Oxidative thermal decomposition of poly(vinyl chloride) compositions

“Pure” poly(vinyl chloride) resin and four compositions containing poly(vinyl chloride) were subjected to oxidative thermal degradation in air at &400°C both in a quiescent and a flow system. The volatiles formed were identified and quantitatively determined on a gram-per-gram basis. Hydrogen chloride was the main product found. The nature and relative concentration of the produced organic chlorinated species appeared to be dependent not only on the poly(vinyl chloride) constituent but also on the other ingredients. All the compositions contained phthalate ester plasticizers. In the dynamic system, these distilled largely unchanged, whereas under static conditions transformation into phthalic anhydride occurred.     

Thermal modification of poly(vinyl chloride) and formation of dehydrochlorinated poly(vinyl chloride)–poly(methyl methacrylate) polymer blend in the process of foaming: Identification and application

Impact resistant plastic foam of dehydrochlorinated poly(vinyl chloride) (DHPVC)—poly(methyl methacrylate) (PMMA) was prepared for cryogenic insulation in space vehicle by the method of compression molding and chemical blowing. Impact resistance was achieved by the formation of the polymer blend, dehydrochlorinated poly(vinyl chloride)-poly(methyl methacrylate), during the process of foaming the mold at the temperature of 200°C. The polymer blend was separated from the plastic foam and the compatibility was investigated by ultraviolet, infrared spectral studies and differential scanning calorimetry (DSC). The compatibility of dehydrochlorinated poly(vinyl chloride) and poly(methyl methacrylate) was highlighted on the basis of allylic activation introduced in the thermally modified poly(vinyl chloride). The thermodynamic views were also correlated. The versatility of the present method for impact-resistant foam was pointed out.     

Self-crosslinkable plastic-rubber blend system based on poly (vinyl chloride) and acrylonitrile-co-butadiene rubber

That the melt-mixed blend of poly (vinyl chloride) and acrylonitrile-co-butadiene rubber becomes crosslinked during high-temperature molding is evident from Monsanto rheometric, solvent swelling, and infrared spectroscopic studies. Dynamic mechanical analysis shows that such a self-crosslinkable plastic-rubber blend is miscible in different blend ratios. The degree of crosslinking depends on the blend ratios and the molding conditions. The cross-linking reaction involves the allylic chlorine sites in poly (vinyl chloride) and the ? C?N group in the nitrile rubber. © 1993 John Wiley & Sons, Inc.     

Mechanochemical synthesis and characterization of poly(vinyl chloride)-block-poly(ethylene-co-propylene) copolymers by ultrasonic irradiation

Mechanical degradation and mechanochemical reaction in heterogeneous and homogeneous systems of poly(vinyl chloride) and poly(ethylene-co-propylene) polymer have been studied by ultrasonic irradiation at 30 °C. The rates of decrease in the number-average molecular weights of the degraded poly(vinyl chloride) and poly(ethylene-co-propylene) polymer were much faster in order of the solid poly(vinyl chloride)—poly(ethylene-co-propylene) polymer solution, the swelled poly(vinyl chloride)—poly(ethylene-co-propylene) polymer solution, and the homogeneous solution systems. On the other hand, mechanochemical reaction occurred by free radicals produced from the chain scissions of both polymers by ultrasonic waves. The changes in the composition of the total block copolymer, the unreacted poly(vinyl chloride), and the unreacted poly(ethylene-co-propylene) polymer in individual reaction systems were obtained. In addition, the microscopic observation of the surfaces of the polymers on before and after mechanochemical reaction is carried out. Received: 10 May 2000/Revised version: 1 August 2000/Accepted: 3 August 2000     

Mechanochemical block copolymerization of poly(vinyl chloride) with methyl methacrylate by ultrasonic irradiation

Summary Mechanical degradation and mechanochemical block copolymerization in systems of poly(vinyl chloride)-methyl methacrylate-solvents have been studied by ultrasonic irradiation at 60°C. The effect of the concentrations of poly(vinyl chloride) on mechanical degradation was investigated. In addition, the effects of poly(vinyl chloride) and methyl methacrylate concentrations on mechanochemical block copolymerization were investigated. The rate equation for mechanochemical block copolymerization has been deduced, and the experimental results were in fairly good agreement with the equation. The changes in the composition of the block copolymer and homopolymers in the reaction products were followed by turbidimetric titration.     

