Experimental investigation of vinyl chloride polymerization at high conversion—temperature/pressure/conversion and monomer phase distribution relationships

An equilibrium model relating temperature, pressure, monomer conversion and monomer phase distribution for vinyl chloride polymerization has been developed. This model can be used to determine the monomer conversion beyond the pressure drop by measurement of reactor temperature and pressure. It can also be used to estimate monomer conversion at the pressure drop point and the distribution of monomer in all the phases over the entire extent of polymerization. A series of experiments to measure the solubility of VCM in water and PVC were carried out in the temperature range 40–70°C. Correlations of the solubility of VCM in water and the VCM–PVC interaction parameter with temperature, respectively, were obtained from the experimental data.     

In situ mass-suspension polymerisation

In situ mass-suspension polymerisation of MMA was carried out in a single reactor. The mass polymerisation was carried out in a gently agitated monomer layer of a two stratified layers of monomer and water in the reactor. The degree of conversion at which mass polymerisation changed to suspension polymerisation, by increasing the rate of agitation, was altered systematically. The polymer content of the monomer/polymer solution, formed during the mass polymerisation stage, significantly affected the evolution of the particle size distribution. Mass-suspension polymerisation was found to be more vulnerable to drop coalescence and process failure than conventional suspension polymerisation. The results indicate the importance of the transition stage in a typical suspension polymerisation during which the rate of polymerisation is very low and the adsorption of stabiliser on the surface of drops is completed. The polymer beads from the mass-suspension polymerisation had a very broad size distribution with a large contribution from satellite particles.     

Drop coalescence processes in suspension polymerization of vinyl chloride

A tracer dye technique was used to investigate the effect of turbulence intensity, stirring time, and the type and concentration of the suspending agent, partially hydrolyzed poly(vinyl acetate) (PVA), on the coalescence rate of vinyl chloride monomer (VCM) droplets in an agitated liquid–liquid dispersion. It was found that the extent of coalescence rises slowly with mixing time, is roughly proportional to the agitation speed, and decreases sharply when the concentration of stabilizer is increased. Coalescence rate depended on the degree of hydrolysis of the stabilizer. The method of addition of initiator during VC suspension polymerization was also studied and its effects on the polymerization conversion and final PVC particles' properties were determined. It was found that the polymerization reaction occurs more uniformly in all the VCM droplets when the initiator was predissolved in the VCM prior to reaction compared with the case when the initiator was predispersed in the continuous water phase. Also, for the same reaction time, the conversion was higher in the former case. During polymerization, the concentration of PVA in the aqueous phase decreased substantially and the porosity of the polymer particles was reduced. © 1996 John Wiley & Sons, Inc.     

二氯乙烷裂解管式反应器二维模拟

建立了二氯乙烷在管式反应器中进行气相热裂解的二维模型 ,模型考虑了二氯乙烷热解生成氯乙烯的主反应和生成焦前体的副反应以及气体密度变化对裂解反应的影响 .模拟计算表明 ,二氯乙烷和氯乙烯的浓度沿径向分布平坦 ;但是管内近壁面处由于存在边界层 ,始终存在着明显的径向温差 ;近管壁处始终是裂解的高速率区 ,副反应也主要发生在管壁区 .表明确定最优的炉管管径时必须考虑提高裂解速率与降低结焦速率之间的平衡 .在距进口量纲 1管程 0 .3左右的管壁处裂解速率达到最高 ;副反应速率的最大点位于出口管壁处 .与工业数据比较后发现 ,炉管出口的转化率、选择性、出口压力和温度等数据与模型预测值一致 ,表明模型具有较高的可信度     

Dynamic modelling of the continuous emulsion polymerization of vinyl chloride

A dynamic model for the continuous emulsion polymerization of vinyl chloride (VCM) in a train of stirred tank reactors has been developed. This model can predict monomer conversion, polymer particle size distribution (PSD), molecular weight distribution and long and short chain branching frequencies under non-steady reactor operation during startup, reactor switching and during unstable operation when conversion and polymer and polymer particle properties oscillate with time. The model has been used to design a flexible reactor train configuration which operates in a stable mode and can produce latexes with a wide range of properties including a bimodal polymer particle size distribution.     

