Preparation and characterization of trilayer core–shell polysilsesquioxane–fluoroacrylate copolymer composite emulsion particles

Polysilsesquioxane–fluoroacrylate copolymer [poly(methyl methacrylate)–butyl acrylate–dodecafluoroheptyl methacrylate)] (FPSQ) composite latex particles with a trilayer core–shell morphology were manufactured by seeded emulsion polymerization, where PSQ latex particles bearing reactive methacryloxypropyl moieties were first produced by the hydrolysis‐condensation of (3‐methacryloxypropyl)trimethoxysilane, and then they were utilized as seeds, with methyl methacrylate, butyl acrylate, and dodecafluoroheptyl methacrylate as the inner and outer shell monomers. Fourier‐transform infrared spectra and ¹H‐NMR confirm the structure of the FPSQs. Transmission electron microscopy and scanning electron microscopy demonstrate that the obtained composite emulsion particles emerge with the trilayer core–shell pattern. Due to the anchoring of PSQ nanoparticles, the thermal stabilities of the FPSQ films are strengthened, and the resistance to heat is gradually improved along with the increase of the fluoroacrylate dose in the polymer matrix composite. X‐ray photoelectron spectroscopy, atomic force microscopy (AFM), and hydrophobicity investigations indicate that the fluorinated chain segments tend to concentrate at the film–air two‐phase interface. In addition, the AFM result denotes that importing more fluorine into the FPSQ hybrid material will engender greater phase separation and enrichment of the fluoroalkyl segments and a rougher morphology. Thus, the water contact angle of the FPSQ film can ultimately reach 121.4°. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44845.     

Synthesis and characterization of low‐dielectric photosensitive polyimide/silica hybrid materials

Photosensitive polyimide/silica hybrid materials were synthesized by reaction between 4,4′‐hexafluoroisopropylidene diphthalic anhydride (6FDA) and 4,4′‐oxydianiline. The intrachain chemical bonding and the interchain hydrogen bonding between the polyimide and silica moieties were increased by the incorporation of 2‐(dimethylamino) ethyl acrylate and 3‐aminopropyl trimetho xysilane, respectively. The photoinitiator was bis(2,4,6‐trimethyl benzoyl) phenylphosphine oxide (Irgacure‐819). The various coupling agents were utilized included tetrakis (allyloxy) silane (TAL). Most silica hybrid films showed better volume shrinkage and temperature resistance. The cooperation of octavinyl POSS, as the coupling agent, can lower dielectric constant (k) down to 2.48 but with the poorer volume shrinkage and temperature resistance than the other silica hybrid films. The addition of tetramethyl orthosilicate and 3‐methacryloxy propyltrimethoxysilane with silica content of 5.6 wt % can reduce k down to 2.26 but with worse volume shrinkage than the incorporation with TAL. The TAL hybrid film with degree of polymerization of 25 showed the best properties that optimized photolithography, dielectric constant (k = 3.81), volume shrinkage, and temperature resistance (Td5% = 378°C) with only 0.22 wt % silica content. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of styrene‐butyl acrylate polymers,varying feed composition in a semicontinuous emulsion process

Two‐stage polymerization has been used to improve properties of two‐component polymers. In this work, a semicontinuous emulsion process varying feed composition along the reaction is used to produce copolymer chains of different composition as conversion proceeds. Polymer composition and evidence of branching were determined by ¹H‐NMR. Polymer molecular weight values determined by GPC are beyond the range where mechanical properties depend on molecular weight. Mechanodynamic properties show a copolymer type behavior with a synergistic effect around the 50/50 styrene/butyl acrylate composition ratio. For such composition, mechanical performance superiority of variable composition copolymer with respect to two‐stage polymer was confirmed with stress–strain tests carried out at several temperatures. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3964–3971, 2007     

Preparation and characterization of titanium dioxide core/polymer shell hybrid composite particles prepared by emulsion polymerization

