Preparation of Organic/Inorganic Hybrid Polymer Emulsions with High Silicon Content and Sol-gel-derived Thin Films

A novel polymer/SiO2 hybrid emulsion(PAES)was prepared by directly mixing colloidal silica with polyacrylate emulsion(PAE)modified by a saline coupling agent.The sol-gel-derived thin films were obtained by addition of co-solvents into the PAES.The effects ofγ-methacryloxypropyltrimethoxysilane(KH-570)content and co-solvent on the properties of PAES films were investigated.Dynamic laser scattering(DLS)data indicate that the average diameter of PAES(96 nm)is slightly larger than that of PAE(89 nm).Transmission electron microscopy (TEM)photo discloses that colloidal silica particles are dispersed uniformly around polyacrylate particles and some of the colloidal silica particles are adsorbed on the surface of PAE particles.The crosslinking degree data and Fourier transform infrared(FT-IR)spectra confirm that the chemical structure of the PAES is changed to form Si-O-Si-polymer crosslinking networks during the film formation.Atomic force microscope(AFM)photos show the solvent induced sol-gel process of colloidal silica and the Si-based polymer distribution on the film surface of the dried PAES.Thermogravimetric analysis(TGA)curves demonstrate that the PAES films display much better thermal stability than PAE.

Properties and Microstructure of Polymer Emulsions Modifi ed Fibers Reinforced Cementitious Composites

The synthesis and characterization of a new class of cementitious composites filled with polymer emulsions were investigated, and their superior mechanical strength and durability properties compared to composites devoid of fi llers were reported. Polymer emulsions were utilized to mechanically reinforce the composite and bridge the cement, fly ash, aggregate and fibers. The results reveal that the epoxy emulsion and poly（ethylene-co-vinyl acetate） emulsion markedly enhance the mechanical and durability properties of cemetitious composites. The fi bers can be pulled out in the form of slip-hardening and the abrasion phenomenon can be observed clearly on the surface of the fibers. The hydration extent of cement is higher than that of the pristine composites. The polymer modified cementitious composites designed on micromechanics, have fl exibility and plasticity which could be applied for a novel form of multifunctional materials with a range of pipeline coatings applications.

FT-IR Study on Crosslin king Reaction of Acrylates Copolymer Emulsions

Introduction The emulsion of acrylate copolymers with actively functional groups have been widely developed and used as coating, adhesive and handling agent in spinning and weaving industry. Bessett, D. R. et al. studied the thermoset of N-(isobutoxymethyl) acrylamide by thermal evolution analysis and thermal gas chromatogram. Krejcar,

Preparation of poly （methyl methacrylate）／nanometer calcium carbonate composite by in-situ emulsion polymerization

Methyl methacrylate (MMA) emulsion polymerization in the presence of nanometer calcium carbonate(nano-CaCO3) surface modified with γ-methacryloxypropyltrimethoxysilane (MPTMS) was carried out to prepare poly (methyl methacrylate) (PMMA)/nano-CaCO3 composite. The reaction between nano-CaCO3 and MPTMS, and the grafting of PMMA onto nano-CaCO3 were confirmed by infrared spectrum. The grafting ratio and grafting efficiency of PMMA on nano-CaCO3 modified with MPTMS were much higher than that on nano-CaCO3 modified with stearic acid. The grafting ratio of PMMA increased as the weight ratio between MMA and nano-CaCO3 increased, while the grafting efficiency of PMMA decreased. Transmission electron micrograph showed that nano-CaCO3 covered with PMMA was formed by in-situ emulsion polymerization.

Measurement methods of particle size distribution in emulsion polymerization

The particle size distribution of polymer always develops in emulsion polymerization systems,and certain key phenomena/mechanisms as well as properties of the final product are significantly affected by this distribution.This review mainly focuses on the measurement methods of particle size distribution rather than average particle size during the emulsion polymerization process,including the existing off-line,on-line,and in-line measurement methods.Moreover,the principle,resolution,performance,advantages,and drawbacks of various methods for evaluating particle size distribution are contrasted and illustrated.Besides,several possible development directions or solutions of the in-line measurement technology are explored.

PARTICLE MORPHOLOGY OF POLY(VINYL CHLORIDE)RESIN PREPARED BY SUSPENDED EMULSION POLYMERIZATION

Suspended emulsion polymerization was used to prepare poly(vinyl chloride) (PVC) resin. Fine PVC particleswere formed at low polymerization conversions. The amount of fine panicles decreases as conversion increases anddisappears at conversions greater than 30%. Scanning electron micrographs show that PVC grains are composed of looselycoalesced primary particles, especially for PVC resins prepared in the presence of poly(vinyl alcohol) dispersant. The size ofprimary particles increases and porosity decreases with the increase of conversion. In view of the particle features of PVCresin, a particle formation mechanism including the formation of primary particles and grains is proposed. The formationprocess of primary particles includes the formation of particle nuclei, coalescence of particle nuclei to form primary particles,and growth of primary particles. PVC grains are formed by the coagulation of primary particles. The loose coalescence ofprimary particles is caused by the colloidal stability of primary particles and the low swelling degree of vinyl chloride in the primary particles.

