Direct synthesis of electrorheological suspension containing salt of poly(methacrylic acid) and its electrorheological effect

Colloidal suspensions containing salts of poly(methacrylic acid) which exhibit high electrorheological (ER) activity were synthesized by inverse emulsion polymerization. Factors influencing the ER effect were studied. The results showed that maximum yield stress occurred at optimum amounts of both polymeric stabilizer and crosslinking agent used in the inverse emulsion polymerization as well as a certain water content of the particles, while yield stress increased with electric field strength, average diameter of the particles below 0.9 μm, or the molar ratio of the salt to the acid. The ER activity for the suspensions containing different monovalent counter ions decreased in the following order: Li⁺ > Na⁺ > K⁺ > NH₄⁺. The phenomena were discussed with the ionic polarization mechanism. © 1995 John Wiley & Sons, Inc.     

Study on emulsion and suspension in situ polymerization

A novel and simple method of emulsion and suspension in situ polymerization was designed for preparing a composite of polystyrene containing core–shell emulsion particles. The advantage of this method was that it did not need a complex process, such as emulsion breaking, washing, drying, and so on, during transforming from emulsion polymerization to suspension polymerization. First, the core–shell particles of poly(styrene/bisphenol A dimethyl methacrylate)/polystyrene [P(St/BPADA)/PS] with crosslinking structure were synthesized by emulsion polymerization. Then the latex was broken with electrolyte dripping and the emulsion particles became swollen and transformed into the monomer in the suspension polymerization system. Thus the emulsion and suspension in situ polymerization could be carried out successfully. The mechanism of the process was investigated in detail. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 404–412, 2005     

Preparation and structure control of hollow polymer particles: Influence of seeded emulsion polymerization and alkalization treatment process

Hollow polymer latex particles containing a hydrophilic core were prepared by seeded emulsion polymerization with MAA/BA/MMA/St as comonomers, followed by stepwise alkalization treatment with ammonia. The size and morphology of composite latex particles was determined by TEM. The effects of the seeded emulsion polymerization conditions and alkalization treatment on the size and hollow structure of latex were investigated. The results showed that the optimum content of crosslinking agent in the shell polymers was about 0.5–1.0 wt %, emulsifier was about 0.8–1.1 wt %, and the core/shell weight ratio was 1/7. To obtain uniform hollow latex particles with large size, the starved feeding technique should be adopted in seeded emulsion polymerization, and the neutralization temperature should equal to the T_g of the shell polymer. Then, the obtained polymer particles under this condition had an excellent hollow structure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Electrorheological effects of polyaniline‐type electrorheological fluids

Three kinds of particles—polyaniline (PANI), poly(o‐toludine) (POT), and brominated polyaniline (Br‐PANI)—were synthesized. With chlorinated paraffin as a disperse oil, their electrorheological (ER) effects were determined so that the influence of the phenyl substitute group on the ER effects could be considered. POT exhibited the strongest ER effect, whereas the Br‐PANI ER effect was relatively poor. With the concept of polarization, this phenomenon was interpreted. The influence of the antidoping condition on the ER effects was also examined. An optimal antidoping condition was found for each kind of particle. Composite PANI/polyacrylamide (PAAm) and PANI/lithium polyacrylate (PAA‐Li) particles were further prepared by emulsion polymerization. The testing results showed that the composite particles with certain amounts of PAAm or PAA‐Li exhibited good ER effects. The dielectric and conductive behaviors were also determined so that the results could be explained. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 733–740, 2003     

聚丙烯酸钠高吸水性树脂的制备及性能研究

以环己烷为连续相 ,Span - 6 0为悬浮稳定剂 ,过硫酸钾为引发剂 ,N ,N′ 亚甲基双丙烯酰胺为交联剂 ,对反相悬浮聚合制备聚丙烯酸钠高吸水性树脂进行了研究。结果表明 ,影响合成树脂吸水率最主要的因素是交联剂质量分数 ,当交联剂质量分数为 0 .0 15 %时合成树脂的吸水率出现极大值 ,而且当反应温度控制在 6 5℃、引发剂质量分数为 0 .18%时所得树脂的吸水率可达 5 0 0g/g。对合成树脂吸水、保水性能的进一步测试发现 ,树脂在吸水的初始阶段吸水速率较快 ,随着吸水时间的延长逐步下降 ,当树脂吸水饱和后水分损失则很慢 ,在 84℃下 2 .5h仅损失 17%。     

