Mass transfer and radical flux effects in dispersed‐phase polymerization of isooctyl acrylate

The kinetics of dispersed phase polymerization of a highly water‐insoluble monomer (isooctyl acrylate) were explored in emulsion, miniemulsion, and microsuspension polymerization. The effects of monomer water solubility and choice of initiator (oil‐ vs. water‐soluble) strongly impact the final product (particle size and molecular weight distribution). For emulsion polymerization, as the surfactant concentration was increased, there was a transition from homogenous to micellar nucleation near the CMC, then a drop in nucleation rate at high surfactant concentration due to insufficient radical flux to support more nucleation. For miniemulsion polymerization, a slow rate of growth of (droplet) nucleation with surfactant concentration was found, followed (at the CMC) by an increase in the rate of nucleation with added surfactant as the mode of nucleation switched to micellar. The conversion‐time kinetics of microsuspensions could be modeled with a bulk polymerization model. IOA is sufficiently insoluble in the aqueous phase that emulsion polymerization may or may not be reaction limited. The presence of a stabilizer such a PAA, the use of an oil‐soluble initiator such as BPO, and the insolubility of IOA in the aqueous phase all push the polymerization locus toward droplet (microsuspension) nucleation and bulk kinetics.© 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5649–5666, 2006     

Emulsifier‐free miniemulsion polymerization of styrene using a cationic initiator

Polystyrene latex particles were synthesized using a method based on emulsifier‐free miniemulsion polymerization under ultrasonic irradiation in the presence of 2,2′ azobis (2‐amidinopropane) dihydrochloride (V‐50) as a cationic ionizable water‐soluble initiator and cetyl alcohol as costabilizer. The optimized conditions were obtained by using various parameters, such as the amounts of monomer and initiator, and the time and power of ultrasonic irradiation. In optimal conditions, the latex particles appeared to be about 250 nm in diameter through scanning electron microscopy (SEM). The SEM and gel permeation chromatography (GPC) analyses and monomer conversions of emulsifier‐free miniemulsion polymerization were compared with those of conventional emulsifier‐free emulsion polymerization using V‐50 as initiator in both cases. The results showed that in the miniemulsion polymerization, the rate of polymerization (Rp) was significantly higher, and latex particles were significantly smaller than those in the conventional emulsion polymerization. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Fabrication and characterization of cypermethrin nanocapsules in miniemulsion polymerization system

The nanoencapsulation of cypermethrin (CP) was carried out by miniemulsion polymerization, a convenient one‐pot encapsulation technique for nanocapsules. The encapsulation was achieved by polymerization inducing phase separation within minidroplets dispersed in an aqueous phase. For nanocapsules prepared in this way, the type of surfactant and initiator, the level of the crosslinking agent or chain‐transfer agent, and the monomer/CP ratio play a significant role in defining the end morphology of the latex particles. Specifically, for a styrene (St)/CP system, there were optimum levels of ionic surfactant (1.0 wt % sodium dodecyl sulfate), nonionic surfactant [0.5 wt % poly(ethylene glycol) monooctylphenyl ether], oil‐soluble initiator [1.0 wt % azobis(isobutyronitrile)], crosslinking agent (1.0 wt % divinylbenzene), and a St/CP ratio of 1 : 1 for obtaining well‐defined nanocapsules of CP. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

2‐Hydroxypropylmethacrylate based mono‐ and bifunctional gel beads prepared by suspension polymerization

Spherical and swellable gel beads in the size range 35–200 µm were prepared by suspension polymerization of 2‐hydroxypropylmethacrylate (HPMA). In the proposed method, a mixture of cyclohexanol and octanol was used as a diluent phase dispersed in an aqueous medium including poly(vinyl pyrrolidone) (PVP) as the stabilizer. The polymerization was initiated within the organic phase including the monomer and the crosslinker (ethylene glycol dimethacrylate) by an oil soluble initiator benzoyl peroxide. Spherical and swellable gel beads carrying both hydroxyl and carboxyl functional groups were also prepared by suspension copolymerization of HPMA and a water soluble comonomer (methacrylic acid). For this purpose, the suspension polymerization method proposed for HPMA was modified by using poly(vinyl alcohol) as a stabilizer instead of PVP. The effect of initiator concentration, polymerization temperature, monomer/diluent ratio, crosslinker concentration, stirring rate on yield, average size, size distribution, and carboxyl content of the HPMA based gel beads, were investigated. The swelling characteristics of the gel beads were defined. © 2000 Society of Chemical Industry     

