Preparation and performance of nano‐SiO2 stabilized Pickering emulsion type sizing agent for glass fiber

The nano‐SiO₂ particles modified by silane coupling agent A‐1100 were used for preparing the vinyl ester resin (VE) Pickering emulsion. The stable emulsion could be served as the film former of sizing agent for glass fiber (GF). The influence of the wettability and the addition amount of nano‐SiO₂ on the stability of film former emulsion was explored. The effect of nano‐SiO₂ Pickering emulsion type sizing agent on the properties of GF was investigated. SEM images show that there existed a layer of sizing agent film with nano‐SiO₂ particles evenly on the GF surface. The abrasion resistance of the sized GF reached 3,579 times and the stiffness was 69 mm. The strand integrity also performed well. The fracture strength of GF bundles treated by Pickering emulsion type sizing agent increased by 28.6% to 0.504 N/Tex compared with that of the unsized GF bundles. The interlaminar shear strength (ILSS) of GF/VE composites sized by self‐made sizing agent which contained nano‐SiO₂ has improved, compared to the unsized GF reinforced VE composite. POLYM. COMPOS., 37:334–341, 2016. © 2014 Society of Plastics Engineers     

Polymethacrylic acid/Na-montmorillonite/SiO<Subscript>2</Subscript> nanoparticle composites structures and thermal properties

In this article, polymethacrylic acid/Na-montmorillonite/SiO₂ nanoparticle (PMAA/Na-MMT/SiO₂) composites were prepared via in situ polymerization. Fourier transform infrared spectroscopy (FTIR) indicated that the polymerization of SiO₂ nanoparticle and MAA have been taken place. X-ray diffraction (XRD) results suggest that Na-MMT layers are exfoliated during the polymerization process. As evidenced by the transmission electron microscopy (TEM), the Na-MMT layers and SiO₂ nanoparticles exhibit good dispersion in the polymer matrix. It was found that the PMAA/Na-MMT/SiO₂ composite exhibit considerably enhanced thermal properties compared with the PMAA/Na-MMT.     

改性纳米SiO2/聚氨酯-含氟丙烯酸酯无皂乳液合成及其胶膜性能表征

引言水性聚氨酯相对溶剂型聚氨酯具有不燃、气味小、不污染环境等优点[1-2],从而广泛用于涂料[3]、胶黏剂[4]、油墨[5]等领域。目前,常用于软包装领域的薄膜主要是表面能很低的非极性膜,而水性聚氨酯胶黏剂具有较高的表面自由能,对非极性膜的润湿性差,因此需要降低水性聚氨酯的表面张力,达到润湿非极性膜的目的。     

Ionic liquid mediated synthesis of silica/polystyrene core–shell composite nanospheres by radical dispersion polymerization

This report describes the novel preparation of silica/polystyrene (SiO₂/PS) core–shell composite nanospheres by in situ radical dispersion polymerization in an ionic liquid (IL). Silica nanoparticles were first surface modified by the silane coupling agent methacryloxypropyltrimethoxysilane (MPTMS), which is capable of copolymerizing with styrene and provided a reactive CC bond. Transmission electron microscopy (TEM) revealed core–shell morphology with smooth surfaces. X-ray photoelectron spectroscopy (XPS) analysis demonstrated that almost all of the SiO₂ nanoparticles were encapsulated by the polymer. The composite particles were also analyzed by FT-IR spectroscopy and thermogravimetric analysis (TGA). In principle, this simple and environmentally-friendly synthetic procedure can be employed to prepare other inorganic oxide-containing polymer composites.     