Titanium dioxide inorganic core and polymer shell composite poly(methyl methacrylate‐co‐butylacrylate‐co‐methacrylic acid) [P(MMA‐co‐BA)‐MAA] particles were prepared by emulsion copolymerization. Fourier transform IR (FTIR) spectroscopy was used to measure the content of MAA composite particles. Dynamic light scattering (DLS) characterized the composite particle size and size distribution. The field emission SEM (FE‐SEM) results of the composite particles showed regular spherical shape and no bare TiO₂ was detected on the whole surface of the samples. The composite particles were produced, showing good spectral reflectance compared with bare TiO₂. TGA results indicated the encapsulation efficiency and estimated density of composite particles. Encapsulation efficiency was up to 78.9% and the density ranged from 1.76 to 1.94 g/cm³. Estimated density of the composite particles is suitable to 1.73 g/cm³, due to density matching with suspending media. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2970–2975, 2004     

Toughening modification of PS with n‐BA/MMA/styrene core–shell structured copolymer from emulsifier‐free emulsion polymerization

Core–shell structured particles, which comprise the rubbery core and glassy layers, were prepared by emulsifier‐free emulsion polymerization of poly(n‐butyl acrylate/methyl methacrylate)/polystyrene [P(n‐BA/MMA)/PS]. The particle diameter was about 0.22 μm, and the rubbery core was uncrosslinked and lightly crosslinked, respectively. The smaller core–shell structured particle–toughened PS blends were investigated in detail. The dynamic mechanical behavior and observation by scanning electron microscopy of the modified blend system with core–shell structured particles indicated good compatibility between PS and the particles, which is the necessary qualification for an effective toughening modifier. Notched‐impact strength and related mechanical properties were measured for further evaluation of the toughening efficiency. The notched‐impact strength of the toughened PS blends with uncrosslinked particles reached almost sixfold higher than that of the untoughened PS when 15 phr of the core–shell structured particles was added. For the crosslinked particles the toughening effect for PS was not obvious. The toughening mechanism for these smaller particles also is discussed in this article. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1290–1297, 2003     

纳米SiO2/聚氨酯-含氟丙烯酸酯杂化乳液的合成与表征

采用种子乳液聚合法,以聚氨酯（PU）乳液为种子（在聚合过程中为壳相）,甲基丙烯酸甲酯（MMA）、丙烯酸丁酯（BA）、甲基丙烯酸十二氟庚酯（DFMA）和γ-甲基丙烯酰氧丙基三甲氧基硅烷（KH-570）改性的纳米SiO₂组成的混合物为核相,合成了具有核壳结构的纳米SiO₂/聚氨酯-含氟丙烯酸酯（SiO₂/FPUA）复合乳液。考察了纳米SiO₂和DFMA用量对乳液聚合过程及乳胶膜性能的影响。通过傅里叶红外光谱（FT-IR）、接触角（CA）、透射电子显微镜（TEM）、热重（TG）、差示扫描量热仪（DSC）和力学性能测试（MPT）等表征乳液的结构形态、乳胶膜的表面性能和综合性能。结果表明：乳胶粒子呈现“反相核壳”结构,以聚丙烯酸酯（PA）相为核,PU相为壳;由于纳米SiO₂和DFMA的协同作用,涂膜的疏水性和综合性能得到了较大的提高。     

Preparation of titanium dioxide/poly(methyl methacrylate‐co‐n‐butyl acrylate‐co‐methacrylic acid) hybrid composite particles via emulsion polymerization