Reactive extrusion of poly(vinyl chloride) compounds with polyethylene and with ethylene-vinyl acetate copolymers

The mechanical properties of poly(vinyl chloride)/polyethylene blends can be improved by a reactive extrusion process in the presence of an organic peroxide and a coupling agent. With a judicious loading of dibenzoyl peroxide and triallyl isocyanurate coupling agent, such blends generally exhibit significantly greater ultimate tensile strengths and dynamic moduli. The nature of the sample posttreatment after compression molding is shown to have a major impact upon the relative magnitude of these differences. Evidence is also presented to suggest that such improvements result from a superior physical interlocking between blend components, rather than through the formation of co-crosslinked graft segments (which would, presumably, impart a compatibilization effect). Similar extrusion trials with a poly(vinyl chloride)/poly(ethylene-stat-vinyl acetate) mixture revealed a general worsening of material properties with increasing dibenzoyl peroxide levels. These observations can be rationalized by examination of the degradation reactions that likely occur in these reacting systems.     

Mechanochemical synthesis and characterization of poly(vinyl chloride)-block-poly(vinyl alcohol) copolymers by ultrasonic irradiation

Mechanical degradation and mechanochemical reaction in heterogeneous systems of the solid poly(vinyl chloride)-poly(vinyl alcohol) aqueous solutions have been studied by ultrasonic irradiation at 30 °C. The rate of decrease in the viscosity-average degree of polymerization of the degraded poly(vinyl chloride) was much faster than that of the degraded poly(vinyl alcohol). Mechanochemical reaction occurred by free radicals produced from the chain scissions of both polymers by ultrasonic waves. The copolymer was obtained and the molar ratio of the vinyl chloride and the vinyl alcohol units in its copolymer can be determined. In addition, the changes in the composition of the total block copolymer, the unreacted poly(vinyl chloride), and the unreacted poly(vinyl alcohol) were obtained. Received: 1 October 1998/Revised version: 9 January 1999/Accepted: 13 January 1999     

Thermal degradation of ternary blends of poly(ε‐caprolactone)/poly(vinyl acetate)/poly(vinyl chloride)

The thermal degradation of ternary blends of poly(ε‐caprolactone) (PCL), poly(vinyl acetate) (PVAC), and poly(vinyl chloride) (PVC) was studied using a thermogravimetry analyzer under dynamic heating in flowing nitrogen atmosphere. PCL degraded in a single stage, whereas the PVAC and PVC degraded in two stages during which acid is released in the first stage followed by backbone breakage in the second stage. The addition of PVC to either PCL or PVAC affected the thermal stability of the blend, whereas the addition of PVAC to PCL did not alter the thermal stability of the blend. In ternary blends, the addition of PVC affected the degradation of PVAC but did not influence the degradation of PCL in the range investigated. The increased addition of PCL to the binary blends of PVC/PVAC decreased the extent of thermal instability of PVAC because of the addition of PVC. The addition of even 10% PVAC to the PCL/PVC blend removed the thermal instability of PCL resulting from the addition of PVC and can be attributed to the ease of chlorine or hydrogen chloride capture of PVAC over PCL. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1378–1383, 2004     

Thermal degradation of poly(vinyl chloride) blends

Poly(vinyl chloride) was mixed with various poly(methacrylate)s and polycarbonates by combined precipitation from common solutions. The thermal stability of the samples was measured at 180°C under nitrogen, the HCl evolved was detected by conductometry. UV-Vis-spectra of degraded samples were measured to investigate the influence of the poly(methacrylate)s on the lengths of polyenes formed during the degradation of poly(vinyl chloride). The experiments show that the nature of the ester group is the dominating factor for the thermal stability of poly(vinyl chloride) in these blends. Poly(n-butylmethacrylate) exhibits the best stabilization for poly(vinyl chloride) in this series. Polycarbonates with a higher glass transition temperature than the temperature of degradation destabilize poly(vinyl chloride). Stabilization experiments with dibutyltin-bis(isooctylthioglycolate) show a costabilizing effect of the poly(methacrylate)s and polycarbonates.     

