Continuous dosing of fast initiator during vinyl chloride suspension polymerization: Polymerization rate and PVC properties

Continuous dosing of a fast initiator during the suspension polymerization of vinyl chloride has been carried out in a pilot‐scale reactor. The kinetics course of this polymerization and the particle features of the resulting grains were discussed and compared to the conventional polymerization with the same conversion and maximum reaction rate. It was found for the system used that a suitable dosage trajectory allows the reaction rate to remain constant during polymerization. This decreases the polymerization time up to 53% compared with the conventional suspension polymerization, while the molecular weight distribution and molecular weight of the final grains remained almost unchanged. SEM micrographs revealed that PVC grains prepared using this polymerization process had irregularly shaped, uneven particle surfaces and larger particle sizes. The grains also featured high porosity with loosely aggregated smaller primary particles that led to low levels of residual unreacted monomer. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44079.     

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     

Calcium carbonate and wood reinforced hybrid PVC composites

In this article, poly(vinyl chloride) (PVC) sandwich‐structured hybrid composites with amorphous calcium carbonate and wood‐filled cores were obtained by compression molding. It has been determined that wood addition up to a weight ratio of 33% reported to the total filler amount is beneficial in improving both the inter‐filler and filler‐matrix interfacial adhesion, which alongside with the promoting of the amorphous PVC matrix crystallization is responsible for an increase up to 34% in the flexural strength of the composites, compared to unfilled PVC. The hybrid filled composites present up to 35% lower friction coefficients and up to 20% higher Brinell hardness values than the composites filled with calcium carbonate alone. Subsequently, wood addition determines an increase in the oxidation onset temperature for PVC and an increase with up to 20% in the sound and thermal‐insulative properties of the composites, compared to unfilled PVC. The dominating dispersive part of the composites surface energy aids in improving the mass and dimensional stability of the assembly to both water and dilute hydrochloric acid aqueous solutions. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46317.     

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     

Thermal stability of poly(vinyl chloride)/layered double hydroxide nanocomposites

Effects of nanoscale dispersed layered double hydroxides (LDHs) on thermal stability of poly(vinyl chloride) (PVC) in thermal and thermooxidative degradation processes are investigated by dynamic and isothermal thermogravimetric analysis (TGA), discoloration test, fourier transform infrared (FTIR), and ultraviolet‐visible (UV‐vis) spectroscopic techniques. During both stages of thermal degradation, the degradation temperatures, including onset degradation temperature and temperature of the maximum degradation rate, increase, and the final residue yield of the PVC/LDH nanocomposites reaches 14.7 wt %, more than double that for neat PVC. The thermooxidative degradation process is more complex. During the first two stages, the presence of nanoscale dispersed LDH particles enhances the thermal stability, whereas in the last stage accelerates the thermal degradation possibly due to the accumulation of heat released. Additionally, the studies of the isothermal thermooxidative degradation process by FTIR and UV‐vis spectra indicate that both polyene backbone formation and some carbonyl groups are simultaneously developed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

原位悬浮聚合PVC/纳米CaCO3的制备及其性能

利用原位悬浮聚合法制备了聚氯乙烯(PVC)／纳米CaCO3复合树脂,并对其性能进行了研究。结果表明。与PVC相比,PVC／纳米CaCO3复合树脂的热稳定性、增塑剂吸收量及表观密度等有所提高;冲击强度Eh4．9kJ／m^2增加到13．0kJ／m^2：拉伸强度由58．2MPa增加到59．5MPa;断裂伸长率由57．8％增加到75．6％,达到了增韧增强的效果。     

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。     

Rigid poly(vinyl chloride) (PVC) gelation in the brabender measuring mixer. I. Equilibrium state between sliding,breaking, and gelation of PVC

This article discusses the first part of the Brabender typical torque process curves. Rigid poly(vinyl chloride) (PVC; Polanwil S‐61) was processed at various temperatures between 160 and 200°C with blade speeds in the range of 5–40 min^?1. The morphological changes of the processed compound was characterized by scanning electron microscopy and optical microscopy, and the degree of gelation was estimated on the basis of DSC thermograms. The values of torque minimum strongly depends on temperature. Shear rate affects mainly the time of reaching the minimum torque. The grains are disintegrated into the nonuniform particles and aggregates of the dimensions between 20 and 4 μm. The significant variation of the gelation degree was found for the sample produced in the same conditions and unloaded from Brabender chamber at minimum of torque. It was found that the value of the minimum of torque described momentary equilibrium state between sliding of breaking grains and increasing degree of PVC gelation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 966–971, 2004     

Hierarchical structure and properties of rigid PVC foam crosslinked by the reaction between anhydride and diisocyanate