Kinetic study of the polymerization of ethyl acrylate in an aqueous nitric acid medium

A kinetic study of the aqueous polymerization of ethyl acrylate (EA) was carried out at 30°C in a dilute nitric acid medium with ammonium ceric nitrate (ACN)–n‐propanol (nPA) and ACN–ethanol as redox initiator systems. The ceric‐ion consumption was first‐order with respect to the ceric‐ion concentration with both initiator systems. The formation of complexes between Ce(IV) and reducing agents was observed. The orders with respect to the Ce(IV), reducing agents, and monomer were evaluated for aqueous polymerizations of EA initiated by Ce(IV)–nPA and Ce(IV)–ethanol redox initiator systems. The overall activation energy for the aqueous polymerization of EA was evaluated in the temperature region of 27–40°C with both initiator systems. A kinetic mechanism for the aqueous polymerization of EA initiated by redox initiator systems is presented. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 218–224, 2006     

Synthesis in inverse emulsion and associating behavior of hydrophobically modified polyacrylamides

An inverse free‐radical emulsion polymerization technique was used to prepare copolymers of acrylamide and two different hydrophobic comonomers: N,N‐dihexylacrylamide (diC6) or N,N‐diphenylacrylamide (diPh). The products of the reaction were high molecular weight hydrophobically modified water‐soluble polymers (HMWSPs) encapsulated within water droplets dispersed in an organic medium. A comparison of the copolymer compositions prepared under different experimental conditions showed that the level of incorporation of diPh in the final copolymer depended strongly on its localization in the emulsion (aqueous or oil phase) and on the nature of the redox initiator pair (water‐soluble or oil‐soluble). The rheological properties of the HMWSPs in aqueous solution were investigated as a function of the comonomer content and the nature of the initiator, using steady‐flow experiments. The thickening properties were found to be directly correlated to the conditions of synthesis and were optimal when the initiator and the hydrophobic comonomer were located in two distinct phases. An examination of the viscosity as a function of shear rate showed that these solutions exhibit typical characteristics of hydrophobically associative polymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 916–924, 2004     

High pressure semibatch emulsion and miniemulsion copolymerization of vinyl acetate and ethylene

This study presents the experimental study of semibatch emulsion and miniemulsion copolymerization of vinyl acetate (VAc) and ethylene to vinyl acetate-ethylene (VAE) copolymer at 60°C and 80–300 psig. In the miniemulsion copolymerization, a water-soluble initiator (K₂S₂O₈) is used and VAc miniemulsion is prepared in presence of surfactant and cosurfactant using a sonicator or a high-shear homogenizer. Then, ethylene gas is supplied to the reactor at constant partial pressure. In a miniemulsion process, the mass transfer limitations of VAc from monomer droplets to the aqueous phase, and to micelles or polymer latex particles that are present in conventional macro-emulsion polymerization can be eliminated and the transfer of ethylene dissolved in the aqueous phase to the miniemulsion droplets is the major ethylene transport process for the polymerization. The experimental data show that the amount of ethylene incorporation into the copolymer is higher in miniemulsion polymerization than in emulsion polymerization. The ethylene pressure has been found to have a strong impact on the ethylene incorporation into the copolymer phase in both emulsion and miniemulsion copolymerizations but the increase is more pronounced in miniemulsion case. The VAE copolymer latex particles prepared by miniemulsion polymerization exhibited higher storage stability than those prepared by macro-emulsion polymerization.     

