Hybrid titanium catalyst supported on core‐shell silica/poly(styrene‐co‐acrylic acid) carrier

Hybrid titanium catalysts supported on silica/poly(styrene‐co‐acrylic acid) (SiO₂/PSA) core‐shell carrier were prepared and studied. The resulting catalysts were characterized by Fourier transform infrared (FTIR) spectroscopy, laser scattering particle analyzer and scanning electronic microscope (SEM). The hybrid catalyst (TiCl₃/MgCl₂/THF/SiO₂·TiCl₄/MgCl₂/PSA) showed core‐shell structure and the thickness of the PSA layer in the two different hybrid catalysts was 2.0 μm and 5.0 μm, respectively. The activities of the hybrid catalysts were comparable to the conventional titanium‐based Ziegler‐Natta catalyst (TiCl₃/MgCl₂/THF/SiO₂). The hybrid catalysts showed lower initial polymerization rate and longer polymerization life time compared with TiCl₃/MgCl₂/THF/SiO₂. The activities of the hybrid catalysts were enhanced firstly and then decreased with increasing P/P. Higher molecular weight and broader molecular weight distribution (MWD) of polyethylene produced by the core‐shell hybrid catalysts were obtained. Particularly, the hybrid catalyst with a PSA layer of 5.0 μm obtained the longest polymerization life time with the highest activity (2071 kg PE mol^?1 Ti h^?1) and the resulting polyethylene had the broadest MWD (polydispersity index = 11.5) under our experimental conditions. The morphology of the polyethylene particles produced by the hybrid catalysts was spherical, but with irregular subparticles due to the influence of PSA layer. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Solvent diffusion in silica/poly[styrene‐co‐(acrylic acid)] core‐shell microspheres by pulsed field gradient NMR techniques

Polymer‐coated SiO₂ particles are prepared by precipitation of poly[styrene‐co‐(acrylic acid)] on SiO₂ microspheres through an improved phase inversion method. The diffusion resistance of the polymer membrane was considered to be the critical reason for producing tailor‐made polyethylene by catalysts supported on these polymer‐coated particles. This paper employs pulsed field gradient NMR (PFG‐NMR) to distinguish diffusion of n‐hexane in different regimes, i.e., in the space between each particle, the pores in SiO₂ and the polymer shell, by their respective diffusion coefficients. By varying the observation time, the time scale of the molecular exchange is discussed. A three‐region ansatz was used to interpret the exchange and diffusion in polymer‐coated SiO₂ system, and was compared with results acquired with noncoated particles. At long diffusion times, the mean‐squared displacement, and thus the averaged self‐diffusion coefficient, of hexane in the system of polymer‐coated SiO₂ particles is significantly reduced. The PSA membrane is identified as an efficient barrier against molecular exchange between the pores in SiO₂ and the intraparticle space. Consistently, the relaxation measurements indicated that the mobility of n‐hexane molecules, especially the rotation of n‐hexane, was limited by the PSA membrane. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40160.     

Preparation of core–shell poly(acrylic acid)/polystyrene/SiO2 hybrid microspheres

Core–shell poly(acrylic acid)/polystyrene/SiO₂ (PAA/PS/SiO₂) hybrid microspheres were prepared by dispersion polymerization with three stages in ethanol and ethyl acetate mixture medium. Using vinyltriethoxysilane (VTEOS) as silane agent, functional silica particles structured vinyl groups on surfaces were prepared by hydrolysis and polycondensation of tetraethoxysilane and VTEOS in core stage. Then, the silica particles were used as seeds to copolymerize with styrene and acrylic acid sequentially in shell stage I and stage II to form PAA/PS/SiO₂ hybrid microspheres. Transmission electron microscope results show that most PAA/PS/SiO₂ hybrid microspheres are about 40 nm in diameter, and the silica cores are about 15 nm in diameter, which covered with a layer of PS about 7.5‐nm thick and a layer of PAA about 5‐nm thick. This core–shell structure is also conformed by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and differential scanning calorimetry. FTIR results show that silica core, PS shell, and PAA outermost shell are bonded by covalents. In the core–shell PAA/PS/SiO₂ hybrid microsphere, the silica core is rigidity, and the PAA outermost shell is polarity, while the PS layer may work as lubricant owning to its superior processing rheological property in polymer blending. These core–shell PAA/PS/SiO₂ hybrid microspheres have potential as new materials for polar polymer modification. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1729–1733, 2006     