Hierarchical ordered meso/macroporous H<Subscript>3</Subscript>PW<Subscript>12</Subscript>O<Subscript>40</Subscript>/SiO<Subscript>2</Subscript> catalysts with superior oxidative desulfurization activity

A series of phosphotungstic acid (HPW)/SiO₂ materials with hierarchical meso/macroporous structure were synthesized by evaporation-induced self-assembly method (EISA), using nonionic surfactant (P123) and polystyrene (PS) spheres as templates. SEM images displayed uniform macropores with an average pore size of 210 nm. TEM, small-angle XRD and N₂ adsorption–desorption isotherms confirmed the existence of the ordered mesoporous structures, embedded in the wall of macropores. The wild-angle XRD and FT-IR spectra proved Keggin-type HPW dispersed homogeneously in the silica framework. With the amount of added PS spheres, the density of the macropores increased, the hierarchically ordered porous HPW/SiO₂ possessed two-dimensional (2D) hexagonal (p6mm) mesostructures and uniform periodic macropores. The ODS catalytic activity of these samples were tested, the result showed that the meso/macroporous HPW/SiO₂ catalyst with proper PS beads usage displayed much higher catalytic activity than other catalysts. In addition, the reusability of the meso/macroporous HPW/SiO₂ catalyst was investigated, the activity of catalyst has not obviously decreased even after eight times.     

Facile fabrication of superhydrophobic raspberry‐like SIO2/polystyrene composite particles

A facile and novel strategy was reported on the fabrication of raspberry‐like SiO₂/polystyrene (SiO₂/PS) composite particles by emulsion polymerization in the presence of vinyl‐functionalized silica (vinyl‐SiO₂) particles, which were prepared via a one‐step sol–gel process using vinyltriethoxysilane as the precursor. The submicron vinyl‐SiO₂ particles were used as the core, and nanosized PS particles were then adsorbed onto the vinyl‐SiO₂ particles to form raspberry‐like composite particles during the polymerization process. The composition, morphology, and structure of the vinyl‐SiO₂ particles and the SiO₂/PS hybrid particles were characterized by thermogravimetric analysis, nuclear magnetic resonance, Fourier transform infrared spectroscopy, transmission electron microscopy, and scanning electron microscopy. Superhydrophobic surface can be constructed by directly depositing the raspberry‐like SiO₂/PS composite particles on glass substrate, and the water contact angle can be adjusted by the styrene/SiO₂ weight ratio. In addition, the superhydrophobic film possessed a strong adhesive force to pin water droplet on the surface even when the film was turned upside down. POLYM. COMPOS., 2013. © 2012 Society of Plastics Engineers     

Suspension polymerization based on inverse Pickering emulsion droplets for thermo-sensitive hybrid microcapsules with tunable supracolloidal structures

Polymerization using Pickering emulsion droplets as reaction vessels is being developed to become a powerful tool for fabrication of hybrid polymer particles with supracolloidal structures. In this paper, two kinds of thermo-sensitive hybrid poly(N-isopropylacrylamide) (PNIPAm) microcapsules with supracolloidal structures were successfully prepared from suspension polymerization stabilized by SiO₂ nanoparticles based on inverse Pickering emulsion droplets. SiO₂ nanoparticles could self-assemble at liquid-liquid interfaces to form stable water-in-oil inverse Pickering emulsion. NIPAm monomers dissolving in suspended aqueous droplets were subsequently polymerized at different temperatures. The hollow microcapsules with SiO₂/PNIPAm nanocomposite shells were obtained when the reaction temperature was above the lower critical solution temperature (LCST) of PNIPAm. While the core-shell microcapsules with SiO₂ nanoparticles' shells and PNIPAm gel cores were produced when the polymerization was conducted at the temperature lower than LCST using UV light radiation. The supracolloidal structures with different cores could be tuned by simply changing reaction temperature, which was confirmed by confocal laser scanning microscopy and scanning electron microscopy. The interesting properties of both microcapsules were their ability of reversibly swelling during drying/wetting cycles and responsive to temperature stimulus. Such functional microcapsules may find applications in double control release system due to the presence of the supracolloidal structures and thermo-sensitivity.     