Polymerizable oil‐in‐oil emulsions: poly(vinyl pyrrolidone) dispersions in reactive PDMS medium

The system N‐vinyl‐2‐pyrrolidone (VP)/polydimethylsiloxane diglycidylether (PDMS‐DGE) is a typical example of an oil‐in‐oil emulsion formed by two non‐miscible liquids, where both phases are polymerizable in a ‘one‐pot’ procedure by two distinct reaction mechanisms. These oil‐in‐oil emulsions were characterized by their stability and by the particle size of the dispersed VP phase. Non‐aqueous dispersions (NADs) are obtained in a first step by free radical polymerization of the dispersed VP phase. The reaction kinetics, studied as a function of the initiator type and concentration, show that the polymerization rate is mainly influenced by the partition coefficient of the initiator between both phases. The NAD particle size could be tailored from a micrometer to a nanometer range by in situ formation of PVP‐PDMS graft copolymer. Hydrophilic–hydrophobic two‐phase materials can be obtained by polycondensation, in the presence of polyamines, of the epoxy‐functionalized PDMS continuous NAD phase. Copyright © 2007 Society of Chemical Industry     

丙烯酸丁酯细乳液单电子转移-蜕化链转移聚合反应

单电子转移-蜕化链转移(SET-DT)聚合是一种单体适用性广、对聚合环境要求不苛刻的活性自由基聚合方法。以Na_2S_2O_4为催化剂,CHI3为引发剂,采用水相细乳液聚合法进行丙烯酸丁酯(BA)的SET-DT活性自由基聚合,考察了聚合温度、引发剂/催化剂浓度、催化剂滴加方式和乳化剂浓度对聚合动力学、聚丙烯酸丁酯(PBA)数均分子量和分子量分布的影响。结果表明,细乳液聚合速率明显大于悬浮聚合,可在较低温度(30℃以下)、较低引发剂和催化剂浓度(BA,CHI_3和Na_2S_2O_4的初始摩尔浓度比为1 600:1:8)下实现BA的快速聚合;通过聚合过程滴加Na_2S_2O_4催化剂和增加十二烷基硫酸钠主乳化剂浓度,可提高聚合速率;采用低引发剂浓度和催化剂逐步滴加聚合得到的PBA的平均分子量较大,分子量分布较窄。     

Kinetics of radical polymerization of glycidyl methacrylate initiated by multi‐site phase transfer catalyst–potassium peroxydisulfate in two‐phase system

The kinetics of radical polymerization of glycidyl methacrylate, initiated by the free radicals formed in situ in the multi‐site phase transfer catalyst (PTC), 1,1,2,2‐tetramethyl‐1‐benzyl‐2‐n‐propylethylene‐1,2‐diammonium bromide chloride–potassium peroxydisulfate system was studied in an aqueous–organic two‐phase media at 60°C ± 1°C under inert and unstirred condition. The rate of polymerization (R_p) was determined at various concentrations of the monomer, initiator, catalyst, and volume fraction of aqueous phase. The effect of acid, ionic strength, and water‐immiscible organic solvents on the R_p was examined. The temperature dependence of the rate was studied, and activation parameters were calculated. R_p increased with an increase in the concentrations of monomer, initiator, multi‐site PTC, and increase in the polarity of solvent and temperature. The order with respect to monomer, initiator, and multi‐site PTC was found to be 0.50. A feasible free‐radical mechanism consistent with the experimental data has been proposed, and its significance was discussed. The synthesized polymer was confirmed by Fourier transform infrared spectral analysis. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mathematical modeling of molecular weight distribution in miniemulsion polymerization with oil‐soluble initiator

A mathematical model for the study of reaction kinetics and molecular weight distributions in miniemulsion polymerization systems with oil‐soluble initiators is presented. The mathematical model allows the computation of the evolution of the complete molecular weight distribution with chain lengths of up to 10⁵ mers in miniemulsion polymerization by direct integration in reasonable computational time. Also, no restriction in the kinetic regime is needed, as the model is able to represent both compartmentalized and pseud‐bulk systems. The model was validated with experimental results for methyl methacrylate and styrene homopolymerizations, with two different oil‐soluble initiators, and adequately represented both the kinetics and molecular weight distributions of these systems. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2128–2140, 2017     

