Particle nucleation in emulsion copolymerization containing multifunctional monomers

Characteristic features of particle nucleation and growth in the emulsion copolymerization of styrene and multifunctional monomers such as ethylene glycol dimethacrylate and divinylbenzene were investigated. It was found that in these emulsion copolymerization systems the rate of polymerization per particle decreased drastically with an increase in the content of the multifunctional monomer in the initial monomer feed, and the number of polymer particles produced, on the other hand, increased corresponding to the decrease in the rate of polymerization per particle. The increase in the number of polymer particles produced was explained on the basis of Smith-Ewart theory, which predicts that the number of polymer particles produced would increase inversely proportional to the 0.4 power of the volumetric growth rate per particle, that is the rate of polymerization per particle during the interval of particle formation (Interval I). It was pointed out that the decrease in the rate of polymerization per particle in Interval I would be due mainly to a decrease in the monomer concentration in the polymer particles which was caused by crosslinking networks of the resultant polymer.     

Morphology of poly(isoprene-co-styrene-co-methacrylic acid) latex prepared by two-stage seeded emulsion polymerization

Heterogeneous latexes were prepared by a two-stage seeded emulsion polymerization process at 80°C using potassium persulfate as the initiator and sodium dodecyl sulfate as the emulsifier. Poly(styrene-co-methacrylic acid) latexes containing varying amounts of methacrylic acid (MAA) were used as seeds. The second-stage polymer was poly(isoprene-co-styrene-co-methacrylic acid). By using different methods for the addition of the MAA and by varying the amount of MAA, the hydrophilicity of the polymer phases could be controlled. The morphologies and size distributions of the latex particles were examined by transmission electron microscopy. The latexes were in all cases unimodal, and had narrow particle size distributions. The particles displayed different morphologies depending on the polymerization conditions and monomer composition. The hydrophilic properties of the two phases in combination with the internal particle viscosity and crosslinking of the second phase during polymerization were found to be the major factors influencing the particle morphology. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1543–1555, 1997     

Anionic ring-opening polymerization of octamethylcyclotetrasiloxane in emulsion above critical micelle concentration

Batch anionic ring-opening polymerization of octamethylcyclotetrasiloxane in emulsion using nonionic and cationic emulsifiers was studied. The concentration of emulsifiers was set above their critical micelle concentration. Effects of emulsifier concentration, nonionic/cationic emulsifier ratio and cationic emulsifier/initiator (KOH) ratio on the kinetics, average particle size and distribution and on the average molecular weight and distribution were investigated and discussed. At the beginning of the polymerization, empty micelles, active micelles (polymer particles) and monomer droplets co-exist in emulsion. The transport of monomer from monomer droplets toward empty micelles was confirmed by monomer droplets and empty micelles disappearance and by formation of smaller particles. The transport of monomer from monomer droplets toward polymer particles was not confirmed, since the average polymer particle size did not increase during polymerization. It was proposed, that at lower conversions, monomer diffuses from polymer particle interior to particle surface, while at higher conversions, the monomer diffuses from larger to smaller polymer particles. Emulsifier concentration, nonionic/cationic emulsifier ratio and cationic emulsifier/KOH ratio have an evident effect on the kinetics and on the average molecular weight, thus demonstrating that cationic emulsifier participates to the initiation reaction.     

Semibatch anionic ring-opening polymerization of octamethylcyclotetrasiloxane in emulsion

The semibatch anionic ring-opening polymerization of octamethylcyclotetrasiloxane in emulsion was studied under the condition of no seed particles used in polymerization system. Concentration of emulsifier was set above critical micelle concentration. Effect of monomer feed rate on the chemical kinetics, average particle size and distribution and on the polymer molar mass and distribution was investigated. During monomer addition, polymerization rate was constant and controlled by the monomer feed rate. According to the proposed mechanism for anionic polymerization in emulsion, it was assumed that also the number of active polymerization sites and monomer concentration at the particle surface, where propagation occurs, remain constant. A continuous increase of average particle size and absence of extensive condensation reactions at high conversion suggested that the freshly added monomer diffuses toward hydrophobic polymer particles, where it is consumed in propagation reaction and/or accumulated in the particle core.     

