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.     

铅盐稳定剂对低卤阻燃PVC/PNBR热稳定性的影响

采用刚果红法研究了铅盐热稳定剂对低卤阻燃聚氯乙烯/粉末丁腈橡胶热塑性弹性体脱氯化氢热降解性的影响。结果表明:铅盐类热稳定剂在低卤阻燃PVC/PNBR热塑性弹性体中单独使用时,热稳定效果总体是三盐基硫酸铅>二盐基亚磷酸铅。当二盐基亚磷酸铅、三盐基硫酸铅并用时可提高体系的初始变色温度。     

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     

Effects of silver nanoparticles on thermal properties of DBSA-doped polyaniline/PVC blends

Dodecylbenzenesulfonic acid (DBSA)-doped polyaniline (PAND) has been synthesized by redoping (PANDR) and aqueous polymerization (PANDA) methods. Silver nanoparticles were incorporated into the PANDR/tetrahydrofuran solution (PANDS) and then mixed with poly (vinyl chloride) (PVC) solution to prepare PANDS/PVC nanocomposites. In the present study, effects of silver nanoparticles on thermal properties of PAND/PVC blends have been investigated by employing thermal gravimetric analysis and heat flow microcalorimetry techniques. From these results it has been observed that the thermal stability of blends have increased by increasing the concentration of PAND in blends and nanocomposites. Addition of silver nanoparticles has suppressed the dehydrochlorination process and evolution/degradation of DBSA in PANDS/PVC nanocomposites. Presence of silver nanoparticles in PAND/PVC nanocomposites has reduced the mobility of PANI chains which in turn inhibited the transfer of free radicals formed during degradation of PAND and PVC through inter-chain reactions; hence, degradation process has been slowed down and thermal stability has been improved. Embedment of silver nanoparticles has reduced thermal weight loss corresponding to polymer degradation step and attains lower heat flow level in inert atmosphere for nanocomposites in contrast to those with no nanoparticles, thereby further improving thermal stability of nanocomposites. The heats of oxidation measured for blends and nanocomposites were independent of PAND/PVC blends composition.     

Kinetics and mechanism of the thermal degradation of poly(vinyl chloride)

The kinetics of the thermal degradation of solid powdered poly(vinyl chloride) (PVC) under nitrogen was studied by thermogravimetry, rate of hydrogen chloride evolution, and rate of polyene sequence formation. These results are accommodated by a chain mechanism involving initiation by random dehydrochlorination at normal monomer residues of PVC, and a series of intermediates, each leaking to a stable conjugated polyene sequence. Structural irregularities such as allylic and tertiary chlorine are responsible for a fast initiation process at the very beginning of the degradation. Mean rate constants and activation parameters for random initiation, propagation, and termination reactions of the PVC degradation chain were calculated by simulation. Activation enthalpy/entropy correlations for the experimental data available for dehydrochlorination of chloroalkanes and chloroalkenes in the gas and in the liquid phase or nonpolar solvents and elementary reactions of PVC degradation show that initiation is an HCl elimination through a transition state of four centers requiring a synperiplanar conformation of the >CH–CCl< group, whereas propagation is a dehydrochlorination through a transition state of six centers requiring a cis configuration of the double bond.     

Comparative study of the effects of chlorinated polyethylene and acrylic impact modifier on the thermal degradation of poly(vinyl chloride) compounds and poly(vinyl chloride)/(oil palm empty fruit bunch) composites

The effects of chlorinated polyethylene (CPE) and acrylic impact modifier (AIM) on the thermal degradation of poly(vinyl chloride) (PVC) compounds and composites were investigated. The amounts of AIM and CPE used were fixed at 9 parts per hundred parts of resin (phr), while oil palm empty fruit bunch (OPEFB) fiber content was increased from 0 to 40 phr. To produce composites, the PVC formulations were dry‐blended by using a laboratory blender before being milled into sheets on a two‐roll mill at 165°C. The milled sheets were then hot‐pressed at 180°C. The thermal degradation of the specimens was evaluated by using thermogravimetry in a nitrogen environment. Thermal stability of the PVC/CPE compounds and PVC/CPE/OPEFB composites was improved by the addition of CPE. The CPE retarded the dehydrochlorination of PVC. However, the stabilization effect was reduced by the incorporation of OPEFB at levels of 30 and 40 phr. The presence of AIM accelerated the dehydrochlorination of PVC/AIM compounds and PVC/AIM/OPEFB composites. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

Kinetic model for thermal dehydrochlorination of poly(vinyl chloride)

In this paper, a novel method for calculating degradation kinetics is presented. The method has been applied to the thermal dehydrochlorination of two different samples of PVC. It has been observed that this dehydrochlorination is complex and involves two different processes. A model that accounts for the entire dehydrochlorination is proposed. This model involves nucleation and growth and diffusion controlled mechanisms. The kinetic parameters are obtained from linear heating rate, isothermal and sample controlled thermal analysis experiments. Kinetic results obtained from the macroscopic thermal analysis measurements demonstrate the correlation between the kinetics of the thermal dehydrochlorination of PVC and the structure of this macromolecule.     

