无皂乳液聚合法制备P(St-MMA-SPMAP)单分散乳胶颗粒

利用无皂乳液聚合 ,分别用一步法和两步法合成了单分散的聚 (苯乙烯 甲基丙烯酸甲酯 甲基丙烯酸丙基磺酸钾 ) (P(St MMA SPMAP) )乳胶颗粒 .在该聚合体系中 ,当水溶性磺酸基单体SPMAP的浓度小于 17mmol L时 ,为均相成核过程 ,能制备单分散的乳胶颗粒 .其中 ,用两步法制备的乳胶颗粒相互之间无粘连 .此外 ,还对一步法合成苯乙烯 甲基丙烯酸甲酯 甲基丙烯酸辛基磺酸钠 (P(St MMA SOMAS) )乳胶颗粒进行了初步研究 .     

Influence of the synthesis conditions of emulsion poly(methyl methacrylate) on the surface structure of the specimens

The surface structure of poly(methyl methacrylate) specimens prepared by emulsifier-free emulsion polymerization of methyl methacrylate was examined in relation to the synthesis conditions (pH of the medium, initiator concentration, and addition of organosilicon compounds).     

KINETICS OF SUSPENDED EMULSION POLYMERIZATION OF METHYL METHACRYLATE

The kinetics of suspended emulsion polymerization of methyl methacrylate (MMA), in which water acted as the dispersed phase and the mixture of MMA and cyclohexane as the continuous phase, was investigated. It showed that the initial polymerization rate (Rp0) and steady-state polymerization rate (Rp) were proportional to the mass ratio between water and oil phase, and increased as the polymerization temperature, the potassium persulphate concentration ([I]) and the Tween20 emulsifier concentration ([S]) increased. The relationships between the polymerization rate and [I] and [S] were obtained as follows: Rp0 ∝ [I]0.73[S]0.32 and Rp ∝ [I]0.71[S]0.23. The above exponents were close to those obtained from normal MMA emulsion polymerization. It also showed that the average molecular weight of the resulting poly(methyl methacrylate) decreased as the polymerization temperature, [I] and [S] increased. Thus, MMA suspended emulsion polymerization could be considered as a combination of many miniature emulsion polymerizations proceeding in water drops and obeyed the classical kinetics of MMA emulsion polymerization.     

Photoenzymatic RAFT Emulsion Polymerization with Oxygen Tolerance

Photoenzymatic reversible addition-fragmenatation chain transfer(RAFT) emulsion polymerization, surfactant-free or ab initio, of various monomers is reported with oxygen tolerance. In surfactant-free emulsion polymerizatoin, poly(N,N-dimethylacrylamide)s were used as stabilizer blocks for emulsion polymerization of methyl acrylate, n-butyl acrylate and styrene, producing well-defined amphiphilic block copolymers, including those with an ultrahigh molecular weight, at quantitative conversions. The controlled character of surfactant-free emulsion polymerization was confirmed by kinetic studies, chain extension studies and GPC analyses. Temporal control was demonstrated by light ON/OFF experiments. In ab initio emulsion polymerization of methyl acrylate and methyl methacrylate, low-dispersity hydrophobic polymers were synthesized with predictable molecular weights. This study extends the monomer scope suitable for photoenzymatic RAFT polymerization from hydrophilic to hydrophobic monomers and demonstrates that oxygen-tolerance can be equally achieved for emulsion polymerization with excellent RAFT control.     

In‐Situ Kinetic Pursuit of Emulsion Crosslinking Copolymerizations of Monomethacrylate and Dimethacrylate by Means of ReactIR®

The usefulness of the ReactIR® reaction analysis system as a powerful tool to in‐situ monitor the kinetics of the emulsion polymerization of vinyl monomers was verified by comparison with the conventional gravimetric method and by checking the rate dependencies on initiator and surfactant concentrations in the emulsion polymerization of butyl methacrylate (BMA). The system was then applied to the kinetic monitoring of emulsion crosslinking copolymerizations of monomethacrylate and dimethacrylate, including methyl methacrylate/ethylene dimethacrylate and BMA/1,6‐hexanediol dimethacrylate systems of different hydrophilicities.     

