Miniemulsion copolymerization of styrene and butyl acrylate initiated by redox system at lower temperature-preparation and polymerization of miniemulsion

Miniemulsions of styrene and butyl acrylate with sodium dodecyl sulfate (SDS) as the surfactant and hexadecane (HDE) and cetyl alcohol (HDL) as cosurfactants were prepared under high-speed stirring or ultrasonification. Results indicate that the stability of miniemulsions produced with HDE is more stable than that with HDL, when the feeding method, in which the cosurfactant is mixed with monomers, is used. There is an optical ratio (¼) of the surfactant to the cosurfactant for maximum stabilization of the miniemulsions. The miniemulsions prepared by ultrasonification are much more stable than those by high-speed stirring. Also, a stable miniemulsion can be prepared at lower temperature (45°C) when homogenizing way of ultrasonification is used. The emulsions were of a droplet-size range common to miniemulsions and some of them exhibited long-term stabilities (3 months). When these emulsions were initiated, particle formation occurred predominantly by monomer droplet nucleation. The effects of temperature, ultrasonification time, ratio of monomers, and concentrations of surfactant, cosurfactant, and initiator on the polymerization rate, conversion, and particle size were determined. It was found that the miniemulsion copolymerization of styrene and butyl acrylate with a midial amount of a redox initiator ((NH₄)₂S₂O₈/NaH SO₃) at lower temperature (45°C) can be carried out successfully by using a suitable amount of the surfactant SDS (10 mM) and the cosurfactant HDE (40 mM), when a homogenizing way of ultrasonification is applied. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 2029–2039, 1998     

Miniemulsion polymerization of styrene with polymeric costabilizers

The polymeric costabilizers poly(stearyl methacrylate‐co‐2‐hydroxyethylmethacrylate) (PSH) and poly(lauryl methacrylate‐co‐2‐hydroxyethylmethacrylate) (PLH), composed of a hydrophilic backbone and several hydrophobic alkyl (stearyl or lauryl) side chains, were prepared by the free‐radical copolymerization of stearyl methacrylate (SMA) or lauryl methacrylate (LMA) with 2‐hydroxyethylmethacrylate and evaluated in the miniemulsion polymerization of styrene (ST). For comparison, the reactive costabilizers SMA and LMA were also included in this work. The hydrophobicity of costabilizers in increasing order was PLH < PSH < LMA < SMA. Only a small amount of these comb‐like copolymers was capable of producing kinetically stable ST emulsion droplets. The more hydrophobic the costabilizer was, the more effective was the costabilizer in the retardation of Ostwald ripening. About 30–40% of the monomer droplets were successfully converted into latex particles during the polymerization. The degree of monomer droplet nucleation increased with increasing hydrophobicity of the costabilizer. The formation of particle nuclei in the continuous aqueous phase played a crucial role in the polymerization kinetics. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1961–1969, 2004     

氧化还原体系引发苯乙烯乳液聚合

以不同的过氧化物引发剂分别与硫酸亚铁组成氧化还原引发体系,引发苯乙烯的乳液聚合,研究反应温度和还原剂用量等对聚合的影响.采用气相色谱、三检测体积排除色谱、动态光散射对单体转化率、聚苯乙烯的相对分子质量及其分布和乳胶粒径进行了分析.结果表明:升高温度或增加还原剂用量均会使聚合物的相对分子质量增大,聚合反应速率加快,与常规...     

Miniemulsion polymerization of styrene in the presence of macromonomeric initiators

Macromonomeric azo initiators (macroinimers, MIM) which have the properties of macromonomers, macrocrosslinkers and macroinitiators in a macrostructure were used in miniemulsion polymerization of styrene in the presence or absence of any other stabilizer and initiator. MIMs were prepared from the reaction of 4,4′-dicyano-4,4′-azovaleryl chloride, with poly(ethylene glycol) (PEG) of different molecular weights (400 and 2000 g/mol) and with 4-vinylbenzyl chloride. The stabilizing and initiator efficiency of MIMs and the effect of the chain length of PEG units were evaluated.     

树状分子引发苯乙烯的原子转移自由基聚合

从第2代端羟基树状聚芳醚出发,合成了2－溴异丁酸聚芳醚酯（G2－Br),并用红外,核磁,MALDI－TOF质谱和元素分析对其进行了表征,以C2-Br为大分子引发剂,在CuBr/2,2′－联吡啶催化作用下引发苯乙烯的原子转移自由基聚合。考察了聚合时间,单体和引发剂配比,聚合温度等因素对聚合的影响,合成了结构规整,分子量分布较窄的树状－线型嵌段共聚物。     

High-conversion diffusion-controlled polymerization of styrene. I

A kinetic model based on the free volume theory has been proposed for the polymerization of styrene. The model, which is capable of describing the course of polymerization in both bulk and solution, accounts for diffusion-controlled termination and propagation and gives a limiting conversion.     