Preparation and characterization of poly(chlorotrifluoroethylene‐co‐ethylvinyl ether)/poly(styrene acrylate) core–shells and SiO2 nanocomposite films via a solution mixing method

Nanocomposite particles of poly(chlorotrifluoroethylene‐co‐ethylvinyl ether) [poly(CTFE‐co‐EVE)]/poly(styrene acrylate) (PSA)/SiO₂ were prepared with poly(CTFE‐co‐EVE)/PSA [CS(FS); core–shell (CS) fluoro surfactant (FS)] and hydrophilic SiO₂ nanoparticles by a solution mixing method. This method yielded a homogeneous dispersion of hydrophilic SiO₂ nanoparticles in the CS(FS) matrix. The nanocomposite particle composition was confirmed by Fourier transform infrared spectroscopy and thermogravimetric analysis. A slight improvement in the thermal stability was observed and the glass‐transition temperature of the nanocomposite particles increased compared with the CS(FS) matrix. A remarkable enhancement was observed in the mechanical properties with an increase in the tensile strength from 1.1 to 6.2 MPa and with an increase in the elongation at break from 209.6 to 350.1% for the films with 15 wt % SiO₂. The presence of a wettable PSA shell on the fluorocore made interaction possible with SiO₂; this made it more hygroscopic with a decent water uptake capacity and an enhanced water contact angle. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2012     

Advanced antistatic/anticorrosion coatings prepared from polystyrene composites incorporating dodecylbenzenesulfonic acid‐doped SiO2@polyaniline core–shell microspheres

We present the preparation of advanced antistatic and anticorrosion coatings of polystyrene (PS) incorporating a suitable amount of dodecylbenzenesulfonic acid (DBSA)‐doped SiO₂@polyaniline (SP) core–shell microspheres. First, aniline‐anchored SiO₂ (AS) microspheres that were about 850 nm in diameter were synthesized using the conventional base‐catalyzed sol–gel process with tetraethyl orthosilicate in the presence of N‐[3‐(trimethoxysilyl)propyl]aniline. SP core–shell microspheres were then synthesized by chemical oxidative polymerization of aniline monomers with ammonium persulfate as an oxidizing agent in the presence of the AS microspheres. The polyaniline shell thickness of the as‐prepared core–shell microspheres was estimated to be about 120 nm. The AS and SP microspheres were further characterized using Fourier transform infrared spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy. The as‐synthesized DBSA‐doped SP core–shell microspheres were then blended into PS using N‐methyl‐2‐pyrrolidone as solvent and then cast onto a cold–rolled steel (CRS) electrode to obtain antistatic and anticorrosion coatings with a thickness of about 10 µm. The corrosion protection efficiency of the as‐prepared coating materials on the CRS electrode was investigated using a series of systematic electrochemical measurements under saline conditions. The enhanced corrosion protection ability of the PS/SP composite coatings may be attributed to the formation of a dense passive metal oxide layer induced by the redox catalytic effect of the polyaniline shell of the as‐synthesized core–shell microspheres, as evidenced by electron spectroscopy for chemical analysis and SEM observations. Moreover, the PS composite coating containing 10 wt% of the SP core–shell microspheres showed an electrical resistance of about 3.65 × 10⁹Ω cm^?2, which meets the requirements for antistatic applications. Copyright © 2012 Society of Chemical Industry     

Preparation and properties of core–shell nanosilica/poly(methyl methacrylate–butyl acrylate–2,2,2‐trifluoroethyl methacrylate) latex

A core–shell nanosilica (nano‐SiO₂)/fluorinated acrylic copolymer latex, where nano‐SiO₂ served as the core and a copolymer of butyl acrylate, methyl methacrylate, and 2,2,2‐trifluoroethyl methacrylate (TFEMA) served as the shell, was synthesized in this study by seed emulsion polymerization. The compatibility between the core and shell was enhanced by the introduction of vinyl trimethoxysilane on the surface of nano‐SiO₂. The morphology and particle size of the nano‐SiO₂/poly(methyl methacrylate–butyl acrylate–2,2,2‐trifluoroethyl methacrylate) [P(MMA–BA–TFEMA)] core–shell latex were characterized by transmission electron microscopy. The properties and surface energy of films formed by the nano‐SiO₂/P(MMA–BA–TFEMA) latex were analyzed by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy/energy‐dispersive X‐ray spectroscopy, and static contact angle measurement. The analyzed results indicate that the nano‐SiO₂/P(MMA–BA–TFEMA) latex presented uniform spherical core–shell particles about 45 nm in diameter. Favorable characteristics in the latex film and the lowest surface energy were obtained with 30 wt % TFEMA; this was due to the optimal migration of fluorine to the surface during film formation. The mechanical properties of the films were significantly improved by 1.0–1.5 wt % modified nano‐SiO₂. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