Titanium dioxide core and polymer shell composite poly(methyl methacrylate‐co‐n‐butyl acrylate‐co‐methacrylic acid) [P(MMA‐BA‐MAA)] particles were prepared by emulsion copolymerization. The stability of dispersions of TiO₂ particles in aqueous solution was investigated. The addition of an ionic surfactant, sodium lauryl sulfate, which can be absorbed strongly at the TiO₂/aqueous interface, increases the stability of the TiO₂ dispersion effectively by increasing the absolute value of the ζ potential of the TiO₂ particles. The adsorption of the nonionic surfactant, Triton X‐100, on the surface of TiO₂ particles is less than that of the ionic surfactant. Fourier transform IR spectroscopy was used to measure the content of MAA composite particles. Dynamic light scattering characterized the composite particle size and size distribution. The field‐emission scanning electron microscopy results for the composite particles showed a regular spherical shape, and no bare TiO₂ was detected on the entire surface of the samples. The composite particles that were produced showed good spectral reflectance compared to bare TiO₂. Thermogravimetric analysis results indicated the encapsulated TiO₂ and estimated density of composite particles. There was up to 78.9% encapsulated TiO₂ and the density ranged from 1.76 to 1.94 g/cm³. The estimated density of the composite particles is suitable at 1.73 g/cm³, which is due to density matching with the suspending fluid. The sedimentation experiment indicates that reducing the density mismatch between the composite particles and suspending fluid may enhance the stability. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 72–79, 2005     

Synthesis of core‐shell fluoroacrylate copolymer latex via emulsion polymerization and its application in ink‐jet ink

Core‐shell fluoroacrylate copolymer latex was synthesized via semicontinuous seed emulsion polymerization, in which ethyl acrylate was utilized to prepare core, and methyl methacrylate, butyl acrylate, methacrylate acid, and hexafluorobutyl methacrylate were employed to constitute the shell. So the yielded latex particles had the soft core and hard shell. Multifunction and low viscosity of the latex had been applied as the binder of latex inks. The ζ potential showed that the latex particles had high thermodynamic stability. The latex and latex inks exhibited viscosity plateau of Newtonian fluid behaviors. Rheological tests revealed that viscous behaviors dominated in the latex and latex inks. However, there was some interaction among the latex and pigment particles. The hydrophobicity of the cast films of the latex increased with the amount of the fluoroacrylate monomer. Fluorine tended to migrate to the interface between the cast film and air. Therefore, the hydrophobicity was derived from the fluorine enrichment phenomena on the top side of the cast films. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Particle size and morphology of poly[styrene‐co‐(butyl acrylate)]/nano‐silica composite latex

Nanocomposite latex with nano‐silica of varying particle sizes was prepared via in situ polymerization and investigated by submicron particle size analysis, transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier‐transform infrared spectrometry (FTIR) and Raman spectrometry. It was found that nanocomposite latex exhibited a core–shell structure with nano‐silica particles enwrapped, resulting in an increase in the latex particle size. The smaller the nano‐silica particles, the more were embedded in each latex particle. The increase in the particle size of latex depended not only on the particle size of nano‐silica, but also on the number of nano‐silica particles in each latex particle. Copyright © 2004 Society of Chemical Industry     

Synthesis and characterization of poly(methyl methacrylate–butyl acrylate–acrylic acid)/polyaniline core–shell nanoparticles in miniemulsion media

Conductive polymer particles, polyaniline (PANI)‐coated poly(methyl methacrylate–butyl acrylate–acrylic acid) [P(MMA–BA–AA)] nanoparticles, were prepared. The P(MMA–BA–AA)/PANI core–shell complex particles were synthesized with a two‐step miniemulsion polymerization method with P(MMA–BA–AA) as the core and PANI as the shell. The first step was to prepare the P(MMA–BA–AA) latex particles as the core via miniemulsion polymerization and then to prepare the P(MMA–BA–AA)/PANI core–shell particles. The aniline monomer was added to the mixture of water and core nanoparticles. The aniline monomer could be attracted near the outer surface of the core particles. The polymerization of aniline was started under the action of ammonium persulfate (APS). The final product was the desired core–shell nanoparticles. The morphology of the P(MMA–BA–AA) and P(MMA–BA–AA)/PANI particles was characterized with transmission electron microscopy. The core–shell structure of the P(MMA–BA–AA)/PANI composites was further determined by Fourier transform spectroscopy and ultraviolet–visible measurements. The conductive flakes made from the core–shell latexes were prepared, and the electrical conductivities of the flakes were studied. The highest conductivity of the P(MMA–BA–AA)/PANI pellets was 2.05 S/cm. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of poly(butyl acrylate)/silica and poly(butyl acrylate)/silica/poly(methyl methacrylate) composite particles

