Continuous dosing of fast initiator during vinyl chloride suspension polymerization: Thermal stability of PVC resin

Thermal stability of poly(vinyl chloride) (PVC) produced using continuous dosages of a fast initiator method was investigated in terms of morphological and microstructural characteristics. The results were compared with the properties of the PVC prepared by conventional polymerization method. The Brabender^® Plastograph and DSC results showed a lower fusion time, higher stable time, and greater degree of fusion for PVC obtained by polymerization using initiator continuous dosage method. Also, chemical analysis indicated that the PVC produced under an initiator continuous dosage system have lower structural defects, that is, branch numbers, internal double bonds, labile chlorine, and tacticity index, thereby improving the thermal stability of PVC resin. The results obtained from dehydrochlorination and thermogravimetry analysis confirm the improvement of thermal stability of PVC chains synthesized with continuous dosages of a fast initiator. Moreover, it was found that the concentration of microstructural defects and the dehydrochlorination rates of the PVC samples prepared by both processes increase with monomer conversion, particularly after critical conversion. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44480.     

Nonaqueous polymerization of vinyl chloride: An environmentally friendly process

Poly(vinyl chloride) (PVC) is produced via a nonaqueous polymerization process in which hexane is used as a diluent. This nonaqueous process can lead to significant energy savings, significant reductions in carbon dioxide emissions, and the elimination of wastewater. Various suspending agents have been used to evaluate their effects on the shape and morphology of PVC grains. The nonaqueous process leads to the formation of PVC grains with higher porosity than that of typical suspension PVC. The bulk density is slightly lower than that of suspension PVC, but the thermal stability seems to be similar. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

氯乙烯悬浮(本体)聚合用过氧化物引发剂

介绍了氯乙烯(VC)悬浮(本体)聚合常用过氧化引发剂的合成方法，着重阐述引发剂与聚合动力学的关系以及聚合动力学的检测方法。研究了单一和复合引发剂条件下的VC聚合动力学，为优化引发剂体系、缩短聚合时间、提高聚合釜的生产能力提供理论基础。     

新型过氧化物引发剂引发氯乙烯悬浮聚合动力学

研究了新型过氧化物引发剂过氧化新癸酸 1,1 二甲基-3-羟基丁基酯(Lup 610)在51.3与56.8℃以及过氧化新庚酸叔丁酯(Lup 701)和过氧化新戊酸叔己酯(HPV)在61.8℃单一引发剂引发氯乙烯悬浮聚合动力学,并采用模型计算结果绘制转化率 时间曲线,取与实验数据符合最好的f值作为引发剂的引发效率,求得引发剂Lup 610在51.3与56.8℃的引发效率分别为0.80与0.75,引发剂Lup 701和HPV在61.8℃下的引发效率分别为0.55和0.50。研究了上述引发剂与过氧化二碳酸二(2-乙基己酯)、过氧化新癸酸叔丁酯在各温度下复合引发剂引发氯乙烯悬浮聚合的动力学,与模型值相比较,发现两者能很好吻合。     

An experimental investigation of poly(vinyl chloride) emulsion polymerization: Effect of initiator and emulsifier concentrations on polymerization kinetics and product particle size

Effects of concentration changes in initiator species Na₂SO₃, (NH₄)₂S₂O₈ and CuSO₄, and emulsifier, ammonium stearate, on poly(vinyl chloride) (PVC) emulsion polymerization kinetics and on product particle size were experimentally investigated. It was observed that to obtain industrially significant rates and overall conversions, not only an optimum concentration ratio of Na₂SO₃/(NH₄)₂S₂O₈/CuSO ₄ must be used, but also the concentrations of these species must be above certain limits. Increasing the concentration of the emulsifier used did not influence the rate of polymerization, but led to increases in limiting conversions. Product particle size analyses indicate that average particle size is independent of initiator concentration and rate of initiation. An increase in the emulsifier concentration on the other hand appears to lead to an increase in number of particles in the system and thus promotes smaller particle sizes.     

Estimation of intrinsic rate coefficients in vinyl chloride suspension polymerization

The pre-exponential factor and the activation energy of the intrinsic rate coefficients for propagation, chain transfer to monomer, chain initiation by a Cl radical and termination in the suspension polymerization of vinyl chloride are estimated by regression of experimental data for the monomer conversion, ranging from 3 to 85%, and for the moments of the molecular mass distribution as a function of batch time over the temperature range of 308-338 K and for initiator (tert-butyl peroxyneodecanoate) concentrations from 0.026 to 3.0 wt%, based on the monomer. Termination by combination is the dominant termination mechanism. Cl radicals, formed in the chain transfer to monomer, contribute to the termination by recombination with macroradicals and, hence, attenuate the gel effect. Physically meaningful and statistically significant estimates for the pre-exponential factors and activation energies, 24.9 kJ mol⁻¹ for propagation and 54.3 kJ mol⁻¹ for chain transfer, allow to describe the experimental data over the full range of investigated conditions.     

