Control of free-radical emulsion polymerization of methyl methacrylate by oxygen injection. I. Modeling study

Oxygen injection has been proposed as an effective control measure for limiting the rate of heat release and altering the rate of polymerization in emulsion processes. A detailed mathematical model is developed to describe the system behavior with and without oxygen injection. Because of the rapid penetration of dissolved oxygen into the polymer particles, growing radical chains are terminated prematurely, lowering product molecular weights. Moderate oxygen flows and moderate set point temperatures are found to give the optimal response without significant lowering of the final molecular weight.     

Soapless emulsion polymerization of methyl methacrylate. II. Simulation of polymer particle formation

In this work, a generalized mathematical model was developed to estimate the variation of particle concentration during the entire course of soapless emulsion polymerization of methylmethacrylate (MMA). All of the factors, such as oligomeric radical absorption or desorption by polymer particles, coagulation between polymer particles, and the termination effect on the formation mechanism of polymer particles, were considered and included in this model. When appropriate parameters were selected, this model could be successfully used to interpret the experimental behavior of particle concentration during the entire reaction. Under different conditions, the rate of polymerization, the number of radicals in each particle, the instantaneous average molecular weight of polymers, and the rate constant of termination were also calculated. All of them coincided with the experimental results quite well. © 1996 John Wiley & Sons, Inc.     

Poly(methyl methacrylate)-block-polysulfide-block-poly(methyl methacrylate) copolymers obtained by free-radical polymerization combined with oxidative coupling

Summary Poly(methyl methacrylate)-block-polysulfide-block-poly(methyl methacrylate) copolymers were synthesized for the first time through a new method involving the free radical polymerization of MMA in the presence of a thiocol oligomer as a chain transfer agent, followed by chemical oxidation of the remaining SH end-groups. The chain transfer constant of the SH end-groups of the thiocol was estimated from the rate of consumption of the thiol groups versus the rate of consumption of the monomer (C_T=0.67). The triblock copolymers synthesized were characterized by SEC and ¹H NMR measurements.     

Kinetic study on the poly(methyl methacrylate) seeded soapless emulsion polymerization of styrene. I. Experimental investigation

In this work, methyl methacrylate (MMA) and styrene (ST) were used as monomers in the first stage and second stage of polymerization, respectively, and potassium persulfate (K₂S₂O₈) was used as the initiator to synthesize the poly(methyl methacrylate)-polystyrene (PMMA/PS) composite latex by the method of two-stage soapless emulsion polymerization, i.e., PMMA seeded soapless emulsion polymerization of styrene. The morphology of the latex particles was observed by transmission electron microscopy (TEM). It showed that the composite latex particles had a core–shell structure. The particlesize distribution of the composite latex was very uniform. The kinetic data of seeded soapless emulsion polymerization showed that the square root of polymer yield (Wp)^1/2 was proportional to the reaction time in the earlier period of the reaction. The slope of the line of (Wp)^1/2 vs. reaction time was independent of the content of the seed, but proportional to 0.5 power of the initiator concentration. The gel effect was apparent after monomer droplets disappeared. A glassy effect was found in the latter period of the reaction. The number-average molecular weight of the polymers increased but the weight-average molecular weight of the polymers decreased with decrease of the MMA/ST weight ratio. The number- and weight-average molecular weight increased with decreasing the temperature significantly. © 1995 John Wiley & Sons, Inc.     