Poly(butyl acrylate)/poly(methyl methacrylate) (PBA/PMMA) core–shell particles embedded with nanometer‐sized silica particles were prepared by emulsion polymerization of butyl acrylate (BA) in the presence of silica particles preabsorbed with 2,2′‐azobis(2‐amidinopropane)dihydrochloride (AIBA) initiator and subsequent MMA emulsion polymerization in the presence of PBA/silica composite particles. The morphologies of the resulting PBA/silica and PBA/silica/PMMA composite particles were characterized, which showed that AIBA could be absorbed effectively onto silica particles when the pH of the dispersion medium was greater than the isoelectric potential point of silica. The critical amount of AIBA added to have stable dispersion of silica particles increased as the pH of the dispersion medium increased. PBA/silica composite particles prepared by in situ emulsion polymerization using silica preabsorbed with AIBA showed higher silica absorption efficiency than did the PBA/silica composite particles prepared by direct mixing of PBA latex and silica dispersion or by emulsion polymerization in which AIBA was added after the mixing of BA and silica. The PBA/silica composite particles exhibited a raspberrylike morphology, with silica particles “adhered” to the surfaces of the PBA particles, whereas the PBA/silica/PMMA composite latex particles exhibited a sandwich morphology, with silica particles mainly at the interface between the PBA core and the PMMA shell. Subsequently, the PBA/silica/PMMA composite latex obtained had a narrow particle size distribution and good dispersion stability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3425–3432, 2006     

Preparation and characterization of core–shell polystyrene and polymethylsilsesquioxane structure latex particles by seeded polymerization

Composite polystyrene and polymethylsilsesquioxane (PS‐PMSSQ) latices were prepared by hydrolysis and polycondensation of triethoxylmethylsilane (TEOMS) in the presence of PS seed latices, obtained by gamma ray induced polymerization. Morphology of the composite latex particles was observed by transmission electronic microscopy and their size distribution was measured by dynamic laser light scattering. It was found that if 1 wt% silicon‐containing surfactant (SCS) and 0.4 wt% dodecylbenzene sulphonic acid (DBSA) were both used, core–shell/PS‐PMSSQ latex particles could be prepared at 30 °C. The core–shell structure was further characterized by X‐ray photoelectron spectrometry. With 0.5 wt% SCS or 0.2 wt% DBSA, the capsulation was incomplete. At 0 and 90 °C, the PMSSQ phase penetrated into the seed particles. No core–shell structure was observed when DBSA was replaced by hydrochloric acid or SCS was replaced by poly(ethylene glycol) monooctylphenyl ether. Copyright © 2006 Society of Chemical Industry     

An improved phase‐inversion process for the preparation of silica/poly[styrene‐co‐(acrylic acid)] core–shell microspheres: synthesis and application in the field of polyolefin catalysis

