Kinetic study of emulsion copolymerization of ethyl methacrylate/lauryl methacrylate in propylene glycol,stabilized with poly(ethylene oxide)–block–polystyrene–block–poly(ethylene oxide) triblock copolymer

The kinetics of emulsion copolymerization of ethyl methacrylate (EMA)/lauryl methacrylate (LMA) in propylene glycol is very similar to the emulsion copolymerizations of water‐soluble monomers in water because of the high solubility of EMA/LMA in propylene glycol. The initial rate of polymerization depends only on initiator concentration and is not affected by either monomer concentration or stabilizer concentration. The overall rate of polymerization is only slightly dependent on monomer concentration and stabilizer concentration and is independent of initiator concentration. The final particle number density increases with increasing amount of stabilizer and decreases with increasing monomer concentration. The total surface area increases with stabilizer concentration and is not governed by either initiator concentration or monomer concentration. Homogeneous nucleation is the dominant mechanism of particle nucleation, as shown by the kinetic data on seeded polymerization and monomer partition behavior. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1691–1704, 2001     

Heterogeneous styrene–divinylbenzene copolymers. Stability conditions of the porous structures

The change in the porosity of styrene–divinylbenzene (S–DVB) copolymers during drying as a function of the quality of the diluent and of the divinylbenzene (DVB) concentration was investigated after drying the networks from water (maximum porosity) and from toluene (stable porosity). Two different diluents, namely toluene and cyclohexanol, were used in the polymerization system at a fixed volume fraction of the organic phase (0.50). The phase separation in toluene is accompanied by a slight deswelling of the network phase, whereas that in cyclohexanol leads to largely unswollen network phase. The stable porosity increases abruptly over a narrow range of the DVB concentration, i.e., between 40 and 50% DVB in toluene and between 15 and 25% DVE in cyclohexanol. The maximum porosity increases almost linearly with increasing DVB concentration up to a certain value, and then remains constant. The results indicate that the two main factors which determine the physical state of the swollen heterogeneous S–DVB copolymers, as well as the stability of the porous structures, are (1) the critical conversion at the incipient phase separation and (2) the degree of the inhomogeneity in crosslink distribution.     

The SCOPE dynamic model for emulsion polymerization II. Comparison with experiment and applications

Paper I provides the underlying theoretical framework for the SCOPE dynamic model of emulsion copolymerization. The present paper compares the model predictions for styrenemethyl methacrylate copolymerizations with experimental measurements made at a variety of polymerization conditions. The SCOPE model predicts conversion–time profiles reasonably well over wide ranges of initiator concentration, monomer concentration and monomer composition. In addition, the model accurately predicts number average molecular weights and copolymer compositions over the entire range of monomer composition. Like previous investigations of this system, the present study suggests that free radical desorption from polymer particles plays a dominant role on the copolymerization kinetics: Simple case II Smith-Ewart kinetics do not apply. The model for this system was applied to understand how changing reaction conditions could effect polymer properties such as particle size and molecular weight distributions. The power of the SCOPE model is illustrated by using it to predict conversion profiles, temperature profiles and copolymer properties for some large-scale versions of these recipes.     

偏二氯乙烯-丙烯腈悬浮共聚动力学

研究了单体配比、引发剂浓度、聚合温度、转化率等因素对偏二氯乙烯(VDC)-丙烯腈(AN)悬浮共聚树脂的组成、相对分子质量和聚合速率的影响,建立了动力学模型,讨论了AN的水溶性对树脂组成的影响,提出了相对分子质量与聚合温度及引发剂浓度关系的模型。     

VAc／BA／AA乳液共聚反应动力学研究

用丙烯酸丁酯（BA）和丙烯酸（AA）对醋酸乙烯酯（VAc）进行共聚改性,制备了稳定的VAc／BA／AA共聚乳液。研究了该聚合体系的动力学特征,讨论了乳化剂浓度（CE）、引发剂浓度（C1）和反应温度（T）对聚合速率和单体转化率的影响。实验结果表明,乳液聚合速率随着CE、C1和T的增加而增大;单体转化率随着CE和C1的增加而增大,在75℃时转化率有最大值;得到该共聚乳液体系的表观活化能Ea=64．4kJ·mol^-1;聚合反应速率Rp^∝CE^0.45C1^0．76该式与经典的乳液聚合动力学模型有较大偏差。     

