Microemulsion polymerization of styrene

Initiation of polymerization in styrene oil-in-water microemulsions by water-soluble potassium persulfate of oil-soluble 2,2′-azobis-(2-methyl butyronitrile) at 70°C gave stable latexes which were bluish and less translucent than the original microemulsions. The effects of initiator concentration, polymerization temperature, and monomer concentration on the kinetics, particle size distributions, and molecular weight distributions were investigated. The kinetics of polymerization were measured by dilatometry. In all cases, the polymerization rate shows only two intervals, which increased to a maximum and then decreased. There was no apparent constant rate period and no gel effect. A longer nucleation period was found for polymerizations initiated by potassium persulfate as compared to 2,2′-azobis-(2-methyl butyronitrile). The small latex particle size (20–30 nm) and high polymer molecular weight (1–2 × 10⁶) implies that each latex particle consists of two or three polystyrene molecules. The maximum polymerization rate and number of particles varied with the 0.47 and 0.40 powers of potassium persulfate concentration, and the 0.39 and 0.38 powers of 2,2′-azobis-(2-methyl butyronitrile) concentration, respectively. This is consistent with the 0.4 power predicted by Smith–Ewart Case 2 kinetics. Microemulsion polymerizations of styrene–toluene mixtures at the same oil-water phase ratio gave lower polymerization rates and lower molecular weights, but the same latex particle size as with styrene alone. A mechanism is proposed, which comprised initiation and polymerization in the microemulsion droplets, by comparing the kinetics of microemulsion polymerization with conventional emulsion and miniemulsion polymerization systems.     

Styrene miniemulsion polymerization initiated by 2,2′-azobisisobutyronitrile

The effects of various parameters on the dodecyl methacrylate (DMA) or stearyl methacrylate (SMA) containing styrene miniemulsion polymerizations were investigated. These parameters include the type of initiators [2,2′-azobisisobutyronitrile (AIBN) vs. sodium persulfate (SPS)], the size of the homogenized monomer droplets, the AIBN concentration, and the SDS concentration. A small quantity of a water-insoluble dye was also incorporated into the polymerization system to study the related particle nucleation mechanisms. The oil-soluble AIBN promotes nucleation in the monomer droplets, whereas homogeneous nucleation predominates in the reaction system with the water-soluble SPS. Homogeneous nucleation, however, cannot be ruled out in the DMA or SMA containing polymerizations with AIBN as the sole initiator. Increasing the level of AIBN or SDS enhances formation of particle nuclei via homogeneous nucleation. The reaction kinetics is primarily controlled by the competitive events of monomer droplet nucleation and homogeneous nucleation. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2537–2550, 1999     

Comparison of oil-soluble and water-soluble initiation of styrene polymerization in a three-component microemulsion

The polymerization of styrene in three-component oil-in-water microemulsions made with the cationic surfactant dodecyltrimethylammonium bromide is studied by dilatometry and quasielastic light scattering as a function of type and concentration of initiator. Fast polymerization rates, high conversions, and high molecular weight polymers are achieved with both oil-soluble (AIBN) and water-soluble (potassium persulfate) initiators. The rate of polymerization shows initiation and termination intervals, but no constant-rate interval is observed. Stable monodisperse microlatexes are obtained with both types of initiators. For both AIBN and potassium persulfate, polystyrene molecular weight is proportional to initiator concentration [I]^–0.4 and particle radii decrease as [I]^–0.2. Polymerization initiation occurs in or at the microemulsion droplets, and polymer particles grow by recruiting monomer and surfactant from uninitiated swollen micelles.     

