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 of crosslinked polystyrene particles by seeded batch polymerization with monomer absorption

A highly crosslinked, monodispersed polystyrene（PS） particle was prepared by a seeded batch dispersion polymerization with a monomer absorption method. Prior to polymerization, 1,9 lam monodispersed PS seed particles were treated under an optimum condition of monomer absorption. The effects of divinylbenzebe（DVB） concentration and polymerization temperature were examined for styrene（in PS seed）/styrene（in the second stage） mass ratio of 1：1 in the medium range of EtOH/water mass ratio of 100/0-80/20 and 2.3 μm uniform crosslinked PS particles containing 15%-20% （mass fraction） DVB were prepared at 60-70 ℃. The results show that monomer absorption before the second stage of polymerization is more effective to prepare highly crosslinked monodispersed PS particles.

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.

SEED SEMICONTINUOUS EMULSION MULTI-COPOLYMERIZATION OF (METH) ACRYLATES WITH HIGH-SOLID CONTENT: EFFECT OF THE OPERATION CONDITIONS

The seeded semicontinuous emulsion multi-copolymerization of butyl acrylate (BA), 2-ethylhexyl acrylate (2EHA), methyl methacrylate (MMA), 2-hydroxyl propyl acrylate (HOPA) and acrylic acid (AA) was used to prepare the acrylic latexes with high-solid content. The effects of monomer emulsion feed rates (R(a)) and (R/E)(E) values, the ratio of emulsifier amount between the initial charge (R) and the addition monomer emulsion (E), on the polymerization reaction features, the viscosities, surface tensions,particle sizes and particle sizes distributions of latexes, T-g and the insoluble fractions of films, the 180 degrees peel strength, tack and holding power of pressure-sensitive adhesive (PSA) tapes, prepared from the latexes, were studied. Experimental study shows that the grafting and crosslinking fraction in the PSA tapes must be controlled within a suitable range to keep the balance of the 180 degrees peel strength, tack and holding power.

SYNTHESIS OF BOWL-LIKE PARTICLES BY EMULSION POLYMERIZATION AND RELEASE BEHAVIOR OF SOLVENT FROM THE PARTICLES

Poly(styrene-glycidyl methacrylate) particles having bowl-shaped hollow structures were synthesized by swollen seed emulsion polymerization. The PS emulsion synthesized through soap-free emulsion polymerization was swollen by toluene, and then the mixture of second monomers was added under polymerization condition. So a thin shell of poly(styrene-glycidyl methacrylate) cross-linked by triethylene glycol diacrylate was formed around the swollen PS particle. The bowl-shaped particles were obtained after the collapsing of the thin shell when the toluene emanated from the particles, but the shapes were effected by the degrees of cross-linking. The shape of the particles was observed by SEM. The release behavior of solvent from the particles was examined by TG.

Synthesis and Characterization of Fluorine-containing Polyacrylate Emulsion with Core-Shell Structure

A fluorine-containing polyacrylate copolymer emulsion was synthesized by a seed emulsion polymerization method, in which methyl methacrylate （MMA） and butyl acrylate （BA） were used as main monomers and hexafluorobutyl methacrylate （HFMA） as fluorine-containing monomer. The structure and properties were characterized by Fourier transform infrared spectrum （FT-IR）, transmission electron microscopy （TEM）, particle size analysis, X-ray photoelectron spectroscopy （XPS）, contact angle （CA）, differential scanning calorimetry （DSC） and thermogravimetry （TG） analysis. The FTIR and TEM results showed that HFMA was effectively involved in the emulsion copolymerization, and the formed emulsion particles had a core-shell structure and a narrow particle size distribution. XPS and CA analysis revealed that a gradient concentration of fluorine existed in the depth profile of fluorine-containing emulsion film which was richer in fluorine and more hydrophobic in one side. DSC and TG analysis also showed that a clear core-shell structure existed in the fluorine-containing emulsion particles, and their film showed higher thermal stability than that of fluorine-free emulsion.

Synthesis of submicron-sized peanut-shaped poly(methyl methacrylate)/polystyrene particles by seeded soap-free emulsion polymerization

Submicron-sized peanut-shaped poly（methyl methacrylate）/polystyrene （PMMA/PS） particles were successfully synthesized by seeded soap-free emulsion polymerization of styrene on the spherical crosslinked PMMA seed particles. The obtained peanut- shaped particles showed a novel internal morphology： PS phase formed one domain which linked to the other domain having PMMA core encased by PS shell.

The Doubly Thermo-responsive Triblock Copolymer Nanoparticles Prepared through Seeded RAFT Polymerization

The doubly thermo-responsive triblock copolymer nanoparticles of polystyrene-block-poly（N- isopropylacrylamide）-block-poly[N,N-（dimethylamino） ethyl methacrylate] （PS-b-PNIPAM-b-PDMAEMA） are successfully prepared through the seeded RAFT polymerization in situ by using the PS-b-PNIPAM-TTC diblock copolymer nanoparticles as the seed. The seeded RAFT polymerization undergoes a pseudo-first-order kinetics procedure, and the molecular weight increases with the monomer conversion linearly. The hydrodynamic diameter （Dh） of the triblock copolymer nanoparticles increases with the extension of the PDMAEMA block. In addition, the double thermo-response behavior of the PS-b-PNIPAM-b-PDMAEMA nanoparticles is detected by turbidity analysis, temperature-dependent 1H-NMR analysis, and DLS analysis. The seeded RAFT polymerization is believed as a valid method to prepare triblock copolymer nanoparticles containing two thermo-responsive blocks.

