60Co-initiated copolymerization of styrene with vinyl acetate

The kinetic behavior of the ⁶⁰Co-initiated copolymerization at 25°C of styrene with vinyl acetate at 1100 and 2000 rad/hr was studied. As in the case of thermal and photochemical copolymerizations of these monomers, the growing chains are particularly rich in styrene units, and the overall rate is affected by a diluent effect due to the vinyl acetate monomer. However, in the case of the radiation copolymerization, this effect is partially counterbalanced by an increase of the initiation rate with the vinyl acetate concentration; the polymerization rate curve shows a maximum at a vinyl acetate molar fraction of 0.25. This effect is due to the very different free radical yields of these two monomers. The experimental results may be understood on the basis of a kinetic scheme which involves an energy transfer process from the excited vinyl acetate molecules to the styrene monomer and a termination reaction of the growing chains by very short styrene radicals when the mixture is rich in vinyl acetate.     

Emulsion polymerization. VI. Concentration of monomers in latex particles

Nonpolymerizing latex particles surrounded by an aqueous phase saturated with monomer absorb only a finite amount of monomer, even if the monomer is a good solvent for the polymer, because the surface energy of each particle increases on swelling. At equilibrium the change in surface energy and the free energy of mixing exactly balance. Equations based on this thermodynamic principle predict with good accuracy the saturation swelling of crosslinked and uncrosslinked latex particles and the partitioning of monomer between the aqueous phase and latex particles at partial saturation. The available experimental data on swelling of latex polymers with monomers are reviewed. Earlier papers assumed that during emulsion polymerization the monomer concentration in the latex particles is independent of conversion as long as monomer droplets are present. This assumption is shown to be a justifiable approximation. The thermodynamics of the swelling of latex particles with a blend of two monomers is presented. The calculations indicate that copolymerization in emulsion should define reactivity ratios differing from those of homogeneous copolymerization by not more than 40% if the solubility of the comonomers in water is low. The reactivity ratio scheme is strictly applicable to emulsion copolymerization if the solvent properties of the two comonomers are identical.     

Emulsion copolymerization of styrene and methyl methacrylate

Chain transfer constants to monomer have been measured by an emulsion copolymerization technique at 44°C. The monomer transfer constant (ratio of transfer to propagation rate constants) is 1.9 × 10^?5 for styrene polymerization and 0.4 × 10^?5 for the methyl methacrylate reaction. Cross-transfer reactions are important in this system; the sum of the cross-transfer constants is 5.8 × 10^?5. Reactivity ratios measured in emulsion were r₁ (styrene) = 0.44, r₂ = 0.46. Those in bulk polymerizations were r₁ = 0.45, r₂ = 0.48. These sets of values are not significantly different. Monomer feed compcsition in the polymerizing particles is the same as in the monomer droplets in emulsion copolymerization, despite the higher water solubility of methyl methacrylate. The equilibrium monomer concentration in the particles in interval-2 emulsion polymerization was constant and independent of monomer feed composition for feeds containing 0.25–1.0 mole fraction styrene. Radical concentration is estimated to go through a minimum with increasing methyl methacrylate content in the feed. Rates of copolymerization can be calculated a priori when the concentrations of monomers in the polymer particles are known.     

Preparation of polystyrene latex particles by γ-rays-induced emulsifier-free emulsion polymerization

Monodisperse polystyrene latex particles were prepared by ⁶⁰Co-γ-ray radiation-induced emulsifier-free emulsion polymerization with the use of surfactant monomer at room temperature. The surfactant monomer 10(9)-hydroxyl-9(10)-allyl ether octadecanoic acid (HAEOA) was synthesized and characterized by FT-IR and ¹H-NMR spectra. TEM was used to characterize the polystyrene latex particles. HAEOA acted as not only a comonomer but also a stabilizer to copolymerize with styrene and stabilize the polystyrene latex particles. Kinetics analysis shows that there is no constant rate stage which seems to indicate a droplet nucleation mechanism.     