Synthesis of micron-sized polymeric particles in soap-free emulsion polymerization using oil-soluble initiators and electrolytes

Soap-free emulsion polymerization of styrene using oil-soluble initiators and electrolytes was investigated to synthesize micron-sized polystyrene particles. It was clear that an oil-soluble initiator, such as AIBN, worked like a water-soluble initiator in soap-free emulsion polymerization of styrene to prepare monodispersed particles with negative charges, probably because of the polarization of the electron-attractive functional groups decomposed from the initiators and the pi electron cloud of benzene in a styrene monomer. The addition of an electrolyte enabled secondary particles to effectively promote hetero-coagulation for particle growth by reduction of an electrical double layer and prevention of self-growth. Changing the concentration and type of electrolyte enabled us to control the size up to 12 μm in soap-free emulsion polymerization of styrene using AIBN. Conventionally, organic solvents and surfactants have been used to prepare micron-sized polymeric particles, but this method enabled the synthesis of micron-sized polymeric particles in water using electrolytes without surfactants.     

Miniemulsion copolymerization of styrene–methyl methacrylate

Miniemulsion copolymerization of 50 : 50 weight fraction of styrene–methyl methacrylate monomer, using hexadecane as the cosurfactant, was carried out in both unseeded and seeded polymerizations. Effects of the hexadecane concentration and the ultrasonification time on the conversion–time curves and particle size of the final latex were investigated for unseeded polymerization. The kinetic and particle size distribution results showed that an increase in hexadecane concentration and ultrasonification time cause faster polymerization rate and smaller particle size. The mechanism of mass transport from miniemulsion droplets to polymer particles was also investigated for seeded polymerization. For this purpose a monomer miniemulsion was mixed with a fraction of a previously prepared miniemulsion latex particles prior to initiation of polymerization, using residual oil-soluble initiator in the seed latex. The concentration of hexadecane and a water-insoluble inhibitor (2,5 di-tert-butyl hydroquinone) in the miniemulsions were the main variables. Seeded polymerizations were also carried out in the presence of miniemulsion droplets containing a water-insoluble inhibitor and water-soluble initiator. The inhibitor concentration and the agitation speed during the course of polymerization were the experimental variables. The kinetic and particle size results from these seeded experiments suggested that collision between miniemulsion droplets and polymer particles may play a major role in the transport of highly water-insoluble compounds.     

Polymerization of styrene miniemulsions

Polymerization of styrene miniemulsions, prepared using a mixed emulsifier system comprising sodium lauryl sulfate and cetyl alcohol, was carried out using both water-soluble (potassium persulfate) and oil-soluble [2,2′-azobis-(2-methyl butyronitrile)] initiators. The effects of variation of initiator concentration, polymerization temperature, and added inhibitor on the kinetics and particle-size distributions were investigated to obtain more quantitative evidence concerning the locus of polymerization in miniemulsion systems. Experimental results for the kinetics and particle-size distributions clearly showed that monomer droplets became the main source of polymer particle formation. This was attributed to the fact that stable emulsions with droplet diameters in the range of 0.05 to 0.15 μm were produced using this mixed-emulsifier system. In this size range, droplet initiation could effectively compete with other mechanisms due to their large surface area. Their size was indeed similar to the corresponding latex particle size obtained after polymerization.     

Impact of initiators in preparing magnetic polymer particles by miniemulsion polymerization

Sub-micron sized polystyrene particles containing magnetite more than 30 wt.% were prepared by miniemulsion polymerization with commercially available ferricolloid. The effects of some water-soluble initiators and/or oil-soluble initiators on the particles characteristics, such as the size, morphology, magnetic properties and colloidal stability, were studied. The size of monomer droplets/polymer particles increased from 60 to 300 nm during polymerization, keeping magnetic in core when potassium persulfate (KPS) or ammonium persulfate (APS) was used as the sole initiator. These particles were easily separated from the medium within short time scale in external magnetic field, while such characteristics were controlled by the amount of persulfate used for the polymerization. In contrast, when 2,2′-azobis isobutyronitrile (AIBN) was used as the initiator, the size of droplets/particles was retained to be 90 nm at the most and magnetite nanoparticles located at the surface of polystyrene particles, which were so colloidally stable that they were not separated in external magnetic field. The above-mentioned effect of initiators on particle size in persulfate system was likely originated from the decrease of pH value and the increase of ionic strength, which induced the fusion of droplets/particles containing magnetite. Mixed-initiators system resulted in intermediate characteristics, compared with each initiator system. The location of magnetite in the particle seems to depend on where initiation/polymerization occurred in each initiator system.     