α‐Amylase immobilized by Fe3O4/poly(styrene‐co‐maleic anhydride) magnetic composite microspheres: Preparation and characterization

Fe₃O₄/poly(styrene‐co‐maleic anhydride) core–shell composite microspheres, suitable for binding enzymes, were prepared using magnetite particles as seeds by copolymerization of styrene and maleic anhydride. The magnetite particles were encapsulated by polyethylene glycol, which improved the affinity between the magnetite particles and the monomers, thus showing that the size of the microspheres, the amount of the surface anhydrides, and the magnetite content in the composite are highly dependent on magnetite particles, comonomer ratio, and dispersion medium used in the polymerization. The composite microspheres, having 0.08–0.8 μm diameter and containing 100–800 μg magnetite/g microspheres and 0–18 mmol surface‐anhydride groups/g microsphere, were obtained. Free α‐amylase was immobilized on the microspheres containing reactive surface‐anhydride groups by covalent binding. The effects of immobilization on the properties of the immobilized α‐amylase [magnetic immobilized enzyme (MIE)] were studied. The activity of MIE and protein binding capacity reached 113,800 U and 544.3 mg/g dry microspheres, respectively. The activity recovery was 47.2%. The MIE had higher optimum temperature and pH compared with those of free α‐amylase and showed excellent thermal, storage, pH, and operational stability. Furthermore, it can be easily separated in a magnetic field and reused repeatedly. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 328–335, 2005     

Organic/inorganic support for immobilizing (n‐BuCp)2ZrCl2/TiCl3 hybrid catalyst for use in the preparation of polymer blends

Reactor blends of ultrahigh‐molecular‐weight polyethylene (UHMWPE) and low‐molecular‐weight polyethylene (LMWPE) were synthesized by two‐step polymerization using a hybrid catalyst. To prepare the hybrid catalyst, styrene acrylic copolymer (PSA) was first coated onto SiO₂/MgCl₂‐supported TiCl₃; then, (n‐BuCp)₂ZrCl₂ was immobilized onto the exterior PSA. UHMWPE was produced in the first polymerization stage with the presence of 1‐hexene and modified methylaluminoxane (MMAO), and the LMWPE was prepared with the presence of hydrogen and triethylaluminium in the second polymerization stage. The activity of the hybrid catalyst was considerable (6.5 × 10⁶ g PE (mol Zr)^?1 h^?1), and was maintained for longer than 8 h during the two‐step polymerization. The barrier property of PSA to the co‐catalyst was verified using ethylene polymerization experiments. The appearance of a lag phase in the kinetic curve during the first‐stage polymerization implied that the exterior catalyst ((n‐BuCp)₂ZrCl₂) could be activated prior to the interior catalyst (M‐1). Furthermore, the melting temperature, crystallinity, degree of branching, molecular weight and molecular‐weight distribution of polyethylene obtained at various polymerization times showed that the M‐1 catalyst began to be activated by MMAO after 40 min of the reaction. The activation of M‐1 catalyst led to a decrease in the molecular weight of UHMWPE. Finally, the thermal behaviors of polyethylene blends were investigated using differential scanning calorimetry. Copyright © 2011 Society of Chemical Industry     

TiCl4 immobilized on a composite support SiO2/MgCl2·x(1,4-butanediol)/poly[styrene-co-(acrylic acid)] for ethylene polymerization: The barrier effect of poly[styrene-co-(acrylic acid)]

By immobilizing titanium-based Ziegler–Natta catalyst on composite support, SiO₂/MgCl₂·x(1,4-butanediol)/poly[styrene-co-(acrylic acid)] (SiO₂/MgCl₂·xBD/PSA) and SiO₂/MgCl₂·xBD/PSA/TiCl₄ (SMPT) were synthesized for ethylene polymerization. SiO₂/MgCl₂·xBD/TiCl₄ without PSA was also prepared for comparison. The results of energy-dispersive X-ray analysis, SEM, and thermogravimetric analysis demonstrated that SMPT had a unique core-mantle-shell structure. The PSA layer can be considered as a barrier for the mass-transfer of reactants based on the results of self-diffusion measurement by pulsed field gradient NMR and ethylene polymerization. The polyethylene produced by SMPT showed high molecular weight (MW) and broad molecular weight distribution (MWD). The influences of PSA content, hydrogen, and comonomer on the ethylene polymerization behavior were also investigated. The results further demonstrated that the PSA layer in the composite support had different diffusion capabilities to the reactants. The physical properties of the produced polyethylene implied the possibility to control the MW and MWD of polyethylene by the manipulation of PSA layer. The catalyst fragmentation during ethylene polymerization was also affected by the PSA shell due to its barrier effect. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Nano‐SiO2/PMMA‐PU composite particles with core‐shell structure via emulsion polymerization and their application in epoxy resin