聚丙烯酸类超强吸水剂的反相悬浮法制备

以 6号溶剂油为分散介质 ,Span85 - OP7为分散剂 ,N,N′-亚甲基双丙烯酰胺为交联剂 ,过硫酸钾 -亚硫酸钠为氧化还原引发剂 ,采用反相悬浮聚合法合成丙烯酸 -丙烯酸钠交联共聚超强吸水剂。探讨了该合成工艺的最佳反应条件。产物呈均匀微粒状 ,易干燥 ,吸水率达 1 2 60 g/g,对0 .9%盐水溶液的吸液率为 1 1 0 g/g     

Synthesis and characteristics of poly(methyl methacrylate-methacrylic acid-3,3-(trimethoxysilyl) propyl methacrylate) hollow latex particles and their application to drug carriers

In this study, the hollow latex particle was synthesized by three processes. The first process was to synthesize the poly(methyl methacrylate-co-methacrylic acid) (poly(MMA-MAA)) copolymer latex particles by the method of soapless emulsion polymerization. Following the first process, the second process was to polymerize MMA, MAA, 3,3-(trimethoxysilyl) propyl methacrylate (MPS), and ethylene glycol dimethacrylate in the presence of poly(MMA-MAA) latex particles to form the linear poly(MMA-MAA)/crosslinking poly(MMA-MAA-MPS) core–shell latex particles. In the third process, the core–shell latex particles were heated in the presence of ammonia to form the poly(MMA-MAA-MPS) hollow latex particles. A sufficient heating time and high-heating temperature were necessary for the ammonia to dissolve the linear poly(MMA-MAA) core to form a perfect hollow structure. The crosslinking poly(MMA-MAA-MPS) shell was a barrier for the ammonia to diffuse into the latex particles so that the latex particle with the high-crosslinking shell showed an imperfect hollow structure. Besides, the hollow poly(MMA-MAA-MPS) latex particles reacted with ZnO nanoparticles, which were synthesized by a traditional sol-gel method, to form the polymer/inorganic poly(MMA-MAA-MPS)/ZnO composite hollow latex particles. With the increase of crosslinking degree would increase the amount of ZnO bonding. Moreover, the poly(MMA-MAA-MPS) hollow latex particles were used as carriers to load with the model drug, caffeine. The release of caffeine from poly(MMA-MAA-MPS) hollow latex particles was investigated.     

Syntheses of acrylate core/shell imbiber beads by seeded suspension copolymerization and one‐stage copolymerization for solvent absorption–desorption

Seeded suspension copolymerization or a one‐stage copolymerization was used to synthesize acrylate core/shell imbiber beads. A two‐stage polymerization technique was used for seeded suspension polymerization. The seed particles for poly(methyl acrylate) or poly(2‐ethylhexyl acrylate) were synthesized first in a mixed solvent of toluene/isooctane containing the ethylene glycol dimethacrylate (EGDMA) crosslinking agent. These beads were swollen in styrene‐EGDMA‐BPO (benzoyl peroxide) and then polymerized in the aqueous phase to produce the polystyrene (PS) shell. The one‐stage copolymerization was carried out in toluene/isooctane containing methyl methacrylate (MMA), styrene (St), EGDMA, and BPO at 75°C for 10 h to give a core/shell copolymer of St‐MMA morphology. The appearance of core/shell imbiber beads prepared from these two techniques varied from monomer to monomer. This article describes the preparation, characterization, and application of the core/shell beads for organic solvent absorption/desorption. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 670–682, 2002     

Preparation and characterization of poly(butadiene-stat-styrene)/poly(styrene-stat-acrylonitrile) structured latex particles