Iron (II) chloride catalyzed emulsion polymerization of methyl methacrylate using different initiators

The emulsifier and emulsifier-free emulsion polymerization of methyl methacrylate (MMA) using sodium bisulphite, acetaldehyde sodium bisulphite (ACSB), octyladehyde sodium bisulphite (OSB), benzaldehyde sodium bisulphite (BSB), and acetone sodium bisulphite (ASB) as different initiators, and dodecyl benzene sodium sulphonate (DBSS) as an emulsifier, were carried out at 30, 40, and 50°C. The effect of iron (II) chloride on the rate of polymerization and on the viscosity-average molecular weight was investigated. The effect of temperature, iron (II) chloride, and the type of initiator on the tacticity of the obtained polymers was investigated by means of nuclear magnetic resonance (NMR) spectroscopy. The effect of iron (II) chloride and the four carbonyl adducts (ACSB, OSB, BSB, and ASB) on the volume-average diameter and the number of polymer particles per unit volume was investigated. It was found that iron (II) chloride has a pronounced catalytic effect on the emulsion polymerization. The initiating powers of the four carbonyl adducts, ACSB, BSB, OSB, and ASB, were found to be 3.27, 0.6, 1.78, and 0.23, respectively. The rate of emulsion polymerization and viscosity-average molecular weight were found to be dependent on the emulsifier concentration, initiator type and concentration, temperature, and amount of the catalyst (FeCl₂). © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1725–1738, 1998     

The manganic hydroxide–hydrazine system as an initiator of vinyl polymerization. II. The emulsion polymerization of methyl methacrylate

The reaction between hydrazine hydrate and manganic hydroxide has been studied as an initiator for the emulsion polymerization of methyl methacrylate. The system has proved to be effective, and polymerization occurs at favorable rates over a wide temperature range extending from below 10°C to over 50°C. The pH range, however, is rather limited, the most effective value being 9. The main features of the initiator's behavior are similar to those found previously in the corresponding solution polymerization and are explained on the basis of a surface reaction between the hydrazine and the insoluble hydroxide. A complicating feature is the reaction between hydrazine and monomer, which exerts an inhibiting influence.     

Poly(methyl acrylate-co-methyl methacrylate)/montmorillonite nanocomposites fabricated by soap-free emulsion polymerization

The exfoliated poly(methyl acrylate-co-methyl methacrylate)/montmorillonite (MMT) nanocomposite latex solutions fabricated by soap-free emulsion polymerization were able to cast into a film. The films were transparent and ductile unless more than 5 wt% of MMT was incorporated. With the MMT content higher than 5 wt%, the inflammable residuals of nanocomposites after combustion could preserve their original film profile acting like an inflammable scaffold. Moreover, as 20 wt% MMT was incorporated, the yield strength of the films was increased up to 20 times and Young’s modulus up to 2,000 times. However, the water vapor permeability coefficient of the films was only decreased down to its half value. This unexpected behavior of permeability was associated with the decrease of T _g as the content of MMT was increased, owing to the large difference of the reactivity ratios between methyl acrylate and methyl methacrylate monomers and their differential absorption to the MMT during copolymerization.     

Kinetics of emulsifier–free emulsion polymerization of methyl methacrylate

The influences of polymerization temperature, initiator and monomer concentrations, ionic strength of the aqueous phase, as well as ethylene glycol dimethacrylate (EGDM) co-monomer, on the kinetics of the emulsifier-free emulsion polymerization of methyl methacrylate (MMA) and on the properties of the resulting poly(methyl methacrylate) (PMMA) lattices were studied. The polymerizations were carried out using potassium persulfate (KPS) as the initiator. Monodisperse PMMA lattices with particle diameters varying between 0.14–0.37 μm and polymer molecular weights of the order 0.4 × 10⁶ to 1.2 × 10⁶ g/mol were prepared. The initial rate of polymerization increases with increasing temperature, KPS-MMA mole ratio, EGDM content, or with decreasing ionic strength of the aqueous phase. It was shown that the bead size can be limited by reducing the monomer concentration or by using the cross-linking agent EGDM. The ionic strength of the aqueous phase has a dominant effect on final particle diameter and polymer molecular weight. The uniformity of the latex particles increases as the temperature increases or as the initiator concentration decreases. The experimental results can be reasonably interpreted by the homogeneous nucleation mechanism of the emulsifier-free emulsion polymerization of MMA. © 1996 John Wiley & Sons, Inc.     