Thermal Degradation of Poly (vinyl chloride)-Stabilization Effect of Dichlorotin Dioxine

Abstract

Thermal degradation of polyvinyl chloride (PVC) and the effect of dichlorotin dioxine (DCTD) on this process have been investigated using dehydrochlorination (DHCl) and thermogravimetric techniques. A significant decrease in the rate of degradation was observed when PVC was mixed with a small amount which was maximum with 0.25 pph of DCTD and thermal decomposition temperature with DCTD was found to be higher than that of pure PVC. The value of apparent activation energy of the dehydrochlorination process has been calculated and a suitable mechanism for the stabilizing action of DCTD on PVC has been purposed.     

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。     

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.     

Studies in the thermal degradation of poly(vinyl chloride)

Thermal degradation of poly(vinyl chloride) (PVC) was studied in nitrogen atmosphere in the presence of rubber seed oil and epoxidized rubber seed oil, barium and lead soaps of rubber seed oil, and epoxidized seed oil at various temperatures. The rate of dehydrochlorination at 1% degradation and the time required to attain 1% degradation were used to assess the effect of the thermal susceptibility of PVC to dehydrochlorination. It was found that epoxidized rubber seed oil, the metal soaps of rubber seed oil, and epoxidized rubber seed oil markedly enhance the thermal stability of PVC. The order of increasing stabilizing influence was metal soaps of epoxidized rubber seed oil > metal soaps of rubber seed oil > epoxidized rubber seed oil > rubber seed oil. © 1993 John Wiley & Sons, Inc.     

Liquid-phase degradation of poly(vinyl chloride)

The main kinetic regularities of the thermal and thermal-oxidative degradation of poly(vinyl chloride) (PVC) in the liquid phase have been analyzed in comparison with the solid-phase degradation of PVC. The thermal (in an N₂ atmosphere) degradation of PVC in the form of dilute solutions is characterized by a number of essential distinctions, the primary peculiarity consisting of a lower dehydrochlorination rate due to the retarded reaction of the formation of bond polyconjugated systems. The same is observed for the thermal degradation of PVC plasticized with di- and polyesters. On the contrary, in an oxygen-containing atmosphere the solvents promote PVC decomposition. Accelerated PVC degradation under such conditions is due to the solvent oxidation that causes the appearance, within the system, of products activating the PVC macromolecular decomposition. The intensified degradation processes are accounted for, in the first place, by an increased reaction rate of the statistical (by the random law) detachment of HCl from normal macromolecular units. In general, the kinetics of the thermal-oxidative liquid-phase degradation of PVC is determined by the partial pressure of oxygen in the reaction zone, by the quantity of the solvent introduced into the polymer, as well as by the oxidative stability of the solvent. It has been shown that an effective stabilization of PVC in the liquid phase, particularly in the systems highly plasticized with esters, can be achieved through stabilizing the solvent, first of all, rather than the polymer, against oxidative decomposition. In this case the PVC dehydrochlorination rate decreases sharply and may reach an essentially lower value than under similar conditions of the solid-phase thermal degradation of PVC. PVC stabilization with respect to the reaction of HCl elimination achieved through the solvent stabilization against thermal-oxidative decomposition has been called the effect of “echo-stabilization” of PVC.     

Thermal dehydrochlorination of poly(vinyl chloride). I. Effect of iron oxide on the rate of dehydrochlorination

The thermal degradation of poly(vinyl chloride) (PVC) was studied by following the rates of dehydrochlorination at temperatures between 180°C in pure nitrogen and air flow. Iron oxide accelerates the elimination of hydrogen chloride from PVC. The accelerating effect depends on the concentration of the oxide, and it has a maximum. This work tried to explain these behaviors. A mechanism of dehydrochlorination is suggested for polymer containing iron oxide.     

DEVELOPMENT OF SYNERGISTIC HEAT STABILIZERS FOR PVC FROM ZINC BORATE-ZINC PHOSPHATE

The importance of flame-retardant and smoke-suppressed poly(vinyl chloride) (PVC) compositions is increasing gradually in the polymer industry since PVC releases smoke and toxic gases (hydrogen chloride, HCl) during heating at temperatures above 140°C with the result of dehydrochlorination reaction. In this study, the synergistic effects of zinc borate (ZB)-zinc phosphate (ZP) on the thermal stability of PVC were investigated using thermal techniques. The induction and stability time values of PVC plastigels were obtained at 140° and 160°C. The results revealed that PVC plastigels having only ZP and ZB retarded dehydrochlorination of PVC compared with the unstabilized sample. However, the plastigels with both ZB and ZP had a superior synergistic effect on char formation of PVC. Since the induction periods of the samples having both ZB and ZP were higher than those of the unstabilized samples having only ZB or only ZP, the synergistic effect was observed.     