Encrustation Prevention in PVC Reactors

Poly(vinyl chloride) is one of the world's most important bulk thermoplastics. Approximately 15 million tons are produced annually. About 80% of this is made by the suspension process. Suspension polymerization of vinyl chloride is almost invariably accompanied by the formation of scale on the internal surfaces of the polymerization reactor, including moving surfaces such as those of the impeller. The formation of scale, or deposits of PVC, on the internal surfaces of reactors has always been a problem in the manufacture of PVC because of reduced heat transfer, large alteration of the agitation regime present in the reactor, and broken-off scale fragments that block transfer systems and contaminate the product. Therefore scale must be cleaned periodically. Until the early 1970s these deposits were removed manually; PVC workers were exposed to high levels of VCM and considerable production time was lost. The introduction of large reactors in 1975 made it practical to mechanize the cleaning. High-pressure water sprays are employed for this purpose. However, such devices remove only the slightly adherent sandy deposits. For strongly attached deposits, a thorough manual cleaning is necessary after a series of polymerization batches. Manual cleaning requires extensive safety measures to protect the workers from VCM vapor inside the reactor. In addition, such cleaning is costly and undesirable. In more recent years, methods have been developed to suppress or inhibit the formation of scale on the reactor walls. Proposed solutions in this field are sparese. The patient literature claims many chemical treatments to resuce reactor fouling. Many PVC producers have developed effective buildup-suppressant treatments, which significantly reduce the need for reactior cleaning. They vary from treatments to render the reactor wall hydrophilic and reduce the adsorption of VCM (e.g., application of a sulfonic acid polymer to the reactor surface [1]) to systems containing polymerization inhibitors and radical traps (e.g., organic dyes and phenolic resins). The most successful of these probably work by a combination of both mechanisms. In this paper the soultions are reviewed brifly and emphasis is given to suspension polymerization where the initiator is monomer soluble.     

Effect of Polymer Growth Rate and Diffusion Resistance on the Behavior of Industrial Polyethylene Fluidized Bed Reactor

The two‐phase model developed for the UNIPOL polyethylene process is improved by introducing polymer diffusion resistance, this means modelling of polyethylene fluidized bed reactors has been examined on two levels, at small scale of individual polymer particle, and macroscale of the whole reactor. The model utilizes the multigrain model that accounts for the reaction rate at catalyst surface to explore the static and dynamic bifurcation behavior of the fluidized bed catalytic reactor. Detailed bifurcation diagrams are developed and analyzed for the effect of polymer growth factor and Thiele modulus (the significance of the porous medium transport resistance is characterized by Thiele modulus) on reactor dense phase monomer concentration and reactor temperature as well as polyethylene production rate and reactor single pass conversion for the safe temperature region. The observations reveal that significant diffusion resistance to monomer transport exists, and this can mask the intrinsic rate constants of the catalyst. The investigation of polymer growth factor indicates that, the nascent stage of polymerization is highly gas phase diffusion influenced. Intraparticle temperature gradients would appear to be negligible under most normal operating conditions.     

Melt polymerization of bisphenol‐A and diphenyl carbonate in a semibatch reactor

The effect of thermodynamic phase equilibrium on the kinetics of semibatch melt polycondensation of bisphenol‐A and diphenyl carbonate was studied for the synthesis of polycarbonate. In the melt‐polymerization process, a partial loss of diphenyl carbonate occurs as the reaction by‐product phenol is removed from the reactor. To obtain a high molecular weight polymer under high temperature and low‐pressure conditions, a stoichiometric mol ratio of the two reactive end groups needs to be maintained during the polymerization. In this work, vapor–liquid equilibrium data for a binary mixture of phenol and diphenyl carbonate are reported and they are used in conjunction with the Wilson equation to calculate the exact amounts of diphenyl carbonate and phenol returned from a reflux column to the reactor. A good agreement between the reactor model simulations and the experimental polymerization data was obtained. It was also observed that diphenyl carbonate is quickly consumed during the early stage of polymerization and the fraction of evaporated diphenyl carbonate refluxed to the reactor is essentially constant during this period. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1253–1266, 2001     