甲基丙烯酸甲酯与丙烯酸正丁酯乳液聚合的研究

以甲基丙烯酸甲酯与丙烯酸正丁酯为主要原料,过硫酸铵为引发剂,OP-10、十二烷基硫酸钠(K12)为乳化剂,用乳液聚合法合成了聚丙烯酸酯类共聚乳液,考察了聚合条件对乳液聚合的影响。实验结果表明,在单体、引发剂、水用量一定时,合适的反应条件为乳化剂(OP-10∶K12=1∶1)2%,单体滴加时间以60~90min,80℃反应2h左右。     

Ultrasound‐assisted emulsion polymerization of methyl methacrylate and styrene

In this article, we report on the effect of using ultrasound during emulsion polymerization. This work differs somewhat from that previously reported in that ultrasound is used in conjunction with conventional initiators. The aim is to observe the changes in the nature of polymerization and the synthesized polymer. In this work, reaction conditions and compositions typical of conventional emulsion polymerization are used. Azo‐bisisobutyronitrile and potassium per sulfate are the initiators used. The initial indication is that the rate of polymerization and the final conversion are higher when ultrasound is introduced into the polymerization system. This effect is more pronounced at lower temperatures (50°C) and low initiator concentrations (0.01%). At higher temperatures (70°C) the polymerization rate is seemingly unaffected by the use of ultrasound. The final product in all the experiments is a latex. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 101–104, 2000     

Concentrated emulsion polymerization of methyl methacrylate/butyl acrylate initiated by a redox system

Stable concentrated emulsions of methyl methacrylate/butyl acrylate were prepared with sodium dodecyl sulfate and cetyl alcohol as the compound surfactant and poly(vinyl alcohol) as the major reinforcer of the liquid film. With a redox system based on benzoyl peroxide/N,N′‐dimethyl phenylamine introduced into the concentrated emulsions, polymer particles with different shapes and sizes were obtained by initiation of the polymerization at low temperatures. We investigated the kinetic behaviors of concentrated emulsion polymerization and drew linear regression diagrams of its time–conversion curves in a constant rate phase (conversions ranged from 20 to 70%), and the experimental results show that the variation of the concentrations of the compound surfactant and initiator, the categories of reinforcers of the liquid film, the temperatures, and so on were responsible for the polymerization stability and the polymerization rate. Finally, the kinetics equation and activation energy of the initiator were obtained. The particle size and distribution of particle diameters of latex particles were determined by photon correlation spectroscopy. The determination results reveal that concentrations of the compound surfactant, polymerization temperatures, and so on affected the shape and size of the polymer particles greatly. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1695–1701, 2005     

Poly(methyl methacrylate) nanoparticles prepared through microwave emulsion polymerization

The emulsifier‐free emulsion polymerization of methyl methacrylate (MMA) was conducted with microwave irradiation. Superfine and monodisperse poly(methyl methacrylate) (PMMA) microspheres were obtained. Microwave irradiation notably promoted the polymerization reaction. This phenomenon was ascribed to the acceleration of the initiator [potassium persulfate (KPS)] decomposition by microwave irradiation. The experimental results revealed that the apparent activation energy of KPS decomposition decreased from 128.3 to 106.0 kJ/mol with microwave irradiation. The average particle size of the prepared PMMA latex was mainly controlled with the MMA concentration; it increased linearly from 103 to 215 nm when the MMA concentration increased from 0 to 0.3 mol/L and then remained almost constant at MMA concentrations of 0.3–1.0 mol/L. The KPS concentration had no effect on the average particle size, but the particle size dispersity was significantly reduced by a high KPS concentration. With a mixed polymerization phase (water/acetone = 1:3 v/v) or a redox initiation system, PMMA nanoparticles were obtained with an average particle size of 45 or 67 nm, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2815–2820, 2004     

