Investigation of the effects of nonisothermal suspension polymerization of vinyl chloride on the fusion and degradation behavior of poly(vinyl chloride)

Thermal stability of poly(vinyl chloride) (PVC) samples polymerized under a temperature trajectory was studied from the point of view of morphological and microstructural characteristics. The results are compared with those of the PVC samples obtained by polymerization at constant temperature having the same K value. The Brabender^® plastograph data indicated that the final PVC synthesized with the temperature trajectory showed lower fusion time and higher thermal stability time. The nonisothermal condition also increased the degree of fusion of the final PVC resin, reflecting lower temperature/time required to process it. It was found that the thermal stability of nonisothermally produced PVC as characterized by dehydrochlorination rate decreased (improved) with the increasing monomer conversion until a minimum value was reached that corresponded to the conversion at the pressure drop. However, the dehydrochlorination rate remains almost constant with conversion for an isothermal grade PVC resin. Although the evolution of the number of internal double bonds as well as extent of discoloration of PVC with conversion shows a decreasing trend, the labile chlorine concentration exhibits a maximum at early conversion. The reason for the former can be explained by the temperature dependence of reactions forming defect structures, which are kinetically controlled and thus favored at higher temperatures. The latter, however, can be explained because of the increasing importance of transfer reactions to polymer with increasing polymer concentration. Finally, the results from differential thermogravimetry verify an improvement in thermal stability of the final PVC prepared by using a temperature trajectory during vinyl chloride monomer suspension polymerization. J. VINYL ADDIT. TECHNOL., 23:259–266, 2017. © 2015 Society of Plastics Engineers     

Structural heterogeneities of suspension poly(vinyl chloride). II. Formation of compact glassy particles and the cause of their difficult processing

By modifying the polymerization process of suspension polymerization of vinyl chloride, poly(vinyl chloride) (PVC) samples were prepared containing various amounts of compact glassy particles. It was found that these particles probably arise by a different polymerization mechanism than usual suspension particles, namely, as a result of the nonhomogeneous distribution of initiator in vinyl chloride drops of the polymerization system. It was proved experimentally that the lower heat stability of difficultly processible particles is due to a side reaction between the initiator radical and the PVC polymer chain which causes dehydrochlorination of PVC already under polymerization conditions. This reaction may also explain the yet unknown mechanism of formation of internal double bonds in PVC produced by the radical polymerization of vinyl chloride. In conclusion, the difficult processibility of compact glassy particles is discussed as a consequence of the insufficient drying of these particles in the usual drying process.     

Enhancement of poly(vinyl chloride) productivity by continuous initiator injection

Polymerization of vinyl chloride monomer with continuous initiator dosage at constant temperature was modeled. Initiators with a half‐life shorter than 0.4 hour at the reaction temperature are suitable for continuous injection. Using a suitable initiator dosage regime, it is possible to keep the reaction rate at its maximum permissible value until critical conversion. It is found that a suitable dosage regime allows the total polymerization time to be reduced by as much as 38.6%, while the final conversion remains unchanged from standard isothermal polymerization. Also, addition of initiators with a half‐life greater than 0.47 hour, preferably from 0.47 hour to the time needed to reach the critical conversion, at the polymerization temperature at the beginning of the reaction are required to achieve a high conversion. The injection of initiators during polymerization into the reactor causes the weight‐averaged molecular weight and corresponding K value of the product to decrease. The drop in K value can be compensated by a decrease in reaction temperature. Initiator dosage shows no significant effect on the structural chemical defects in the PVC chains. Dispersibility and persistent gels (fisheyes) were not measured. J. VINYL ADDIT. TECHNOL., 23:248–258, 2017. © 2015 Society of Plastics Engineers     

Continuous Dosing of a Fast Initiator during Suspension Polymerization of Vinyl Chloride for Enhanced Productivity: Mathematical Modeling and Experimental Study