Effect of the structures of microemulsions on chemical reactions

Two kinds of chemical reactions were studied in two different microemulsion systems: cetyltrimethylammonium bromide/1-butanol/10 and 25% n-octane/water and sodium dodecyl sulfonate/1-butanol/20% styrene/water. One reaction is a hydrolysis reaction, in which aspirin and 2,4-dinitrochlorobenzene were used as the hydrolysis substrates. The second reaction is the polymerization of styrene, which was initiated by using two initiators, water-soluble K₂S₂O₈ and oil-soluble 2,2′-azobis(isobutyronitrile), and, at the same time, the polymerization of acrylamide, which was initiated by NaHSO₃, was also studied. All the hydrolysis reaction experimental results show that the hydrolysis is greatly affected by the structures and the structural transitions of microemulsions. The hydrolysis rates are higher in water-in-oil (W/O) microemulsion media and decrease with the addition of water. The rates increase in bicontinuous (BC) microemulsions and decrease in oil-in-water (O/W) microemulsions. The transition points of the hydrolysis rates occurred at the two microemulsion structural transition points from W/O to BC and from BC to O/W. The polymerization relationships between the conversions of styrene, the molecular weights of polystyrene and the water contents of the microemulsion system were obtained. The effects of microemulsion structures on the sizes of the polystyrene particles and on the molecular weights of the polymers are discussed. Polystyrene particles with diameters of 10–60 nm were observed by microscopy. Our experimental polymerization results show that microemulsions are suitable as media for the production of polymers, the molecular weights and the particle sizes of which can be controlled and predicted by variations in microemulsion structures. Received: 11 July 1999/Accepted: 26 July 1999     

Oil-continuous microemulsions mixed with an amphiphilic graft copolymer or with the parent homopolymer Polymer–droplet interactions as revealed by phase behavior and light scattering

Polymer–droplet interactions have been studied in AOT/water/isooctane oil-continuous microemulsions mixed with an amphiphilic graft copolymer, or with the parent homopolymer (AOT = sodium bis(2-ethylhexyl) sulfosuccinate). The graft copolymer has an oil-soluble poly(dodecyl methacrylate) backbone and water-soluble poly(ethylene glycol) side chains. Pseudo-ternary polymer/droplet/isooctane phase diagrams have been established for both the parent homopolymer and the graft copolymer, and the two types of mixture display entirely different phase behavior. The homopolymer–droplet interaction is repulsive, and a segregative phase separation occurs at high droplet concentrations. By contrast, the graft copolymer–droplet interaction is attractive: the polymer is insoluble in the pure oil, but dissolves in the microemulsion. A comparatively high concentration of droplets is required to solubilize even small amounts of polymer. Static and dynamic light scattering has been performed in order to obtain information on structure and dynamics in the two types of mixture. For optically matched microemulsions, with a vanishing excess polarizability of the droplets, the polymer dominates the intensity of scattered light. The absolute intensity of scattered light increases as phase separation is approached owing to large-scale concentration fluctuations. Dynamic light scattering shows two populations of diffusion coefficients; one population originates from “free” microemulsion droplets and the other from the polymer (for homopolymer mixtures) or from polymer–droplet aggregates (for mixtures with the graft copolymer). The graft copolymer forms large polymer–droplet aggregates with a broad size distribution, which coexist with a significant fraction of free droplets.     