Emulsion copolymerization of styrene and methacrylic acid in the presence of a polyethylene oxide based-polymerizable stabilizer with a shorter chain length

The emulsion copolymerization of styrene and methacrylic acid (MAA) was performed in the presence of a relatively new macromonomer, poly(ethylene glycol) ethyl ether methacrylate (PEG-EEM) as a stabilizer. In contrast to similar studies, a macromonomer having relatively shorter polyethylene oxide chain length (i.e., M_n:246, n ≈ 3.0) was selected for this study. Highly uniform and carboxyl functionalized latex particles in the size range of 0.16–0.50 μm were obtained by changing MAA, PEG-EEM, total monomer, and initiator concentrations. The use of PEG-EEM as a stabilizer resulted in larger monodisperse particles relative to those obtained by the emulsifier-free emulsion copolymerization of styrene and MAA. The particle size decreased and the polymerization rate increased with the increasing MAA feed concentration. The application of power law model indicated that MAA concentration was more effective in the presence of PEG-EEM for control of particle size relative to similar systems. The latex particles with higher numbers of surface-carboxyl groups were obtained with the higher MAA feed concentrations. Although the particle size decreased and the polymerization rate increased with the increasing PEG-EEM concentration in the emulsion polymerization of styrene, both of them remained roughly constant with the increasing PEG-EEM concentration in the presence of MAA. Received: 21 December 2000 Accepted: 13 July 2000     

Effect of Monomer Feeding Mode on thePreparation of Hollow Latexes with High MAA Content in the Core Latex Preparation简

In order to prepare hollow latex particles with optimum morphology based on osmotic swelling principle, three- layer core/shell latex particles with 40 wt% MAA in the core were first prepared via multistep seeded emulsion copolymerization, in which monomers were added by a semi-continuous process with monomer addition under two different forms： pure monomers＇ mixture （monomer addition）, and pre-emulsified monomers （pre-emulsion addition）. Then, the hollow latex particles with different morphologies were obtained after alkali post-treatment. Influences of the monomer feeding mode on the emulsion polymerization and the particle morphology were investigated. Results showed that the pre- emulsion addition could significantly improve the polymerization stability in each step, and greatly enhance the uniformity of shell encapsulation. The sizes of the core and core/shell latex particles obtained by the pre-emulsion addition were smaller and more uniform than those synthesized by the monomer addition, and the hollow latex particles with intact morphology were generated by alkali post-treating of the core/shell latexes prepared from the pre-emulsion addition. As the core size increased, the morphology of the post-treated particles underwent evolution from hollow to collapse. Moreover, the mechanism of the particle morphological evolution was proposed.     

Persulphate initiated graft copolymerization of methacrylamide in natural rubber latex—II. A kinetic study

A kinetic study of the persulphate initiated polymerization of methacrylamide in natural rubber latex has shown that the overall course of polymerization resembles the analogous aqueous polymerization. However, the rate of polymerization increases with increasing rubber concentration in a complex manner, together with a concomitant decrease in induction period. The overall activation energy of polymerization decreases from 18.4 to 11.8 kcal mole^?1 as the rubber concentration is increased from 0–306 gl^?1, at constant monomer and initiator concentrations. Activation of polymerization probably occurs by increase in the rate of initiation perhaps by interaction of the negatively charged latex particles with the persulphate dianion. The kinetic results indicate that, in contrast to earlier studies with oil soluble monomers, the site of polymerisation is the aqueous phase or surface of the rubber particles rather than the rubber interior.     