An adopted mathematical model was developed to reduce the batch time required for the suspension polymerization of vinyl chloride in order to improve the productivity by continuous dosage of a fast initiator during polymerization reaction. The model was accompanied by a particle swarm optimization (PSO) algorithm, so as to optimize the initiator dosage rate during the process for a certain conversion. A pilot scale reactor was employed to verify the mathematical model predictions. This showed that the model predictions are in very good agreement with the experimental data. A proper initiator dosage trajectory during the course of the reaction was obtained in such a way that the reaction rate over the course of polymerization was constant and corresponded to the maximum rate in the conventional case (non-continuous addition of a mild initiator). The maximum reduction in reaction time relative to conventional polymerization for the predefined conversion was 53%. Analyzing the molecular characteristics of the samples showed that the molecular characteristics of the final poly(vinyl chloride) (PVC) product remained relatively unchanged under an optimum initiator dosage trajectory compared with the conventional process.     

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     

Sur la dégradation thermique du polychlorure de vinyle. V. Stabilité thermique de polyméres semicristallins

The thermal dehydrochlorination of semicrystalline, but rather low molecular weight, PVC fractions, prepared by ionic polymerization catalyzed by tert-butylmagnesium chloride was studied under an inert atmosphere and compared with that of commercial polymer. When the samples are in powder form, the crystallinity of some fractions, which are insoluble at room temperature in all the usual solvents for PVC, induces a tremendous thermal stability, which is observed so long as the temperature is under the melting point of the sample. In dilute solution, the dehydrochlorination of all the samples is much slower, but the differences between the samples are less important; besides, a catalytic effect of some metallic impurities is observed. This catalytic effect is chiefly relative to a process of intermolecular condensation which causes the formation of a labile tertiary chlorine structure and so initiates or accelerates the purely thermal chain dehydrochlorination. It is suggested that, besides the crystallization and the catalytic effects, the configuration of the structural units could be an important factor in the course of the dehydrochlorination process.     

The concentration and possible source of unstable sites in PVC

Copolymers of vinyl chloride with 2-chloropropene were prepared as models for tertiary-chlorine branching in PVC. Rates of thermal dehydrochlorination of copolymers containing up to 2 mol percent 2-chloropropene were found to be a linear function of composition. By comparing the decomposition rates of the copolymers with that of PVC prepared under similar conditions, we estimate the maximum tertiary-chlorine content of PVC at 0.1 to 0.2 mol percent. This figure is of the same magnitude as estimates of the content of tertiary-chlorine, random unsaturation, and long-chain branching obtained in previously published studies of PVC. Possible mechanisms for tertiary-chlorine branch formation include chain-transfer to polymer and copolymerization with unsaturated chain-ends. By applying the conventional copolymerization equation, using the reactivity ratios of the vinyl chloride/2-chloropropene system, it is shown that the copolymerization mechanism predicts a tertiary-chlorine branch content close to the estimated value. Both mechanisms also agree qualitatively with reported effects of polymerization temperature and conversion on branching and thermal stability.     

金属氧化物硫化体系对PVC—CR共混物热稳定性的影响

聚氯乙烯－氯丁橡胶（ＰＶＣ－ＣＲ）共混物是一种很有发展前途的材料,但在研究中发现在某些体系中共混物的热稳性比综们各自均聚物的热稳定性差。因此,在实验中对影响ＰＶＣ－ＣＲ共混物热稳定性的诸进行探讨,同时也讨论了共混物的脱ＨＣｌ机理。用静态Ｐ金属氧化物硫化体系（ＭｇＯ－ＺｎＯ＿ＮＡ＿２２－ＨＳｔ）对ＰＶＣ－ＣＲ共混物热稳定性的影响。当ＰＶＣ与ＣＲ共混时,ＰＶＣ热稳定性受ＣＲ硫化体系的影响。在ＣＲ与Ｚ     

十一烯酸根插层水滑石对聚氯乙烯热稳定性的影响

采用共沉淀法制备了十一烯酸根插层水滑石（LDH—U）并用于聚氯乙烯（PVC）改性,研究了LDH—U对原位悬浮聚合和熔融复合法制备的聚氯乙烯（PVC）／水滑石复合材料热稳定性的影响。刚果红变色、热失重和动态加工热稳定性测试表明,PVC与LDH—U直接熔融复合,热稳定性较未改性PVC差;而采用原位聚合得到的PVC／LDH—U复合材料的热稳定性优于未改性PVC,且稳定时间随着LDH—U含量的增加而不断提高。导致以上差异的原因是原位聚合可使插层十一烯酸与氯乙烯发生共聚。     