Radical polymerization of acrylamide initiated by ceric ammonium nitrate-methionine redox initiator system

The polymerization of acrylamide, initiated by a cerium (IV) [Ce(IV)] ammonium nitrate-methionine redox initiator system, was carried out in an aqueous solution at different reaction conditions. The dependence of molecular weight and polymerization yield on the concentration of Ce(IV), polymerization time, and temperature was determined. The molecular weight distributions (MWD) of the resulting polymers were examined using the HPLC method. Based on the HPLC results, optimum reaction conditions were determined that provided an opportunity to obtain a polymer that had a narrow MWD. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1643–1648, 1997     

Rapid polymerization initiated by redox initiator for the synthesis of polyaniline nanofibers

High quality polyaniline nanofibers have been synthesized by a rapid polymerization of aniline using ammonium peroxydisulfate (APS)/Fe²⁺ redox initiator as the oxidant without any hard or soft templates. The addition of Fe²⁺ in conventional polymerization system plays an important role in changing the bulk morphologies of polyaniline from irregular particle agglomerates to nanofibers. Open-circuit potential measurements indicate that the rate of polymerization of aniline with the aid of Fe²⁺ ions has a substantial increase. The influences of synthetic parameters, such as the concentrations of aniline, dopant, and redox initiator, and reaction time, on the sizes and morphologies of polyaniline nanostructures have been investigated for elucidating the formation of polyaniline nanofibers. Fourier transform infrared spectrum, UV-vis spectrum, and cyclic voltammograms reveal that the molecular structures and electrochemical properties of polyaniline nanofibers do not differ significantly from that of conventional polyaniline.     

Modelling of free radical polymerization of styrene and methyl methacrylate by a tetrafunctional initiator

A mathematical model for free radical polymerizations initiated by tetrafunctional initiators is described in detail with comparisons to experimental results. Reactions involving the fate/efficiency of functional groups are properly accounted for, while in the past, kinetic models for difunctional initiators found in the literature have ignored this. Free volume theory is used to describe the diffusion-controlled regime. Based on model predictions, multi-radical concentrations were estimated to be several orders of magnitude smaller than mono-radical concentrations. Through various case studies, the model was able to demonstrate that the concentration and chain length of various polymer structures (i.e., linear, star or coupled stars) depend upon monomer type and reaction conditions. The model was found to be useful in explaining experimentally observed differences in the behaviour of a tetrafunctional initiator with styrene compared to methyl methacrylate (MMA). In both cases, higher reaction rates could be obtained when switching from a mono- to a tetrafunctional initiator; however, the influence on molecular weight was found to vary between the two systems. Work with styrene showed similar trends as with difunctional initiators, where the tetrafunctional initiator maintained similar molecular weights compared to a monofunctional initiator. Yet, for MMA, replacing the monofunctional initiator with its tetrafunctional counterpart decreased the molecular weight.     

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.     

Dynamics of a CSTR for styrene polymerization initiated by a binary initiator system

The steady state and dynamic behavior of a continuous stirred tank reactor has been analyzed for free radical solution polymerization of styrene initiated by a mixture of two initiators having different thermal stabilities. From the steady state analysis of the reactor model with a mean residence time as a bifurcation parameter, four unique regions of steady state solutions are identified in an operating parameter space for a given initiator feed composition. A variety of complex bifurcation behavior such as multiple steady states, Hopf bifurcation and limit cycles have been observed and their stability characteristics have been analyzed. The effects of feed initiator composition and the concentration of the initiator in the feed stream on the reactor dynamics are also presented.     

Free‐radical bulk polymerization of styrene with a new trifunctional cyclic peroxide initiator

The bulk free‐radical polymerization of styrene in the presence of a new cyclic trifunctional initiator, 3,6,9‐triethyl‐3,6,9‐trimethyl‐1,4,7‐triperoxonane, was studied. Full‐conversion‐range experiments were carried out to assess the effects of the temperature and initiator concentration on the polymerization kinetics, molecular weight, and polydispersity. Gel permeation chromatography was used to measure the molecular weight and the molecular weight distribution of polystyrene. When this multifunctional initiator was used for styrene polymerization at higher temperatures, it was possible to produce polymers with higher molecular weights and narrower molecular weight polydispersity at a higher rate. This showed that the molecular weight and polydispersity were influenced by the initiator concentration and the polymerization temperature in an unusual manner. Moreover, polystyrene, obtained with trifunctional peroxide, had O? O bonds in the molecular chains and was investigated with differential scanning calorimetry and gel permeation chromatography. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1035–1042, 2004     

Calculation of molecular weight distribution in styrene polymerization initiated by a binary initiator system

A computational scheme is presented for the calculation of molecular weight distribution in styrene polymerization initiated by a binary initiator system. In this paper, the method of finite molecular weight moment is presented by calculation of the polymer chain length distribution. This method is compared with the method of integrating an infinite number of polymer population balance equations. The results of the two methods show a reasonably good agreement. It is possible to produce polymer having the same molecular weight distribution.     