Evidence for and against concentration gradients in polymerizing latex particles

A single-charge emulsion polymerization involving a monomer which is a good solvent for its polymer is considered. It is shown to be unlikely that within the polymerizing latex particles there are concentration gradients large enough measurably to affect the kinetics of the reaction. The average displacement of monomers due to Brownian motion within the latex particles and in the absence of concentration gradients is calculated. This diffusive mean free path, corresponding to an interval involving less than 1% change in conversion, is shown to be much longer than the radius of the latex particle. Consequently, loci where monomer concentration is perturbed by conversion to polymer are immediately swamped by unreacted monomer. Also, direct experimental evidence exists showing that the monomer concentration in latex particles is about the same when nonpolymerizing latex particles are saturated or during polymerization in the presence of monomer excess. The thermodynamics of saturation swelling preclude the possibility of the existence of large concentration gradients. The arguments that have been advocated in the literature for core–skin separation within polymerizing latex particles were based on conversion data which were thought to be linear with time, while a reexamination indicates that they were not. The observed core–skin separation obtained when butadiene or tritiated styrene were copolymerized with styrene in the presence of a polystyrene homopolymer seed latex has questionable relevance to single-charge homopolymerization. There are reasons to doubt that the distribution of co-monomers within latex particles can be frozen by their conversion to polymers in a two-stage emulsion polymerization.     

Microemulsion copolymerization of styrene and acrylonitrile with n‐butanol as the cosurfactant

The microemulsion copolymerization of styrene and acrylonitrile in an n‐butanol/cetyltrimethylammonium bromide/oil/water microemulsion system was studied. The solubilization sites of the two monomers were determined with an NMR technique. The results showed that the solubilization behaviors of the two monomers were quite different. Most of the styrene was solubilized in the palisade layer of the microemulsion, whereas the acrylonitrile had an equilibrium distribution in the aqueous phase and palisade layer of the microemulsion. The reactivity ratios of styrene and acrylonitrile in the microemulsion system were different from those in other media. The effect of the monomer feed composition on the copolymerization kinetics was investigated, and the mechanism of nucleation of the latex particles was examined. The experimental results showed that the copolymerization loci were changed from the microemulsion droplets to the aqueous phase when the concentration of acrylonitrile in the monomer feed reached approximately 80%; this could be further proved by the effect of the monomer feed composition on the copolymerization kinetics. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 203–216, 2005     

Radiation Graft Copolymerization of a Mixture of Styrene and n-Butyl Acrylate on Natural Rubber Latex

The radiation graft copolymerization of a mixture of styrene (St) and n-butyl acrylate (NBA) monomers on natural rubber (NR) latex has been studied. An irradiation dose of about 18 kGy was needed to attain a conversion of about 80%. The tensile strength of the grafted NR film increases with increasing irradiation dose. A film tensile strength of about 155 kg/cm² was attained by irradiation of a mixture of St, NBA, and NR latex with a dose of about 14 kGy. At low concentrations of monomer in the latex, the Mooney viscosity of the film increases with increasing irradiation dose. At higher monomer concentration, grafting and homopolymerization proceed more favorably than crosslinking, and thus the Mooney viscosity decreases with increasing dose. Thermal analysis of the film showed that the grafted NR was more heat resistant than ungrafted NR.     

The emulsion copolymerization of styrene and sodium styrene sulfonate

The emulsion copolymerization of styrene and sodium styrene sulfonate has been shown to be a feasible preparative route to ionomeric sulfonated polystyrene. The properties of these copolymers are reported elsewhere. The copolymerization rate was found to be dramatically enhanced when compared to that for the emulsion copolymerization of styrene under identical conditions. This copolymerization was studied in detail and two mechanisms were proposed to account for these rate differences. An increase in the number of polymerizing particles in the copolymerization with consequent rate enhancement was substantiated by electron microscopy. However, the data indicate that the rate differences cannot be fully accounted for by this effect. In addition, a gel effect is proposed as a second contributor to the enhanced rate. This gel effect is believed to result from the intermolecular association of the incorporated metal sulfonate units in the growing polymer particles. When a third monomer that plasticizes the ionic interactions is used the polymerization rate decreases. This supports the gel effect hypothesis.     

