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.     

Influences of individual and composed poly(vinyl alcohol) suspending agents on particle morphology of suspension poly(vinyl chloride) resin

Effects of individual and composed poly(vinyl alcohol) (PVA) suspending agents on the particle morphology of poly(vinyl chloride) (PVC) resins were investigated and discussed in the view of PVA absorption at the oil/water interface and interfacial behavior. It was shown that the percentage and surface coverage of PVA at the oil/water interface decreased with the increase of the degree of hydrolysis (DH) of PVA in the DH range of 70–98 mol %, while the interfacial tension of VC/PVA aqueous solution increased linearly with the increase of DH of PVA. PVC resin with more regular particle shape, increased agglomeration and fusion of primary particles, lower porosity and higher bulk density, was prepared by using PVA with a higher DH as a suspending agent. This was caused by the occurrence of drop coalescence at the very early stage of VC polymerization, the increase of particle shrinkage, and the lower colloidal protection to primary particles. It was also shown that the interfacial tension of VC/water in the presence of composed PVA suspending agents varied linearly with the weight composition of the composed PVA suspending agents. The particle properties of PVC resin prepared by using the composed PVC suspending agents were usually situated in between the properties of PVC resins prepared by using the corresponding individual PVA suspending agent. The particle morphology and properties of PVC resin could be controlled by the suitable choice of the composed PVA suspending agents. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3848–3855, 2003     

分散剂和非离子型表面活性剂对悬浮聚氯乙烯树脂颗粒特性的影响

研究了聚乙烯醇(PVA)分散剂和非离子型表面活性剂对悬浮聚氯乙烯(PVC)树脂颗粒特性的影响。结果表明随着PVA醇解度的增加，PVC树脂的颗粒规整性和表现密度增加，孔隙率和吸油率降低；随着非离子型表面活性剂添加量的增加，PVC树脂的平均粒径和吸油率增大。从PVA和表面活性剂在水一油两相分配出发，讨论了PVA醇解度和添加非离子型表面活性剂对PVC树脂的颗粒特性影响机理。     

Utilizing cellulose ethers as suspension agents in the polymerization of vinyl chloride

Proper choice of a suspending agent will help the PVC manufacturer achieve control of resin particle size, particle size distribution, and resin bead porosity. The results of research work at Dow has revealed that certain properties of cellulsoe ethers (a hydroxypropyl methylcellulose ether structure) are useful in helping control the properties of the PVC resin. In vinyl chloride polymerizations, cellulose ethers act as both an emulsifier; and during the polymerization, as a protective colloid to prevent excessive coalescence of the monomer droplets. The average particle size of the organic droplets in the aqueous phase during the PVC polymerization reaction is a function of the interfacial tension, intensity of agitation, viscosity of the two phases, and the volume fraction of the dispersed phase. The average particle size of the PVC resin was found to be a direct function of the interfacial tension multiplied by the 0.2 power of the gel strength of the cellulose ether solution. The interfacial tension of the cellulose ether solution/organic interface is probably the most important factor in determining the resin particle size. Particle size distribution widens with an increase in interfacial tension. Resin bead porosity is also important and is directly related to the solubility of the cellulose ethers in the organic phase. This observation supports the proposed seed stabilization theory that can explain the formation of a porous resin bead. The use of a proper suspension agent like cellulose ethers with or without a secondary surfactant will help control important properties of the PVC resin product. Control of the average molecular wight, degree of substitution, and grouping distribution on the cellulose chain of the cellulose ether suspension agent (all of which affect interfacial tension) is important for the PVC manufacturer.     

Influences of initiator addition methods in suspension polymerization of vinyl chloride on poly(vinyl chloride) particles properties

Vinyl chloride suspension polymerization was carried out in a pilot‐scale reactor to study the effects of different methods of initiator addition on poly(vinyl chloride) (PVC) resin properties. The experiments used different arrangements for adding the initiator to the reactor, whereas other reaction conditions were the same: (i) initiator was added to the continuous aqueous phase and then monomer was dispersed in it (conventional method); (ii) initiator was predissolved in monomer before dispersing in the continuous aqueous phase; and (iii) suspending agents along with initiator were added to the monomer before polymerization. The PVC resin prepared by method of (i) had a higher monomer conversion and a higher Sauter mean diameter of grains with a narrow particle size distribution comparable to that of PVC resins by other methods. Scanning electron microscopy showed more uniform particles and fused primary particles in the grains, which confirms lower porosity and lower cold plasticizer absorption (CPA) for PVC grains produced by procedure of (ii). The results showed that when the suspending agents were also predispersed in monomer along with initiator (iii), CPA increases dramatically due to internal porosity of the grains. Simultaneously, a marked decrease in Sauter mean diameter was apparent. Scanning electron microscopy micrographs show that primary particles in the interior of PVC grains prepared by the latter method are looser, and there is more free volume between primary particles resulting the high internal porosity and consequently higher CPA. Mercury porosimetry analysis also confirms these results. K value as a molecular weight characteristic for all methods was the same . J. VINYL ADDIT. TECHNOL., 24:116–123, 2018. © 2016 Society of Plastics Engineers     