In rubber toughening of thermoplastics, core/shell polymers have been used extensively. This work introduces the synthesis and characterization of polybutadiene based core/shell latex particles with controlled particle size and crosslinking density of the core. A lithium soap recipe was employed to prepare a series of poly(butadiene-stat-styrene) (90/10 by wt) core particles by conventional emulsion polymerization through a batch process. The shell polymer, poly(styrene-stat-acrylonitrile) (72/28 by wt), was polymerized by a semicontinuous process in the presence of the core particles to form a core/shell morphology. The effects of initiator concentration, monomer feeding rate, core/shell ratio, and gel-fraction of the core on the core/shell particle morphology were studied. The degree of grafting of the shell polymer on the core particles was determined as well. The morphology and glass transitions of these particles were characterized by transmission electron microscopy, differential scanning calorimetry, and dynamic mechanical spectroscopy. These latex particles can be used specifically in toughening polycarbonate. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1123–1134, 1997     

Synthesis of spherical core‐shell poly(vinyl acetate)/poly(vinyl alcohol) particles for use in vascular embolization: Study of morphological and molecular modifications during shell formation

Transarterial vascular embolization and chemoembolization has become common medical procedures, where partially hydrolyzed poly(vinyl alcohol) (PVA) beads remains as one of the most used embolic agent materials. Although synthetic, PVA cannot be synthesized by direct polymerization and must be obtained by chemical modification of another polymer, usually poly(vinyl acetate) (PVAc). The aim of the present work is to synthesize spherical core‐shell PVAc/PVA particles and study the morphological and molecular modifications during shell formation. The polymer particles where produced in two stages, where first the PVAc core was obtained by suspension polymerization of vinyl acetate (VAc) and then the PVA shell synthesized through hydrolysis. Spherical PVAc particles were successfully produced and isolated using an optimized suspension polymerization process. During the shell formation, it was shown that none of the conditions used affected the overall morphology of the particles although changes in the final size distribution could be observed. However, it was possible to identify the process variables and reaction condition that affect the molecular weight averages and polydispersities of the final copolymer. POLYM. ENG. SCI., 55:2237–2244, 2015. © 2015 Society of Plastics Engineers     

Core-shell structured latex particles. I. Copolymerization of styrene/benzyl methacrylate as a choice for shell material and characterization of poly(n-butyl acrylate) core latex particles

Composition, molecular weight, and microstructure of the “shell” polymer in core-shell structured latex particles, designed for toughening polycarbonate matrix, should be controlled for enhanced miscibility between the shell polymer and the matrix. Various “shell polymer” systems based on styrene (St) and benzyl methacrylate (BM) were synthesized. Reactivity ratios were determined for (St) and (BM). Chain transfer efficiency studies revealed the susceptibility of styrene to transfer to a chain transfer agent. Benzyl methacrylate was found to have steric and stability factors hindering its tendency to chain transfer with various chain transfer agent. Miscibility tests between P(St/BM) and polycarbonate (PC) indicated different degrees of miscibility, depending upon polymerization conditions. Factors other than molecular weight, such as branching and crosslinking, were found to play a role in the miscibility. Monodisperse poly(n-butyl acrylate) (PBA) seed latex particles of variable degree of crosslinking and particle size were successfully synthesized by batch emulsion polymerization. © 1995 John Wiley & Sons, Inc.     

Synthesis and properties of new thermosensitive polymer systems

The controlled thermal release of aqueous solvent mixtures from polymeric gel particles was investigated. A new type of a polymeric gel consisting of a maleic anhydride/poly(ethylene glycol) condensation product as a crosslinking macromonomer and acrylamides was synthesized by solution or inverse emulsion polymerization for the investigation. Afterward a shell of crosslinked polystyrene was coated to stabilize this new kind of “microcontainer” for the application. This concept was shown as generally useful for various mixtures of organic solvents and water. The cloud point temperature of the polymer gel strongly depended on the following parameters: the type and content of organic cosolvent, the degree of polymerization and constituents of the polyester moiety, and the type and content of the comonomers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