Preparation of partly hydrophobized,crosslinked polyacrylamide particles by terpolymerization of acrylamide/ N,N‐methylenebisacrylamide/styrene in inverse microemulsion

Free‐radical polymerization of a termonomer system comprising acrylamide (AAm) N,N ′‐methylenebisacrylamide (MBAAm) and styrene (S) initiated by water‐soluble ammonium peroxodisulphate (APS) or by toluene‐soluble dibenzoyl peroxide (DBP) in inverse microemulsion (toluene/S/AOT//water//AAm/MBAAm), leads to the formation of partly hydrophobized crosslinked polymer particles of tailored chemical composition, degree of crosslinking and polymer particle size. Styrene strongly decreases the rate of terpolymerization, while the presence of MBAAm has almost no effect on the polymerization rates observed. This conclusion is valid for both APS and DBP initiators. Increase of the S/T mass ratio (T is toluene) in inverse microemulsion leads to an increase of polymer particle diameter from about 20 nm to about 50 nm attributed to toluene swelling of the styrene‐rich structural moieties of AAm‐co‐S copolymer located on the surface of polymer particles. Polymerization kinetics measurements pointed to the important role of exiting water soluble AAm and MBAAm monomer radicals generated by thermal decomposition of APS in water pools of inverse micelles for initiation of polymerization reactions of sparingly water‐soluble S monomer in the oil‐phase of the inverse microemulsion. It was shown that the polymerization and copolymerization reactions of S in the presence of AAm and/or MBAAm are effectively initiated by water‐soluble APS and also by oil‐soluble DBP initiators. During dialysis the polymerized single‐phase water/oil Winsor IV inverse microemulsion gradually converts itself into a two‐phase oil/water Winsor I dispersion system with volume fraction of aqueous phase Φ_aw ≈ 0.950. The water phase contains water swelled, crosslinked polymer particles of diameters 80–300 nm. During dialysis, toluene and the sodium salt of bis(2‐ethyl hexyl)sulphosuccinic acid (AOT) partition between the oil phase of the dialysed dispersion system and the water dialysate. After evaporation of water from the dialysed inverse microemulsion, solid, dried, crosslinked polymer particles in the form of a transparent film, almost uncontaminated by AOT surfactant, were obtained. © 2000 Society of Chemical Industry     

A new polymerization method and kinetics for acrylamide: Aqueous two‐phase polymerization

The concept of aqueous two‐phase polymerization and a new polymerization method for the preparation of water‐soluble polymers are presented. The phase diagram of poly(acrylamide) (PAAm)‐poly (ethylene glycol) (PEG)‐water two‐phase system was measured by the gel permeation chromatography (GPC). The aqueous two‐phase of PAAm‐PEG‐water system can be easily formed. The critical concentration of phase separation was affected by the molecular weight of PEG. The aqueous two‐phase polymerization of acrylamide (AAm) has been successfully carried out in the presence of PEG by using ammonium persulfate (APS) as the initiator. The polymerization behaviors with varying concentration of AAm, initiator and PEG, the polymerization temperature, the molecular weight of PEG, and emulsifier types were investigated. The activation energy of aqueous two‐phase polymerization of AAm was 132.3 kJ/mol. The relationship of initial polymerization rate (R_p0) with APS and AAm concentrations was R_p0 ∝ [APS]^0.72 [AAm]^1.28. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Water‐soluble/dispersible cationic pressure‐sensitive adhesives. II. Adhesives from emulsion polymerization