Preparation of Covalently‐colored Polymer Latex via Batch Emulsion Polymerization

Covalently‐colored polymer latex was synthesized via batch emulsion copolymerization of styrene, butyl acrylate and methacrylic acid in the presence of red polymerizable dye monomer consisting of anthraquinone chromophore, alkyl spacer and acryloyl group, and the influences of the initiator, surfactant and polymerizable dye on the polymerization and the latex properties were investigated. Results showed that the initiator amount was a determinative factor for the monomer conversion, and a high conversion of the polymerizable dye could be achieved when the ammonium persulfate amount was equal to or more than 1 wt% to the total monomers. Most of the chromophores were covalently bonded to the polymer chains if the polymerizable dye was used in the range of 0–1.5 wt%. The light fastness of the resulting latex film was much better than that of the noncovalently‐colored polymer film.     

The Growth of Polystyrene Latex Particles

Our understanding of the factors controlling the growth of polystyrene latex particles has recently undergone extensive revision. For this compatible monomer-polymer system, it was generally presumed that monomer and polymer were uniformly distributed throughout the particles, whereas we have found quite the contrary. Under a wide range of conditions, growing latex particles actually exhibit a distributed structure in which a monomer-rich shell encapsulates a polymer-rich core. First elucidated in kinetic studies of styrene emulsion polymerization, this behavior has also been observed in particles which reside in a state of equilibrium saturation with monomer. The encapsulation phenomenon is governed by the microscopic thermodynamic environment of the latex particles which has, in turn, a profound effect upon the conformational behavior of the long-chain polymer molecules as they interact with the particle-water interface. The control of latex particle properties by the staged addition of several monomers (overcoating) has been part of the industrial lore for many years. The successful execution of this technique has been attributed to either a slow monomer addition technique or to the inherent incompatibilities of the successive generations of polymer. In situations involving the addition of a monomer which is compatible with the seed polymer, the encapsulation phenomenon is probably the controlling factor in the overcoating process.     

Polymerization of styrene with ionic comonomer,nonionic comonomer,or both

Nanosized polystyrene latexes with high polymer contents were obtained from an emulsifier-free process by the polymerization of styrene with ionic comonomer, nonionic comonomer, or both. After seeding particles were generated in an initial emulsion system consisting of styrene, water, an ionic comonomer [sodium styrenesulfonate (NaSS)] or nonionic comonomer [2-hydroxyethyl methacrylate (HEMA)], and potassium persulfate, most of the styrene monomer or a mixture of styrene and HEMA was added dropwise to the polymerizing emulsion over 6 h. Stable latexes with high polystyrene contents (≤25%) were obtained. The latex particle weight-average diameters were largely reduced (41 nm) by the continuous addition of monomer(s) compared with those (117 nm) obtained by the one-pot polymerization method. Latex particles varied from about 30 to 250 nm in diameters, whereas their molar masses were within 10⁴ to 10⁵ g/mol. The effect of the comonomer concentration on the number of polystyrene particles per milliliter of latex and the weight-average molar masses of the copolymers during the polymerization are discussed. The surface compositions of the latex particles were analyzed by X-ray photoelectron spectroscopy, which indicated that the surface of the latex particles was significantly enriched in NaSS, HEMA, or both. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1634–1645, 2001     

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.     

Charged polystyrene nanoparticles: role of ionic comonomers structures

Emulsion copolymerizations of styrene were carried out with four structurally different ionic comonomers namely acrylic acid (AAc), methacrylic acid (MAA), 2-hydroxyethyl methacrylate (HEMA), and sodium styrene sulfonate (NaSS) to study the effect of monomer structure on the copolymerization kinetics and size, morphology, charge density, and the self-assembly of the particles. The copolymerization kinetics was found to be highly dependent upon the ionic comonomer structure, and the nature of this dependence altered from homogeneous to micellar nucleation regime. The decrease in particle size (D) with increasing surfactant concentration (S) was observed in all the cases; however, the exponents of D vs. S were not similar for all the cases. In the homogeneous nucleation regime, exponents followed the order as AAc (0.446) > MAA (0.396) > NaSS (0.252) > HEMA (0.241), whereas the order was almost reversed in the micellar nucleation regime as NaSS (0.406) > HEMA (0.228) > AAc (0.206) > MAA (0.172). The hydrophobic/hydrophilic character and the steric factors were found to be the driving force for the variation in D vs. S exponents with ionic comonomer structure. The presence of charges on the particle surface contributed by the ionic comonomers triggered the self-assembly of the particles upon sedimentation and diffracted visible light obeying Bragg's law.     