Synthesis of Polystyrene/Hydrophobic SiO2 Composite Particles via Oil‐in‐Water Pickering Emulsion Polymerization

The aim of this work is to present a facile Pickering emulsion polymerization method for the synthesis of submicron polystyrene/SiO₂ core/shell composite particles. The commercial hydrophobic SiO₂ nanoparticles were used as stabilizing agent for creating a stable oil‐in‐water emulsion. Although the adsorption of hydrophobic SiO₂ nanoparticles in the emulsion system was unfavorable in terms of thermodynamics, by ultrasound treatment, self‐assembly of hydrophobic SiO₂ nanoparticles effectively stabilized oil‐in‐water Pickering emulsions during polymerization. Using 3 wt.% SiO₂ nanoparticles (based on styrene monomer) and 1:10 volume ratio of styrene monomer:water, the composite particles having average size of 790 nm and relatively narrow particles distribution were produced. With decreasing the volume ratio, smaller composite particles were created. Results from scanning electron microscope revealed that SiO₂ nanoparticles were located exclusively at the surface of the polystyrene latex particles. The SiO₂ content, determined by thermogravimetric analysis, was 12.6 wt.% in the composite particles. The route reported here may be used for the preparation of other composite nanostructures. POLYM. ENG. SCI., 59:E195–E199, 2019. © 2018 Society of Plastics Engineers     

Hydrophilicity and crystallization behavior of PVDF/PMMA/TiO<Subscript>2</Subscript>(SiO<Subscript>2</Subscript>) composites prepared by in situ polymerization

Composites with enhanced hydrophilicity were prepared by adding TiO₂ or SiO₂ nanoparticles during the in situ polymerization of methyl methacrylate (MMA) in poly(vinylidene fluoride) (PVDF). The hydrophilicities of the PVDF/PMMA/TiO₂(SiO₂) composites generated in this manner were characterized by contact angle measurements and atomic force microscopy (AFM). The hydrophilicity was dependent on nanoparticle content; it gradually increased with increasing TiO₂ (or SiO₂) content when the TiO₂ (or SiO₂) content was no more than 4 wt% of PVDF. A homogeneous dispersion of the TiO₂ (or SiO₂) nanoparticles in the composite matrix was observed in scanning electron microscope (SEM) images. Based on Fourier transform infrared (FTIR) spectra and wide angle X-ray diffraction (WAXD) analyses, the crystalline phase composition of PVDF was not influenced by the addition of TiO₂ (or SiO₂); PVDF crystallized predominantly in the α phase after in situ polymerization. Nevertheless, the nanoparticles can promote the formation of the β phase of PVDF in composites; the β-phase content increased with increasing TiO₂ content, while it was almost independent of SiO₂ content.     

二氧化钛纳米管稳定Pickering乳液制备PS/TiO2纳米管复合微球

利用γ-甲基丙烯酰氧基丙基三甲氧基硅烷（KH-570）,对水热法制备的TiO₂纳米管进行了表面改性,并用改性的纳米管为稳定剂,采用Pickering乳液聚合法制备了聚苯乙烯/TiO₂纳米管复合微球。采用红外光谱（IR）、光学显微镜、高分辨透射电镜（HRTEM）、高分辨扫描电子显微镜（FESEM）、X射线光电子能谱（XPS）等分析手段,对改性前后TiO₂纳米管以及复合微球的结构和形貌进行了表征,用三相接触角仪测试并优化了TiO₂纳米管的表面润湿性。研究结果表明,当m_KH-570/m_TiO2=15%时,改性TiO₂纳米管表面润湿性最佳,能很好地稳定Pickering乳液聚合,聚合后可以得到壳层为致密均匀TiO₂纳米管,核为聚苯乙烯的复合微球。     

Pickering emulsion polymerization: Preparation of polystyrene/nano-SiO2 composite microspheres with core-shell structure

Polystyrene/nano-SiO₂ composite microspheres (PS/nano-SiO₂) with core-shell structure were successfully synthesized in a Pickering emulsion route using nano-SiO₂ particles as stabilizers, which were organically modified by methacryloxypropyltrimethoxysilane (MPTMS) which containing a reactive CC bond. The products were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), fourier transformation infrared spectrum (FTIR), thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). In addition, bare PS spheres could also be obtained by changing synthetic conditions. It was found that the morphology of the resulting products depends on particle concentration, particle wettability and pH value of particle dispersion. A possible mechanism for the formation of the composites with different morphologies is proposed.     