Synthesis of chitosan‐modified poly(methyl methacrylate) by emulsion polymerization

Emulsion polymerization of methyl methacrylate (MMA) in the presence of chitosan was studied and a reaction mechanism was proposed. It was proved in the companion article that potassium persulfate (KPS) free radicals can degrade chitosan chains into chain free radicals. Therefore, it is possible to produce a chitosan copolymer when the monomer and the KPS initiator are added into the chitosan solution. According to the proposed mechanism, concentrations of different species such as the initiator, total free radicals, and degraded chitosan chain were calculated with the reaction time. All the results agreed with the experimental observation. The results showed that the polymerization rate varied with 0.83‐ and 0.82‐order of the total free‐radical concentration and chitosan repeating unit concentration, respectively. It was also verified that chitosan played multiple roles in the reaction system. If the monomer was added into the chitosan solution before the addition of KPS, chitosan served mainly as a surfactant. Consequently, the polymer particle number was increased with the chitosan addition and so was the polymerization rate. However, if the monomer was added into the solution where the chitosan was already degraded by KPS, the polymerization rate was decreased with the predegradation time of chitosan. In both cases, the final polymer particles consisted of the poly(methyl methacrylate) (PMMA) homopolymer and the chitosan‐PMMA copolymer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3047–3056, 2002     

Mechanistic study of the formation of amphiphilic core-shell particles by grafting methyl methacrylate from polyethylenimine through emulsion polymerization

The mechanism for the formation of amphiphilic core-shell particles in water is elucidated via a kinetic study of semi-batch polymerization of methyl methacrylate (MMA) grafted from polyethylenimine (PEI) initiated with tert-butyl hydroperoxide in an emulsion polymerization. The monomer conversion, the polymerization kinetics, the particle size, the particle number density, the poly(methyl methacrylate) (PMMA) core diameter, the percentage of unbound PEI, and the grafting efficiency of PMMA were determined at various times during the polymerization. The particle number density and the percentage of unbound PEI were almost independent of the controllable variables. The particle sizes and the core diameters increased with each consecutive batch of monomer addition, while the grafting efficiency of PMMA decreased. These data supported the hypothesis that the PEI-g-PMMA graft copolymers were formed early in the polymerization and later self-assembled to a new phase, micellar microdomains. These microdomains act as loci for subsequent MMA polymerization as the monomer is fed into the reaction, without subsequent formation of new particles. The size of the resulting highly uniform core-shell particles (99-147 nm) can be controlled by choosing the amount of monomer charged. Thus, this polymerization method is viable for a large scale production of core-shell particles with high solids content.     

Soapfree emulsion polymerization of methyl methacrylate in the presence of CaSO3

In the soapfree emulsion polymerization of a methyl methacrylate-K₂S₂O₈-CaSO₃-H₂O system, the polymerization rate, average molecular weight of polymer, particle size and particle concentration would vary with the concentration of CaSO₃. It was shown that when the concentration of CaSO₃ was well below the saturation concentration (3 × 10^?4mol/litre H₂O), the polymerization rate was higher than that of the system not containing CaSO₃. On the other hand, when the concentration of CaSO₃ was above the saturation concentration, the polymerization rate at the latter stage was lower than that of the system not containing CaSO₃ within our experimental conditions. The molecular weight of polymer was measured by Gel Permeation Chromatography (GPC). It decreased initially and then increased due to the gel effect over the entire course of polymerization. The size of the polymer particles was measured by both photo correlation spectroscopy (PCS) and transmission electron microscopy (TEM), The reaction mechanism was studied according to the above observation. The mechanical property of poly(methyl methacrylate)-CaSO₃ composite obtained from soapfree emulsion polymerization was tested and compared with that obtained from mechanical blending.     

