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 ...

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, mol 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 emulsion 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.

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.

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

亚微米大小塑造花生(甲基 methacrylate ) poly， /polystyrene (PMMA/PS ) 粒子被苯乙烯的播种没有肥皂的乳剂聚合成功地在球形的 crosslinked PMMA 种子粒子上综合。获得的塑造花生的粒子显示出新奇内部形态学：PS 阶段形成了连接了到把 PMMA 核心被 PS 壳装入箱内的另外的领域的一个领域。

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.

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 Ca2+>>K+>Na+>Li+,and the effect of haloids was Br>Cl>F.

Synthesis and Characterization of Poly (Methyl Methacrylate)/Polyethylenimine Grafting Core-Shell Nanoparticles for CO2 Adsorption Using Soap-Free Emulsion Copolymerization

Unlike previous emulsion polymerization, we used grafting reactions in soap-free emulsion systems. In this study, we synthesized grafted PMMA/PEI core-shell nanoparticles by varying the MMA/PEI content and molecular weight of PEI (Mn = 600, 8000, and 10,000). The size and morphology of the core-shell nanoparticles were characterized by a particle size analyzer and scanning electron microscopy. The nanoparticles were 178 - 408 nm in diameter and swelled in water or methanol by 30 - 75 nm. The size of the nanoparticles increased with MMA contents, whereas the size distribution progressively became homogeneous with increasing molecular weight of PEI. Lastly, we measured CO2 adsorption capacity of the grafted PMMA/PEI core-shell nanoparticles, and we found the capacity to be limited at a level of 0.69 mg, which occurred for nanoparticles prepared from emulsions at a pH value of 11.

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.

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.

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 μm have been prepared in basic(NH3solution) 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(HCl)medium with aniline/surfactants molar ratio at 1/2 and polymerization carried out without stirring for24 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 m V/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.

Grafting Methyl Methacrylate onto Silk via Emulsion Graft Copolymerization Using a Diethylzinc Complex Initiator

Methyl methacrylate (MMA) was grafted onto silk fiber in a one-step emulsion system using a diethylzinc and 1,10-phenanthroline complex. The reaction conditions were investigated by varying temperature and initiator to monomer ratio. Fourier transform infrared (FTIR) spectrum, thermogravimetric analysis (TGA), and scanning electron microscopy (SEC) techniques were used to characterize the structure, thermal stability, and surface morphology of the obtained product, respectively. Grafting of MMA onto silk increased the thermal stability of silk. The FTIR spectrum and SEM images provided further evidence that MMA has been successfully grafted onto the silk fiber. A peak ascribed to the C=O stretching vibration of MMA was detected in the FTIR spectrum of grafted silk fiber, which was not present in the spectrum of pure silk fiber. Moreover, the SEM images illustrated the increase in diameter and surface roughness of grafted silk compared with pure silk. Lastly, the dyeing performance of the modified silk was significantly increased.

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 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.

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.

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.

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 particles were formed at low polymerization conversions. The amount of fine particles decreases as conversion increases and disappears at conversions greater than 30%. Scanning electron micrographs show that PVC grains are composed of loosely coalesced primary particles, especially for PVC resins prepared in the presence of poly(vinyl alcohol) dispersant. The size of primary particles increases and porosity decreases with the increase of conversion. In view of the particle features of PVC resin, a particle formation mechanism including the formation of primary particles and grains is proposed. The formation process 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 of primary 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.

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

在这研究， P ( StMAA )种子乳胶粒子首先经由苯乙烯(圣)和甲基丙烯酸( MAA )的没有肥皂的乳剂聚合被准备，然后，种子粒子被允许在房间温度与圣胀大，并且 P ( StMAA ) /P ( StNaSS )核心/壳乳胶粒子然后面对 N 作为开始者用 AIBN 经由圣和钠苯乙烯磺酸盐( NaSS )的播种乳剂 copolymerization 被综合， N-methylenebisacrylamide (咩，水溶性的 crosslinker )。当到全部的单体的咩的比率是不到 3 mol%时，结果证明聚合能顺利被执行，有有粒子的 /P ( StNaSS )核心/壳乳胶大约 200 nm 缩放的 150 nm 和 P ( StMAA )的直径的狭窄的驱散的 P ( StMAA )种子粒子被综合。当NaSS/(圣+ MAA )和咩的 2 mol%的 25/75 鼹鼠比率在播种乳剂聚合被使用时，结果的 P ( StMAA ) /P ( StNaSS )乳胶产品在水抽取以后显示出低重量损失，并且在整个粒子并且在壳的 NaSS 单位内容分别地到达了 11.7 mol%和 34.6 mol%。

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-solidcontent. The effects of monomer emulsion feed rates (R_a) and (R/E)_E values, the ratio ofemulsifier amount between the initial charge (R) and the addition monomer emulsion (E),on the polymerization reaction features, the viscosities, surface tensions,particle sizes andparticle sizes distributions of latexes,T_g and the insoluble fractions of films, the 180° peelstrength, tack and holding power of pressure-sensitive adhesive (PSA) tapes, preparedfrom the latexes, were studied. Experimental study shows that the grafting and cross-linking fraction in the PSA tapes must be controlled within a suitable range to keep thebalance of the 180° peel strength, tack and holding power.