Synthesis,characterization and electrical properties of polypyrrole/V<Subscript>2</Subscript>O<Subscript>5</Subscript> composites

Polypyrrole (PPy) and its composites with vanadium pentoxide (V₂O₅) were synthesized in aqueous medium by chemical oxidation polymerization using FeCl₃·6H₂O as an oxidant. The materials were characterized by Fourier transform infrared (FT-IR) spectroscopy, X-ray diffractometry (XRD), thermogravimetry analyzer (TGA), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), UV/visible spectroscopic techniques and LCR-meter. The FT-IR results confirmed the successful synthesis of PPy and PPy/V₂O₅ composites. The XRD study showed the amorphous and crystalline nature of PPy and PPy/V₂O₅ composites, respectively. The TGA analysis showed slight increase in the thermal stability of the composites. The SEM data verified the porous nature of PPy and the composites. The UV/visible spectrometry confirmed the doping of PPy in composites. The electrical properties of the materials displayed their semiconducting nature. The resistance of the samples was found to be dependent on temperature and the contents of V₂O₅ in the composites.     

Synthesis,characterization, and properties of polystyrene/SiO2 hybrid materials via sol–gel process

Isocyanate‐functionalized polystyrene (P(St‐co‐TMI)) was successfully synthesized by solution free radical polymerization, which was then used to react with (3‐aminopropyl) triethoxysilane (APTES) to prepare a precursor of polystyrene/inorganic composites (PS/SiO₂). To obtain PS/SiO₂ composites with chemical bond, the precursor was mixed with triethoxysilane (TEOS) under the sol–gel reaction condition. The chemical bond between the PS and SiO₂ particles made the crosslink network more stable and avoided aggregation compared with the physical connection and barely mechanical mixing. The Fourier transform infrared (FT‐IR) results indicate that the isocyanate group ( NCO) was completely reacted with APTES. The field‐emission scanning electron microscopy results show that the morphology of composites and the distribution of the particles, which exhibit good compatibility between organic and inorganic phases, and the inorganic particles show good spatial uniformity. The differential scanning calorimetry shows that the glass transition temperature (T_g) of the PS/SiO₂ composites was shifted to high temperature when the amount of APTES increased. The thermal degradation temperature of the PS/SiO₂ composites increases with the increasing of APTES content. Master curves at 200°C are constructed for the storage and loss modulus as well as complex viscosity. POLYM. COMPOS. 36:482–488, 2015. © 2014 Society of Plastics Engineers     

Preparation of styrene‐acrylic emulsion by using nano‐SiO2 as seeds

A styrene‐acrylic/SiO₂ nanoparticle composite emulsion was prepared by using SiO₂ nanoparticles as seeds. The effect of factors such as the level of nano‐SiO₂, reaction temperature and ultrasound treatment of nano‐SiO₂ on the stability of the polymerization reaction was investigated. Water‐resistance of the emulsion was measured. The level of nano‐SiO₂ in the emulsion was determined by inductively coupled plasma (ICP) spectrometry. The particle morphology of the emulsion with nano‐SiO₂ was observed with transmission electron microscopy (TEM). The kinetics of the polymerization was also studied at various temperatures and various levels of nano‐SiO₂. They showed that the level of nano‐SiO₂ and reaction temperature had a great influence on the monomer conversion, particle size, coagulum content and viscosity of the emulsion. Nano‐SiO₂ treated by ultrasonics can increase the coagulum content greatly, but it does not improve the water resistance of the emulsion. The level of nano‐SiO₂ in the emulsion was lower than the theoretical value. The reaction kinetics indicated that the level of nano‐SiO₂ had less influence on the reaction rate than the reaction temperature. Even a small amount of nano‐SiO₂ can decrease the reaction rate. Copyright © 2004 Society of Chemical Industry     

