Preparation of a self‐compatibility alloy via a seed‐graft concentrated‐emulsion pathway

A novel polymerization procedure, the concentrated‐emulsion graft polymerization of styrene monomer with poly(butyl acrylate) seed, was proposed for the production of a self‐compatibility macromolecule alloy. The effects of the butyl acrylate content, sodium dodecyl sulfate concentration, and polymerization temperature on the graft ratio were investigated. Scanning electron microscopy, transmission electron microscopy, and impact strength were used to characterize the microstructure and mechanical performance of the self‐compatibility macromolecule alloy. The results showed that increasing the butyl acrylate content, reducing the sodium dodecyl sulfate concentration, and improving the polymerization temperature all favored an increased graft ratio, which resulted in increased impact strength of the self‐compatibility macromolecule alloy. Therefore, the concentrated‐emulsion polymerization method is particularly suitable for seed‐graft polymerization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2915–2920, 2002; DOI 10.1002/app.10288     

Preparation of flexible polyhedral particles via concentrated emulsion templating polymerization

This paper presents recent efforts on the preparation of flexible polyhedral particles via concentrated emulsion templating polymerization in which the hydrophilic monomer (acrylamide) and hydrophobic monomer (butyl acrylate) are polymerized simultaneously in the continuous and dispersed phase, respectively. Such templating polymerization has been enhanced in our systems owing to the introduction of acrylamide monomer and their higher polymerization rate in continuous phase as compared with butyl acrylate in dispersed phase. Diffusion between the different phases was also inhibited. Furthermore, the stability of the concentrated emulsion and the molecular weight of the produced poly(butyl acrylate) were found to be significantly affected by the amount of redox initiator. The morphology of the particles could be controlled by varying the volume fraction of the dispersed phase and the polyhedral particles were achieved at higher volume fraction. Copyright © 2005 Society of Chemical Industry     

The effect of varied monomer composition on adhesive performance and peeling master curves for acrylic pressure‐sensitive adhesives

A group of pressure‐sensitive adhesives were prepared with constant glass transition temperature, using emulsion polymerization. The monomers chosen were butyl acrylate, 2‐ethylhexyl acrylate, and methyl methacrylate, along with a small amount of acrylic acid. The proportion of acrylic acid monomer was held constant for each polymer preparation but acrylic ester monomer levels were varied. The glass transition temperatures of the acrylate copolymers were measured by using differential scanning calorimetry. Drying and weighing the tetrahydrofuran‐insoluble polymer fractions were used to determine the polymer gel fractions. Films of constant coating thickness were applied to poly(ethylene terephthalate) film and adhesive properties (tack and shear) were examined. Peel was examined through the construction of master curves derived from peel tests conducted over a range of temperatures and peel rates. As the 2‐ethylhexyl acrylate content increased, the latex gel fractions were found to increase. With increasing EHA and gel fraction, peel shear was found to increase. When peel force master curves were compared, divergence in peel master curves occurred as peel rates increased where polymers with higher butyl acrylate contents reached greater peel stress values. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2909–2917, 2004     

Preparation and properties of poly(WPSF‐co‐butyl acrylate) copolymer emulsion with ultrasonic radiation II. Monomer conversion rate and characterization

A stable emulsion of poly(WPSF‐co‐butyl acrylate) based on butyl acrylate, waste polystyrene foam was synthesized through emulsion polymerization using sodium dodecyl sulfate and octyl phenyl polyoxyethylene ether as surfactant, ammonium persulfate and sodium hydrogen bisulfate as mixed redox initiator, under ultrasound irradiation in the absence of inert gas. The effects of various copolymerization conditions on the monomer conversion were reported. The copolymers were characterized by means of IR, ¹HNMR, and gel permeation chromatography. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation of porous polymer materials using water‐in‐oil gel emulsions as templates

Water‐in‐oil gel emulsions consisting of water and n‐butyl acrylate were successfully prepared using N‐3‐hydroxybutylcarbonyl‐l ‐isoleucylaminooctadecane and sorbitan monooleate (Span 80) as gelator and surfactant, respectively. Stable gel emulsions were formed using aqueous phase fractions (APFs) ranging from 10 to 90 vol%. Creaming, flocculation and coalescence were not observed. Low‐temperature polymerization of the gel emulsions with a redox initiator gave the corresponding low‐density, highly porous poly(n‐butyl acrylate)s (PBAs). The microstructures of the PBAs were observed using scanning electron microscopy. All the porous PBAs comprised numerous spherical structures whose sizes could be controlled by adjusting the gel emulsion APF. The densities and porosities of the porous PBAs decreased and increased, respectively, with increasing APF. The absorption capacities of the porous PBAs in organic solvents were studied. The porous PBAs selectively absorbed kerosene from water instantly and the kerosene could then be recovered by physical compression of the PBAs. Further porous polymers were prepared from gel emulsions containing styrene, methyl methacrylate (MMA) or 2‐ethylhexyl acrylate (EHA) as continuous oil phases. The order of absorption capacity and swelling ratio in kerosene was poly(EHA) > PBA ? poly(MMA). Porous copolymers were also prepared from gel emulsions containing a mixture of EHA and MMA as the oil phase. Their absorption and swelling in liquids could be controlled by changing the ratio of EHA and MMA in the gel emulsions. poly(EHA‐co‐MMA) (6:4) was the best polymer when absorption capacity, swelling ratio and durability were simultaneously considered. © 2018 Society of Chemical Industry     