Preparation of highly monodisperse poly(methyl methacrylate) particles incorporating fluorescent rhodamine 6G for colloidal crystals

Soap-free emulsion polymerization was extended to preparation of monodisperse poly(methyl methacrylate) (PMMA) particles incorporating rhodamine 6G (R6G) fluorescent molecules. The polymerization was conducted in the presence of an anionic monomer, p-styrenesulfonate (NaSS), which improved dispersion stability of the polymer particles. NaSS concentrations was ranged up to 2 mol/m3 H2O in the polymerization at 0.5 kmol/m3 H2O methyl methacrylate (MMA) monomer and 5 mol/m3 H2O potassium persulfate (KPS) initiator for R6G concentrations from 0.1 to 10 mol/m3-polymer. At R6G concentrations lower than 1.0 mol/m3-polymer, PMMA particles were highly monodisperse and incorporated most R6G molecules. The average sizes of PMMA particles were in a rage of 160-300 nm, and decreased with the concentration of NaSS. The high monodispersity of the particles enabled the fabrication of colloidal crystals of the particles with a vertical deposition method.     

On the rate of soapless emulsion polymerization of methyl methacrylate

The rate of soapless emulsion polymerization is studied experimentally and theoretically. The soapless emulsion polymerization of methyl methacrylate (MMA) in water is carried out with potassium persulfate as initiator. It is shown that the soapless emulsion polymerization of MMA gives different time-conversion and time-average molecular weight curves from those of bulk and emulsion polymerizations. Comparing the experimental results with those of the other types of polymerization, features of the rate of soapless emulsion polymerization are discussed and a kinetic model is proposed to apply the soapless emulsion polymerization of MMA in water. The experimental results can be well expressed by this model.     

Synthesis of Monodisperse Polymethyl Methacrylate Particles in Buffer Solutions under the Action of Carboxyl-Containing Initiator

Influence exerted by salts with buffering action and by the initial pH of the reaction mixture on the polymerization kinetics, viscosity-average molecular weight, and amount and degree of surface carboxylation of polymethyl methacrylate particles formed in the course of emulsifier-free emulsion polymerization of methyl methacrylate initiated by 4,4'-azobis(4-cyanoisovaleric acid) was studied.     

纳米SiO_2粒子锚固偶氮引发剂及接枝聚甲基丙烯酸甲酯

对纳米SiO2 粒子锚固偶氮引发剂 ,进而引发甲基丙烯酸甲酯聚合而制备聚甲基丙烯酸甲酯(PMMA) 纳米SiO2 复合粒子进行了研究 .纳米SiO2 先用环氧型硅烷偶联剂处理 ,再与偶氮二氰基戊酸发生缩合反应而锚固上偶氮引发剂 ,通过差示扫描量热和元素分析证明了引发剂在纳米SiO2 表面的锚固 .通过改性纳米SiO2 存在下MMA的乳液聚合 ,制备得到了接枝率为 2 3 2 %、接枝效率为 36 1%的PMMA 纳米SiO2 复合粒子 .经乳液聚合后 ,纳米SiO2 粒子团聚程度减小 ,在水相中分散稳定 .     

Modeling of unseeded emulsion copolymerization of styrene and methyl methacrylate

A mathematical model for the unseeded emulsion copolymerization of styrene and methyl methacrylate has been developed. This model, which includes a new rate coefficient for radical desorption, was used to analyze the effect of the styrene/methyl methacrylate molar ratio in the initial charge on the number of particles, overall conversion and copolymer composition. It was found that the number of particles increased with the methyl methacrylate content and that a drift of the copolymer composition resulted during the polymerization of styrene/methyl methacrylate molar ratios other than 50/50. Good agreement between experimental results and model predictions was achieved.     