Spherical and well‐dispersed silica/poly[styrene‐co‐(acrylic acid)] (SiO₂/PSA) core–shell particles have been synthesized using an improved phase‐inversion process. The resulting particles were successfully used as supports for polyolefin catalysts in the production of polyethylene with broad molecular weight distribution. Through the vapor phase, instead of the liquid phase in the traditional process, a non‐solvent was introduced into a mixture of micrometer‐sized SiO₂ and PSA solution. The core–shell structure of the resulting SiO₂/PSA microspheres was confirmed using optical microscopy, scanning electron microscopy, Fourier transfer infrared spectrometry, thermogravimetric analysis and measurement of nitrogen adsorption/desorption isotherms. In order to avoid agglomeration of particles and to obtain a good dispersion of the SiO₂/PSA core–shell microspheres, the non‐solvent was added slowly. As the concentration of PSA solution increased, the surface morphology of the core–shell particles became looser and more irregular. However, the surface area and the pore volume remained the same under varying PSA concentrations. The SiO₂/PSA core‐shell microspheres obtained were used as a catalyst carrier system in which the core supported (n‐BuCp)₂ZrCl₂ and the shell supported TiCl₄. Ethylene/1‐hexene copolymerization results indicated that the zirconocene and titanium‐based Ziegler–Natta catalysts were compatible in the hybrid catalyst, showing high activities. The resulting polyethylene had high molecular weight and broad molecular weight distribution. Copyright © 2010 Society of Chemical Industry     

Preparation and characterization of core–shell polystyrene–polydimethylsiloxane particles by seeded polymerization

Nanometer scale particles of seed latex were successfully prepared by polymerization induced by gamma rays. By modification of the coupling agent 3‐methacryloxylpropyltrimethoxylsilane (MPS) at the surface of polystyrene (PSt) particles, polydimethylsiloxane (PDMS) was introduced outside the PSt particles and composite latex particles with a core–shell (PSt–PDMS) structure were successfully prepared. Because of the chemical bond linkage between the core and the shell, such a structure is stable. Direct evidence of the core–shell structure was observed by transmission electron microscopy (TEM). In addition the chemical bond linkage was confirmed by Fourier‐transfer infrared (FT‐IR) spectroscopy. An indirect proof of the core–shell structure was given by water absorption ratio determination of the different samples. Copyright © 2004 Society of Chemical Industry     

Core–shell particles to toughen epoxy resins. I. Preparation and characterization of core–shell particles

A two-stage, multistep soapless emulsion polymerization was employed to prepare various sizes of reactive core–shell particles (CSPs) with butyl acrylate (BA) as the core and methyl methacrylate (MMA) copolymerizing with various concentrations of glycidyl methacrylate (GMA) as the shell. Ethylene glycol dimethacrylate (EGDMA) was used to crosslink either the core or shell. The number of epoxy groups in a particle of the prepared CSP measured by chemical titration was close to the calculated value based on the assumption that the added GMA participated in the entire polymerization unless it was higher than 29 mol %. Similar results were also found for their solid-state ^13C-NMR spectroscopy. The MMA/GMA copolymerized and EGDMA-crosslinked shell of the CSP had a maximum glass transition temperature (T_g) of 140°C, which was decreased with the content of GMA at a rate of −1°C/mol %. However, the shell without crosslinking had a maximum T_g of 127°C, which decreased at a rate of −0.83°C/mol %. The T_g of the interphasial region between the core and shell was 65°C, which was invariant with the design variables. The T_g of the BA core was −43°C, but it could be increased to −35°C by crosslinking with EGDMA. The T_g values of the core and shell were also invariant with the size of the CSP. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2069–2078, 1998     

Study of the preparation of silicone rubber particles with core–shell structure by seeded emulsion polymerization

Silicone rubber particles with core–shell structure were prepared by polymerization of vinyl monomers in the presence of linear or cross-linked poly(dimethyl siloxane–methyl vinyl siloxane) latexes. The monomers were added in either continuous or swelled-continuous modes. Core–shell particles with poly(butyl methacrylate), or poly(methyl methacrylate), as the shell were obtained by using either addition mode. The core–shell structure was not observed for polysiloxane–polystyrene particles. The influence of monomer addition mode, the compatibilities of the monomers and their homopolymers with silicone rubber, and the reactivity ratios of the vinyl monomers with the vinyl group of linear polysiloxane particles, on the formation of the core-shell structure is discussed.     