Influence of Suspended Emulsion Polymerization Conditions on Particle Characteristics of Polyvinyl Chloride Resin

Suspended emulsion polymerization of vinyl chloride was carried out in a 5 L autoclave. The influence of agitation, polymerization conversion, dispersant and surfactant on the average particle size (PS) and particle size distribution (PSD), particle morphology and porosity of polyvinyl chloride (PVC) resin was investigated. It showed that the agitator had great influence on the smooth operation of polymerization, PS and PSD. The PS increased and PSD became narrow as polymerization conversion became high. The porosity decreased with the increase of conversion. A convenient choice of additives, both dispersants and non-ionic surfactants, allows one to adjust PS and PSD. The PS decreased with the addition of polyvinyl alcohol or hydroxypropyl methylcellulose dispersants,and increased with the addition of Span surfactants. The addition of dispersants or surfactants also affected the morphology and porosity of resin, and PVC resin with looser agglomeration and homogeneous distribution of primary particles was prepared.

MORPHOLOGY EVOLUTION OF POLY(St-co-BuA)/SILICA NANOCOMPOSITE PARTICLES SYNTHESIZED BY EMULSION POLYMERIZATION

Poly（St-co-BuA）/silica nanocomposite latexes were synthesized via conventional emulsion polymerization in the presence of 3-（trimethoxysilyl）propyl methacrylate modified colloidal nano-silica. The effects of surface property, particle size and content of colloidal nano-silica as well as the concentrations of monomer and surfactant on the morphology of nanocomposite latex particles were investigated by transmission electron microscope （TEM） and scanning electron microscope （SEM） in detail. Various interesting morphologies such as grape-like, Chinese gooseberry-like, pomegranate-like and normal core-shell structures were observed. Droplet nucleation mechanism competing with micelle nucleation mechanism was proposed to explain the morphological evolution of the nanocomposite particles.

Preparation of multihollow P(St-MAA) particles by sequence soap-free/soap emulsion polymerization and followed by stepwise alkali/acid posttreatment

The effects of ionic emulsifier, sodium dodecylbenzene sulfate (SDBS), on the formation of the multihollow structures in sub-micron sized polymer particles produced by alkali/acid posttreatment were investigated. The original latex particles with narrow size distribution were synthesized by a new sequence emulsifier-free/emulsifier emulsion copolymerization of styrene (St) and methacrylic acid (MAA). Results indicated that the pore size decreased and the pore number increased with the increase of SDBS amount, and the morphology of the posttreated latex particles was also significantly influenced by the introducing time of SDBS in the preparation of the original latex particles, and a suitable introducing time was 3 h of polymerization. (c) 2007 Cheng You Kan. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

PREPARATION AND CHARACTERIZATION OF AFFINITY POLYMER BASIC MICROSPHERES BY SOAP-FREE EMULSION POLYMERIZATION

Poly(styrene-co-glycidyl methacrylate) latex microspheres with uniform size and high-density epoxy groups on the surface were prepared by soap-free emulsion polymerization with batch wise operation mode in the presence of 2.2′- azobis(2-methylpropionamidine) dihydrochloride as an initiator.The kinetics of soap-free emulsion polymerization and the effects of polymerization factors were examined.In addition,the optimum polymerization conditions of poly(styrene-co- glycidyl methacrylate) latex microspheres for...

Facile synthesis of metal-organic frameworks embedded in interconnected macroporous polymer as a dual acid-base bifunctional catalyst for efficient conversion of cellulose to 5-hydroxymethylfurfural

5-Hydroxymethylfurfural(5-HMF),as a key platform compound for the conversion of biomass to various biomass-derived chemicals and biofuels,has been attracted extensive attention.In this research,using Pickering high internal phase emulsions(Pickering HIPEs)as template and functional metal-organic frameworks(MOFs,UiO-66-SO;H and UiO-66-NH;)/Tween 85 as co-stabilizers to synthesis the dual acid-base bifunctional macroporous polymer catalyst by one-pot process,which has excellent catalytic activity in the cascade reaction of converting cellulose to 5-HMF.The effects of the emulsion parameters including the amount of surfactant(ranging from 0.5%to 2.0%(mass)),the internal phase volume fraction(ranging from 75%to 90%)and the acid/base Pickering particles mass ratio(ranging from 0:6 to 6:0)on the morphology and catalytic performance of solid catalyst were systematically researched.The results of catalytic experiments suggested that the connected large pore size of catalyst can effectively improve the cellulose conversion,and the synergistic effect of acid and base active sites can effectively improve the 5-HMF yield.The highest 5-HMF yield,about 40.5%,can be obtained by using polymer/MOFs composite as catalyst(Poly-P12,the pore size of(53.3±11.3)μm,the acid density of 1.99 mmol·g^(-1)and the base density of 1.13 mol·g^(-1))under the optimal reaction conditions(130℃,3 h).Herein,the polymer/MOFs composite with open-cell structure was prepared by the Pickering HIPEs templating method,which provided a favorable experimental basis and theoretical reference for achieving efficient production of high addedvalue product from abundant biomass.