Acrylonitrile-co-vinyl acetate with uniform composition via adiabatic, self-heating copolymerization in a concentrated emulsion

A copolymer of acrylonitrile and vinyl acetate was prepared via the room temperature-initiated, self-heating polymerization of a concentrated emulsion. A mixture of the monomers containing an oxidant was first dispersed in an aqueous solution of surfactants to generate a concentrated emulsion with a volume fraction of 0.8 of the dispersed phase. An aqueous solution of reductants was subsequently introduced into the concentrated emulsion to initiate polymerization together with the oxidant. Since the container was properly insulated, the system self-heated because of the energy released from polymerization, and achieved a high conversion in 30 min. The molecular weight distribution was determined using the gel permeation chromatography (GPC), and the composition of the product was determined via elemental analysis. The GPC traces indicated that the molecular weight was a function of time. The longer the polymerization time, the greater the molecular weight. During polymerization, the composition remained almost unchanged. These two results differ from those of the traditional radical polymerization.     

Preparation of poly(vinyl alcohol)/poly(acrylic acid) microcapsules and microspheres and their pH-responsive release behavior

The pH-responsive poly(vinyl alcohol)/poly(acrylic acid) hydrogel microparticles containing vitamin B₁₂ were prepared with emulsion polymerization. Both microcapsule and microsphere were easily produced by simply changing the sequence of ingredient addition during the emulsion polymerization. The microparticles showed the faster and larger release of vitamin B₁₂ due to the higher swelling of hydrogel by electrostatic repulsion of carboxylate groups in poly(acrylic acid) as the pH was changed into more basic condition. The microcapsules showed a faster release than the microspheres did due to the less hindered passage through the thinner shell of microcapsules. The poly(vinyl alcohol)/poly(acrylic acid) hydrogel microparticles either protected or released the vitamin B₁₂ effectively depending on pH.     

氧化还原引发剂对丙烯酸酯乳液性能及聚合机制的影响

以过硫酸钾(KPS)和亚硫酸氢钠(NaHSO3)为自由基聚合体系的氧化-还原型引发剂,以十二烷基硫酸钠(SDS)和脂肪醇聚氧乙烯醚硫酸钠(AES)为阴/非离子型复合乳化剂,制备甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)和甲基丙烯酸(MAA)共聚物乳液。研究了引发剂种类及用量对该乳液性能及聚合过程等影响,探讨并提出了酸性条件下丙烯酸酯乳液体系的新型引发机制。结果表明:在其他条件保持不变的前提下,当m(KPS):m(NaHSO3)=1.00:0.45、w(KPS+NaHSO3)=0.6%时,乳液的单体转化率(98%)和黏度(5.900 Pa.s)相对最高,反应时间(2.0 h)相对较短且初始聚合温度(60℃)相对最低,此时乳液质量最稳定。     

Microporous polyurethane/acrylate gel polymer electrolyte obtained by emulsion polymerization

A novel polyurethane/acrylate (PUA) porous gel electrolyte was prepared by a new method, emulsion polymerization. Compared with the traditional phase inversion method, the new method can eliminate the pollution from solvent and decrease the cost of production. The swelling properties and morphology of the porous polymer membranes were characterized. The porous membranes, made by emulsion polymerization, could absorb large quantities of electrolyte solution to form porous gel electrolytes. The gel electrolytes have good solvent retention ability and high ionic conductivity. Copyright © 2004 Society of Chemical Industry     

Concentrated emulsions pathways to polymer blending

A new method of preparation of polymer composites involving the concentrated emulsion polymerization is described. In this kind of emulsion, the volume fraction of the dispersed phase is very large (as large as 0.99), while the volume fraction of the continuous phase is very small. In the present case, a monomer containing an appropriate initiator constitutes the dispersed phase and a dilute solution of surfactant in water constitutes the continuous phase. In a first step, two such concentrated emulsions containing different monomers were prepared and each of them was subjected to heating at 40°C for partial polymerization. Subsequently, the two partially polymerized systems were mechanically mixed, and the mixture was subjected to additional polymerization, drying, and sintering by heating at various temperatures for various time intervals. Partially polymerized concentrated emulsions of polystyrene, poly(buthyl methacrylate), poly(buthyl acrylate), and cross linked polystyrene, whose conversions were less than 5%, were employed. Conversions higher than 5% led to large increases in the viscosity of the concentrated emulsions, making their mixing difficult. N.m.r. spectroscopy was used to obtain information about the extent of copolymerization between the two monomers. Electron microscopy examination of the surfaces obtained by the fracture of the composites revealed that the latex particles aggregated with relatively slight changes in size and shape.     

