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 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.

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 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.

On the Mechanism of Latex Particles Formation in Polymerization in Heterogeneous Monomer-Water System

Investigations show that in monomer water heterogeneous systems polymerization, located in the interface, can disperse the system. Following polymerization in the density gradient field it is shown that in such systems latex particles are nucleated from monomer microdroplets, containing a certain amount of polymer molecules. It could be considered that, independently of the nature of the monomer itself, polymerization in monomer water statistic heterogeneous systems modulate emulsion polymerization process.

Preparation and Application of the Hydrophilic Amino-Silicone Softener by Emulsion Polymerization

The amino poly-siloxane was modified with self-made polyether silicones by the crafts of emulsion polymerization. We studied the emulsifier, the dosage of emulsifier initiator, polyether/silane coupling agent, pH value. There are some results of the research indicated in the following. First, there are many factors for the hydrophilic amino-silicone softener both on the polymerization process and the performance, such as the proportion and amount of emulsifier, initiator dosage, the mass ratio of the polyether and hydrogen silicone oil, the choice of silicone coupling agent, and the ratio and dosage of polyether silicones silane coupling agent. Second, the amount of hydrogen of the hydrogen silicones and the choice of catalyst are the key points on the synthesis of polyether silicones. The amount of hydrogen should be low and the catalyst must be economical and efficient and its introduction should be small and times, other more the holding time is not too long. The next one is that, in the process of hydrolysis of silane coupling agent, we need some acid to adjust pH value, or they will be broken down. The most important one but not the last is that the epoxy group can improve the products low-temperature supple and the persistence of the finishing fabric, furthermore it can reduce yellowing and has a good stability of the inorganic salt, however, it will be destroyed if the reaction temperature for epoxy is too high. What’s more, it is very economical and environmental that the process of emulsion is simple and with less emulsifier.

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.

THE EFFECT OF MONOMERS FEEDING METHODS ON EMULSION COPOLYMERIZATION OF VINYLIDENE CHLORIDE AND ACRYLATES

The emulsion copolymerization of vinylidene chloride (VDC) with methyl-methacrylate(MMA) and acrylonitrile (AN) was carried out by batch, seeded batch and semicontinuous pro-cesses,respectively. Significant differences were found in the physical and mechanical propertiesof the latexes and films, depending on the methods of monomer feeding. The results both intheory and experiments demonstrated that the copolymer composition and the length of the VDC sequences in the copolymer could be controlled by the modes of monomer feeding process.

Investigation on the Inverse Emulsion Polymerization of Acrylic Acid

Polyacrylic acid particles in nano-scale were synthesized using an inverse (W/O) emulsion polymerization method. The particle size and size change of inverse micelles which solubilize a part of monomer solution was monitored by PCS (photon correlation spectroscopy) and the particles of polyacrylic acid were viewed in scanning electron microscope for the first time. It was concluded that the inverse micelles were primarily the polymerization reaction sites.

Self-assembly of Gradient Copolymer Synthesized by Spontaneous Batch RAFT Emulsion Polymerization and Its Application on Encapsulating Ag Nanoparticles

The gradient copolymers of acrylic acid and trifluoroethyl methacrylate（coded as P（TFEMAgrad-AA）） were synthesized via reversible addition-fragmentation transfer（RAFT） emulsifier-free emulsion polymerization. The spontaneous batch feeding approach was used to control the gradient chain sequence. Transmission electron microscopy（TEM） analysis revealed that the P（TFEMA-grad-AA） can self-assemble to form spherical micelles, rodlike micelles or vesicles in selective solvents. Morphological transition of the P（TFEMA-grad-AA） micelles was sensitive to the water content of the dioxane/water mixed solvent. More interestingly, Ag nanoparticles（NPs） were encapsulated by the P（TFEMA-grad-AA） micelles during the selfassembly process. The gradient chain sequence made the Ag NPs easily enter the core of the micelles, even when P（TFEMA-grad-AA） had less hydrophobic fluoro-units and more hydrophilic units. TEM images with energy dispersive spectrometer indicated that the nanocomposite micelles consisted of a Ag NPs core and a gradient copolymer shell.

INFLUENCES OF ACID POST-TREATMENT ON THE MORPHOLOGY OF SOAP-FREE P(MMA-EA-MAA)PARTICLES PREPARED BY SEEDED EMULSION POLYMERIZATION

Soap-free poly（methyl methacrylate-ethyl acrylate-methacrylic acid） latex particles with narrow size distribution were synthesized by seeded emulsion polymerization, and the porous particles were created by a stepwise alkali/acid treatment method. Effects of acid treatment conditions on the particle morphology were investigated. Results show that one to three pores were formed inside most of particles after post-treatment. At pH 7.0, when the treatment temperature was lower than 70℃, the size of particles and the volume of pores remained almost unchanged, and these two values increased significantly when the temperature was higher than 70℃. Both the particle size and the pore volume decreased with the increase of initial pH value and treatment time in the acid treatment. As the pH was below 4.0 and the treatment time was longer than 180 min, the particles shrunk in size.