In our previous work, we reported that cationic water‐soluble pressure‐sensitive adhesives (PSAs) could be synthesized in ethanol or methanol. These cationic water‐soluble adhesives would not cause a stickies problem during paper recycling and can be easily removed from the papermaking system by adsorbing on wood fibers. In this study we report the synthesis and application of water‐based cationic PSAs using miniemulsion polymerization. A redox initiator system of cumene hydroperoxide/tetraethylenepentamine was used to force interfacial polymerization. The end‐use properties of the PSAs were evaluated, and the repulpability of the PSAs in paper recycling was studied. It was found that the cationic PSA from miniemulsion polymerization itself was insoluble and nondispersible in water during the paper recycling process. However, if this water‐insoluble cationic PSA from miniemulsion was formulated with a water‐soluble cationic PSA made from ethanol, the solubility or dispensability of the former PSA in water was improved. The molecular weight and degree of crosslinking of the PSA polymer have significant effects on the properties and dispersability of PSA. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 347–353, 2004     

Kinetics and colloidal parameters of miniemulsion polymerization of butyl acrylate

BACKGROUND: The miniemulsion polymerization of butyl acrylate initiated by a macromonomeric azoinitiator (macroinimer, MIM) and stabilized by the non‐ionic emulsifier Tween 60 (TW‐60) was investigated. RESULTS: The monomer conversion and the polymerization rate increase with the amount of MIM and then decrease. The desorption rate constants were estimated using the Ugelstad/O'Toole, Gilbert and Nomura models. The Ugelstad/O'Toole and Gilbert models suggest an increase in the k′_des value with increasing emulsifier concentration at the highest MIM concentration while the Nomura model proposes no variation in k′_des with an increase in both TW‐60 and MIM concentrations. The polymerization rate increases in the following order with regard to initiator: MIM < ammonium persulfate < dibenzoyl peroxide < 2, 2′‐azobisisobutyronitrile. CONCLUSION: The increase in the rate of polymerization can be discussed in terms of both increased particle concentration and the gel effect. The size of the polymer particles decreases and the number of polymer particles increases with both TW‐60 and MIM concentrations. This behaviour is attributed to the formation of a larger number of smaller monomer and/or polymer particles and higher particle nucleation rate. The observed long nucleation period for the MIM‐initiated polymerization is attributed to the creation of a crosslinked structure and the immobilization of MIM chains. Copyright © 2009 Society of Chemical Industry     

Study of the preparation and mechanism of formation of hollow monodisperse polystyrene microspheres by SPG (Shirasu Porous Glass) emulsification technique

In a previous study, it was found that monodisperse polystyrene (PSt) hollow particles can be prepared under special conditions by combining a Shirasu Porous Glass (SPG) emulsification technique and subsequent suspension polymerization process. That is, a mixture of styrene (St), N,N‐dimethylamino ethyl methacrylate (DMAEMA), hexadecane (HD), and initiator N, N′‐azobis(2,4‐dimethylvaleronitrile) (ADVN) was used as the dispersed phase in an aqueous phase containing poly(vinyl pyrrolidone) (PVP), sodium lauryl sulfate (SLS), and water‐soluble inhibitor. The dispersed phase was created by pushing the oil phase through the uniform pores of an SPG membrane into the continuous phase to form uniform droplets. Then, the droplets were polymerized at 70°C. It has been puzzling that hollow microspheres were obtained only when sodium nitrite (NaNO₂) was used as a water‐soluble inhibitor, while one‐hole particles were formed when hydroquinone (HQ) or diaminophenylene (DAP) was used. In this study, the mechanism of formation of the hollow microspheres was verified by measuring the variation of diameter, molecular weight distribution, and monomer conversion, and by observing morphological changes during the polymerization, as well as by changing the type and amount of hydrophilic monomer, and initiator. It was found that the diameter of the oil droplets decreased, and a large amount of secondary new particles formed immediately after polymerization started in the case of NaNO₂. However, there was no such apparent behavior to be observed when HQ or DAP was used. It was determined that the hollow particles formed due to the rapid phase separation between PSt and HD, and as a consequence, a large amount of monomer diffused into the aqueous phase to form the secondary particles. Rapid phase separation confined the HD inside the droplets, a nonequilibrium morphology. On the other hand, one‐hole particles, representing an equilibrium morphology, formed when the phase separation occurred slowly because a lot of monomer existed inside of the droplets to allow mobility of the PSt. The addition of DMAEMA allowed the hollow particles to be formed more easily by decreasing the interfacial tension between the copolymer and aqueous phase. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1530–1543, 2002     