The preparation and characteristics of poly(methyl methacrylate–methylacrylate acid)/nano-ZnO composite latex particles

In this work, poly(methyl methacrylate-co-methylacrylate acid)/ZnO (poly(MMA–MAA)/ZnO) composite latex particle was synthesized by three steps The first step was to synthesize poly(MMA–MAA) copolymer latex particles by soapless emulsion polymerization. Following the first step, the second step was to polymerize MMA, MAA and 3,3-(trimethoxysilyl) propyl methacrylate (MPS) in the presence of poly(MMA–MAA) seed latex particles to form the poly(MMA–MAA)/poly(MMA–MAA–MPS) core–shell latex particles. In the third step, the poly(MMA–MAA)/poly(MMA–MAA–MPS) latex particles reacted with ZnO nanoparticles, which were synthesized by a traditional sol gel method, to form the polymer/inorganic poly(MMA–MAA)/poly(MMA–MAA–MPS)/ZnO composite latex. In this study, MPS with silanol groups essentially was used as the coupling agent to couple with ZnO nanoparticles, while the results of the study showed that there was not covalent bond existed between ZnO particles and polymer latex. The ZnO particles were adsorbed on the surface of polymer latex by electrostatic interaction. Besides, the linear poly(MMA–MAA)/crosslinking poly(MMA–MAA–MPS) core–shell latex particles which were synthesized in the second step were heated in the presence of ammonia to form the hollow poly(MMA–MAA–MPS) latex particles. The factors of heating time and concentration of crosslinking agent significantly influenced the morphology of hollow poly(MMA–MAA–MPS) latex particles.     

Preparation and electrorheological characterization of suspensions of poly(urethane acrylate)/clay nanocomposite particles

Micron‐sized poly(urethane acrylate) (PUA)/clay nanocomposite particles were synthesized by suspension polymerization. UA containing a poly(ethylene oxide) group in the main chain was first inserted into the silicate layers of montmorillonite clay through mixing the UA with the clay. Then, ethylene glycol dimethacrylate and an oil‐soluble initiator were added into this UA/clay mixture, followed by the emulsification of the monomer mixture in an aqueous solution of polymeric stabilizer. Suspension polymerization was carried out at 60°C for 12 h to obtain the PUA/clay composite particles. The incorporation of clay into the polymer phase was verified by FTIR spectroscopy, and the intercalation structure of the clay composite was confirmed by X‐ray diffraction analysis. Other characterizations including thermal analysis, morphological observation, and dielectric analysis were also performed. After suspensions of bare PUA and PUA/clay nanocomposite particles in silicone oil were prepared, their electrorheological properties were measured under various electric fields and compared. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 458–464, 2003     

Morphology control of hollow polymer latex particle preparation

Hollow polymer latex particles containing a hydrophilic core fully encapsulated with a hydrophobic shell were prepared by multistage polymerization followed by neutralization with a base. The diameters of the particles were monodispersed and void fractions of the prepared latex particles as high as 50% were achieved. High instantaneous monomer conversion was found to be the key point to minimize the interdiffusion of the core–shell polymer chains. The influences of the shell crosslinking agent and shell carboxyl content on the hollow morphology were also investigated. The maximum hollow diameter was observed with crosslinking agent contents of 7.5–12.5 wt %. The shell carboxyl content had an appropriate value, and an excess of it resulted in an excentric hollow structure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 860–863, 2005     

Semibatch styrene suspension polymerization processes

Emulsion and suspension polymerization processes have widely been studied for more than 40 years. Although both polymerization processes are performed in heterogeneous media, each one presents its own typical characteristics, such as the particle size distribution, molecular weight distribution, polymer particle nucleation rate, and polymerization rate. In this study, semibatch styrene suspension polymerizations were carried out with feed compositions typical of emulsion processes. The initial reactor charge resembled the recipe of standard styrene suspension polymerizations, and the emulsion polymerization constituents were added during the batch. The influence of the moment at which the emulsion feed was started on the course of the polymerization and the effects of the feed on the polymer properties were analyzed. The polymer particle morphology and the average molecular weights changed very significantly with the emulsion feed time, and the changes could lead to the production of broad molecular weight distributions. Core–shell polymer particles could also be obtained, with the core being formed of polymer particles originating from the suspension polymerization process and the shell being formed of polymer particles originating from the emulsion polymerization. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3021–3038, 2003     