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     

Experimental investigation of vinyl chloride drop behavior during suspension polymerization

The effects of some polymerization conditions on poly(vinyl chloride) (PVC) particles produced by the suspension polymerization process were studied on a laboratory scale. The different stages of vinyl chloride suspension polymerization were investigated experimentally by using an on-line sample withdrawal technique during reaction. It was found that the method of addition of initiator has a great effect on the PVC particle uniformity as well as the size distribution. Furthermore, when the initiator was predispersed in the continuous phase, some latex particles were formed. The effect of the type of stabilizer was also studied with two different types of PVA [partially hydrolyzed poly(vinyl acetate)]. It was found that by changing the stabilizer, the particle size, the porosity, and the morphology could change. When H80 (PVA with a degree of hydrolysis of 80% and a molecular weight of 259,000) stabilizer was used, the rigidity of the PVC particles was weak. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 127–134, 1997     

Thermal characterization of poly(vinyl chloride) samples prepared by living radical polymerization: Comparison with poly(vinyl chloride) prepared by free radical polymerization

Poly(vinyl chloride) (PVC) samples were synthesized by a living radical polymerization (LRP) method and compared with commercial PVC prepared by the conventional free radical polymerization (FRP). The differences were assessed, for the first time, in terms of viscosimetry parameters and thermal analysis. The LRP method used to prepare the PVC‐LRP samples is the only one available to obtain this polymer free of structural defects, being of commercial interest in a view of preparing a new generation of PVC‐based polymer with outstanding performance. The polymerization temperature selected (35°C) to prepare the LRP samples is currently used in the industry to prepare PVC‐FRP grades with moderate to high molecular weight. Since the thermal stability is a direct consequence of the polymer structure, this study is of vital importance to understand the potential of new PVC‐LRP. The thermoanalytical measurements demonstrate an enhanced thermal stability of PVC‐LRP when compared with its FRP counterpart. The PVC‐LRP sample with very low molecular weight reveals a higher thermal stability than the most stable PVC‐FRP sample. It is the first report dealing with thermal analysis of PVC prepared by LRP. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

Synthesis of random and block copolymers of vinyl chloride and vinyl acetate by RAFT miniemulsion polymerizations mediated by a fluorinated xanthate

Reversible addition–fragmentation chain transfer miniemulsion (co)polymerizations of vinyl acetate (VAc) and vinyl chloride (VC) are conducted in the presence of a fluorinated xthanate (X1). VAc miniemulsion polymerization can be well controlled by X1, and PVAc with small polydispersity index (PDI, <1.20) are obtained. X1 also shows well mediative effect to VC‐VAc miniemulsion copolymerization, while the PDI of VC‐VAc copolymer is greater than that of PVAc since a chain transfer rate to VC is greater than that to VAc. PVAc‐b‐PVC copolymers are synthesized by VC miniemulsion polymerizations mediated by X1‐terminated PVAc. PDIs of PVAc‐b‐PVC copolymers are greater than that of PVAc and VC‐VAc random copolymers with close monomer compositions, and increase with the increase of VC conversion. This is caused by the increased chain transfer to monomer and the formation of monomer‐rich and polymer‐rich phases during the VC polymerization stage. As‐prepared PVAc‐b‐PVC copolymers exhibit a micro‐phase separated morphology. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45074.     

The influence of poly(vinyl alcohol) suspending agents on suspension poly(vinyl chloride) morphology

The requirements for PVC suspension resin have changed considerably in the last few years, so much so that few companies have products on their ranges that are more than 4 or 5 years old. The suspending agent has a crucial influence on the morphology of the resin, so the changes in resin characteristics have largely been achieved by changes in the suspending agent systems. After a brief review of the mechanism of PVC suspension polymerisation, the properties of polymers made using PVOH suspending agents are related to changes in the latter. The effect of variations in PVAc degree of hydrolysis and viscosity are related to changes in surface tension. Methods of achieving higher porosity by using low hydrolysis co-suspending agents are described. It is shown that higher bulk densities can be achieved by delayed addition of the PVOH. Levels of conjugated unsaturation and copolymer distributions are also shown to have important influences.     