A novel method of nano‐SiO₂/poly(methyl methacrylate)(PMMA)‐polyurethane(PU) composite particles modifying epoxy resin is reported. The composite particles with the obvious core‐shell structure were prepared by emulsion polymerization of PMMA and PU prepolymer on the surface of nano‐SiO₂. The diameter of the composite particles was 50–100 nm with dark core SiO₂ (30–60 nm) and light shell polymer of PMMA and PU (20–30 nm); moreover, PU was well distributed in PMMA with about 10 nm diameter. After nano‐SiO₂ was encapsulated by PMMA and PU, the Si content on the surface decreased rapidly to 2.08% and the N content introduced by PU was about 1.27%. The ratio of polymer to original nano‐SiO₂ (f_p), the grafting ratio of polymer to original nano‐SiO₂ (f_r) and the efficiency grafting ratio of polymer (f_e) were, respectively, about 116.7%, 104.4%, and 89.5%. The as‐prepared composite particles were an effective toughness agent to modify epoxy resin, and the impact strength of the modified epoxy resin increased to 46.64 kJ m^?2 from 19.12 kJ m^?2 of the neat epoxy resin. This research may enrich the field of inorganic nanoparticles with important advances toward the modification for polymer composite materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41919.     

Preparation of antireflection coatings with novel cationic–nonionic PU‐SiO2 core–shell particle dispersions

A novel polyurethane (PU)‐SiO₂ core–shell particle dispersion was prepared by an acid‐catalyzed sol–gel process using cationic–nonionic PU particle as template. Results of average sizes, polydispersity index, and transmission electron microscope indicated that tetramethylorthosilicate were first diffused to the surface of PU particles, then occurring hydrolysis–condensation reaction to form core–shell particles. Antireflection coating formulation was prepared by as‐prepared core–shell particle dispersion and SiO₂ sol binder. After dip‐coating in the formulation, antireflection coating was formed on glass surface by calcination. Scanning electron microscopy images showed that pores had been formed inside coating after removing PU template particles, and the coating surface could be almost fully closed. In addition, ultraviolet–visible spectrophotometer analysis showed that the maximum transmittance of antireflection glasses can be as high as 98.6% at 548 nm. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45762.     

Solid‐phase preparation method of silica‐supported 2,2′‐methylenebis(6‐tert‐butyl‐4‐methyl‐phenol) and its antioxidative behavior in styrene‐butadiene rubber

A solid‐phase preparation method is applied to the synthesis of a novel supported rubber antioxidant, silica–supported 2,2′‐methylenebis(6‐tert‐butyl‐4‐methyl‐phenol) (SiO₂‐2246), by directly reacting 2,2′‐methylenebis (6‐tert‐butyl‐4‐methyl‐phenol)(antioxidant 2246) with silica. FTIR, Raman spectroscopy and TGA confirm that the antioxidant 2246 is chemically bonded on the surface of the silica particles. The SEM observation shows that the SiO₂‐2246 is homogeneously dispersed in the styrene‐butadiene rubber (SBR) matrix. The results of the apparent activation energy and the attenuated total reflectance infrared spectrometry indicate that the antioxidative efficiency of the SiO₂‐2246 in SBR is superior to the corresponding low‐molecular‐weight 2246. The thermal oxidative stability of the SBR/SiO₂‐2246 composites is much higher than that of the SBR/SiO₂/2246 composites by comparing their mechanical properties retentions and crosslinking densities. Additionally, the advantages of SiO₂‐2246 also include low migration, low volatility, and low pollution. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43014.     