Winsor I-like (micro)emulsion polymerization of styrene initiated by oil-soluble initiator

Batch emulsion polymerization of styrene initiated by an oil-soluble initiator and stabilized by non-ionic emulsifier (Tween 20) has been investigated. The rate of polymerization vs. conversion curve shows the two non-stationary rate intervals typical for the non-stationary-state polymerization. This behavior is a result of the continuous particle nucleation and the decrease of monomer concentration at the reaction loci with increasing conversion. The initial increase of the polymerization rate is attributed to the increase of particle number and the polymerization proceeding under the monomer-saturated condition—the Winsor I-like (micro)emulsion polymerization. The decrease of the polymerization rate is the result of the depressed transfer of monomer from the monomer reservoir to the reaction loci. Above 50 °C the monomer emulsion separates into two phases: the upper transparent monomer phase and the lower blue colored (microemulsion) phase. The polymerization mixture consists of the microdroplets (act as the reaction loci) and large degradable monomer droplets (act as the reservoir monomer and emulsifier). The continuous release of emulsifier from the monomer phase and the microdroplets induce the continuous particle nucleation up to high conversion. The initial formation of large particles results from the agglomeration of unstable growing particles and monomer droplets. The size of large (highly monomer-swollen) particles decreases with conversion and they merge with the growing particles at ca. 40-50% conversion. The coarse initial emulsion transformed during polymerization to the fine (semitransparent) polymer emulsion as a result of the continuous particle nucleation, the shrinking of highly monomer-swollen polymer particles and the depletion of monomer droplets. The low overall activation energy of polymerization is mainly ascribed to the decreased barrier for entering radicals into the latex particles with increasing temperature.     

Effect of carboxylic acid monomer and butadiene on particle growth in the emulsifier-free emulsion copolymerization of styrene-butadiene-carboxylic acid monomer

Carboxylated styrene-butadiene rubber (XSBR) latexes were prepared by emulsifier-free batch emulsion copolymerization of styrene and butadiene with different types of carboxylic acid monomers (AA, MAA, IA). It was found that the particle growth is dependent on the hydrophilic nature of carboxylic acid monomers. SEM studies showed that N_p is almost constant in the particle growth stage (conversion above 10%). Through some calculations by data obtained from DLS technique, average diameter of monomer swollen polymer particles of all the XSBR latexes at the same conversion of 0.4 was obtained to be 368.91, 174.17 and 437.15 nm for AA, MAA and IA, respectively. Several kinetic parameters related to the particle growth stage such as the average number of growing chain per particle were calculated to be 0.474, 0.370 and 1.685 for AA, MAA and IA, respectively. It was observed that these kinetic parameters increase with increasing average diameter of monomer swollen polymer particles, which is consistent with the emulsion polymerization kinetics. Moreover, results indicated that the polymerization rate per particle or equivalently the average number of the growing chain per particle (particle growth stage) decreases by replacing a part of styrene with butadiene in the emulsion copolymerization recipe of styrene-carboxylic acid monomer.     

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     

核壳结构聚硅氧烷/丙烯酸酯复合乳液(Ⅰ)乳化剂对乳液聚合过程及粒径分布和粒子形态的影响

采用种子乳液半连续法合成了具有高有机硅含量的聚硅氧烷/丙烯酸酯核壳结构复合乳液,研究乳化剂的种类、复配比例及质量浓度对有机硅／丙烯酸酯壳核乳液性能与乳胶粒径、分布和结构的影响.结果表明：阴离子乳化剂十二烷基硫酸钠(SDS)、十二烷基磺酸钠(SDS-2)、十二烷基苯磺酸钠(SDBS)所合成的乳胶粒子粒径依次增大,SDS与非离子型乳化剂OP-10复配使用时,随OP-10质量分数的增加,聚合速率和转化率降低,化学稳定性增加,乳胶粒子粒径增大,分布变宽,确定了复合乳化剂的最佳配比.随复合乳化剂浓度的增加,聚合速率加快、转化率增加,乳胶粒子粒径减小而分布加宽.通过改变乳化剂加入方式可减小乳胶粒子的粒径分布.为减少壳层聚合物新粒子的产生,需严格控制乳化剂的浓度,使加入的壳层单体处于“饥饿”状态,在乳胶粒子表面富集、引发聚合,形成表层“过渡层”,最终形成核壳结构复合粒子.     