乙烯基三乙氧基硅烷/丙烯酸酯共聚乳液的研究

以聚丙烯酸丁酯为种子乳液，将乙烯基三乙氧基硅烷（VTES）与丙烯酸酯进行乳液共聚，制成了聚合稳定性良好，性能稳定的有机硅／丙烯酸酯共聚乳液，详细讨论了VTES用量对聚合过程稳定性和乳液粒径大小及分布的影响，采用动态光散射法跟踪了聚合过程的粒径大小及分布，采用TEM表征了粒子形态；同时研究了乳液的粘度及乳胶膜的耐水性能，结果表明：乳胶粒的平均粒径随聚合时间的延长逐渐增大，乳胶粒呈球形，具有核壳结构，随着VTES用量的增加，乳液聚合的稳定性变差，乳胶粒的平均粒均增大，乳液的粘度增加，乳胶膜的吸水率减小。     

Preparation and properties of modified PHEMA hydrogel with sulfonated PEG graft

A novel poly(ethylene glycol) (PEG) macromer with a methacryloyl and sulfonic acid group at each end of the chain was prepared. Modified hydroxyethyl methacrylate (HEMA) based hydrogels were synthesized by crosslinking polymerization of HEMA in the presence of the above‐mentioned PEG macromer. The effect of the sulfonated PEG graft was examined by comparing the swelling properties with those of a pure poly(hydroxyethyl methacrylate) (PHEMA) hydrogel. The modified PHEMA hydrogel exhibited increasing water absorbency with increasing sulfonated PEG content up to 15 wt %. These hydrogels with the sulfonated PEG graft exhibited a more hydrophilic character than the pure PHEMA gel. Also the swelling degree varied slightly with pH, showing increased swelling at higher pH probably due to the presence of the anionic sulfonate group on the PEG end chain. In addition, the protein adsorption test showed a lower level of fibrinogen adsorption from the sulfonated poly(ethylene glycol) (SPEG) modified gel than on the homo PHEMA hydrogel. Interestingly, scanning electron microscopy showed that the porous and rather uniform morphology of the gels changed with increasing sulfonated PEG content in PHEMA. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2484–2489, 2007     

粒径可控的聚丙烯酸丁酯/聚甲基丙烯酸甲酯核壳乳液的制备及表征

采用种子乳液聚合法制备了聚丙烯酸丁酯(PBA)乳液,然后通过第二单体甲基丙烯酸甲酯的预溶胀法聚合制备了PBA/聚甲基丙烯酸甲酯(PMMA)乳液,用激光散射粒度仪和透射电子显微镜对乳液粒径和结构进行了表征.结果表明,当乳化剂十二烷基硫酸钠质量分数为丙烯酸丁酯的1.5%时,可制备粒径为53.6 nm且分布窄的PBA种子乳液;通过调整补加乳化剂、单体与种子乳液的用量,可制得粒径为53.6～443.8 nm的一系列单分散PBA乳液;PBA/PMMA乳液具有完善的核壳结构,且在核壳两相间存在着一个过渡层.     

Preparation of carboxylated polymer emulsion particles in which carboxyl groups are predominantly localized at surface layer by using the seeded emulsion polymerization technique

It was studied how to localize carboxyl groups at the particle surface in a preparation of styrene (S)/butyl acrylate (BA)/methacrylic acid (MAA) polymer emulsion. The relative distribution of carboxyl groups in the emulsion was determined by conductometric titration method: in serum, at surface, and inside particle. By seeded (two-stage) emulsion polymerization that S–BA–MAA terpolymer emulsion was first prepared at low pH and then second stage polymerization of S–BA was continued at high pH, S/BA/MAA polymer emulsion particles in which carboxyl groups are localized predominantly at the surface could be prepared.     