Synthesis of poly(methyl methacrylate)/silica nanocomposite through emulsion polymerization using dimethylaminoethyl methacrylate

Polymer/Silica nanocomposite latex particles were prepared by emulsion polymerization of methyl methacrylate (MMA) with dimethylaminoethyl methacrylate (DM). The reaction was performed using a nonionic surfactant and in the presence of silica nanoparticles as the seed. The polymer‐coated silica nanoparticles with polymer content and number average particle sizes ranged from 32 to 93 wt % and 114–310 nm, respectively, were obtained depending on reaction conditions. Influences of some synthetic conditions such as MMA, DM, surfactant concentration, and the nature of initiator on the coating of the silica nanoparticles were studied. Electrostatic attraction between anionic surface of silica beads and cationic amino groups of DM is the main driving force for the formation of the nanocomposites. It was demonstrated that the ratio of DM/MMA is important factor in stability of the system. The particle size, polymer content, efficiency of the coating reaction, and morphology of resulted nanocomposite particles showed a dependence on the amount of the surfactant. Zeta potential measurements confirmed that the DM was located at the surface of the nanocomposites particles. Thermogravimeteric analysis indicated a relationship between the composition of polymer shell and polymer content of the nanocomposites. The nanocomposites were also characterized by FTIR and differential scanning calorimetry techniques. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The stabilization effect of mixed-surfactants in the emulsion polymerization of methyl methacrylate

Summary The emulsion polymerization of methyl methacrylate (MMA) was conducted at 50°C using either anionic or nonionic surfactants, or a mixture of the two at different surfactant concentrations. In the singlesurfactant systems a proportional relationship was observed between the total particle surface area per cm³ of aqueous solution at 90% conversion (TS) and the amount of surfactant used. For mixed-surfactant systems, a relationship close to an additive one was found between the TS value and the amount of each surfactant used. The particle number did not remain constant during the polymerization, while the TS value continuously increased. It was also found that MMA formed a paste easily at higher (M/W) ratios, which could be alleviated by using higher surfactant concentrations.     

Effects of mesoporous silica particles on the emulsion polymerization of methyl methacrylate

Rod‐like and spherical mesoporous SBA‐15 silica particles were synthesized as pure silicas and surface modified by organosilane coupling agents firstly, and then the effects of these mesoporous materials on the critical micelle concentration (CMC) of sodium dodecylsulfate (SDS), the stabilities of batch and semi‐continuous MMA emulsion polymerizations, and the molecular weights and molecular weight distributions of the polymer products were studied. The incorporation of both unmodified and silane‐modified forms of the mesoporous silica particles in the polymerization reaction increased the CMC of SDS. The presence of the unmodified mesoporous silica in the polymerization process led to instability in the batch emulsion polymerization process, as indicated by the formation of increased amounts of coagulum, and a decrease in the molecular weight of the polymer product. However, in comparison to the polymer formed in the absence of particle additives the molecular weight of the PMMA polymer increased with the amount of emulsifier and the addition of silane‐modified SBA‐15 particles, suggesting the growth of the polymer chains is facilitated at least in part by reaction in the pores of the particles. The improvement in molecular weight indicates that semi‐continuous MMA emulsion polymerization is best suited for the preparation of PMMA–mesoporous silica composites. POLYM. ENG. SCI., 54:2746–2752, 2014. © 2013 Society of Plastics Engineers     

甲基丙烯酸甲酯的原子转移自由基沉淀聚合

以乙醇为溶剂,溴化亚铜(CuBr)为催化剂,溴乙酸乙酯为引发剂,1,10菲罗啉和N,N,N',N',N'-五甲基二乙烯基三胺(PMDETA)分别为配体的催化体系,进行了甲基丙烯酸甲酯的原子转移自由基沉淀聚合,通过GPC和称重量法对聚合物进行表征。结果表明,两种催化体系下MMA的转化速率较快,甲基丙烯酸甲酯的原子转移自由基沉淀聚合得到了较好的实现,得到了分子量分布较窄的聚合物。