One-step preparation of electrorheological suspension containing poly(lithium acrylate) via inverse emulsion polymerization and study of its electrorheological effect

Electrorheological (ER) fluid or suspension containing lithium salt of poly(acrylic acid) were synthesized directly by inverse emulsion polymerization. Effects of the amounts of crosslinking agent and the stabilizer and neutralization degree used in the polymerization, as well as water content of the polymer particles on the ER activity were investigated. The ER suspension exhibited maximum yield stress at optimum amounts of stabilizer and crosslinking agent used in the inverse emulsion polymerization, as well as at optimum water content of the polymer particles. Glycerol was tried to be used as an activator instead of water and was shown to have a favorable effect on the thermal stability of the ER suspension. Core–shell-type polymer particles were synthesized through inverse emulsion polymerization with supplemental addition of a second monomer. The ER suspension containing particles with poly(lithium acrylate) as core and polyacrylamide as shell showed better ER behavior than those without the polyacrylamide shell. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 2169–2174, 1998     

Semibatch emulsion polymerization of butyl acrylate. II. Effects of emulsifier distribution

The effects of emulsifier distribution ratio between the initial charge and the feed on particle formation and kinetics of butyl acrylate emulsion polymerization, using sodium lauryl sulfate as emulsifier and potassium persulfate as initiator, were investigated. The number of particles increased with initial emulsifier concentration in the reactor charge. It was shown that traditional ranking, in terms of number of particles produced, of semibatch emulsion polymerization with monomer emulsion feed is not always justified and a semibatch emulsion polymerization can produce far more particles than a conventional batch emulsion polymerization. The number of polymer particles was found to be practically independent of the emulsifier distribution ratio between the charge and the feed for a high overall emulsifier concentration, while for a low overall emulsifier concentration, the number of particles increased with initial loading of the emulsifier. The polydispersity index (PDI) of the final latexes showed a minimum with emulsifier distribution. A bimodal particle size distribution, and a latex with a large PDI, was obtained when there was no emulsifier in the charge. As the initial emulsifier charge increased, a unimodal PSD with a smaller PDI was obtained. With higher proportions of emulsifier in the initial charge, the PDI rose again due to particle nucleation at monomer‐starved conditions, and a skewed unimodal PSD was obtained. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 582–597, 2001     

Novel method of preparation of a charged mosaic membrane by using dipole‐like microspheres. II. Preparation of dumbbell/egg‐like microspheres

The dumbbell‐like/egglike microspheres of poly(4‐vinylpyridine/n‐butyl acrylate)/polystyrene [P(4VP/nBA)/PS] were prepared by soap‐free seed emulsion polymerization. The effects of various polymerization parameters, such as the amount of ethyl acetate (EA) in the continuous phase, swelling time, degree of crosslinking of seed polymer, polymerization temperature, and compatibility of seed polymer and the secondary polymer, and so forth, on the formation of dumbbell‐like/egglike morphology were investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was found that secondary particles could be eliminated either by drastically increasing the number of seed particles or by stripping EA from the seed latex by dialysis and evaporation under a vacuum. Swelling the seed particle with the secondary monomer was essential for the preparation of egglike microspheres. For the localization of PS domains on one side of the egglike particle, the most effective factors were to elevate the polymerization temperature up to 90°C and simultaneously to lower the compatibility of the polymer on the seed particle surface with the phase of PS, while using the uncrosslinked seed latex. Crosslinking the seed latex was not suitable for localizing the PS domains in the seed particle, especially when the degree of crosslinking exceeded 0.5 wt % of EGDMA. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2002–2017, 2001     

Mechanism and grafting reactions in seeded emulsion polymerization with emulsified monomer feeding

The seeded emulsion polymerization of styrene with emulsified monomer feeding was performed by polyethyl acrylate (PEA) latex as seed emulsion. It was shown that the grafting reactions occurred between two components on the composite latex particles. The loci of seeded polymerization were studied by the kinetics of grafting reaction. The highest grafting efficiency in the initial period of seeded emulsion polymerization supported the fact that the surfaces of PEA particles are the sites of polymerization of styrene. The grafting efficiency decreased with increasing monomer‐to‐polymer ratio and initiator concentration. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1495–1499, 1999     

Semibatch anionic ring‐opening polymerization of octamethylcyclotetrasiloxane in emulsions: effect of the amount of seed polymer particles

Semibatch anionic ring‐opening polymerization of octamethylcyclotetrasiloxane with the use of seed polymer particles in emulsions was studied. The concentration of the emulsifier was set above the critical micelle concentration. We investigated the effect of the amount of seed polymer particles on the chemical kinetics and the average particle size and distribution. During monomer starving conditions the polymerization rate strongly depended on the monomer feed rate and not on the amount of seed particles. Throughout the entire monomer feed period the average particle size increased. This increase depended on the number and the size of seed particles. In emulsions with higher particle sizes higher equilibrium conversions were obtained. In our opinion, a greater extent of backbiting reactions is responsible for lower equilibrium conversions during and at the end of the process. The seeded semibatch process seems a reasonable choice for designing emulsion products with high monomer conversion and desired particle size. © 2012 Society of Chemical Industry     