Controllable synthesis of EU-1 molecular sieve with high SiO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> ratios in thermodynamic stable sol system

A new green chemical route was designed in this paper for the synthesis of high-silica EU-1 molecular sieve in TEAOH–SiO₂–Al₂O₃–HMBr₂–H₂O system in which tetraethylammonium hydroxide (TEAOH) substituted for sodium hydroxide (NaOH) as an alkali source. The physicochemical properties of the synthesized samples characterized by such means as X-ray powder diffraction (XRD), electrophoresis apparatus, precise pH meter, scanning electron microscope, Fourier infrared spectrometer (FT-IR), thermo gravimetric analyzer (TG) and temperature programmed desorption (NH₃-TPD). The research results showed that the SiO₂/Al₂O₃ ratio of EU-1 molecular sieve could reach 706 with TEAOH as an alkali source. The SiO₂/Al₂O₃ ratio of the product was improved greatly to 1046 with the template agent increasing. The new synthetic route has also significantly expanded the synthetic phase region. The absolute value of zeta potential of the TEAOH sol system was obviously higher than that of the NaOH sol system, indicating the thermodynamic stability of the former sol system was higher and better for the synthesis of pure high-silica EU-1 molecular sieve. The FT-IR spectra and TG/DTG diagrams of products indicated that TEA⁺ occluded in the final products could balance electronegative framework. The amount of strong, weak and the total acidity reduced with the increase of SiO₂/Al₂O₃ ratio. The catalytic results of methanol-to-hydrocarbon demonstrated that the molecular sieve prepared by the new method has better catalytic performance.     

Synthesis and characterization of core‐shell SiO2 nanoparticles/poly(3‐aminophenylboronic acid) composites

SiO₂/Poly(3‐aminophenylboronic acid) (PAPBA) composites were synthesized under different experimental conditions, using ultrasonic irradiation method. Polymerization was carried out in the presence of sodium fluoride and D ‐fructose to anchor 3‐aminophenylboronic acid groups on to SiO₂ surface. The SiO₂/PAPBA nanocomposite prepared by NaF and D ‐fructose in the polymerization medium was found to show different morphology, electrical properties, thermal behavior and structural characterization in comparison to the nanocomposites prepared under other conditions. Ultrasonic irradiation minimizes the aggregation of nanosilica and promotes anchoring of PAPBA units over SiO₂ surface. The morphology of PAPBA/ SiO₂ nanocomposite was investigated by using transmission electron microscopy, UV‐visible spectroscopy; thermogravimetric analysis, Fourier transform infrared spectroscopy, and X‐ray diffraction analysis were used for characterization. Transmission electron microscope of the nanocomposites observation shows that SiO₂/PAPBA composite, prepared with D ‐fructose and NaF under ultrasonication has a core–shell morphology. The thermal and crystalline properties of core‐shell SiO₂/PAPBA nanocomposite was prepared via ultrasonication method is different from the SiO₂/PAPBA nanocomposite prepared via conventional stirring method, in which SiO₂ nanoparticles are submerged in PAPBA. Conductivity of the composite prepared via ultrasonication shows around 0.2 S/cm. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2743–2750, 2007     

Enhancement of polystyrene composites by hyper-branched polymer-grafted nano-SiO2

Hyper-branched poly(styrene) (HPS) made from copolymerisation of styrene (St) and a branching monomer divinylbenzene (DVB) in the presence of a chain transfer agent n-dodecanethiol (C₁₂SH) was grafted onto the surface of nano-SiO₂ via emulsion polymerisation (donated as HPS-SiO₂). A series of PS/HPS-SiO₂ composites were obtained by the addition of prepared HPS-SiO₂ into the pure PS. The structures and properties of the product were characterised by Fourier-transform infrared spectra (FT-IR), differential scanning calorimetry, thermogravimetric analysis and dynamic mechanical analysis (DMA). The results showed a strong interface interaction between HPS and nano-SiO₂ indicating that the HPS has grafted onto the surface of nano-SiO₂. The storage modulus, Young’s modulus, glass transition temperature (T_g) and thermal decomposition temperature of the composite were increased apparently by loading an appropriate amount of HPS-grafted SiO_2.     