Nitroxide mediated living radical polymerization in miniemulsion

The introduction of the aqueous phase into a living radical polymerization increases the complexity of the kinetics by creating the possibility of species partitioning between the aqueous and organic phases, and introducing aqueous phase reactions which could play a significant role particularly in chain initiation and/or particle nucleation. We have conducted a series of styrene miniemulsion polymerizations in which the solubility of initiator and nitroxide have been systematically varied. Experiments were run using either water-soluble (potassium persulphate) or oil-soluble (benzoyl peroxide) initiator, and either TEMPO or 4-hydroxy-TEMPO. These two nitroxides vary considerably in their water solubility. The effects of initiator and nitroxide solubility in water on conversion-time behaviour, molecular weight and initiator efficiency are presented.     

On the role of oil-soluble initiators in the radical polymerization of micellar systems

Polymerization in micellar systems is a technique which allows the preparation of ultrafine as well as coarse latex particles. This article presents a review of the current literature in the field of radical polymerization of classical monomers in micellar systems initiated by oil-soluble initiators. Besides a short introduction to some of the kinetic aspects of emulsion polymerization initiated by water-soluble initiators, we mainly focus on the kinetics and the mechanism of radical polymerization in o/w and w/o micellar systems initiated by classical oil-soluble initiators. The initiation of emulsion polymerization of an unsaturated monomer (styrene, butyl acrylate,...) by a water-soluble initiator (ammonium peroxodisulfate) is well understood. It starts in the aqueous phase and the initiating radicals enter the monomer-swollen micelle. The formed oligomeric radicals are surface active and increase the colloidal stability of the disperse system. Besides, the charged initiating radicals might experience the energetic barrier when entering the charged particle surface. The locus of initiation with oil-soluble initiators is more complex. It can partition between the aqueous-phase and the oil-phase. Besides, the surface-active oil-soluble initiator can penetrate into the interfacial layer. The dissolved oil-soluble initiator in the monomer droplet can experience the cage effect. The small fraction of the oil-soluble initiator dissolved in the aqueous phase takes part in the formation of radicals. The oligomeric radicals formed are uncharged and therefore, they do not experience the energetic barrier when entering the polymer particles. We summarize and discuss the experimental data of radical polymerization of monomers initiated by oil-soluble initiators in terms of partitioning an initiator among the different domains of the multiphase system. The inhibitor approach is used to model the formation of radicals and their history during the polymerization. The nature of the interfacial layer and the type of oil-soluble initiator including the surface active ones are related to the kinetic and colloidal parameters. The emulsifier type and reaction conditions in the polymerization are summarized and discussed.     

The effect of structure of oil phase, surfactant and co-surfactant on the physicochemical and electrochemical properties of bicontinuous microemulsion

Efforts were made to prepare bicontinuous microemulsions with ten different oil phases involving aliphatic, linear, and aromatic hydrocarbons as oil phases, two co-surfactants (n-butanol and n-pentanol) and two surfactants: cationic (CTAB) and anionic (SDS). Different weight percentages were employed for the preparation of cationic and anionic surfactant based microemulsions as reported in the literature. Out of the 40 compositions (10 oil phasesx2 co-surfactantsx2 surfactants) thus selected only 28 systems showed stable bicontinuous microemulsion phase. This behavior is explained on the basis of the structures of various constituents present in the microemulsions. Viscosity variations of stable bicontinuous microemulsions are found to depend mainly on the nature of co-surfactant. Conductivity behavior on the other hand depends mainly on the weight percentage and composition of aqueous phase. The solubility of pyrene in the oil phase determines the excimer formation and fluorescence behavior in microemulsions. The electron transfer property of both the water-soluble and the oil-soluble redox systems does not depend on the oil phase and the co-surfactant. The significance and importance of characterizing well defined bicontinuous microemulsions is thus highlighted.     