Effects of ethyl acetate on the soap‐free emulsion polymerization of 4‐vinylpyridine and styrene

The properties and morphologies of poly(4‐vinylpyridine‐co‐styrene) [P(4VP/St)] lattices, prepared by soap‐free emulsion polymerization using the water‐soluble initiator 2,2′‐azobis(2‐amidinopropane) · 2HCl (V50), were greatly affected by the addition of ethyl acetate (EA). The properties and morphologies of the resultant lattices were characterized by measuring the zeta potential, viscosity average molecular weight, particle size and distribution, glass‐transition temperature (T_g), and photographs taken by SEM and TEM. The effects of two kinds of monomer feeding modes, that is, the batch and semicontinuous emulsion copolymerization, were also investigated. For batch emulsion copolymerization, by charging EA, the core–shell morphology resulting from the disparate reactivity ratios of the 4VP(1)/St(2) copolymerization system (r₁ = 1.04, r₂ = ?0.73) disappeared. Instead, first a bimodal particle size distribution, with an apparently asymmetric composition structure, and then spherical microspheres were obtained as the amount of EA charged increased from 2 to 10 wt %. The particle size increased twofold by the addition of EA. The zeta potential of particles increased from +64.4 to more than +100 mV, and viscosity average molecular weight decreased from 9.70 to 0.97 × 10⁵ g/mol, as EA increased from 0 to 8 wt %. With the semicontinuous copolymerization, raspberry‐like particles were obtained by charging 10 wt % EA, whereas a sandwich‐like morphology was obtained without EA. The DSC curves showed one T_g for all the lattices prepared with charging EA, but two T_g's for the latex prepared without using EA, regardless of the monomer feeding modes. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1988–2001, 2001     

Simultaneous enhancements of mechanical properties and hydrophilic properties of polypropylene via nano‐silicon dioxide modified by polydopamine

This study is focused on the development of high‐performance composite materials based on nano silicon dioxide (nano‐SiO₂) modified by polydopamine (PDA). A facile one‐step method was developed to synthesize core–shell structured SiO₂@polydopamine (PDA) nanospheres. During the synthesis, a PDA shell was simultaneously coated on the SiO₂ nanospheres to form the core–shell nanostructure which was blended with polypropylene (PP) and β nucleating agent (β‐NA) to enhance both mechanical and hydrophilic properties. Nano‐SiO₂ particles modified by PDA (SiO₂@polydopamine) influence the crystallization of PP seriously. The results indicated that when 1%wt SiO₂@polydopamine was added, the impact strength of composite reached the maximum value 12.60k J/m² increasing 137% compared with PP, the bending strength and bending modulus decreased slightly reaching 41.85 MPa, and 2192 MPa, respectively, the composite possessed hydrophilic performance with the water contact angle of 88.32°. β nucleating agent was used in all formulations, the synergistic effect toward mechanical properties with SiO₂@polydopamine was studied. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45004.     

Blending ultrahigh‐molecular‐weight polyethylene and poly(ethylene/10‐undecen‐1‐ol) in one nascent particle

Ultrahigh‐molecular‐weight polyethylene (UHMWPE)/polar polyethylene (PE) composites were blended in one nascent particle by in situ polymerization with a hybrid catalyst. Polystyrene‐coated SiO₂ particles were used to support the hybrid catalyst. Fe(acac)₃/2,6‐bis[1‐(2‐isopropylanilinoethyl)] was supported on SiO₂ for the synthesis of UHMWPE, whereas [PhN?C(CH₃)CH?C(Ph)O]VCl₂ was immobilized on a polystyrene layer to prepare a copolymer of ethylene and 10‐undecen‐1‐ol (polar PE). Importantly, the core part of the supports (the polystyrene layer) exhibited pronounced transfer resistance to 10‐undecen‐1‐ol; this provided an opportunity to keep the inside iron active sites away from the poisoning of 10‐undecen‐1‐ol. Therefore, UHMWPE was simultaneously synthesized with polar PE by in situ polymerization. Interestingly, the morphological results show that UHMWPE and the polar PE were successfully blended in one nascent polymer. This improved the miscibility of the composites, where most of the chains were difficult to crystallize because of the strong interactions between the PE chains and polar chains. The blends showed an extremely low crystallinity, that is, 9.9%. Finally, the hydrophilic properties of the polymer composites were examined. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46652.     