On the gel effect in the presence of a chain transfer agent in methyl methacrylate polymerization and its copolymerization with various acrylates

The kinetics of methyl methacrylate (MMA) polymerization, and of its copolymerization with various acrylates, at high conversions in the presence of a chain transfer agent, are investigated with a dilatometer over the entire course of reaction. The displacement to higher conversions of the onset of the gel effect in the MMA homopolymerization, in the presence of a chain transfer agent, was determined. Similar information is also provided for the MMA-acrylate copolymerization systems. An increase in polymerization temperature slightly delays the onset of the gel effect in the MMA-acrylate copolymerization, but considerably increases the final conversion. The final conversion in copolymerization for a constant concentration of the chain transfer agent is independent of the initiator concentration, but is a function of the polymerization temperature. The reaction time for reaching the limiting conversion in copolymerization is increased with an increasing amount of the second monomer, as well as with an increasing number of carbon atoms in the acrylate used as the second monomer. © 1993 John Wiley & Sons, Inc.     

Optimization of polymer synthesis through distributed control of polymerization conditions

An optimal control methodology is applied to the goal of lowering polydispersity while increasing conversion in polymerization reactions. An illustration using initiator, heat, and monomer flux control profiles for free‐radical polymerization of styrene in a plug flow reactor is provided and compared with available experimental data. The design calculations use a kinetic model that includes the gel effect. The reactor designs show that distributed initiator, heat, and monomer fluxes along the length of the reactor lower the polydispersity of the styrene polymers and increase conversion for a given reaction time. The monomer flux maintains a nearly constant monomer concentration in the reactor. The initiator and heat fluxes are highly correlated. The temperature rises as a result the heat flux; but the initiator flux results in a lower initiator concentration relative to the initiator cofeed case. At a reaction time of 120 min, a conversion of 44% and a polydispersity of 1.73 have been achieved. The theoretical designs, although not proven to be globally optimal, are of high quality. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2922–2928, 2002     

Kinetic studies on styrene–divinylbenzene copolymerization by suspension technique

Kinetic studies on styrene and divinylbenzene (DVB) copolymerization by the suspension technique in a toluene diluent initiated by benzoyl peroxide are reported. Evaluation of the important reaction parameters is carried out. The crosslinked styrene–DVB copolymers can absorb toluene to a maximum swelling ratio of 17. The absorption/desorption took place instantaneously and reached the maximum value within 10 min, and it could be repeated many times, yet gave the consistent result. Rate equations evaluated by both integral and differential methods are investigated. High monomer orders of 1.5–2.3 were obtained. The activation energy for the polymerization was about 40 kcal/mol^?1. Autoacceleration was found even at low conversions. The acceleration was influenced by both monomer, crosslinker, and initiator concentrations. The integral and differential methods for the rate evaluation were compared, and the relationship between the rate equation and polymerization behavior was elucidated. The kinetic orders determined for this copolymerization show considerable deviation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1521–1540, 2001     

Molgewichtsverteilung und Langkettenverzweigung bei der anionischen Polymerisation von Butadien

The copolymerization of butadien with small amounts of divinyl benzene (DVB) has been investigated. The polymerization has been carried out with a lithiumamide as initiator in n-hexane as solvent under addition of tetrahydrofuran (THF) to govern the content of vinyl groups. By gel permeation chromatography coupled with a viscometer the molecular weight distribution (MWD) and long chain branching as a function of the conversion and of the molecular weight have been determined. Using a differential refractometer and a UV-photometer as detectors the distribution of the branching agent DVB vs. molecular weight has been studied. With our example long chain branching decreases with increasing conversion. The insertion of DVB occurs mainly in the first phase of the reaction. With increasing conversion the MWD becomes broader. At very high degrees of conversion the molecular weight increases considerably by coupling reactions.     