Kinetics of photopolymerization of acrylamide in AOT reverse micelles

The kinetics of the photoinitiated polymerization of acrylamide in toluene/AOT/water inverse microemulsions have been examined for systems initiated by AIBN or a dye: triethanolamine redox reaction. The rates of polymerization were determined by dilatometry, the data being corrected for the effect of reaction exotermicity. For both the oil-soluble and the water-soluble initiating systems, the rate of polymerization was found to be proportional to the first power of the incident light intensity. For AIBN-initiated systems, the rate of polymerization was also found to be proportional to the first power of the initiator concentration. The molecular weights of the polymers produced were independent of the rates of polymerization and initiation. These results suggest that exclusively monoradical termination, involving a degradative chain transfer, is occurring in these systems     

The effect of cosurfactants and the initiator concentration on the polymer to surfactant concentration in nanolatexes

The effect of cosurfactant and initiator concentration on the ab initio production of nanolatexes using low surfactant levels was investigated. While the use of cosurfactants (acrylic acid and pentanol) increased the amount of monomer that can be used in styrene‐SDS microemulsion formulations to 13 wt %, high surfactant concentrations are still required, resulting in polymer‐to‐surfactant ratios (Pol/Surf) <1. Latexes with particle size of 30 ± 5 nm were produced upon polymerization of these microemulsions. The Pol/Surf can be significantly increased by increasing the initiator concentration of emulsion polymerization recipes. Particle sizes are comparable with microemulsion latexes, however, less surfactant is required. The reduction in the particle size with higher initiator concentration is attributed to a higher efficiency of particle nucleation and to a higher nucleation rate relative to the rate of monomer transfer. Nanolatexes (particle size < 30 nm) were obtained with 19 wt % solids content and Pol/Surf of 3.6 in ab initio. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

A novel approach to prepare core/shell polymer latex particles with high sulphonate contents

Crosslinked x-P(St-MAA) seed latex was first prepared via soap-free emulsion copolymerization of styrene (St) and methyl methacrylic acid (MAA) with divinyl benzene as crosslinker and ammonium persulfate as initiator, and x-P(St-MAA)/x-P(St-NaSS) core/shell latex particles were then synthesized through a novel seeded emulsion copolymerization of St and sodium styrene sulphonate (NaSS) in the presence of water-soluble crosslinker N,N′-methylene bisacrylamide (BAA) using oil-soluble 2,2-azobis isobutyronitrile as initiator. TEM observation indicated that narrow dispersed core/shell latex particles were obtained, and element analysis showed that NaSS unit content in the whole particle and in the shell reached 22.8 wt% and 51.2 wt%, respectively.     

Polyamide capsules via soft templating with oil drops—2. Subsequent radical polymerization of styrene

The production of composite polyamide–polystyrene microcapsules by successive polycondensation and radical polymerization is easily possible in a one-pot multi-step reaction. The first step is the emulsification of the template oil phase that contains terephthaloylchloride, styrene monomer, if necessary a cyclohexane–chloroform mixture, and the oil-soluble radical initiator in an aqueous poly(vinyl alcohol) solution. Then, the polyamide capsule formation (second step) is started by the addition of an aqueous diamine solution at 25 °C. Subsequently, the radical polymerization (third step) is initiated by raising the temperature. The morphology of the composite capsules depends strongly on the amount of styrene monomer in the oil mixture and the nature of the initiator. Interestingly, the styrene conversion is much lower if water-soluble initiators are used.     

Preparation of highly monodisperse fluorescent polymer particles by miniemulsion polymerization of styrene with a polymerizable surfactant