VCM／VAC共聚掺混树脂的合成及性能研究

本文介绍用特殊悬浮法合成共聚掺混树脂的方法,并讨论了粒经、掺混树脂含量等因素对糊性能的影响.结果表明,通过使用多元混合引发剂和悬浮剂及加入适量的助分散剂、界面活性剂、调粒剂等,并通过控制搅拌速率、温度等工艺条件能有效地控制粒子的粒径、粒度分布及粒子形状,从而制得具有良好性能和粒度均匀的掺混树脂;在一定的粒径范围内(25～40μm),掺混树脂的平均粒径越大,对降低糊粘度的效果越好;增加掺混树脂的含量对降低初始糊粘度更为有利,在PVC糊树脂中加入一定量的掺混树脂可降低塑化温度,缩短塑化时间,从而改善了PVC糊树脂的加工性能.     

悬浮态乳液聚合条件对聚氯乙烯树脂颗粒特性的影响

Suspended emulsion polymerization of vinyl chloride was carried out in a 5 L autoclave. The influence of agitation, polymerization conversion, dispersant and surfactant on the average particle size (PS) and particle size distribution (PSD), particle morphology and porosity of polyvinyl chloride (PVC) resin was investigated. It showed that the agitator had great influence on the smooth operation of polymerization, PS and PSD. The PS increased and PSD became narrow as polymerization conversion became high. The porosity decreased with the increase of conversion. A convenient choice of additives, both dispersants and non-ionic surfactants, allows one to adjust PS and PSD. The PS decreased with the addition of polyvinyl alcohol or hydroxypropyl methylcellulose dispersants,and increased with the addition of Span surfactants. The addition of dispersants or surfactants also affected the morphology and porosity of resin, and PVC resin with looser agglomeration and homogeneous distribution of primary particles was prepared.     

两种制备疏松PVC树脂的新型聚合方法

介绍了制备疏松PVC树脂的两种新聚合方法——以正丁烷为反应介质分散聚合和悬浮态乳液聚合，并对树脂颗粒的特性进行了简述。结果表明：以正丁烷为反应介质的非均相VC分散聚合所得树脂的粒径和颗粒形态与聚合体系VC／But比例和转化率等有关，由于存在向But的链转移，PVC分子质量小于相同聚合温度下生产的悬浮PVC树脂。悬浮态乳液聚合所得树脂粒径分布和颗粒形态与水油比、转化率和添加剂品种有关。     

氯乙烯SET-DT悬浮聚合动力学和成粒过程的相互关系

以碘仿为引发剂、连二亚硫酸钠/碳酸氢钠为催化体系、聚乙烯醇(PVA)和/或纤维素衍生物(MC)为分散体系,进行氯乙烯单电子转移-蜕化链转移(SET-DT)活性自由基悬浮聚合,采用在线示踪气相色谱法和激光粒度分析系统研究分散剂种类和浓度、搅拌转速等对聚合动力学和单体液滴/聚合物颗粒粒径分布的影响。发现在相同搅拌转速下,以MC为分散剂的氯乙烯聚合速率最大,以PVA为分散剂时反应速率最小;分散剂种类固定时,聚合速率随分散剂浓度增大而增大。SET-DT悬浮聚合过程中,水相连二亚硫酸钠分解产生的自由基向单体液滴的扩散速率与液滴粒径分布和皮膜结构有关,因此聚合成粒过程影响聚合动力学。尽管不同条件下的聚合均经历液-液分散、液滴黏并、树脂颗粒稳定(转化率>30%)等成粒阶段,但各阶段的液滴/颗粒平均尺寸随分散体系和搅拌转速的变化而变化,引起聚合速率变化;采用MC为分散剂得到的PVC树脂皮膜少,有利于水相产生的自由基向单体相的扩散,聚合速率大。     