Peculiarities of the Anionic Copolymerization of Styrene and Dienes in Non-Polar Solvents with Li+ as Counter-ion mvb

Summary: The anionic copolymerization of styrene and butadiene in hydrocarbon solvents initiated by lithium alkyls was first studied by Korotkov, who reported that the polymerization starts slowly and initially consumes butadiene. On exhaustion of this monomer, the reaction speeds up and then styrene polymerizes rapidly. This peculiar behaviour, which was originally explained by Korotkov by treating the monomers as solvents, butadiene being a preferential solvent for the Li⁺ cation, was later accounted for by considering the cross-over reactions. In this paper an in dept further explanation is given by admitting that the polymerization reactions occur through coordination of the Li ⁺ cation by the monomer followed by insertion of the monomer into the polymer chain. A preliminary MOPAC 93 (PM3) calculation seems to confirm this interpretation.     

Adsorption of Bovine Serum Albumin onto Polystyrene Latex Particles Bearing Saccharidic Moieties

The adsorption of bovine serum albumin (BSA) onto polystyrene latexes bearing various amounts of sugar moieties has been investigated as a function of pH and ionic strength and the results were compared to those for bare polystyrene latexes having negative surface charges. The functionalized latexes were produced by seeded copolymerization of (0.3 μm) liposaccharidic monomer onto polystyrene particles obtained by soap-free emulsion polymerization of styrene using potassium persulfate as initiator. At first, the electrophoretic mobility behavior of the various latexes was examined as a function of pH: a significant decrease was observed in the case of saccharide-containing latex particles compared to the bare particles. The adsorption of BSA onto these latexes exhibited a reduced amount of adsorbed BSA for those latex particles bearing saccharide groups. This adsorbed amount depends on the yield of saccharidic monomer incorporated onto the surfaces of the latex particles.     

镶嵌型乳胶粒子的合成

以苯乙烯、甲基丙烯酸甲酯、丙烯腈等单体或它们的混合物为硬单体,天然胶乳为弹性组分,经多步种子乳液聚合法制得了在天然胶乳的粒子上镶嵌硬聚合物相的互穿网络型乳胶粒子.考察了十二烷基硫酸钠、十二烷基苯磺酸钠、壬基酚聚氧乙烯醚、油酸等乳化体系,过硫酸钾、过氧化苯甲酰热引发体系及异丙苯过氧化氢-四乙烯五胺、叔丁基过氧化氢-四乙烯五胺等氧化还原引发体系对聚合反应的影响.研究了交联剂用量对互穿结合率、溶胶含量的影响及溶胀时间、硬单体组成、乳化剂种类对乳胶粒子形态的影响,确定了适宜的聚合配方和工艺条件.透射电镜观察乳粒形态结果表明,单一使用极性或非极性单体,仅得到核-壳结构乳液,而采用不同极性单体复合、溶胀、互穿,得到的是镶嵌硬聚合物型乳粒结构.     

Styrene emulsion polymerization: Kinetics and particle size distributions in highly swollen latex systems

The results are reported of studies on the kinetics and the time evolution of the particle size distribution in seeded styrene emulsion polymerization systems wherein the seed latex particles were highly swollen with monomer as a result of prior swelling by dodecane. Conditions were such that no new latex particles were formed nor was a significant number of monomer droplets present (“Interval III”). The data were fitted to obtain values for the rate coefficients for entry and exit (desorption) of free radicals. It was found that, during the early part of the polymerization (when the polymer:monomer ratio in the latex particles is considerably less then in an equivalent emulsion polymerization system without dodecane), the entry rate coefficient was much smaller than that measured in systems without dodecane. This effect is consistent with an entry mechanism wherein entering free radicals must displace surfactant molecules from the latex particles.