Two‐stage stabilizer addition protocol as a means to reduce the size and improve the uniformity of polymer beads in suspension polymerization

A two‐stage stabilizer addition protocol is suggested for reducing the size and improving the uniformity of polymer beads resulting from conventional suspension polymerization. The stabilizer load was divided into an initial charge and a secondary addition. The use of a low concentration of stabilizer in the initial charge served to assist drop rupture while avoiding significant reduction in drop size and production of too many satellite droplets. The secondary addition time of stabilizer occurred just before the onset of the growth stage when drops were vulnerable to coalescence but robust against break up due to their high viscosity. The secondary addition of stabilizer served to provide stability to monomer drops during the growth stage and as a result the drops underwent limited coalescence. This resulted in the formation of smaller and more uniform polymer beads in comparison to beads obtained by conventional suspension polymerization at the same overall concentration of stabilizer. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45671.     

Evolution of vinyl chloride conversion below critical micelle concentration: A response surface analysis

Utilizing response surface methodology, the conversion of vinyl chloride monomer (VCM) was monitored when the polymerization temperature, the type of surfactant, and the weight ratio of water‐to‐monomer (W/M) were taken as the emulsion polymerization variables. Because the homogeneous nucleation was found to be the dominant mechanism in VCM emulsion polymerization, irrespective of the surfactant concentration, the whole experiments have been carried out below critical micelle concentration of the used surfactants. Among all the studied variables, the polymerization temperature appeared as the most effective parameter; moreover, its interactive effect with W/M caused different trends in the alteration of final conversion being observed. Also, depending on the reaction temperature, the VCM conversion would be affected by the type of the surfactant used. Contrarily, simultaneous change in the type of surfactant and W/M revealed an insignificant effect on the evolution of VCM conversion. The optimization of final conversion of VCM was also accessible through contour plots of response surface methodology. It is worth noting that, taking a conventional approach into consideration, the alteration of VCM conversion seemed to be a monotonic function of temperature. J. VINYL ADDIT. TECHNOL., 21:157–165, 2015. © 2014 Society of Plastics Engineers     

悬浮聚合用HAP／SDBS无机分散体系的作用机理

研究了ＨＡＰ粉末的沉降特性与生成过程，考察了ＨＡＰ粉末和不同表面活性剂配合在苯乙烯单体分散液中的吸附特性，同时研究了ＨＡＰ粉末复合不同表面活性剂的无机分散体系用于苯乙烯单体悬浮聚合时的聚合稳定性。对ＨＡＰ／ＳＤＢＳ无机分散体系用于悬浮聚合时的分散作用机理进行了探讨。简化了用于苯乙烯悬浮聚合用ＨＡＰ的制备方法：取消缓冲体系，缩短陈化时间，室温制备。且制备的分散剂用于聚合时为常量的１／５。     

偏氯乙烯-氯乙烯悬浮共聚树脂的分子质量及分布

在5L聚合釜中合成了偏氯乙烯(VDC)-氯乙烯(VC)悬浮共聚树脂,研究了聚合温度、转化率、单体配比和助剂对分子质量及分布的影响．结果表明,共聚树脂的分子质量与聚合温度的关系符合Arrhenius方程,其综合活化能为-32．877kJ／mol;聚合物的特性黏数在高转化率阶段基本不变;分子质量随着单体配比中VC含量的增加而降低、分子质量分布也有一定的波动;聚合前加入助剂对共聚树脂的分子质量及分布影响不大。     