Mechanochemical synthesis and characterization of poly(vinyl chloride) -block- poly(acrylonitrile-co-butadiene) copolymers by ultrasonic irradiation

Summary Mechanical degradation and mechanochemical reaction in heterogeneous and homogeneous systems of poly(vinyl chloride) and poly(acrylonitrile-co-butadiene) polymer have been studied by ultrasonic irradiation at 30 °C. The rates of decrease in the number-average molecular weights of the degraded poly(vinyl chloride) and poly(acrylonitrile-co-butadiene) polymer in the swelled poly(vinyl chloride) — poly(acrylonitrile-co-butadiene) polymer solution were much faster than the homogeneous solution system and the final average chain lengths led to the smaller values than those in the latter system. On the other hand, mechanochemical reaction occurred by polymer radicals produced from the chain scissions of both polymers by ultrasonic irradiation. The changes in the composition of the total block copolymer, the unreacted poly(vinyl chloride), and the unreacted poly(acrylonitrile-co-butadiene) polymer in both reaction systems were obtained. Received: 4 September 2001/Accepted: 22 October 2001     

Vinyl molding compounds: Formulation and performance evaluation

Today's vinyl molding compounds are successfully meeting the combined challenges of physical properties, appearance, processability, and cost requirements in a variety of specialty injection molding applications such as appliance parts, business equipment, and electrical enclosures. One of the major reasons why vinyl materials are so versatile is that the poly(vinyl chloride) resins on which they are based can be easily modified with a wide variety of additives to tailor the particular performance features of the compounds to their intended applications. Determination of an appropriate combination of PVC resin and additives to produce an effective and cost-competitive compound, however, is not a simple process. Important considerations in formulating a vinyl molding compound and evaluating its performance are discussed here.     

Vinyl chloride formation from the thermal degradation of poly(vinyl chloride)

The volatile products from the thermal degradation of poly(vinyl chloride) (PVC) resins and compounds are shown to contain trace amounts of vinyl chloride. Data presented show the effect of temperature and resin type on the amount of vinyl chloride formed. At the maximum temperatures involved in PVC processing which may reach 210°C, vinyl chloride monomer (VCM) evolution amounts to less than 1 ppm (resin basis). A technique employing a thermogravimetric balance and charcoal adsorption of volatiles is described for studying thermal degradation of PVC. The volatiles are analyzed for vinyl chloride by gas chromatography. Peak identity was confirmed by mass spectrometry.     

DSC investigation on the thermal degradation of PVC in blends

The thermal degradation of poly(vinyl chloride) (PVC) has been studied by differential scanning calorimetry (DSC). Due to crosslinking, the glass transition temperature (Tg) of PVC raises during the degradation. The thermal degradation of PVC has also been studied for heterogeneous 1:1 (w/w) blends of PVC with polystyrene (PC), poly(styrene-co-acrylonitrile) (SAN), high-impact PS (poly(styrene-g-butadiene)) (HIPS) and poly(SAN-g-butadiene) (ABS). Tg of the PVC phase raises slower during degradation in the PVC/PS-blend, whereas in the other blends the crosslinking is accelerated, due to a negative influence of the double bonds and/or the nitrile groups on the thermal stability of PVC. Since most methods use the determination of eliminated HCl to study the degradation of PVC, the DSC method is very useful in investigations on PVC-containing polymer blends, if there might be a reaction of HCl with one of the blend components.     

Vinyl chloride formation from the thermal degradation of poly(vinyl chloride)

The volatile products from the thermal degradation of poly(vinyl chloride) (PVC) resins and compounds are shown to contain trace amounts of vinyl chloride. Data presented show the effect of temperature and resin type on the amount of vinyl chloride formed. At the maximum temperatures involved in PVC processing which may reach 210°C., vinyl chloride monomer (VCM) evolution amounts to less than 1 ppm (resin basis). A technique employing a thermogravimetric balance and charcoal adsorption of volatiles is described for studying thermal degradation of PVC. The volatiles are analyzed for vinyl chloride by gas chromatography. Peak identity was confirmed by mass spectrometry.     