Preparation of Self-crosslinked Fluorocarbon Polymer Emulsion with Core-shell Structure by the Method of Soap-free Emulsion Polymerization

Using methyl methacrylate （MMA）, butyl acrylate（BA） and hexafluorobutyl acrylate（HFBA） as main raw materials, we prepared self-crosslinked fluorocarbon polymer emulsion with core-shell structure via soap-free emulsion polymerization when the conception of particle design and polymer morphology was adopted. Moreover, the influence of mole ratio of BA to MAA, pH value on the oligomer was studied. And the effects of the added amount of oligomer, self-crosslinked monomer and HFBA, mass ratio of BA to MMA, reaction temperature and the initiator on the polymerization technology and the performance of the product, were investigated and optimized. The structure and performance of the fluorocarbon polymer emulsion were characterized and tested with FTIR, TEM, MFT and contact angle and water absorption of the latex film. The experimental results show that the optimal conditions for preparing fluorocarbon polymer emulsion are as follows： for preparing the oligomer, tool ratio of BA to MAA is equal to 1.0 ： 1.60, and pH value is controlled within the range of 8.0 and 9.0; for preparing fluorocarbon polymer emulsion, the added amount of oligmer[P（BA/MANa）] is 6%; mass ratio of BA to MMA is 40 ＂ 60; the added amount of self-crosslinked monomer is 2%, the added amount of HFBA is 15 %; reaction temperature is 80 ℃; the mixture of potassium persulfate and sodium bisulfite is used as the initiator. The film-forming stability of the fluorocarbon polymer emul- sion and the performance of the latex film, which is prepared with the soap-free emulsion polymerization, are better than that prepared with the conventional emulsion polymerization.

Polyaniline-based electrocatalysts through emulsion polymerization:Electrochemical and electrocatalytic performances

One of the major challenges associated with fuel cells is the design of highly efficient electrocatalysts to reduce the high overpotential of the oxygen reduction reaction (ORR). Here we report Polyaniline (PANI) based micro/nanomaterials with or without transition metals, prepared by the emulsion polymerization and subsequent heat treatment. PANI microspheres with the diameter of about 0.7 mu m have been prepared in basic (NH3 solution) condition, using two different types of surfactant (CTAB, SDS) as the stabilizer, ammonium persulphate (APS) as oxidant with aniline/surfactants molar ratio at 1/1 under the hydrothermal treatment. PANI nanorods, Fe-PANI, and Fe-Co-PANI have been synthesized in acidic (HCI) medium with aniline/surfactants molar ratio at 1/2 and polymerization carried out without stirring for 24 h. Products mainly Fe-Co-PANI have shown high current density with increasing sweep rate and excellent specific capacitance 1753 F/g at the scan rate of 1 mV/s. Additionally, it has shown high thermal stability by thermogravimetric analysis (TGA). Fe-PANI has been investigated for excellent performance toward ORR with four electron selectivity in the basic electrolyte. The PANI-based catalysts from emulsion polymerization demonstrate that the method is valuable for making non-precious metal heterogeneous electrocatalysts for ORR or energy storage and conversion technology. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

AQUEOUS STABLE FREE RADICAL POLYMERIZATION PROCESSES

An overview of aqueous polymerizations, which include emulsion, miniemulsion and suspension polymerizations, under stable free radical polymerization (SFRP) conditions is presented. The success of miniemulsion and suspension SFRP polymerizations is contrasted with the difficulties associated with obtaining a stable emulsion polymerization. A recently developed unique microprecipitation technique is referenced as a means of making submicron sized particles that can be used to achieve a stable emulsion SFRP process.

Synthesis of Bowl-like Particles by Emulsion Polymerization and Release Behavior of Solvent from the Particles

Bowl-like poly (styrene-co-glycidyl methacrylate) was synthesized by swollen seeded emulsion polymerization. The polymerization was carried out in PS seed emulsion swollen by toluene, whereby the bowl-like particles formed at last. The shape was observed by SEM. These particles became ball-like when swollen by toluene, observed by optical microscope, and the release behavior of solvent from them was examined.