Preparation of high molecular weight poly(vinyl alcohol) with high yield by emulsion polymerization of vinyl acetate using 2,2′‐azobis(2‐amidinopropane) dihydrochloride

To prepare high molecular weight (HMW) poly(vinyl acetate) (PVAc) with high yield and high linearity as a precursor of HMW poly(vinyl alcohol) (PVA), vinyl acetate (VAc) was emulsion polymerized using, azo initiator, 2,2′‐azobis(2‐amidinopropane) dihydrochloride (AAPH). This was compared with the polymerization using potassium peroxodisulfate (KPS) as an initiator at various polymerization conditions. PVA, having a maximum number average degree of polymerization (P_n) of 3500 was obtained by the saponification of PVAc with P_n of 13,000–14,000, degree of branching (DB) for the acetyl group of about 3.4–3.5, and a maximum conversion of VAc into PVAc of 95%, which was polymerized by AAPH. These numerical values were superior compared with 14,500–15,000 of P_n of PVAc, obtained by KPS, and 3100 of maximum P_n of resulting PVA, DB of about 3.7–3.8, and maximum conversion of 90%. From the foregoing experimental results, we found that AAPH was a more efficient initiator than KPS in increasing both conversion of PVAc and molecular weight of PVA. In addition, PVAc microspheres, obtained by these emulsion polymerizations, can be converted to PVA / PVAc shell / core microspheres through a series of surface‐saponifications, maintaining their spherical morphology. Various surface morphologies, such as flat or wrinkled and swellable or nonswellable ones formed by the various molecular parameters and saponification conditions, were examined. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2356–2362, 2004     

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     

Design of aerosol particle coating: Thickness,texture and efficiency

Core–shell particles preserve the performance (e.g. magnetic, plasmonic or opacifying) of a core material, while modifying its surface with a shell that facilitates (e.g. by blocking its reactivity) their incorporation into a host liquid or polymer matrix. Here coating of titania (core) aerosol particles with thin silica shells (films or layers) is investigated at non-isothermal conditions by a trimodal aerosol dynamics model, accounting for SiO₂ generation by gas phase and surface oxidation of hexamethyldisiloxane (HMDSO) vapor, coagulation and sintering. After TiO₂ particles have reached their final primary particle size (e.g. upon completion of sintering during their flame synthesis), coating starts by uniformly mixing them with HMDSO vapor that is oxidized either in the gas phase or on the particles’ surface resulting in SiO₂ aerosols or deposits, respectively. Sintering of SiO₂ deposited onto the core TiO₂ particles takes place transforming rough into smooth coating shells depending on the process conditions. The core–shell characteristics (thickness, texture and efficiency) are calculated for two limiting cases of coating shells: perfectly smooth (e.g. hermetic) and fractal-like. At constant TiO₂ core particle production rate, the influence of coating weight fraction, surface oxidation and core particle size on coating shell characteristics is investigated and compared to pertinent experimental data through coating diagrams. With an optimal temperature profile for complete precursor conversion, the TiO₂ aerosol and SiO₂-precursor (HMDSO) vapor concentrations have the strongest influence on product coating shell characteristics.     

Gasphasensynthese von Kern/Mantel‐Partikeln am Beispiel von TiO2‐Nanopartikeln mit elektrisch leitendem Mantel

An advanced process enables synthesis and coating of individual TiO₂‐core particles with a shell of transparent conducting oxide (TCO) from the gas phase in one reactor. TiO₂ particles were coated with fluorine‐doped tin oxide (SnO₂:F) or antimony‐doped tin oxide (SnO₂:Sb). Specific electrical conductivity of the core/shell particles was up to 8 · 10^–3 S cm^–1. Variation of process parameters allows modifying dopant level and conductivity in an easy way.     

Self‐assembly of pH‐responsive acrylate latex particles at emulsion droplets interface

The self‐assembly of pH‐responsive poly (methyl methacrylate‐co‐acrylic acid) latex particles at emulsion droplet interfaces was achieved. Raising pH increases the hydrophilicity of the latex particles in situ and the latex particle acts as an efficient particulate emulsifier self‐assembling at emulsion droplet interface at around pH 10–11 but exhibits no emulsifier activity at higher pH. This effect can be reversibly induced simply by varying the aqueous phase pH and thus the latex emulsifier can be reassembled. The effect factors, including the aqueous phase pH, the surface carboxyl content, ζ‐Potential of the latex particles and oil phase solvent have been investigated. Using monomer as oil phase, the latex particles could stabilize emulsion droplets during polymerization and cage‐like polymer microspheres with hollow core/porous shell structure were obtained after polymerization. The mechanism of the latex particles self‐assembly was discussed. The morphologies of emulsion and microspheres were characterized by optical microscopy, scanning electron microscopy, and transmission electron microscopy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007