–102, 2005     

Effect of silane integrated sol–gel derived in situ silica on the properties of nitrile rubber

Nitrile rubber/silica composites are prepared by a sol–gel process using tetraethoxysilane as precursor in the presence of γ‐mercaptopropyltrimethoxysilane as a silane coupling agent. Here, we follow a novel processing route where the silica particles are generated inside the rubber matrix before compounding with vulcanizing ingredients. The effect of in situ generated silanized silica on the properties of the rubber composite has been evaluated by studying curing characteristics, morphology, mechanical and dynamic mechanical properties. Enhanced rubber–filler interaction of these composites is revealed from stress–strain studies and dynamic mechanical analysis. Excessive use of silane shows an adverse effect on mechanical properties of the composites. Due to finer dispersed state of the in situ silica and enhanced rubber–filler interaction, the mechanical properties and thermal stability of the composites are improved compared to corresponding ex situ processed composite. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40054.     

New epoxy/silica‐titania hybrid materials prepared by the sol–gel process

A new type of inorganic‐polymer hybrid materials of epoxy/silica‐titania had been prepared by incorporating grafted epoxy, which had been synthesized by epoxy and tetraethoxysilane (TEOS), with highly reactive TEOS and tetrabutyltitanate (TBT) by using the in situ sol–gel process. The grafted epoxy was confirmed by Fourier transform infrared spectroscopy (FT‐IR) and ¹H‐NMR spectroscopic technique. Results of FT‐IR spectroscopy and atomic force microscopy (AFM) demonstrated that epoxy chains have been covalently bonded to the surface of the SiO₂‐TiO₂ particles. The particles size of SiO₂‐TiO₂ are about 20–50 nm, as characterized by AFM. The experimental results showed that the glass‐transition temperatures and the modulus of the modified systems were higher than that of the unmodified system, and the impact strength was enhanced by two to three times compared with that of the neat epoxy. The morphological structure of impact fracture surface and the surface of the hybrid materials were observed by scanning electron microscopy and AFM, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1075–1081, 2006     

Mechanical,surface, and thermal properties of polyamideimide–polydimethylsiloxane nanocomposites fabricated by sol–gel process

Polyamideimide (PAI)–epoxysilane (coupling agent) composites were reacted with oligomeric polydimethylsiloxane (PDMS), a condensation product of difunctional silane, by using the sol–gel process, and were then dried into films. After this procedure, the surface, mechanical, and thermal properties were measured. The study showed that PDMS existed in the PAI matrix by the use of FTIR. With respect to mechanical properties, the maximum elongation and toughness were increased in the PAI with silane groups, although the maximum tensile strength was slightly decreased. In this experiment, PAI–30 wt % epoxysilane composite had the best mechanical properties. The intensive dispersion of the silane groups on the surface of PAI was confirmed through XPS measurement. As a function of the siloxane contents, the TGA curve shows less thermal stability in terms of their initial weight loss. However, in an oxygen atmosphere at about 700°C, the series of PAI–siloxane composites indicated a significant increase in char concentration. In the end, PAI with a relevant amount of silane groups was improved in both toughness and surface properties. This experiment showed that PDMS added to PAI had better properties than those of classical materials. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1774–1783, 2004     

Thermally and mechanically enhanced epoxy resin‐silica hybrid materials containing primary amine‐modified silica nanoparticles

In this article, a series of hybrid materials consisted of epoxy resin matrix and well‐dispersed amino‐modified silica (denoted by AMS) nanoparticles were successfully prepared. First of all, the AMS nanoparticles were synthesized by performing the conventional acid‐catalyzed sol–gel reactions of tetraethyl orthosilicate (TEOS), which acts as acceded sol–gel precursor in the presence of 3‐aminopropyl trimethoxysilane (APTES), a silane coupling agent molecules. The as‐prepared AMS nanoparticles were then characterized by FTIR, ¹³C‐NMR, and ²⁹Si‐NMR spectroscopy. Subsequently, a series of hybrid materials were prepared by performing in situ thermal ring‐opening polymerization reactions of epoxy resin in the presence of as‐prepared AMS nanoparticles and raw silica (RS) particles (i.e., pristine silica). AMS nanoparticles were found to show better dispersion capability in the polymer matrices than that of RS particles based on the morphological observation of transmission electron microscopy (TEM) study. The better dispersion capability of AMS nanoparticles in hybrid materials was found to lead enhanced thermal, mechanical properties, reduced moisture absorption, and gas permeability based on the measurements of thermo gravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and gas permeability analysis (GPA), respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Surface and barrier properties of hybrid nanocomposites containing silica and PEO segments

Hybrid organic–inorganic nanocomposites containing PEO segments linked to a methacrylate network were prepared through a dual‐curing process, which involved photopolymerization and condensation of alkoxysilane groups. A system based on an α,ω‐dimethacrylate PEO oligomer (BEMA 1400) added with methacryloyl‐oxypropyl‐trimethoxysilane (MEMO) and tetraethoxysilane (TEOS) was used. The surface properties of the obtained films were investigated through XPS analyses and contact angle measurements. A selective enrichment of the MEMO additive towards the outermost layers of the films was evidenced either in the presence or in the absence of TEOS. SEM analyses were performed on the cross section of the films coated on PET substrates, determining the film composition at different depth by EDS analysis. The Si content was found constant, moving from the PET surface towards the air–surface of the films. The barrier properties, with respect to oxygen, of the hybrid films coated on a PET substrate were measured. A decrease of the permeability and of the oxygen transmission rate using hybrid coatings was observed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 4107–4115, 2007