Rigid crosslinked poly(vinyl chloride) (c‐PVC) foams by forming semi‐interpenetrating network (SIPN) structure via the reaction of phthalic anhydride (PA) and diisocyanate were prepared. The influence of PA on hierarchical structure and mechanical properties of c‐PVC foam was studied. The Fourier transform infrared spectrometer results showed that the presence of PA resulted in the formation of imide structure in the SIPN of obtained c‐PVC foams, which introduced a structural defect of SIPN. Thus, the residue (gel) from tetrahydrofuran extraction of the foams decreased with the increase of PA content. Dynamic thermal analysis showed the presence of three aggregation state structures in the c‐PVC foams, depending on the loading of PA. The addition of PA in the formulations affected cellular structure and mechanical properties of the obtained foams. Furthermore, the influence of chemical environment of anhydride compounds on the formation of imide structure in the crosslinking network of c‐PVC foams was discussed. A strategy for reducing defect of crosslinking network and improving mechanical properties was put forward. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46141.     

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     

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.     

Tough,stable spiroacetal thiol‐ene resin for 3D printing

Though over 30 years old, 3D printing has seen an explosion of interest in recent years as technology has become sufficiently advanced and affordable, enabling widespread usage, and investigation of the technique as a method of manufacture. However, the materials commonly used for printing applications frequently suffer from poor mechanical properties and are only suitable for prototyping and non‐load‐bearing objects. We report a stable, tough resin formulation which incorporates spiroacetal molecules into the polymer backbone and displays widely varying and tunable mechanical properties. We characterize the system via (photo‐)DSC, rheology, and tensile testing; further, we detail a comprehensive heat treatment investigation to optimize material performance and elucidate the structure–property relationships present in the printed and non‐printed semi‐crystalline photopolymer. Annealing the material at 40 °C for 120 hours produced a tough thiol‐ene with a homogenous crystal structure. Printed samples exhibited comparable morphology their cast analogues, but suffered from reduced tensile properties as a result of interlayer adhesion. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46259.     

Effect of zinc maleate/zinc oxide complex on thermal stability of poly(vinyl chloride)

In this study, zinc maleate (ZnMA) and zinc oxide (ZnO) complex (ZnMA/ZnO) was prepared by two methods, namely, by the reaction of maleic acid (MAH) with excess ZnO in aqueous solution and by direct mixing of ZnMA and ZnO at 180°C. The chemical structure of the complex was analyzed by X‐ray diffraction, thermogravimetric analysis (TGA), and Fourier transform infrared (FTIR) spectroscopy. The thermal stabilizing effect of the complex on poly(vinyl chloride) (PVC) was evaluated through static and dynamic stability methods. Compared to calcium and zinc soaps and ZnMA alone, the complex exhibited better thermal stabilizing effect on PVC. The stabilization mechanism was also investigated by ultraviolet–visible spectrometer, FTIR, TGA, and gel content analysis. The results indicated that the complex which involved the replacement of labile chlorine atoms hindered the formation of conjugated double bonds in PVC chains via Diels–Alder reaction, and ZnMA/ZnO complex also exhibited the ability to absorb hydrogen chloride. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41464.     

Preparation of a poly(vinyl chloride) ultrafiltration membrane through the combination of thermally induced phase separation and non‐solvent‐induced phase separation

To regulate the polymer–diluent interaction and control the viscosity of the casting solution, diphenyl ketone (DPK) and a N,N‐dimethylacetamide/N,N‐dimethylformamide mixture were selected as a combined diluent. Poly(vinyl chloride) (PVC) utlrafiltration membranes, which had sufficient mechanical properties for their practical applications because of their bicontinuous spongy structure, were prepared by a combined process of thermally induced phase separation and non‐solvent‐induced phase separation. The phase‐separation mechanism was analyzed. In an air bath, the cast nascent solution immediately transformed into a transparent gel, and liquid–liquid phase separation was induced by a sudden drop in the temperature before crystallization. An ice–water bath was used to coagulate the membrane. The effects of the DPK and PVC concentrations on the membrane structures and performances were mainly investigated. The results show that an increase in the DPK content made the membrane pores change from fingerlike to spongy. Fully spongy pores formed, and the pores size decreased with increasing PVC concentration. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42953.     

The effect of additives on the thermal stability of poly(vinyl chloride)

The effect of a range of organic additives on the thermal stability of poly(vinyl chloride), both with and without a chloroparaffin extender, was studied using a number of experimental techniques. Of the additives used the best overall balance was provided by pentaerythritol, which increased stability when the extender was present and had no effect when it was absent. The congo red test emerged as the most suitable technique, being consistent and inexpensive and able to screen several additives simultaneously. Isothermal differential thermal analysis correlated with the congo red test but required more expensive equipment, was time-consuming and demanded good mixing of the poly(vinyl chloride) compound to give reproducible results. Thermogravimetry was not sufficiently sensitive and the heat stability test was the least useful of all.     

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.