Pore memory of macroporous styrene–divinylbenzene copolymers

The variation of the pore structure of styrene–divinylbenzene (S–DVB) copolymer beads with the drying conditions was investigated. Macroporous S–DVB copolymer beads with various DVB contents were prepared in the presence of toluene‐cyclohexanol mixtures as a diluent. It was found that the pores of 10¹‐nm radius, corresponding to the interstices between the microspheres, collapse upon drying of the copolymers from toluene. The collapsed pores reexpand if the copolymers were dried from methanol. The collapse–reexpansion process of the pores was found to be reversible, indicating that the actual pore structure formed during the crosslinking copolymerization is memorized by the copolymer network. The magnitude of the pore structure variation increased on worsening the polymer–diluent interactions during the gel formation process due to the simultaneous increase in crosslink density distribution. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1055–1062, 1999     

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     

Reactive polymers,XXXVI. The effect of polymerization conditions on the porosity and mechanical properties of macroporous suspension copolymers from glycidylmethacrylate-ethylenedimethacrylate

By the method of design of experiments, the influence of the content and the thermodynamic quality of the mixture of inert solvents (porogenic compounds), of the concentration of the crosslinking agent and initiator in the polymerization mixture and of the reaction temperature in the radical suspension copolymerization was investigated with respect to the pore size, the porosity and the mechanical properties of macroporous copolymers from glycidylmethacrylate and ethylenedimethacrylate. It was found that the predominant effect on these characteristics should be attributed to the volume of the porogenic component in the mixture, and that the pore size and porosity increase at the same time the penetration modulus and the stress-at-break decrease proportionately to this volume. The concentration of the crosslinking agent has an influence only at low crosslinking values. The polymerization temperature and concentration of the initiator have only an insignificant effect on the structure and mechanical properties.     

超声波辅助引发MAA/AN自由基共聚合研究

考察了超声波辅助甲基丙烯酸(MAA)和丙烯腈(AN)共聚合时,单体配比、引发剂浓度、超声波频率以及超声场温度对体系转化率的影响。结果表明,超声波能够辅助MAA/AN进行本体聚合,加快聚合反应速率。超声波辐照下,本体聚合的转化率随反应温度的升高而增大,引发剂用量为0.2%时,反应的转化率最大。外加能量的超声波利于加快聚合反应速率,在频率为24 kHz的超声波辐照下,对提高共聚反应转化率的作用最大。     

Free radical polymerization of methyl methacrylate: Modeling and simulation under semibatch and nonisothermal reactor conditions

For the bulk free radical polymerization of methyl methacrylate (MMA), equations of the material balance can be written that are based on a kinetic diagram that considers initiation by decomposition of an AIBN initiator, propagation, and termination by disproportionation. To quantify the gel and glass effects simple empirical dependences are used between the rate constants of termination and propagation and monomer conversion. Numerical values for the empirical parameters at different temperatures and initiator concentrations are also given. Conversion history and molecular weights are obtained by simulation when an initiator or monomer are added to the reaction mass and the temperature modifies after some reaction has taken place. These intermediate operations are simulated at different moments with respect to the gel and glass effects. The validation of the model for semibatch and nonisothermal conditions are made by comparing the simulation results with literature experimental data. The most important conclusion of the article is that the empirical model proposed for the gel and glass effects can be successfully used under semibatch and nonisothermal reactor conditions. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2561–2570, 1999     

Copolymerization kinetics of acrylonitrile with amino ethyl‐2‐methyl propenoate in H2O/DMSO mixture

Amino ethyl‐2‐methyl propenoate (AEMP) was used successfully to copolymerize with acrylonitrile (AN). This was achieved by using azobisisobutyronitrile as the initiator. Kinetics of copolymerization of AN with AEMP was investigated in H₂O/dimethylsulfoxide (DMSO) mixture between 50 and 70 °C under N₂ atmosphere. The rate of copolymerization was measured. The kinetic equation of copolymerization system was obtained and the overall activation energy for the copolymerization system was determined. Values of monomer apparent reactivity ratios were calculated using Kelen–Tudos method. It has been found that the apparent reactivity ratios in aqueous suspension polymerization system are similar to those in solution polymerization system at polymerization conversion less than 25%. At conversion beyond 45%, the changes of monomer apparent reactivity ratios become less prominent. In water‐rich reaction medium (H₂O/DMSO > 70/30), monomer apparent reactivity ratios are approximately equivalent to those in aqueous suspension polymerization system. In DMSO‐rich reaction medium (DMSO/H₂O > 70/30), apparent reactivity ratios are similar to those in solution polymerization system. With an increase of polarity of solvent, values of apparent reaction ratios both decrease. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2095–2100, 2006     