Influences of some polymerization conditions on particle properties of suspension poly(vinyl chloride) resin

Effects of polymerization temperature, conversions, and nonionic surfactant on the particle properties of suspension poly(vinyl chloride) (PVC) resins were investigated. It was shown that polymerization temperature has no significant influences on the mean particle size of PVC resin, and that the cold plasticiser absorption (CPA) of resin decreases linearly with the increase of polymerization temperature. Agglomeration of VCM droplets finishes before 20% conversion, and the mean particle size keeps almost constant at later stages of the polymerization process, but the CPA continues decreasing with the increase of conversion. Scanning Electron Microscopy (SEM) micrographs show that the degree of agglomeration of primary particles increases with polymerization temperature and conversion. Addition of nonionic surfactant to the VCM suspension system, as a secondary suspending agent, has a great influence on the particle properties of PVC resin. The particle size and CPA increase as the concentration of nonionic surfactant increases. The nonionic surfactant with a greater HLB value is more effective in raising the mean particle size, but is less effective in raising the CPA. It is considered that the added nonionic surfactant would be absorbed faster on the VCM/water interface than the poly(vinyl alcohol) (PVA), which was used as the primary suspending agent. Because the colloid protection ability of the nonionic surfactant is less than that of PVA, droplets become less resistant to coalescence, and the mean particle size of the final PVC resin increases consequently. The increase of porosity is caused by the combined effects of increased coalescence of VCM droplets and the nonionic surfactant's steric effect inside the droplets. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1544–1552, 2002     

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.     

Modeling of ethylene polymerization with difunctional initiators in tubular reactors

The severe thermodynamic conditions of the high‐pressure ethylene polymerization process hinder ethylene from going to full conversion. One remedy to improve the monomer conversion is to make effective use of difunctional peroxides. Multifunctional peroxides can accelerate the polymerization rate, produce branching, and modify the rheological properties of molten polymers. This article proposes a kinetic model based on a postulated reaction mechanism for ethylene polymerization initiated by difunctional initiators in a high‐pressure tubular reactor. Three peroxides suitable for ethylene polymerization were compared for their effectiveness. Compared to dioctanoyl peroxide, the two difunctional peroxides considered performed much better for the higher temperature regions of the reactor and gave ethylene conversions nearly twice as high for only half of the initial amount of dioctanoyl. They also generated low‐density polyethylene polymer with a broader molecular weight distribution and longer chain branching. These two important polymer characteristics can influence the end‐product rheological properties. Injecting fresh ethylene at different points along the reactor improved the conversion and produced more branched polymer. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Swelling of poly(styrene-co-methacrylic acid) latex by isoprene

Carboxylated polystyrene latex was used as seed and isoprene as the second-stage monomer in an inhibited, seeded emulsion polymerization recipe for studies of monomer swelling kinetics at 80°C during interval III of an emulsion polymerization. The isoprene was added to the reactor in small portions using a syringe, and changes in the reactor pressure were continuously measured. Isoprene was added until a free liquid monomer phase was formed; that was, interval II was reached, as indicated by no further pressure increase upon the addition of more monomer. When the observed pressure increment, Op_i, per unit isoprene added was plotted as a function of the volume fraction of polymer in the latex particles, v_p, the graph could be divided into 3 domains. The break points in the Op_i curve could, in an analogous emulsion polymerization, be identified as the glass transition temperature for the polymer, the so-called gel point in interval III and the onset of interval III. In the second domain, where the v_p was between the glass transition temperature, T_g, for the seed polymer and the gel point, the value of Op_i decreased significantly with increasing monomer concentration in the latex particles. This was due to the entropy of mixing and the monomer acting as a plasticizer in the seed polymer. The rate of sorption of monomer to the latex particles was low at high values of v_p. It then increased rapidly with increasing monomer concentrations in the latex particles, [M]_p, and a maximum was observed in domain 2. At lower values of v_p the sorption rate decreased in domain 3 and finally became zero as the free liquid monomer phase started to form. Results from batch polymerization suggested that the rate of diffusion of adsorbed monomer and oligo radicals into the particles was retarded. A simplified form of the Vanzo equation was used to estimate the monomer partitioning. It predicted too high a value of [M]_p, especially in domain 2 of the swelling process. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2041–2051, 1998     