Matting films prepared from waterborne acrylic/micro‐SiO2 blends

Acrylic resin/micro‐SiO₂/polymethyl urea (AC/SiO₂/PMU) composites were prepared by physical blends of acrylic resin latex (AC), polymethyl urea resin (PMU), and modified SiO₂. The effects of SiO₂ and PMU content in the hybrid composites morphology and physical properties were investigated in detail using transmission electron microscopy (TEM), UV‐Vis spectrometry (UV‐Vis), scanning electron microscope (SEM), thermogravimetric analysis (TGA), and contact angle measurement. The results showed that introduction of SiO₂ into AC composites could increase the viscosity which caused by gelation and agglomeration of SiO₂. The TEM, SEM images, and TGA results indicated that hybrid membranes have phase separation. During the film formation process, a high number of PMU and SiO₂ particles of an appropriate size were stranded on the surface of the film to form matting surface. These results highlight the sensitivity of the gloss to the polymer morphology and surface. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41707.     

Synthesis and characterization of PMMA/SiO2 organic–inorganic hybrid materials via RAFT‐mediated miniemulsion polymerization

In this article, we first carried out the surface modification of SiO₂ using silane coupling agent KH570, and then prepared PMMA/SiO₂ organic–inorganic hybrid materials by conventional free radical polymerization and RAFT polymerization in miniemulsion, respectively. The kinetics comparisons of these two polymerizations were studied. PMMA/SiO₂ hybrid materials were characterized by gel permeation chromatography, differential scanning calorimetry and thermogravimetric analysis. Experimental results indicated that the polymerization behavior of MMA in miniemulsion showed controlled/living radical polymerization characteristics under the control of RAFT agent. Incorporation of RAFT agent and SiO₂ nanoparticles improved the thermal properties of polymers, the thermal stability of polymers increased with increasing content of SiO₂ nanoparticles. The structures and morphologies of SiO₂, modified SiO₂, and PMMA/SiO₂ hybrid materials were characterized by FT‐IR and TEM. TEM results showed that the addition of modified SiO₂ nanoparticles to miniemulsion polymerization system obtained different morphology latex particles. Most of modified SiO₂ nanoparticles were wrapped by polymer matrix after polymerization. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Effect of acrylic acid and hydroxyethyl methacrylate modified nano-SiO2 particles on poly(methyl methacrylate-hydroxyethyl methacrylate) soap-free emulsion polymerization

Nano-SiO₂ powder was modified with acrylic acid (AA) and hydroxyethyl methacrylate (HEMA), respectively. The kinetics of the soap-free emulsion polymerization of methyl methacrylate (MMA) and HEMA in the presence of unmodified or modified nano-SiO₂ particles was investigated. The structure of the nano-SiO₂ particles and the Poly(MMA-HEMA) composite emulsion was characterized by Fourier transform infrared spectroscope (FT-IR). The particle size and size distribution of the emulsion, the morphology of emulsion particle, the surface tension, and ionic conductivity of these systems before and after polymerization were determined. The IR spectra showed that the organic modifiers were incorporated onto the surface of the nano-particles. In addition, the solid content and monomer conversion of the Poly(MMA-HEMA) composite emulsion with modified nano-SiO₂ are higher than that with original inorganic particles. The particle size became smaller and the particle distribution narrowed after applying the modified nano-SiO₂ particles. The SEM observation demonstrated that the shapes of these emulsion particles were uniform sphere. The surface tension and ionic conductivity increased significantly after polymerization.