热可逆交联剂对PVC力学性能及热性能的影响

用一种热可逆交联剂与聚氯乙烯(PVC)树脂熔融共混,研究了交联剂用量和交联时间对交联PVC制品力学性能和热性能的影响,分析了交联产物的热可逆转化行为。结果表明:热可逆交联剂能有效提高PVC制品的力学性能和热稳定性,当交联剂用量为3份时,PVC制品的力学性能达到最大值,维卡软化温度提高了4℃;PVC制品的凝胶含量随交联剂用量的增多而增大;交联时间为20 min时,PVC有较高的力学性能和热性能,更为重要的是PVC交联后具有热可逆转化特性。     

Graft copolymerization of poly(vinyl chloride) with styrene. II. Thermal behavior

Thermal behavior of graft copolymers of polyvinyl chloride with polystyrene prepared by using a cationic initiator (AlCl₃) was evaluated by measurement of rates of dehydrochlorination in nitrogen atmosphere. With increase in the extent of grafting the rates were found to decrease. Dynamic thermogravimetric analysis revealed an overall improvement in thermal stability of copolymers. Development of polyene sequences in degraded polymer samples was evaluated by measurement of electronic absorption spectra. In comparison to PVC, graft copolymer samples had fewer conjugated double bonds.     

The copolymerization of vinyl chloride with 1-olefins. V. Heat stability of copolymers of vinyl chloride with propene, 1-butene,and 1-pentene

Copolymers of vinyl chloride with propene, 1-butene, and 1-pentene containing 2–15 mol % of 1-olefinic structural units were prepared. The copolymers were dehydrochlorinated at 180°C in an inert atmosphere; the amount of hydrogen chloride split off was determined by continuous potentiometry. The results show that the heat stability of propene, 1-butene, and 1-pentene copolymers containing the same amount of 1-olefinic structural units does not differ significantly. Compared with the homopolymer of vinyl chloride, it is favorably affected by the presence of 1-olefinic structural units in poly(vinyl chloride) (PVC) chains. On the other hand, however, the heat stability of copolymers is impaired by the higher content of structural defects able to initiate the dehydrochlorination reaction. These structural defects, probably represented by chloroallyl groups, are formed in the copolymers during their synthesis. At the beginning of heating, structural defects produce intensive dehydrochlorination and, therefore, copolymers of vinyl chloride with 1-olefins if processed appear to be less thermally stable than does PVC.     

Polymerization of vinyl chloride at reduced monomer accessibility. IV. The effect of diffusion control on polymerization rate,molecular weight,and thermal stability

The effect of diffusion control on the polymerization of vinyl chloride has been studied by observing the rate as well as the molecular weight and the thermal stability of the polymer formed. The polymerizations were performed at 97% of saturation pressure in a water-suspended system at 55°C, using emulsion PVC latex as seed and a water-soluble initiator. The monomer was charged as vapor from a storage vessel kept at a lower temperature. Characterization included determination of molecular weight distribution by GPC and viscometry, and thermal dehydrochlorination. The gas–liquid contact was varied by changing the speed of agitation and the design of the stirrer. With a propeller the polymerization rate increased with the agitation up to ca. 1000 rpm, where after it became almost constant. Simultaneously, the molecular weight and the thermal stability increased. This indicates diffusion control, and thus decreased monomer concentration, at low agitation speeds, while the polymerization becomes reaction controlled at higher speeds. By a comparison with earlier data, obtained at different pressures and under reaction control, the actual monomer concentration could be calculated, which allowed an evaluation of the mass transfer constant. The possibilities to encounter problems with diffusion control in commercial polymerization of vinyl chloride is discussed. It is demonstrated that diffusion control is utilized in continuous polymerization of vinyl chloride, which explains the lower thermal stability of such materials.     