PREPARATION OF MICRON-SIZED NONSPHERICAL POLYSTYRENE/POLY(STYRENE-co-ETHYLENEGLYCOL DIMETHACRYLATE) PARTICLES BY SEEDED SOAP-FREE EMULSION POLYMERIZATION

Micron-sized nonspherical polymer particles having different morphologies were synthesized by seeded soap-free emulsion polymerization of styrene （St） and ethyleneglycol dimethacrylate （EGDMA, used as a crosslinker） on spherical, linear polystyrene （PS） seed particles. The morphology of the resulting PS/poly（St-co-EGDMA） particles was dependent on the crosslinker concentration and polymerization temperature.

Poly(methyl methacrylate)/Poly(N-isopropylacrylamide) Core-Shell Particles Prepared by Seeded Precipitation Polymerization: Unusual Morphology and Thermo-sensitivity of Zeta Potential

Poly（methyl methacrylate）/poly（N-isopropylacrylamide） （PMMA/PNIPAM） core-shell particles were synthesized by seeded precipitation polymerization of N-isopropylacrylamide （NIPAM） in the presence of PMMA seed particles. The anionic potassium persulfate was used as initiator, and acrylic acid as functional comonomer. It was shown that the weight ratio of the PNIPAM shell to the PMMA core can be greatly increased through continuous addition of NIPAM monomer at a relatively slow rate. PMMA/PNIPAM particles with different shell thickness were obtained by varying the amount of charged NIPAM monomers. These particles exhibited unique nonspherical core-shell morphology. PMMA core was partially coated by dense hair-like or antler-like PNIPAM shell depending on the shell thickness. The measurement of these particles＇ zeta potential at different temperatures showed that the absolute value of zeta potential unusually decreased as the particle size decreased with temperature.

A New Kind of Void Soap-free P(MMA-EA-MAA) Latex Particles

Soap-free P(MMA-EA-MAA) particles with narrow size distribution were synthesized by seeded emulsion polymerization of methyl methacrylate (MMA), ethyl acrylate (EA) and methacrylic acid (MAA), and large voids inside the particles were generated by alkali posttreatment in the presence of 2-butanone. Results indicated that the size of void and the particle volume were related with the amount of 2-butanone. The generation mechanism of voids was proposed.

PREPARATION OF HOLLOW LATEX PARTICLES BY ALKALI-ACID TREATMENT

Hollow polymer latex particles were prepared by seeded emulsion polymerization. A seed latex consisting of styrene (St), butyl acrylate(BA) copolymer was first prepared, and seeded terpolymerization of St BA MA(methacrylic acid) were then carried out in the absence of surfactant. Final latex was treated by a two step treatment under alkaline and acidic conditions, thus, the particles with hollow structure were obtained. We discussed the effects of pH value, temperature and time in alkali and acid treatment processes on hollow structure within the polymer latex particles and amount of carboxylic group on particle surface. The results show that the hollow polymer latex particles with the largest hollow size can be obtained under a certain condition (pH12.5, 90°C, 3 h in alkali treatment stage and pH2.5, 85°C, 3 h in acid treatment stage).

Poly(2-acetoxyethyl methacrylate)/polystyrene latex interpenetrating polymer networks with well-defined phase-separated structure

A series of poly（2-acetoxyethyl methacrylate）/polystyrene（PAEMA/PS） latex interpenetrating polymer networks（LIPNs） were prepared by seeded soap-free emulsion polymerization of styrene on the crosslinked PAEMA seed particles using an oil-soluble initiator.These PAEMA/PS LIPNs showed a well-defined phase-separated structure with PS phase dispersing in continuous PAEMA phase.The domain size of PS phase was found to depend on the crosslinking degree of PAEMA seed particles and the amount of second-stage styrene monomer.

A Novel Approach to Prepare Core/Shell Polymer Latex Particles with High Sulphonate Contents

Crosslinked x-P（St-MAA） seed latex was first prepared via soap-free emulsion copolymerization of styrene （St） and methyl methacrylic acid （MAA） with divinyl benzene as crosslinker and ammonium persulfate as initiator, and x-P（St-MAA）/x-P（St-NaSS） core/shell latex particles were then synthesized through a novel seeded emulsion copolymerization of St and sodium styrene sulphonate （NaSS） in the presence of water-soluble crosslinker N,N＇-methylene bisacrylamide （BAA） using oil-soluble 2,2-azobis isobutyronitrile as initiator. TEM observation indicated that narrow dispersed core/shell latex particles were obtained, and element analysis showed that NaSS unit content in the whole particle and in the shell reached 22.8 wt% and 51.2 wt%, respectively.