Preparation of sulphonate-containing core/shell latex particles via seeded emulsion copolymerization

In this study, P（St-MAA） seed latex particles were first prepared via soap-free emulsion polymerization of styrene （St） and methacrylic acid （MAA）, then the seed particles were allowed to swell with St at room temperature, and the P（St-MAA）/P（St- NaSS） core/shell latex particles were then synthesized via seeded emulsion copolymerization of St and sodium styrene sulphonate （NaSS） using AIBN as initiator in the presence of N,N^-methylenebisacrylamide （BAA, water-soluble crosslinker）. Results showed that the polymerization could be carried out smoothly when the ratio of BAA to total monomers was less than 3 mol%, the narrow dispersed P（St-MAA） seed particles with the diameter of 150 nm and the P（St-MAA）/P（St-NaSS） core/shell latexes with the particle size of about 200 nm were synthesized. When the 25/75 mole ratio of NaSS/（St ＋ MAA） and 2 tool% of BAA were used in the seeded emulsion polymerization, the resulted P（St-MAA）/P（St-NaSS） latex product showed a low weight loss after water extraction, and the NaSS unit content in the whole particle and in the shell reached 11.7 mol% and 34.6 mol%, resoectivelv.

Synthesis, adsorption and selectivity of inverse emulsion Cd(Ⅱ) imprinted polymers

Inverse emulsion polymerization was employed to synthesize inverse emulsion Cd（Ⅱ） imprinted polymers （IEⅡ P）. The morphology and functional groups of IEⅡP were characterized by SEM,FTIR and TG. Static adsorption experiments and competitive adsorption test were used to evaluate the adsorption ability of IEⅡP. The adsorption capacity of polymers could reach 86.7 mg·g^-1 under the optimal adsorption conditions. The pseudo second order kinetic model and Langmuir isotherm model could be used to analyze the experimental data well. The adsorption process of IEⅡP was chemical adsorption process and monomolecular type. Thermodynamic parameters showed that the adsorption process was endothermic and could occur spontaneously. The selectivity coefficients k of Cd^2＋/v, Cd^2＋/Zn^2＋ and Cd^2＋/Cu^2＋ were 2.4998, 1.2437 and 4.6882, respectively. The proposed method provides a new thought for removing Cd（Ⅱ） in water samples.

Nonionic Polymerizable Emulsifier in High-Solids-Content Acrylate Emulsion Polymerization

Stable high-solids-content acrylate emulsion were obtained with a nonionic polymerizable emulsifier allyloxy nonylphenoxy poly （ethyleneoxy） （10） ether （ANPEO10）, and a conventional emulsifier OP-10 as a reference sample. 1H NMR proves that the polymerizable emulsifier ANPEO10 has been incorporated into the resulted acrylate polymers. TEM demonstrates that there are some differences in the particle morphologies. AFM proves that the polymerizable emulsifier ANPEO10 migrating to the surface of the emulsion film was much less than the conventional emulsifier OP-10. The polymerizable emulsifier ANPEO10 can enhance the adhesion with glass plate compared to the conventional emulsifier. Furthermore, with increasing amount of emulsifier, the surface free energy of the films first decreased and then increased, and the adhesion with glass plate is initially enhanced and then attenuated. The water-resistance and solvent-resistance of the films prepared by the polymerizable emulsifier ANPEO10 are superior to those prepared by the conventional emulsifier OP-10.

Influences of Electrolytes on the Soap-free Emulsion Copolymerization of St-MMA-AA

Monodisperse functional polymer microspheres with different particle size and with clean surface were prepared by batch soap-free emulsion polymerization of styrene, methyl methacrylate and acrylic acid in the presence of salts, and the influences of type and amount of electrolytes on polymerization process and particle morphology were investigated. Results showed that there was a critical concentration for different electrolyte to make polymerization process and the resultant emulsion stable, and the particle size increased with the increase of electrolyte concentration. The effect of metal ions was Ca^2＋〉〉K^＋〉Na^＋〉Li^＋, and the effect of haloids was Br〉Cl〉F. Keywords： Electrolyte, soap-free emulsion polymerization, polystyrene, latex particle morphology.

Synthesis of Novel Fluorinated Acrylate Co-polymers and Their Application on Cotton Fabrics

Two novel fluorinated acrylate monomers 4a and 4b containing perfluorohexyl group were designed and synthesized starting from 4-allylanisole and perfluorohexyl iodide.The monomers 4a and 4b were then copolymerized with octadecyl acrylate and 2-hydroxyethyl acrylate by emulsion polymerization to give copolymers PFA 1 and PFA 2 respectively.The co-polymers were characterized by FT-IR and their heat stability was measured by TGA.The surface properties of PFA 1 and PFA 2 were studied by applying on cotton fabrics.The treated cotton fabrics showed good water-repellent property,and the contact angles for water reached 142° for PFA 1 and 136° for PFA 2.