Miniemulsion polymerization of styrene (St) in the presence of a hydrophobe (hexadecane:HD) using a cationic polymerizable surfactant (N,N-dimethyl-N-n-dodecyl-N-2-methacryloyloxyethylammonium bromide:C(12)Br) and a cationic initiator (2,2'-azobis(2-amidinopropane) dihydrochloride:V50), called St/C(12)Br/V50 hereafter, proceeded efficiently compared with that using sodium dodecyl sulfate (SDS) and potassium persulfate (KPS), i.e., St/SDS/KPS, providing monodisperse polystyrene latex particles with a narrower particle size distribution. In St/C(12)Br/AIBN, where an oil-soluble initiator, i.e., 2,2'-azobisisobutyronitrile (AIBN), was used in place of V50, little changes in polymerization kinetics or in particle size distribution were observed, while a significant drop in polymerization rate and a broad particle size distribution were observed with St/SDS/AIBN. A polymerizable pyrene derivative (1-pyrenylmethyl methacrylate: PyMMA) was quantitatively incorporated into monodisperse latex particles in St/PyMMA/C(12)Br/V50 compared to pyrene (Py) in St/Py/C(12)Br/V50. Contrary to our expectation, however, increased excimer emission was observed with St/PyMMA/C(12)Br/V50 particles, indicating less evenly distributed pyrene chromophores in the particles. The fluorescence lifetime of pyrene chromophores in St/Py/C(12)Br/V50 particles was determined to be 286 ns, which was 17 times longer than that of pyrene in THF solution.     

Functional polymers for colloidal applications. V. Novel behavior of polymeric emulsifiers in emulsion polymerization

The polymeric emulsifier poly(dodecyl acrylate-co-acrylic acid) [i.e., the sodium salt (PDA)] and monomeric emulsifier sodium dodecyl glutarate (SDG) have been synthesized. PDA and SDG are used as emulsifiers in the emulsion polymerization of styrene with both the water-soluble initiator potassium persulfate (K₂S₂O₈) and the oil-soluble initiator 2,2′-azobisisobutyronitrile (AIBN). The PDA/K₂S₂O₈ system showed a bimodel distribution of particle sizes (2 and 0.05 μm). A bimodel particle distribution was also found for the PDA/AIBN system, but the distribution for the large particles was wide (0.1–10 and 0.07 μm). The SDG/K₂S₂O₈ system displayed only one kind of particle size (0.05 μm), but the SDG/AIBN system also showed a bimodel distribution of particle sizes (0.05 and 5 μm). These bimodel distribution results for the PDA/K₂S₂O₈, PDA/AIBN, and SDG/AIBN systems indicate that the polymerization sites are both in oil droplets and in micelles (polymer aggregates). This mechanism is interpreted in terms of the formation of polymer aggregates, which is supported by the results of pyrene solubilization, pyrene fluorescence, surface tension, and pyrene excimer experiments. © 1993 John Wiley & Sons, Inc.     

Poly(2-acetoxyethyl methacrylate)/polystyrene latex interpenetrating polymer networks with well-defined phase-separated structure

A series of poly(2-acetoxyethyl methacrylate)/polystyrene(PAEMA/PS) latex interpenetrating polymer networks(LIPNs) were prepared by seeded soap-free emulsion polymerization of styrene on the crosslinked PAEMA seed particles using an oil-soluble initiator.These PAEMA/PS LIPNs showed a well-defined phase-separated structure with PS phase dispersing in continuous PAEMA phase.The domain size of PS phase was found to depend on the crosslinking degree of PAEMA seed particles and the amount of second-stage styrene monomer.     

Kinetics of polymerization of styrene-in-water microemulsions

The kinetics of polymerization of styrene-in-water microemulsions was investigated using dilatometry. From plots of percentage conversion versus time, the rate of polymerization, R _p, was determined. From log-log plots of R _p versus styrene and initiator [2,2′-azobis(isobutyronitrile), AIBN] concentrations the following relationship was established: R _p∝ [styrene]^1.2 [AIBN]^0.46. These exponents are similar to those predicted by the theory of emulsion polymerization. The results also showed a rapid conversion in the initial period (interval 1) followed by a slower rate at longer times (interval 2). It was suggested that in interval 1, the main process in nucleation of the microemulsion droplets, whereas in interval 2 propagation is the more dominant factor. The rapid polymerization of microemulsions is consistent with their structure, whereby very small droplets with flexible interfaces are produced. Received: 2 March 1999 Accepted in revised form: 10 May 1999