Influences of diallyl phthalate as chain extender on the properties of high molecular weight poly(vinyl chloride) resin

A higher porosity with better thermostability is desirable for poly(vinyl chloride) (PVC) resin. In this study, high molecular weight PVC resins are prepared by vinyl chloride monomer (VCM)‐diallyl phthalate (DAP) suspension copolymerization in a 20‐L reactor at 50 °C using DAP as chain extender. SEM, BET, and analyses of plasticizer absorption results show the high molecular weight poly(vinyl chloride) (HPVC) by DAP‐VCM copolymerization is loose and porous. With increasing DAP content when the mass ratio of DAP/VCM (ω) is below the gel point, the porosity and the degree of polymerization increase. Nevertheless, the bulk density and particle size decrease. When more than the gel point, these relationships are reversed. Thermogravimetric analysis revealed that the HPVC had better thermostability than that of commercial PVC, and its thermostability increases with increasing ω before it reaches the gel point. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45093.     

A generalized population balance model for the prediction of particle size distribution in suspension polymerization reactors

In the present study, a comprehensive population balance model is developed to predict the dynamic evolution of the particle size distribution in high hold-up (e.g., 40%) non-reactive liquid-liquid dispersions and reactive liquid(solid)-liquid suspension polymerization systems. Semiempirical and phenomenological expressions are employed to describe the breakage and coalescence rates of dispersed monomer droplets in terms of the type and concentration of suspending agent, quality of agitation, and evolution of the physical, thermodynamic and transport properties of the polymerization system. The fixed pivot (FPT) numerical method is applied for solving the population balance equation. The predictive capabilities of the present model are demonstrated by a direct comparison of model predictions with experimental data on average mean diameter and droplet/particle size distributions for both non-reactive liquid-liquid dispersions and the free-radical suspension polymerization of styrene and VCM monomers.     

Particle features of poly(vinyl chloride) resins prepared by a new heterogeneous polymerization process

The heterogeneous polymerization of vinyl chloride monomer (VCM), with n‐butane as the reaction medium, was used to prepare poly(vinyl chloride) (PVC) resins. The particle features of the resulting resins and the particle formation mechanism of the polymerization process were investigated. The PVC resins prepared by the new polymerization process had a volume‐average particle size comparable to that of suspension PVC resins and a lower number‐average particle size. From scanning electron micrographs, it could be seen that the new PVC resins had a regular particle shape and a smooth surface with no obvious skin. They also had a high porosity. The new PVC resins were composed of individual and loosely aggregated primary particles. The diameter of the primary particles in the top layer of the grains was smaller than that of the primary particles in the center part of the grains. On the basis of the particle features of these PVC resins, a particle formation mechanism for the new polymerization process was proposed. PVC chains precipitate from a VCM/n‐butane mixed medium to form primary aggregates at a very low conversion, and the primary aggregates of the PVC chains aggregate to form primary particles, which further aggregate to form grains. The primary particles and grains grow by the capture of newly formed PVC chains and their primary aggregates and by polymerization occurring inside the aggregates. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 954–958, 2003     

On‐line acoustic attenuation spectroscopy of emulsions stabilized by vinyl alcohol–vinyl acetate copolymers: a model system for the suspension polymerization of vinyl chloride

BACKGROUND: Poly[(vinyl alcohol)‐co‐(vinyl acetate)] (PVA) copolymers obtained by partial hydrolysis of poly(vinyl acetate) are currently used as industrial stabilizers in the suspension polymerization of vinyl chloride monomer (VCM). Their molecular characteristics, mainly the average degree of hydrolysis (DH ) and average degree of polymerization (DPw ), have a major influence on the monomer droplet size and the properties of the final poly(vinyl chloride) resin. RESULTS: The average droplet size and size distribution of chlorobutane/water emulsions, as a model system for VCM/water emulsions, were studied using acoustic attenuation spectroscopy on‐line with an agitated laboratory reactor. The emulsions were stabilized by PVA with DH values between 73 and 88 mol% and DPw values between 450 and 2500. The effects of agitation speed, stirring time and concentration of the PVA copolymers were investigated. An attempt was made to correlate the interfacial tension and the droplet size. CONCLUSION: On‐line acoustic spectroscopy appears to be a suitable technique for the real‐time control of the droplet size of monomer suspensions. The advantages and limitations of the technique are outlined. The validity and the application limits of the commonly cited correlation between the droplet size and the Weber number are established for polymeric surfactant‐stabilized emulsions. Copyright © 2009 Society of Chemical Industry     