悬浮-乳液复合聚合聚苯乙烯-聚甲基丙烯酸甲酯复合粒子的颗粒特性和成粒机理

采用在苯乙烯 (St)悬浮聚合过程中滴加甲基丙烯酸甲酯 (MMA)乳液聚合组分的悬浮 乳液复合聚合方法 ,制备大粒径聚苯乙烯 聚甲基丙烯酸甲酯 (PS PMMA)复合粒子 .研究聚合物粒径分布和颗粒形态的变化发现 ,在St悬浮反应中期滴加MMA乳液聚合组分后 ,聚合体系逐渐由悬浮粒子与乳胶粒子并存向形成单峰分布复合粒子转变 ,最终形成核 壳结构完整的大粒径PS PMMA复合粒子 ;在St悬浮反应初期滴加MMA乳液聚合组分 ,St与MMA一起分散成更小液滴 ,反应后期凝并成非核 壳结构复合粒子 ;在St悬浮反应后期滴加MMA乳液聚合组分 ,PMMA乳胶粒子与PS悬浮粒子基本独立存在 .根据以上结果 ,提出了St MMA悬浮 乳液复合聚合的成粒机理 .     

Stepwise controlled immobilization of colloidal crystals formed by polymer-grafted silica particles

Colloidal crystals formed by polymer-grafted silica particles were immobilized by a stepwise procedure consisting of gelation by radical copolymerization followed by solidification by ring-opening radical polymerization. In the first step, the poly(methyl methacrylate) (PMMA)-grafted silica colloidal crystal suspension was incorporated into the gel without altering the crystal structure by copolymerization of cross-linker, 1,2-dimethylacryloyloxyethane (DME) and methyl methacrylate (MMA). In the second step, ring-opening radical polymerization was performed after substituting the solvent with vinylidene-1,3-dioxolane. By this two-step procedure, the silica particle array of colloidal crystals was immobilized and made into durable material.     

Preparation and properties of monodisperse latex spheres with controlled magnetic moment for field-induced colloidal crystallization and (dipolar) chain formation

We report the preparation and properties of monodisperse magnetic poly(methyl methacrylate) latex spheres that exhibit field-induced colloidal crystallization to exotic morphologies controlled by the geometry of the gradient. The magnetic moment of the novel magnetic spheres is due to an inner core of magnetite particles. These particles, obtained from a conventional ferrofluid, first form a monodisperse emulsion with a silane coupling agent, after which they are directly incorporated in PMMA latex synthesized by standard emulsion polymerization. Scattering from the latex shell dominates over light absorption by the magnetic cores such that visible Bragg reflections of the magnetic crystals can be clearly observed. Concentrated nearly white latex fluids may exhibit near a magnet the warped equilibrium menisci known from the usually dark magnetite ferrofluids. Of the many possible applications, we briefly discuss the subsequent growth and melting of crystals by a slowly oscillating gradient, the formation of radial lattices, and the formation of ordered magnetic dots in PMMA latex films.     

Agitation effect on the rate of soapless emulsion polymerization of methyl methacrylate in water

In order to identify the factors causing an agitation effect on the rate of soapless emulsion polymerization, the polymerization of methyl methacrylate was carried out in water. Experimental results indicated the significance of monomer transfer from monomer droplets to water. A kinetic model was proposed which would take into account this monomer transfer. This model enabled the effect of monomer transfer on the rate of soapless emulsion polymerization to be evaluated for the present system and the experimental results to be interpreted qualitatively.     

Emulsifier‐free,organotellurium‐mediated living radical emulsion polymerization (emulsion TERP): Effect of monomer hydrophilicity

Emulsifier‐free, organotellurium‐mediated living radical emulsion polymerizations (emulsion TERPs) of methyl methacrylate (MMA) and n‐butyl methacrylate (BMA) with dimethyl ditelluride were carried out at two different stirring rates (220 rpm and 1000 rpm). In the emulsion TERP of MMA as a hydrophilic monomer, the molecular weight distribution (MWD) controls with both stirring rates were good with high polymerization rate (100% conversion at 1.5 h). On the other hand, in the emulsion TERP of BMA as a hydrophobic monomer, at 220 rpm the polymerization rate was much slow (～50% conversion at 22 h) and the MWD control was bad, but at 1000 rpm the polymerization was completed within 7 h and MWD control was good. These results suggest that monomer transportation from droplets to polymerizing particles via aqueous medium is important for good MWD control and steady polymerization in the emulsion TERP. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

On the copolymerization of acrylates in the modified microemulsion process

Copolymerization of methyl methacrylate, methyl acrylate, butyl methacrylate, and butyl acrylate in turn was performed in the modified microemulsion polymerization process, i.e., continuous addition of monomer to a preemulsified system. It was found that the particle size of the copolymer microlatex did not change distinctly with the monomer composition. The estimation of emulsifier coverage on the microlatex particles indicated that the process switched from a traditional microemulsion to a normal seeded emulsion polymerization very soon after monomer dropping began. Therefore, a longer dropping time is needed to produce a microlatex with narrow dispersed particle size. Besides, in the modified microemulsion polymerization less emulsifier is needed to produce a stable microlatex. This behavior is related to the mechanism of normal seeded emulsion polymerization during monomer dropping.     