Observation for mechanical property variations of single polymer particles

Monodisperse polymer particles were prepared via conventional microsuspension polymerization or one‐step seeded polymerization, using 1,6‐hexanedioldiacrylate or its mixture with ethylene glycol dimethacrylate (EGDMA) as crosslinking monomer and poly(methyl methacrylate) synthesized by soap‐free polymerization as seed particles. For the study, the effects of the ratio of the absorbed monomer or monomer mixture to the seed polymer particles (swelling ratio), the ratio of EGDMA in absorbed monomer mixture, the dosage of initiator, polymer particle structure, and the electroless Ni plating on the mechanical properties of polymer particles, such as recovery rate, K‐values, breaking strength, and breaking displacement were investigated using micro compression test. It was observed that monomer swelling ratio influenced only on breaking strength, whereas EGDMA ratio in monomer mixture, dosage of initiator, polymer structure and electroless Ni plating did on both K‐values and breaking strength. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

PVC modification through polymerization of a monomer absorbed in porous suspension‐type PVC particles

In‐situ polymerization is the polymerization of one monomer in the presence of another polymer. It can be performed by sequential emulsion polymerization, or by reactions in the melt, in the solid phase, or in solution. The current report describes two methods to obtain poly(vinyl chloride) (PVC) modification through polymerization of a monomer absorbed in commercial porous suspension‐type PVC particles. The generated modified PVC products differ significantly in their structure and properties. The first approach includes absorption of a monomer/peroxide solution within porous suspension‐type PVC particles, followed by polymerization/crosslinking in the solid state at 80°C in an aqueous stabilizer‐free dispersion. The monomer/crosslinker pairs selected are styrene/DVB (divinyl benzene), methylmethacrylate/EGDMA (ethylene glycol dimethacrylate), butyl acrylate/EGDMA, and ethylhexyl acrylate/EGDMA. The influence of composition and nature of the polymerizing/crosslinking constituents on the modified PVC particle structure was studied by microscopy methods, porosity measurements, and dynamic mechanical behavior (DMTA). The level of molecular grafting between PVC and the modifying polymer was determined by solvent extraction experiments. This work shows that the different monomers used represent distinct courses of monomer transport through the PVC particles. The characteristics of the modified PVC particle indicate that the polymerization/crosslinking process occurs in both the PVC bulk, i.e., within the walls constituting a particle, and in the PVC pores. No indication of chemical intermolecular interaction within the modified PVC particles was found. In the second approach, a solution of monomer, initiator, and a crosslinking agent is absorbed in commercial suspension‐type porous PVC particles, thus forming a dry blend. This dry blend is subsequently reactively polymerized in a twin‐screw extruder at an elevated temperature, 180°C, in the molten state. The properties of the reactively extruded PVC/PMMA blends are compared with those of physical blends at similar compositions. Owing to the high polymerization temperature, short‐chain polymers are formed in the reactive polymerization process. Reactively extruded PVC/PMMA blends are transparent, form single‐phase morphology, have a single T_g, and show mechanical properties comparable with those of the neat PVC. The resulting reactively extruded PVC/PMMA blends have high compatibility. J. Vinyl Addit. Technol. 10:109–120, 2004. © 2004 Society of Plastics Engineers.     

Preparation of crosslinked composite nanoparticles

Crosslinked composite nanoparticles were prepared by adding a trifunctional monomer (trimethyol propane trimethacrylate) or a difunctional monomer (divinyl benzene) as a crosslinker into the emulsion polymerization system of styrene in the presence of inorganic nanosilica. A coupling agent, 3‐methacryloxypropyltrimethoxysilane (MPS), was added along with the monomer, crosslinker, and silica to improve the interfacial interaction between silica and polymer and thus to obtain high binding efficiency. The role of MPS was examined. The effects of crosslinkers on the kinetics of emulsion polymerization, monomer conversion, and yield were investigated. The morphology of the composite particles was observed by TEM. The particle size and size distribution of composite latex particles were measured by the dynamic light scattering method. The binding efficiency and swelling ratio were determined by reluxing the sample in xylene using a Soxhlet extraction apparatus. FTIR spectra and TGA verified the participation of crosslinker and silica. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1538–1544, 2005     