二次注入分散剂对悬浮体系稳定性及PVC树脂形态质量的影响

讨论了在VCM悬浮聚合反应过程中,当悬浮体系处于安全允许的高聚并动态和PVC树脂外在形态质量(表观密度、增塑剂吸收量)的最佳起点时,再次加入一定量的主分散剂来增强对VCM聚合处所的最小基元———VCM形态(有相对稳定的形状)小液滴的二次保护,防止其继续聚并,由此实现了稳定悬浮体系批次状态和提高PVC树脂形态质量双赢的目的。     

A combinatorial approach to evaluation of monomer conversion and particle size distribution in vinyl chloride emulsion polymerization

This work is targeted to study emulsion polymerization of vinyl chloride monomer (VCM) using experimental and mathematical methods. To fulfill this goal, a computer code was developed on the basis of zero–one population balance by which the effects of initiator and emulsifier concentration on the evolution of VCM conversion were investigated in the course of polymerization. The model was also trained to capture the coagulation of the particles. This enabled to adopt a reliable way of evaluating the particle size distribution (PSD). In particular, the rates of homogeneous and micellar nucleation mechanisms were simulated and reasonably predicted alterations in the PSD and the number of polymer particles under the influence of aforementioned parameters. The results from modeling were satisfactorily consistent with the experimental outputs and obviously visualized the impact of initiator and surfactant concentration on the PSD of the prepared PVC latexes.     

An investigation of precipitation polymerization in liquid vinyl chloride by photon correlation spectroscopy

Simultaneous photon correlation spectroscopy and light transmittance measurements were used to follow changes in the particle size and particle number density of poly(vinyl chloride) (PVC) particles which phase separated in liquid vinyl chloride (VCM) during the early stages of bulk polymerization. The scope and limitations of these techniques for studying dynamic systems are discussed. The nature and extent of interaction forces are deduced from experimental data together with a proposed mechanism for the colloidal stability of PVC gel particles in liquid VCM.     

VCM质量对PVC树脂质量的影响

通过对VCM质量与PVC树脂质量的跟踪分析,初步掌握了VCM质量对氯乙烯聚合反应及PVC树脂质量影响的规律。结果表明：VCM中的Fe含量、酸含量、水分含量及1,2-EDC含量严重超标会导致PVC树脂的白度下降,影响PVC树脂的热稳定性;氯甲烷、氯乙烷含量超标会使PVC树脂中的“鱼眼”数增多;氯乙烷和1,2-EDC含量超标还会降低PVC树脂的聚合度。     

Use of a gas chromatograph for measurement of the rate of monomer desorption from poly (vinyl chloride) resins

Previous studies by a gravimetric technique have established that the sorption and desorption of small quantities of vinyl chloride monomer (VCM) by poly (vinyl chloride) (PVC) resin powders obeys Fickian diffusion kinetics. Consequently, the rate of sorption or desorption is very sensitive to the size and structure distribution of the resin particles and is a useful measure of these properties. To facilitate the measurement of desorption rates, an “inverse GC” technique has been developed, with the PVC powder taking the place of the usual gas Chromatograph column. The detector and electronics of the GC are used to follow the VCM content of a carrier gas stream passing through a PVC resin sample initially equilibrated to a uniform VCM content. This method yields results consistent with the gravimetric data and provides a convenient means of characterizing PVC particle structure.     

Particle configuration and properties of poly(vinyl chloride)/halloysite nanotubes nanocomposites via in situ suspension polymerization

Poly(vinyl chloride) (PVC)/halloysite nanotubes (HNTs) nanocomposites were synthesized by in situ suspension polymerization of vinyl chloride (VC) in the presence of HNTs. The microstructure, mean particle size, and cold plasticizer absorption (CPA) of these resins and the rheological property, mechanical properties and thermal properties of PVC/HNTs nanocomposites were investigated. The results show that the mean particle size, the degree of porosity, and the CPA of PVC resins decrease with the addition of HNTs. The plasticization time and the equilibrium torque of PVC/HNTs nanocomposites are found to be longer and higher than that for the neat PVC. HNTs are uniformly distributed in the PVC matrix and effective in toughening and stiffening PVC nanocomposites when the addition of HNTs is 4.0 wt% or less. The glass transition temperatures of the PVC/HNTs nanocomposites were nearly identical to that of pure PVC. POLYM. COMPOS., 35:856–863, 2014. © 2013 Society of Plastics Engineers     

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.