Preparation of toughened PMMA through PEG-modified urethane acrylate/PMMA core–shell composite particles

Poly(urethane acrylate) (PUA)/poly(methylmethacrylate) (PMMA) core–shell composite particles were prepared by two-stage emulsion polymerization. The sizes of composite particles could be varied from 25 to 210 nm by introducing polyoxyethylene (POE) groups to the urethane acrylate molecular backbone. Core–shell morphology was identified by investigating the polarity of the surface of the core and shell polymer particles and by measuring the contact angle of the composite particles. A composite particle prepared with relatively small particles (about 20 nm) did not show the core/shell morphology, because the high polar surface of the core polymer particle and the low-stage ratio of the core to the shell cause the formation of a core/shell two-stage latex to be more thermodynamically unstable. The fracture toughness of rubber-toughened PMMA containing PUA/PMMA composite particles increased as the particle sizes decreased and the shell thickness of the composite particles increased. In particular, when the average size of the composite particle was about 43 nm and the stage ratio was 50/50, the fracture toughness of the rubber-toughened PMMA increased more than three times compared with that of pure PMMA. Furthermore, the transparency of toughened PMMA could be maintained up to 91% in the visible spectra range. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2291–2302, 1998     

Molecular dynamics study of TiO2/poly(acrylic acid‐co‐methyl methacrylate) and Fe3O4/polystyrene composite latex particles prepared by heterocoagulation

All‐atom molecular dynamics simulations were used to study the morphology of polymer/inorganic composite particles prepared by heterocoagulation. The results were also compared to those of our previous study of the preparation of TiO₂/poly(acrylic acid‐co‐methyl methacrylate) and Fe₃O₄/polystyrene composite particles. In the simulation system, polymer or inorganic particles were simulated by surface‐charge‐modified C₆₀ or Na atoms. Through a combination of analysis of the radial distribution functions of charged atoms and snapshots of the equilibrated structure, three kinds of particle distributions were observed under different conditions. When the polymer and inorganic particles had opposite surface charges and their sizes were very different, the composite morphology showed a core–shell structure with small particles adsorbed onto the surfaces of large particles. Furthermore, when the polymer and inorganic particles had opposite surface charges but comparable sizes, the polymer and inorganic particles aggregated domain by domain. Finally, when the polymer and inorganic particles were endowed with the same surface charge, the distribution of these two types of particles was homogeneous, regardless of their size difference. The simulation results were in agreement with the experimental results. The electrostatic interaction and the size of the particles dominated the final morphology of the composite particles when the heterocoagulation method was used. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of novel hybrid inorganic–organic hollow microspheres via a self‐template approach

BACKGROUND: Hollow microspheres, especially biodegradable polymeric microspheres, have attracted considerable attention due to their particular characteristics. Up to now, microspheres have been prepared via various strategies, for instance the template synthesis method and the self‐assembly process. However, economic, novel and simple methods to prepare hollow microspheres are still being sought. RESULTS: Phosphazene‐containing microspheres, which contain self‐assembled core‐shell structures, were prepared at high colloid contents using an ultrasonic bath via a self‐template approach. Along with the controlled self‐degradation of the internal core, the corresponding hybrid inorganic–organic hollow microspheres appeared. The mechanism was evidenced by means of transmission and scanning electron microscopy, cross‐polarization with magic angle spinning NMR, Fourier transform infrared spectroscopy, X‐ray diffraction and thermogravimetric analysis. CONCLUSION: It was clarified that the phosphazene‐containing microspheres could be formed and stably dispersed without aggregation even at high colloid contents using the ultrasonic bath method and the microspheres contain self‐assembled core–shell structures. Along with the controlled self‐degradation of the internal core, the corresponding hollow microspheres appeared. The mechanism of this preparation is of great significance because it is completely different from the conventional template synthesis method and the self‐assembly process. The absence of any stabilizing agent and special templates might inspire creative imagination in the design of new morphologies of micro‐ and nanostructures. Copyright © 2007 Society of Chemical Industry