Crosslinking kinetics in emulsion polymerization

Network formation in free-radical polymerization is investigated both from experimental and theoretical points of view. In a bulk free-radical crosslinking copolymerization, the radical concentration increases significantly due to a decrease in the bimolecular termination rate. Some fraction of radicals is trapped during the course of network formation, and the reactivity of the radicals in liquid state is completely different from that in solid state (trapped radicals) in terms of both propagation and termination. In emulsion crosslinking polymerization, the crosslinking density tends to be fairly high even from the start of the polymerization. The crosslinking density development is substantially different from that in bulk and solution polymerizations, in which the crosslinking density increases with time, at least in the earlier stages of polymerization. Due to the elastic contribution of free energy change, the monomer concentration in the polymer particles is lower than for linear emulsion polymerizations as long as the monomer droplets exist, resulting in an enhanced tendency toward crosslinking reactions.     

Poly(methyl methacrylate) and polyacrylonitrile dispersions stabilized by gelatin

Methyl methacrylate was polymerized in an aqueous medium in the presence of gelatin using potassium persulfate as initiator. The dispersion mode of polymerization, when the monomer is completely miscible with water, was investigated and compared with an emulsion process, which proceeds at higher monomer concentration. Spherical and relatively uniform polymer particles were formed. Macroscopic precipitation of polymer is prevented by combination of the steric stabilization by grafted gelatin and of repulsive electrostatic interactions from the initiator residues attached to the particle surface. Static and dynamic light scattering have been used to determine the molar mass (molar mass of the whole dispersion particle, M_wD ～ 10⁸-10⁹ g mol^?1) and hydrodynamic radius (R_hD ～ 50-120 nm) of the particles. The number of particles per unit volume does not depend on overall monomer concentration, and it is higher, and therefore the particle size is smaller, than that observed for the soapless emulsion polymerization. The addition of gelatin may be thus used to modify the particle size. Acrylonitrile dispersions were prepared under similar conditions. Unlike methyl methacrylate, this monomer does not swell the polymer particles. While poly(methyl methacrylate) particles are spherical and relatively uniform, the polyacrylonitrile dispersions consist of polydisperse aggregates of tiny polymer particles.     

Interfacial phenomena controlling particle morphology of composite latexes

A thermodynamic analysis and a mathematical model were derived to describe the free energy changes corresponding to various possible morphologies in composite latex particles. Seeded batch emulsion polymerization was carried out at 70°C using as seed monodisperse polystyrene latex particles having different surface polarity. The surface polarity was estimated by contact angle measurement at the latex “film”/water interface for octane as the probe liquid. Methyl methacrylate and ethyl methacrylate were polymerized in a second stage seeded emulsion polymerization using polystyrene particles as seed in the presence of a nonionic stabilizer, nonyphenol polyethylene oxide (Igepal Co-990). Two types of initiators, potassium persulfate (K₂S₂O₈) and azobisiobutyronitrile (AIBN), were used to change the interfacial tension between the second stage polymer (in monomer) and water interface. The values of the interfacial tension of polymer solutions in the second stage monomer vs. the aqueous phase, measured by drop-weight–volume method under conditions similar to those prevailing during the polymerization, correlated well with the determined particle surface polarity and the observed TEM particle morphology. The results showed that, rather than the polymer bulk hydrophilicity, the surface particle polarity is the controlling parameter in deciding which phase is inside or outside in the composite particle. The variation of the polymer phase interfacial tension with polymer concentration was also estimated. Based on experimentally measured interfacial tensions, composite particle configurations were predicted. The predicted morphologies showed good agreement with the observed particle morphologies of the composite latexes.     

Suspended emulsion,a new process for vinyl chloride polymerization: Morphology control through surface active additives

Suspended emulsion is a new polymerization process in which a water phase containing the initiator is suspended in an organic phase containing the monomer; the polymer formed is insoluble in both the organic and water phase. The final morphology of the polymer is a powder of grains (around 100–300 microns) formed with agglomerates of primary particles (around 1 micron). This article describes the effects of small amounts of either suspending agents (water-soluble polymers) or surfactants. These effects concern mainly the morphology (grain and particle size), but also the polymerization kinetics. A rather homogeneous distribution of grains and particles inside the grain may be obtained by using a cellulosic polymer as the suspending agent and an anionic surfactant such as sodium dodecyl sulfate. © 1994 John Wiley & Sons, Inc.