Microencapsulation of water‐soluble herbicide by interfacial reaction. I. Characterization of microencapsulation

A new microencapsulation was established in which small microcapsules with a hydrophilic polymeric wall could be fabricated, capsulizing the water‐soluble content. The new microencapsulation is based on an emulsion interfacial reaction technique that combines the characteristics of an interfacial reaction and conventional emulsion processes. In this technique, hydrophilic polymers [poly(vinyl alcohol) and chitosan] were used as the wall material of the microcapsules. The microencapsulation process was composed mainly of the following steps: preparation of a water/oil (w/o) emulsion 1 containing hydrophilic polymers and a water‐soluble core material and w/o emulsion 2 containing a water‐soluble crosslinking agent and catalyst; the formation of microcapsules by mixing emulsion 1 and emulsion 2; and washing and drying the formed microcapsules. In the new technique an insoluble polymer film was formed easily by the fast crosslinking reaction on the surface of tiny emulsified polymer solution particles in contact with the emulsified crosslinking agent solution particles under mixing with high speed agitation. Thereby, small stable microcapsules were formed. The emphasis in this study was on the establishment of the microencapsulation process by which microcapsules were formed and controlled. The microencapsulation was characterized by analysis of the size distribution of microcapsules fabricated with process conditions. The clarification of the effect of the preparation conditions was also made on the morphology and diameter of the microcapsules. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1645–1655, 2000     

核壳结构聚(丙烯酸丁酯/甲基丙烯酸十二酯)的制备

以丙烯酸丁酯(BA)为核单体,甲基丙烯酸十二酯(LMA)为壳单体,二甲基丙烯酸乙二醇酯(EGDMA)为交联剂,采用分阶段饥饿态加料方式和半连续乳液聚合方法合成了具有核壳结构的聚(丙烯酸丁酯/甲基丙烯酸十二酯)即P(BA/LMA)乳液。考察了乳化剂十二烷基硫酸钠(SDS)、引发剂过硫酸钾(KPS)和核壳单体配比对乳液性能的影响,结果表明,当复合乳化剂m(OP-10):m(SDS)为2:1且质量分数为4%左右,引发剂KPS质量分数为0.1%,单体m(LMA):m(BA)为55:45时,体系稳定,转化率高,成膜温度最低;研究了交联剂交联场所对聚合物结构的影响,结果表明核交联后形成了核壳结构。     

Effect of reaction parameters on the particle sizes of crosslinked spherical phenolic beads by suspension polymerization of phenol and formaldehyde

The crosslinked spherical phenolic beads (PB) were prepared with phenol and formaldehyde in alkaline medium by suspension polymerization technique. Poly(vinyl alcohol) (PVA) hexamethylenetetramine (HMTA), and triethylamine (TEA) were used as stabilizer, crosslinking agent, and basic catalyst respectively. The resulting PB with higher yield (82.5%) and relatively uniform particle size range (0.2–1.8 mm) were formed at 95–97°C, 550 rpm for 4 h, by using varied amounts of PVA as a stabilizer. The particle size and its distribution could be adjusted by selecting a suitable polymerization medium, consisting of monomer added to water, and by varying their relative amounts, mechanical agitation and stabilizer concentration. The yield % of PB was also varied with the concentration of stabilizer, agitation rate, and monomer‐to‐water ratio. The effects of concentration of the stabilizer, agitation rates, and monomer‐to‐water ratio on PB formation and morphology are described. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2323–2330, 2006     

含功能基的核—壳型聚丙烯酸酯乳液的合成与性能

本文以种子乳液聚合法制备了PBA/MMA-MAA核-壳型聚合物,考察了壳层单体MMA和MAA的含量不同时对聚合反应及聚合物其它性能的影响,并用TEM观察了粒子的形态。