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     

Vergleich von thermisch und photolytisch ausgelöstem Abbau von PVC-Preßlingen und -Folien

Comparative investigations of PVC discs and foils concerning their thermal and photolytical behaviour showed an expiration of thermal degradation in the mass, whilst the photo processes injure only the surface of a sample. The investigations of polymer samples with different masses have demonstrated a constant rate of thermal dehydrochlorination in nitrogen, which was not influenced by the polymer mass. The degradation experiments in air resulted in an increased HCl-elimination with increasing degradation time. Oxidation reactions which occur in the presence of air cause an accelerated degradation and therefore the dehydrochlorination reaction is appointed as an additional reaction and not in competition with the HCl-elimination process. The influence of UV-light on PVC-discs and foils efforted a much higher dehydrochlorination rate; the energy of the rays is able to stimulate all types of chlorine atoms at the surface. The photolytical injury of the surface increased with degradation time resulting in a decrease of the degradation rate. The degraded and cross-linked material is insoluble in all solvents.     

Studies of the solid-state thermal degradation of PVC. I. Autocatalysis by hydrogen chloride

The thermal degradation of virgin and HCI-treated PVC in powder form, as well as of PVC films of different thicknesses, has been studied as a function of time and temperature. The rate of dehydrochlorination was determined conductimetrically and from the polyene sequence distributions as obtained by UV spectroscopy. Increases in the rate of dehydrochlorination, ranging between 30 and 45%, were observed at all temperatures for the samples pretreated with HCI, while the corresponding activation energies were found to be lower by about 20%. For the PVC films, the rate increased with thickness, i.e., with longer residence time of evolved HCI within the sample. The results offer insight regarding the autocatalytic role of evolved HCI.     

Greffages mecanochimiques sur le polychlorure de vinyle. II. Éatude des copolymègres grefféas

The copolymers obtained by mastication of poly(vinyl chloride) (PVC) in presence of methyl methacrylate and styrene monomers, and their fractions, were studied by using infrared spectroscopy, NMR, and flash pyrolysis. The degree of alternation between vinyl chloride and methyl methacrylate or styrene units is very low, and the copolymers are heterogeneous in composition. The results suggest that the mastication medium involves three kinds of domains: the inner part of the elementary grains of PVC is very slightly penetrated by the monomers. The polymerization initiated by the polymeric free radicals created by the rupture of bonds, begins in the surface layers of the grains and cause the formation of a true copolymer which accounts for 5–10% of the material. Light radicals arising from transfer reaction migrate into the third external domain which consists practically entirely of pure monomers and initiate polymerization.     

Structural and mechanistic aspects of the thermal degradation of poly(vinyl chloride)

A critical review of the title subject supports the following major conclusions. Thermal dehydrochlorination of poly(vinyl chloride) (PVC) begins with internal allylic chloride and tertiary chloride structural defects formed during polymerization. The tertiary chloride is associated with 2,4-dichloro-n-butyl, 1,3-di(2-chloroethyl), and chlorinated long branches. Mechanisms for the formation of all of the labile defects are well established. ‘Carbonylallyl’ structures and certain isotactic conformers of ordinary monomer units are unimportant as initiators of thermal dehydrochlorination. Both the initiation and the subsequent formation of conjugated polyene sequences occur via carbenium chloride ion pairs or by a closely related concerted four-center quasi-ionic route. Six-center concerted processes, pathways involving free radicals, and other mechanistic schemes suggested recently are not involved in polyene elongation. However, during thermal degradation, ordinary monomer units are converted into internal allylic chloride defects by a mechanism that may include the abstraction of hydrogen by triplet cation diradicals derived from polyene intermediates. Cyclization reactions seem likely to contribute to the termination of polyene growth. When PVC is thermolyzed in blends with other polymers, unusual kinetic phenomena are detected that remain to be fully explained.     

Isothermal and Dynamic Thermogravimetric Degradation of Rigid and Plasticized Poly(Vinyl Chloride)/Poly(Methyl Methacrylate) Blends

The thermal degradation of rigid and plasticized poly(vinyl chloride) (PVC)/poly (methyl methacrylate) (PMMA) blends was investigated by means of isothermal and dynamic thermogravimetric analysis in a flowing atmosphere of air. For that purpose, blends of variable composition from 0 to 100 wt% were prepared in the presence (15, 30 and 50 wt%) and in the absence of di-(2-ethyl hexyl) phthalate (DEHP) as plasticizer. The thermal degradation of the blends was investigated by isothermal thermogravimetry at 180°C during 120 min. It was found that the main processes are the dehydrochlorination of PVC and depolymerization of PMMA. The dynamic thermogravimetric experiments were carried out in the temperature range of 30 ? 550°C. The results showed that the thermal degradation of rigid and plasticized PVC/PMMA blends in this broad range of temperatures is a three-step process and that PMMA exerted a stabilizing effect on the thermal degradation of PVC during the first step by reducing the dehydrochlorination.