氢化钠/三异丁基铝体系合成星形聚苯乙烯的研究

采用阻滞阴离子调控技术,通过"先核后臂"法以NaH/三异丁基铝(i-Bu3Al)与苯乙烯、二乙烯基苯(DVB)反应制备的多钠引发剂为核,乙苯为溶剂,合成了星形聚苯乙烯(PS)(cs-PS);通过"先臂后核"法,以NaH/i-Bu3Al直接引发苯乙烯聚合,DVB为偶联剂,也合成了星形聚苯乙烯(as-PS)。采用气相色谱测定了聚苯乙烯钠与DVB中四种组分在100℃下的聚合反应速率,并用凝胶渗透色谱分析测试了聚合物的分子参数及平均臂数。结果表明:聚苯乙烯钠与DVB中四种组分的聚合反应速率与单体浓度呈假一级动力学关系;随着n(DVB)/n(NaH)的增加,cs-PS和as-PS的相对分子质量均逐渐增加,相对分子量分布均变宽,平均臂数也随之增大。     

Concentrated emulsion copolymerization of butyl acrylate and vinyl acetate initiated by a redox initiator at lower temperature

The concentrated emulsion copolymerization of butyl acrylate and vinyl acetate with an ammonium persulfate/sodium hydrogen sulfate mixture as a redox initiator, with a sodium dodecyl sulfate/cetyl alcohol mixture as a compound surfactant, and with poly(vinyl alcohol) as a liquid film reinforcer was carried out at lower temperature. In less than 3 h, the polymerization conversion was greater than 95%. The effects of the surfactant, the initiator, the volume fraction of the monomer, and the temperature on the stability of the concentrated emulsion, the kinetic process, and the average size of the latices were examined. The morphology of the polymer particles was observed by transmission electron microscopy, and the average size and distribution of the particle diameter were measured by photon correlation spectroscopy. The kinetic equation was R_p = k[M]^0.38[I]^0.89[E]^?0.80 at 30°C (where R_p is the polymerization rate, [I] is the initiator concentration, [M] is the monomer concentration, and [E] is the concentration of the compound surfactant), and the apparent activation energy was 22.69 kJ/mol. The thin‐layer polymerization of the concentrated emulsions, which enabled the removal of the heat of polymerization, was performed first. In comparison with test‐tube polymerization, thin‐layer polymerization provided a more regular morphology of the polymer particles. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 570–576, 2004     

苯乙烯／双（2,3—二溴丙基）反丁烯二酸酯共聚动力学

研究了苯乙烯／双（２，３－二溴丙基）反丁烯二酸酯共聚动力学，分别讨论了单体的配比，聚合温度，引发剂浓度对共聚合体系的转化率－时间曲线的影响，结果发现，聚合温度和引发剂浓度影响很大，单体的配比影响较小。所建立的反应速率模型可以对转化率小于２０％的聚合速率进行描述，而在高转化率下，由于凝胶效应的影响而难以准确描述。     

Photo-induced graft copolymerization. III. Graft copolymerization of methyl methacrylate onto cellulose using peroxydiphosphate as photoinitiator

Photo-induced graft copolymerization of methyl methacrylate onto cellulose was investigated using peroxydiphosphate ion as the photoinitiator. The percentage graft yield increases with increasing both the monomer and initiator concentration. The reaction was carried out at three different temperatures, and the overall activation energy was computed. The kinetic data and other evidence indicate that the overall polymerization takes place by a radical mechanism. A suitable kinetic scheme has been suggested.     

乙烯基吡咯烷酮与乙酸乙烯酯共聚的研究

以偶氮二异丁腈 (AIBN)为引发剂 ,乙醇为溶剂 ,采用自由基溶液聚合方法研究了乙烯基吡咯烷酮 (VP)—乙酸乙烯酯 (VAC)共聚反应。研究了引发剂质量分数及单体质量分数与转化率和分子质量的关系 ,还研究了聚合反应温度对转化率与分子质量的影响 ,同时探索了控制共聚物组成分布均匀的方法