INFLUENCES OF WATER-SOLUBLE CATIONIC MONOMERS ON THE POLYMERIZATION RATE IN THE INVERSE EMULSION

This investigation deals with the free radical polymerization both of (2-methacryloyloxyethyl) trimethyl ammonium chloride (QACEMA) and of diallyldimethyl ammonium chloride (DADMAC) in inverse emulsion. The influences of some factors, such as the concentration of monomers, initiator and emulsifier are discussed. The polymerization rate equations of above two monomers can be written as follows: R(p) = k[M](1.21)[I](0.82)[E](0.57) (for QACEMA) R(p) = k'[M](1.34)[I](0.90)[E](0.62) (for DADMAC)

Effects of water phase concentration on the emulsion polymerization of polyaniline

The emulsion polymerization of aniline in three phase system of xylene functionalized protonic acid water was carried out using (NH 4) 2S 2O 4 as oxidant. The influences of water phase concentration on the viscosity, conductivity, transmittance of polyaniline(PAN) latex and its powders were studied. The results show that the properties of PAN prepared through the emulsion polymerization are influenced by the amount of water used in the polymerization. The morphology of PAN varies with the water phase concentration used in the polymerization, which may result in the change of properties of PAN latex and its powders. When the volume fraction of water (φ) is about 20% 30%, the prepared PAN powder has higher conductivity, and the PAN latex has appropriate viscosity and particle size. The consumption of xylene was reduced at high φ value.

THE PREPARATION OF DOXORUBICIN-POLYVINYLPYRROLIDONE-NANOPARTICLES BY INVERSE EMULSION POLYMERIZATION

Doxorubicin-loaded nanoparticles, using doxorubicin （ADM） as model drug and vinylpyrrolidone as matrix, were prepared by inverse emulsion polymerization in the paper. The nanoparticles were characterized by telescope electron microscopy （TEM）, laser light scattering technique （LLS） and infrared spectrum （IR）. LLS test showed that the optimal prepared ADM-loaded nanoparticles had an average size 18.8nm and a narrow size distribution between 15nm and 32nm, which was consistent with the result obtained by TEM. And 1R results indicated that the nanoparticles consisted of ADM and polyvinylpyrrolidone （PVP）.

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.

Emulsion Polymerization of Vinyl Acetate in the Presence of a New Cationic Surfactant

In this study, the emulsion homopolymerization system containing vinyl acetate, potassium persulfate, a new cationic polymeric surfactant and water was studied by the applying semi-continuous emulsion polymerization process. The effects of new polymeric emulsifier on the physicochemical properties of obtained vinyl acetate latexes were investigated depending on vinyl acetate percentage in the polymerization recipe, and two thermal initiators in homopolymerization.

Synthesis of ABA Type Block Copolymers of Poly(Ethylene Glycol)and Poly(Dodecyl Vinyl Ether)and Its Using as Surfactant in Emulsion Polymerization

A poly(ethylene glycol) (PEG) based macroinitiator (MI) with terminal chloride atom at both ends was prepared by the reaction of PEG-400 with chloroacetyl chloride and used for the cationic polymerization of dodecyl vinyl ether (DVE) yielding ABA type block copolymer. The block copolymer was then used as the surfactant for the emulsion polymerization of vinyl acetate and styrene in the presence of potassium persulfate as an initiator. The effects of new polymeric emulsifier on the physicochemical properties of obtained latexes were investigated depending on surfactant percentage in homopolymerizations.

STUDY ON SYNTHESIS OF AMPHOTERIC POLYACRYLAMIDE IN INVERSE EMULSION

Amphoteric polyacrylamide was prepared first by the copolymerization of acrylamide with sodium acrylate and then through Mannich reaction.The copolymerization was carried out with a redox initiation system using the method of inverse emulsion polymerization.In this paper the reaction conditions and factors that affect emulsion stability were studied.Experiments show that a stable latex can be obtained under the following conditions:anionic degree is five percent,the ratio among acrylamide,formaldehyde and dimethylamine is 1∶1∶1.2,reaction temperature is 45 ℃,reaction time lasts four hours,and pH equals 5.0.The amphoteric copolymer has a higher molecular weight and cationic degree,so it is an ideal filler retention and drainage aid in paper making.

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.

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.