原位聚合聚氯乙烯树脂的合成及性能

研究了氯乙烯悬浮聚合时添加氯化聚乙烯(CPE)冲击改性剂、CaCO3填料、润滑剂及热稳定剂对聚合反应的影响，并对得到的可直接加工的原位聚合聚氯乙烯(RTUPVC)树脂的性能进行了表征。结果发现：CPE和CaCO3的加入均使达到相同压降的聚合时间缩短，氯乙烯聚合转化率相应减小；RTUPVC树脂的粒径随CPE粒径和用量的增大而增大，而CaCO3含量对RTUPVC树脂粒径影响不大；润滑剂和热稳定剂的加入，对聚合反应起延缓作用，但对RTUPVC树脂粒径影响不大；RTUPVC树脂加工塑化时间随CPE含量的增加而减少；相同CPE用量时，RTUPVC树脂的冲击强度和拉伸强度明显高于PVC/CPE共混物。     

Internal plasticization of poly(vinyl chloride) by grafting acrylate copolymers via copper-mediated atom transfer radical polymerization

Internal plasticization of poly(vinyl chloride) (PVC) was achieved in one-step using copper-mediated atom transfer radical polymerization to graft different ratios of random n-butyl acrylate and 2–2-(2-ethoxyethoxy)ethyl acrylate copolymers from defect sites on the PVC chain. Five graft polymers were made with different ratios of poly(butyl acrylate) (PBA) and poly(2–2-(2-ethoxyethoxy)ethyl acrylate) (P2EEA); the glass transition temperatures (T_g) of functionalized PVC polymers range from − 25 to − 50°C. Single T_g values were observed for all polymers, indicating good compatibility between PVC and grafted chains, with no evidence of microphase separation. Plasticization efficiency is higher for polyether P2EEA moieties compared with PBA components. The resultant PVC graft copolymers are thermally more stable compared to unmodified PVC. Increasing the reaction scale from 2 to 14 g produces consistent and reproducible results, suggesting this method could be applicable on an industrial scale.     

氯乙烯聚合和聚氯乙烯改性的研究

综述2008年CA报道的有关氯乙烯聚合和聚氯乙烯改性的主要文献和专利。     

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.     

非腈复合引发剂用于乙酸乙烯溶液聚合

以生物乙烯法生产的乙酸乙烯为单体、过氧化月桂酰-十二烷基二甲基叔胺为非腈复合引发剂、甲醇为溶剂进行溶液聚合反应的研究。实验考察了反应温度、反应时间、甲醇用量、引发剂用量对反应产物聚合率和聚合度的影响,采用正交试验优化了乙酸乙烯溶液聚合的反应条件,确定反应因素对聚合率和聚合度影响的相对大小。结果表明,最优的乙酸乙烯溶液聚合条件为:反应温度65℃,反应时间3h,甲醇用量10%,引发剂用量0.010%,获得聚乙烯醇产品的聚合度为3776,聚合率为45.29%。直观分析确定影响聚合率的因素主次顺序为引发剂用量> 反应时间> 甲醇用量> 反应温度;影响聚合度的因素主次顺序为甲醇用量 >引发剂用量 >反应温度 >反应时间。     

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。     

Absorption of trioctyl trimellitate into mass‐polymerization and suspension‐polymerization poly(vinyl chloride)

Poly(vinyl chloride) (PVC) slush powder has been widely used; we prepared it by dry blending. We found that the absorption of plasticizer by the PVC resins was the most important factor in the dry‐blending process and, further, that different types of PVC resin had different absorption rates. This results of this study provide new information about the relationship of absorption to PVC and other parameters. Haake rheomix testing and the quantity of plasticizers absorbed by the PVC resins were used to characterize the absorption process. Suspension‐polymerization poly(vinyl chloride) (SPVC) and mass‐polymerization poly(vinyl chloride) (MPVC) in different sizes were used for the test. The results showed that the MPVC absorbed the plasticizer more quickly than SPVC, especially at a higher temperature. However, for the same PVC resin type, the absorbing speeds were nearly independent of particle size. The studies that used a scanning electric microscope and specific surface area revealed that the morphology of the two types of particles was different. The surfaces of the individual particles of SPVC were smoother than those of MPVC. There was a “skin” covering the SPVC particles, whereas with the MPVC particles, the primary polymer was exposed directly on the surface. This difference in morphology was shown to be a significant factor in the different rates of absorption of the plasticizers for the different PVC resins. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2369–2374, 2004