Thermotropic systems with fixed domains exhibiting enhanced overheating protection performance

Within this study, a time saving photo‐initiated miniemulsion polymerization process (duration of polymerization was 15 min) was established in order to encapsulate a paraffin wax with an acrylate polymer shell. The obtained freeze‐dried latex was an off‐white powder exhibiting spherical particles with mean diameters around 400 nm and a concentration of paraffin wax around 56%. Mixing the reaction product with a UV‐curable resin matrix resulted in thermotropic overheating protection glazings with high light‐shielding efficiency. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40417.     

Preparation of polymeric microcapsules enclosing microbial cells by radical suspension polymerization via water-in-oil-in-water emulsion

Polymeric microcapsules enclosing Saccharomyces cerevisiae were prepared by radical suspension polymerization via water-in-oil-in-water emulsion. Trimethylolpropane trimethacrylate and 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) were used as monomer and radical initiator, respectively. A culture medium with suspended yeast cells, monomer solution with the dissolved radical initiator, and poly(vinyl alcohol) aqueous solution were used as inner aqueous phase, oil phase, and outer aqueous phase, respectively. The influence of microcapsule preparation parameters on the viability of encapsulated cells and encapsulation efficiency was investigated. The radical polymerization process did not cause significant damage to encapsulated yeast cells. Decreased weight ratio of aqueous phase to oil phase resulted in increased encapsulation efficiency of the cells. The diameter of the microcapsules could be controlled by varying the agitation rate.     

Controlled preparation of nanocolorants via a modified miniemulsion polymerization process

Nanocolorants were successfully prepared via a modified miniemulsion polymerization process into which styrene, a polar monomer, crosslinkers, a highly hydrophobic solvent, dyes, and so forth were introduced. The obtained nanocolorants were nanocomposite entities in which a fraction of dye molecules attached to the crosslinked macromolecular chains and more dye molecules formed clustering because of the phase separation between the dye and polymer during the polymerization process and were further embedded in the interior of the crosslinked polymer because of the high hydrophobicity of the dyes. The effects of the polar monomers, the amounts of the dyes dissolved in styrene, and the polymer crosslinking, as well as the effects of the water‐soluble and oil‐soluble initiator, the amount of the surfactant, and the ultrasonic homogenization time, on the preserving fastness of the dyes in the polymeric matrix and the morphology and particle size distribution of the nanocolorants were studied. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Inverse emulsion free‐radical polymerization of acrylamide terpolymer for enhanced oil recovery application in harsh reservoir conditions

A free‐radical inverse emulsion polymerization formulation has been developed for preparation of acrylamide (AAm)/sodium 2‐acrylamido‐2‐methylpropanesulfonate (AMPSNa)/N‐vinylpyrrolidone (VP) terpolymers. An aqueous solution of a blend of monomers is emulsified in n‐decane using Tween 85 (Tw85). Ammonium persulfate (APS) and dicumyl peroxide (DCP) were used as initiators for water and oil phases, respectively. The reactions were catalyzed by temperature and by a redox pair; the former is achieved at 60°C and the latter by adding tetramethylethylenediamine (TEMED) and sodium bisulphite (BisNa) to activate the initiator in water and oil phase, respectively. The emulsion type, stability, conversion, and rate of polymerization were analyzed. The obtained terpolymer was characterized by elemental analysis, infrared spectroscopy (FTIR), ¹³C nuclear magnetic resonance (NMR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), gel permeation chromatography (GPC), and rheology. Thermal catalyzed emulsion polymerization initiated with DCP showed the best performance as viscosity control agent and as polymeric precursor for in situ gel forming, for water mobility control and flow diversification, respectively. Both application for enhanced oil recovery purposes in harsh oil reservoir conditions are presented. POLYM. ENG. SCI., 57:1214–1223, 2017. © 2017 Society of Plastics Engineers