Atom transfer radical suspension polymerization of methyl methacrylate catalyzed by CuCl/bpy

Atom transfer radical suspension polymerization (suspension ATRP) of methyl methacrylate (MMA) was carried out using 1-chloro-1-phenylethane (1-PECl) as initiator, copper chloride/bipyridine (CuCl/bpy) as catalyst. The polymerization was accomplished with a mechanical agitator under the protection of nitrogen atmosphere. Apart from the dispersing agent (1% PVA), NaCl was also used in the water phase to decrease the diffusion of CuCl/bpy to water and the influence of the concentration of NaCl was investigated. Subsequently, the kinetic behavior of the suspension ATRP of MMA at different temperatures was studied. At 90 and 95 °C, the polymerization showed first order with respect to monomer concentration until high conversion. The molecular weight (M_n) of the polymer increased with monomer conversion. However, at lower temperatures, different levels of autoacceleration was observed. The polymerization deviated from first order with respect to monomer concentration when the conversion was up to some degree. The lower the temperature was, the more the deviation displayed. On comparison with bulk ATRP of MMA, the rate of suspension ATRP was much faster.     

Emergency stopper for VCM suspension polymerization

Because of the exothermicity of reaction and the necessity of using active initiators for the vinyl chloride monomer (VCM) suspension polymerization reaction, a study was undertaken in order to choose the best polymerization inhibitor for emergency situations such as temperature runaway, power failures, and agitation system problems. The effect of triethylene glycol-bis3(3 terc-butyl-4-hydroxy-5-methyl phenyl) propionate (1) and N-nitrosophenylhydroxylamine ammonium salt (2) cited in the literature as free radical polymerization inhibitors on VCM suspension polymerization reactions is shown.     

Impregnation of mortars with monomers and their radiolytic polymerization

Mortars were cured for a sufficient period to give sufficient strength and were then dried to remove the free water without dehydrating the compounds formed. Dried specimens were evacuated and impregnated with a mixture of styrene and acrylonitrile monomers which gives high mechanical properties after polymerization. Positive pressure was then applied, and polymerization was done radiolytically. The effect of degree and period of evacuation, the positive pressure and the irradiation dose on monomer loading, tensile and compressive strength were studied, and the optimum operating conditions were established. The achieved strength was correlated with the fraction of open pores impregnated. The composites investigated have the same volume fraction of mortar, and the polymer is added at the expense of the open porosity causing nearly an exponential increase in strength. Only 80% of the open pores were filled with polymers due to the difference in density between the polymer and the monomer, loss of monomer, and the presence of entrapped gas consisting of residual air and residual water vapor and monomer vapor, as well as due to the inability to fill all the micropores with monomer. A compressive strength four times that of plain mortar and a tensile strength eight times that of plain mortar were achieved.     

氯化聚乙烯/氯乙烯悬浮溶胀接枝共聚聚合温度-压力-转化率模型

根据氯乙烯(VC)在气相、水相、聚氯乙烯(PVC)富相、氯化聚乙烯(CPE)相和单体富相的分配，建立了CPE／VC悬浮溶胀接枝共聚聚合温度—压力—转化率模型。该模型可用于共聚体系VC临界转化率和临界转化率后VC转化率的预测，实现聚合终点的控制。模型和实验结果表明，随着聚合体系中CPE含量增加，VC临界转化率和一定压降时的转化率减小，这是由于VC在单位质量CPE中的溶胀量大于VC在PVC中的溶胀量所致。实验测定的不同CPE含量或压降时的VC聚合转化率与模型结果吻合较好。