Polymerization of Methyl Methacrylate and Isobutyl Methacrylate in Ternary-Component Emulsions and Microemulsions: Effect of Surfactant Concentration

Abstract

The similarities and differences in the polymerization of MMA (methyl methacrylate) and iBMA (isobutyl methacrylate) in a ternarycomponent system have been investigated from a turbid emulsion to a transparent microemulsion by increasing the surfactant concentration. In spite of the difference in the solubilities of these two monomers in the aqueous phase, the rate dependencies on the surfactant concentration of both monomers were found to be about 0.30 for the emulsion polymerization and about 0.60 for the microemulsion polymerization with monomer concentrations higher than 5 wt%. However, at a low monomer concentration (3 wt%), different negative rate dependencies of ?0.93 and ?1.20 were obtained for microemulsion polymerization of MMA and iBMA, respectively. The results are discussed in terms of particle nucleation mechanisms.     

Preparation of Fluorine-Containing Polyacrylate Emulsion by a UV-initiated Polymerization

A fluorine-containing polyacrylate emulsion was synthesized by a UV-initiated emulsion polymerization from methyl methacrylate (MMA) and hexafluorobutly methacrylate (HFMA) in the presence of 2-hydroxy-4-(2-hydroxyethoxy)-2-methyl-propiophenone (Irgacure 2959) as a hydrophilic photoinitiator at room temperature. The latex and films were characterized by Fourier transformed infrared (FT-IR) spectrometry, nuclear magnetic resonance (¹H-NMR, ¹⁹F-NMR) spectrometry, transmission electron microscopy (TEM), recycling gel permeation chromatography (GPC), dynamic light scattering (DLS), and contact angle (CA) analysis, respectively. The effects of photoinitiator and emulsifier concentration on the polymerization were discussed. Compared to the corresponding thermal polymerization, UV-initiated polymerization of the MMA/HFMA emulsion could be accomplished at a much higher speed. The polymerization conversion in UV-initiated polymerization reached 95% within 10 min at an emulsifier concentration of 0.6 wt%, photoinitiator concentration of 0.4 wt%, and monomer concentration of 10 wt%.     

核／壳结构聚丙烯酸酯塑料增韧剂的制备与结构控制

核／壳结构聚丙烯酸酯塑料增韧剂的制备与结构控制张会轩戴英杨海东＊冯之榴（吉林工学院化工系长春１３００１２）（中国科学院长春应用化学研究所１３００２２）关键词聚丙烯酸酯，增韧剂，制备，种子乳液聚合１９９６－０８－２８收稿，１９９７－０１－０６修回国家自...     

苯乙烯-甲基丙烯酸甲酯悬浮-乳液复合聚合过程中聚合物复合粒子组成的变化

采用苯乙烯(St)悬浮聚合过程中滴加甲基丙烯酸甲酯(MMA)乳液聚合组分,悬浮乳液复合聚合(SECP)方法,制备大粒径聚苯乙烯聚甲基丙烯酸甲酯(PS- PMMA)复合粒子.采用FTIR、1H- NMR、13C- NMR分析方法,研究SECP各个时期复合粒子中MMA- St链节摩尔比,发现悬浮粒子中MMA St链节摩尔比逐渐增大,而PMMA乳胶粒子中逐渐减少,表明悬浮相和乳液相间存在物质传递过程.悬浮粒子中MMA链节质量与MMA总投料质量比主要由乳胶粒子生成速率和乳胶粒子向悬浮粒子凝聚速率决定.最终得到的复合粒子除含PS和PMMA均聚物外,还含少量MMA-St共聚物.