Anomalous particle through soap-free emulsion polymerization of styrene using oil-soluble initiator

One of oil-soluble initiators, VF-096, might work as cross-linker. This initiator would enable to synthesize the particle with cross-linking, which was involved with the particle morphology. Soap-free emulsion polymerization of styrene using this initiator was carried out to develop the method to control the particle morphology in one batch system. As a result, it was found that anomalous particle was generated without stirring and the particle morphology changed to be spherical by increasing shear stress through the stirring. One of the origins of the anomalous particle was the phase separation of the water in the particle and release of it from inside of the particle to the bulk.     

氧化还原引发剂对丙烯酸酯乳液性能及聚合机制的影响

以过硫酸钾(KPS)和亚硫酸氢钠(NaHSO3)为自由基聚合体系的氧化-还原型引发剂,以十二烷基硫酸钠(SDS)和脂肪醇聚氧乙烯醚硫酸钠(AES)为阴/非离子型复合乳化剂,制备甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)和甲基丙烯酸(MAA)共聚物乳液。研究了引发剂种类及用量对该乳液性能及聚合过程等影响,探讨并提出了酸性条件下丙烯酸酯乳液体系的新型引发机制。结果表明:在其他条件保持不变的前提下,当m(KPS):m(NaHSO3)=1.00:0.45、w(KPS+NaHSO3)=0.6%时,乳液的单体转化率(98%)和黏度(5.900 Pa.s)相对最高,反应时间(2.0 h)相对较短且初始聚合温度(60℃)相对最低,此时乳液质量最稳定。     

Anionic polymerization initiated by lamellar compounds of LiC12: 1. Kinetics of the polymerization of styrene and isoprene — initiator efficiency

The polymerizations of styrene and isoprene initiated by LiC₁₂ in cyclohexane are far slower than those observed in homogeneous media. The initiator's efficiency is estimated from a determination of the polymer molecular weight at differents reaction steps. Keeping in mind the monomer diffusion inside the graphite layers and in allowing some assumptions, some of the propagation rate constants were estimated. These values are much lower than those found in homogeneous polymerization. Temperature speeds up the reaction. The initiator's efficiency depends on the rate at which the graphite separates under the conjugated action of temperature and polymer growth.     

Mathematical model for the bulk polymerization of styrene using the symmetrical cyclic trifunctional initiator diethyl ketone triperoxide. I. Chemical initiation by sequential decomposition

In this study, we experimentally and theoretically investigated the use of the symmetrical cyclic trifunctional initiator diethyl ketone triperoxide (DEKTP) in the bulk polymerization of styrene. The experimental study consisted of a series of isothermal batch polymerizations at different temperatures (120 and 130°C) with different initiator concentrations (0.005, 0.01, and 0.02 mol/L). A mathematical model was developed to predict the evolution of the reacting chemical species and the produced molecular weight distributions. The kinetic model included chemical and thermal initiation, propagation, transfer to the monomer, termination by combination, and reinitiation reactions. The simulation results predict the concentration of diradicals, monoradicals, and polymeric chains, characterized by the number of undecomposed peroxide groups. The experimental results showed that at reaction temperatures of 120–130°C, initiation by DEKTP produced an increase in the polymerization rates (R_p's) and average molecular weights, depending on the initiator concentration, due to sequential decomposition. The mathematical model was adjusted and validated with the experimental data. The theoretical predictions were in very good agreement with the experimental results. Also, an optimum initiator concentration was observed that achieved high R_p's and high molecular weights simultaneously. For polymerization temperatures of 120–130°C, the optimum concentration was 0.01 mol/L. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of multiphase block copolymers by redox polymerization process

Redox polymerization of methylmethacrylate (MMA) using Ce(IV) with poly(oxyethylene) having azo and hydroxy functions was carried out to yield methylmethacrylate-ethylene glycol block copolymers with labile azo linkages in the main chain. These prepolymers were used to initiate the radical polymerization of styrene through the thermal decomposition of the azo group, resulting in the formation of multiblock copolymers. Successful blocking has been confirmed by fractional precipitation, a strong change in the molecular weight distribution and spectral measurements.     

The kinetics of two-phase bulk polymerization. I. Monomer and initiator distribution

Rubber-reinforced thermoplastics are produced commercially by dissolving a rubber in the monomer of a glassy polymer and commencing polymerization with a free-radical initiator. Beyond a few per cent conversion, the incompatibility of the two polymers causes a phase separation, with each phase containing one nearly pure polymer. Subsequent polymerization occurs in each phase. The heterogeneous nature of the reaction can influence both the kinetics of the reaction and the amount of grafting in the product. The fact that only monomer which polymerizes in the rubber phase can possibly graft establishes an upper limit to the amount of grafting and hence influences the mechanical properties of the product. It is shown theoretically how unequal partitioning of monomer and initiator between the phases can influence the extent of grafting, and can also explain the kinetic rate reductions which have been observed in such systems. The distributions of monomer and benzoyl peroxide and azobisisobutyronitrile initiators between the phases have been determined experimentally for a styrene–polystyrene–polybutadiene system. They cannot account for the rate reduction observed in such systems.