Concentrated emulsion copolymerization of butyl acrylate and vinyl acetate initiated by a redox initiator at lower temperature

The concentrated emulsion copolymerization of butyl acrylate and vinyl acetate with an ammonium persulfate/sodium hydrogen sulfate mixture as a redox initiator, with a sodium dodecyl sulfate/cetyl alcohol mixture as a compound surfactant, and with poly(vinyl alcohol) as a liquid film reinforcer was carried out at lower temperature. In less than 3 h, the polymerization conversion was greater than 95%. The effects of the surfactant, the initiator, the volume fraction of the monomer, and the temperature on the stability of the concentrated emulsion, the kinetic process, and the average size of the latices were examined. The morphology of the polymer particles was observed by transmission electron microscopy, and the average size and distribution of the particle diameter were measured by photon correlation spectroscopy. The kinetic equation was R_p = k[M]^0.38[I]^0.89[E]^?0.80 at 30°C (where R_p is the polymerization rate, [I] is the initiator concentration, [M] is the monomer concentration, and [E] is the concentration of the compound surfactant), and the apparent activation energy was 22.69 kJ/mol. The thin‐layer polymerization of the concentrated emulsions, which enabled the removal of the heat of polymerization, was performed first. In comparison with test‐tube polymerization, thin‐layer polymerization provided a more regular morphology of the polymer particles. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 570–576, 2004     

Emulsion gel beads prepared by sedimentation polymerization using two-fluid atomization and their Pd(II) ion adsorption properties

An emulsion gel adsorbent which was a polymeric hydrogel containing randomly distributed oil microdroplets of an extractant was developed for improved metal adsorption in our previous study. This study focuses on the preparation of monodisperse, millimeter- or sub-millimeter-sized emulsion gel beads, for which a novel production method combining sedimentation polymerization and two-fluid atomization is proposed. The method involves the drop-wise addition of a pre-gel oil-in-water emulsion solution into a silicone oil through a nozzle, with nitrogen gas flow, and the subsequent free-radical polymerization of the pre-gel droplets during their descent. A novel type of emulsion gel bead composed of a poly(ethylene glycol) methyl ether acrylate hydrogel and di-n-hexylsulfide as an extractant was developed. The size of the emulsion gel beads was controlled by adjusting the gas flow rate. The emulsion gel beads successfully adsorbed Pd(II) ions that were used as a model metal.     

醇酸交联型丙烯酸酯乳液的制备研究

以丙烯酸丁酯(BA)、丙烯酸甲酯(MA)和丙烯腈(AN)为主要原料,烷基酚聚氧乙烯醚(OP-10)和十二烷基磺酸钠(SDS)为复合乳化剂,过硫酸铵(APS)和亚硫酸氢钠(NaHSO3)为氧化还原型引发剂,采用种子乳液聚合法制备了丙烯酸酯乳液;然后以多元醇A作为丙烯酸酯乳液的交联改性剂,制备了醇酸交联型丙烯酸酯乳液,实现了热交联体系无甲醛化。结果表明:当聚合温度为70℃、w(引发剂)=2.4%、m(BA)∶m(MA)∶m(AN)=33∶11∶6、w(复合乳化剂)=5%且m(OP-10)∶m(SDS)=1∶1.5时,丙烯酸酯乳液的综合性能较好;当n(丙烯酸)∶n(多元醇A)=30∶1、w(丙烯酸)=1.0%时,交联改性乳液的固含量为51.40%、单体转化率为98.3%;交联改性乳液的胶膜吸水率(10.08%)比未改性乳液降低了82.4%,但两者的热稳定性均较高且相差不大。     

Preparation of poly(acrylonitrile-butyl acrylate) gel electrolyte for lithium-ion batteries

Poly(acrylonitrile-butyl acrylate) gel polymer electrolyte was prepared for lithium ion batteries. The preparation started with synthesis of poly(acrylonitrile-butyl acrylate) by radical emulsion polymerization, followed by phase inversion to produce microporous membrane. Then, the microporous gel polymer electrolytes (MGPEs) was prepared with the microporous membrane and LiPF₆ in ethylene carbonate/diethyl carbonate. The dry microporous membrane showed a fracture strength as high as 18.98 MPa. As-prepared gel polymer electrolytes presented ionic conductivity in excess of 3.0 × 10⁻³ S cm⁻¹ at ambient temperature and a decomposition voltage over 6.6 V. The results showed that the as-prepared gel polymer electrolytes were promising materials for Li-ion batteries.     

聚丙烯酸钠改进乳化切削液研究

本文论述了金属切削液的发展现状，探讨了国内发展的方向，并对乳化切削液引入水溶性聚丙烯酸钠予以改进进行了研究，测试并分析了聚丙烯酸钠对乳化切削液的性能影响。     

新型核-壳结构丙烯酸酯乳胶涂料

采用无皂种子乳液聚合合成出聚甲基丙烯酸甲酯（ＰＭＭＡ）为核,聚丙烯酸正丁酯（Ｐｎ－ＢＡ）为壳的复合乳液,并以此乳液为基材配制出性能优良的建筑外用乳胶涂料。研究了单体配比、增稠剂用量、ｐＨ值等因素对涂料性能的影响。