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     

Thermal stability of blends of poly(vinyl chloride) with polyester elastomer

The thermal stability of poly(vinyl chloride) (PVC) under air atmosphere was improved by blending with PETE (polyester elastomer). Its enhanced stability could be explained by a reaction between the ester component of PETE and HCl from dehydrochlorination of PVC, which was identified by IR- and ¹H-NMR spectroscopy. The best result of thermal stability was shown at a composition of 100 parts of PVC with 4 parts of PETE. By surveys of glass transition temperatures, it was found that all PVC/PETE blends were ununiformly distributed. During processing, the fusion time and torque at fusion decreased as the quantity of PETE increased. The mechanical properties of the blends were also changed; as the quantity of PETE increased, tensile strength of the blends decreased, while impact strength increased.     

Effect of polymerization initiator on early colour of poly(vinyl chloride)

The development of early colour and the dehydrochlorination rate were compared for poly(vinyl chloride) samples obtained by suspension polymerization using two different initiators, dicetylperoxydicarbonate and butylperoxyneodecanoate. The degree of discolouration was measured on pressed plates and expressed as yellowness index (YI), the polyene sequence distribution was monitored by UV/Vis-spectroscopy, and the degradation rate was determined by measuring evolved HCI conductometrically. The PVC sample initiated by dicetylperoxydicarbonate exhibited more extensive early colour and a higher dehydrochlorination rate as compared to the sample obtained with butylperoxyneodecanoate as initiator. The UV/Vis-spectra showed that the early colour originates from polyene sequences. After extraction of the PVC resins with heptane: acetone (85 : 15) the early colour turned out to be almost the same for the two samples. From ¹³C-NMR measurements it was found that the extract of the sample polymerized with dicetylperoxydicarbonate contains unreacted initiator. We suggest that the radicals formed when the remaining initiator decomposes initiate dehydrochlorination. Our results also indicate that radicals from dicetylperoxydicarbonate may cause long-chain branches during polymerization. The radicals formed from butylperoxyneodecanoate, on the other hand, do not seem to react with the polymer molecules. © 1993 John Wiley & Sons, Inc.     

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.     

EA-AA共聚物增容的PVC-木质素共混物的热稳定性

木质素分子中含有阻碍酚结构,可抑制基于自由基连锁机理的反应。而聚氯乙烯(PVC)的热降解属于自由基反应,因此用木质素与PVC共混,共混物的热稳定性应高于PVC,但PVC与木质素直接共混物的热稳定性一般都劣于PVC。制备了丙烯酸乙酯(EA)-丙烯酸(AA)共聚物乳液并用其对木质素粉末进行包覆处理。用处理后的木质素与PVC进行共混制备成PVC-木质素共混物。用热重分析法研究了共混物的热稳定性,并据扫描电子显微镜观测结果,结合木质素分子结构推测了共混物热稳定性的改善机理。结果表明,木质素用EA-AA共聚物处理后,共混物的热稳定性得到了明显改善,且优于PVC参照样(其初始分解温度和最大分解速率温度分别比PVC参照样高13℃和27℃左右)。扫描电子显微分析表明,木质素经丙烯酸酯共聚物处理后,与PVC的相容性改善显著,在PVC基体中分散良好。木质素羟基与EA-AA共聚物羧基的结合和分散颗粒的减小有效减弱了木质素的脱水作用,抑制了它对PVC的自催化脱氯化氢的促进作用,从而有效发挥了它的阻碍酚结构对PVC自催化脱氯化氢过程的抑制作用。     

Greffages mecanochimiques sur le polychlorure de vinyle. III. Stabilitéa thermique des polymègeres modifiéas

The mastication of poly(vinyl chloride) (PVC) in presence of monomers causes important changes of the thermal stability of the polymer when the last one possesses a basic character (e.g., 2-vinylpyridine). The dehydrochlorination rate is greatly increased, even if the monomer is present in only small amounts. In the most cases (styrene, acrylic ester) a better thermal stability is observed with respect to the acceleration of the dehydrochlorination, which is retarded or even suppressed. Infrared spectroscopy and differential thermal analysis show that the improved stability is due to an improved crystalline organization. When mastication causes the polymerization of the monomer (methyl methacrylate), degradation of the PVC part and depolymerization of the rafted part are observed simultaneously; this fact supports a radical mechanism for the thermal degradation of the PVC.