Chlorinated poly(vinyl chloride) and plasticized chlorinated poly(vinyl chloride)—thermal decomposition studies

The thermal decomposition of chlorinated poly(vinyl chloride) and three plasticized chlorinated poly(vinyl chloride) systems has been investigated. The routes of decomposition of these systems have been elucidated by investigating char formation and by using a combination of thermogravimetric analysis (TGA) and prolysis/gas chromatography/mass spectroscopy methods (Py/GC/MS). The effects of the charforming/smoke‐suppressing iron(III) compound FeOOH in these polymer systems has also been investigated. The structure of both CPVC polymer and plasticzer determine the path of thermal decomposition and also the quantity and nature of the decomposition compunds formed. Changes in oxygen index and the formation of smoke during burning in these systems have been related to the char that is formed and also to the chemical nature of the decomposition products.     

The degradation of poly(vinyl chloride). II. Oxidative degradation in solution

The results of studies on the oxidative degradation of poly(vinyl chloride) in a solvent, triphenyl phosphate, are described and compared with results previously reported for the oxidative degradation of bulk polymer samples. A range of chain-breaking and peroxide-decomposing antioxidants of the type commonly used to stabilize polyolefins were not effective in reducing the rate of dehydrochlorination of poly(vinyl chloride).     

Processing effects on poly(ethylene terephthalate) from bottle scraps

Processing of virgin and recycled poly(ethylene terephthalate) (PET) in a twin screw extruder evidences the degradative effect caused by thermal decomposition of poly(vinyl chloride) (PVC) and other impurities, e.g. adhesives, at the processing temperature. Lower melt viscosity and molecular weight, along with higher carboxylic end group concentration, were observed for recycled PET, the extent depending on PET purity. In an attempt to investigate the correlation between the kinetics of degradation phenomena and the level of thermomechanical stress, a novel dynamic method of evaluating thermal stability in processing conditions was developed. Such a method allows the achievement of long equivalent residence times while using lab-scale extruders. As a result of these experiments, PVC-rich recycled PET was shown to reach very low melt viscosity after less than 10 min in processing conditions, while virgin PET retained high viscosity even after 30 min.     

Thermal dehydrochlorination of poly(vinyl chloride) in the presence of Jatropha seed oil

Thermal degradation of poly(vinyl chloride) was studied in a nitrogen atmosphere in the presence of Jatropha seed oil, epoxidized Jatropha seed oil, and soaps (barium and cadmium) of Jatropha seed oil at various temperatures. The rate of dehydrochlorination measurement at 1% degradation, R_DH, and the time required for dehydrochlorination to attain 1% conversion were used to assess the effect of the additives on the susceptibility of the polymer to dehydrochlorination. It was found from the kinetic studies and the results from viscosity measurements on degraded polymer samples that the Jatropha seed oil derivatives suppressed the initial loss of HCl from the polymer and the extent of polymer chain scission accompanying the dehydrochlorination process. Thermal degradation studies of poly(vinyl chloride) in the presence of mixtures of barium and cadmium soaps of Jatropha seed oil were also carried out. It was found that soap mixtures containing less than 80 wt% cadmium soap exerted a deleterious (antagonistic) effect on the degradation of poly(vinyl chloride) while in the presence of soaps containing more than 80 wt% cadmium soap, considerably lower values of R_DH and higher values of t_DH were observed. The soap mixture containing 90 wt% cadmium soap was found to exhibit a remarkedly improved stabilizing effect on the dehydrochlorination of poly(vinyl chloride). © 1995 John Wiley & Sons, Inc.     

Understanding the functions of acrylic processing aids in rigid PVC injection molding

Poly(vinyl chloride) (PVC) compound use is growing in specialty injection molding applications such as appliances, business equipment, and electrical enclosures. A key factor in determining the appearance and physical properties of the molded parts is the processability of the PVC compounds, which can be improved through the use of acrylic processing aids. Processing aids promote PVC fusion, modify the melt rheology, and/or provide lubrication. Some processing aid products are designed to serve one of these functions while others provide a combination of functions. Each of these functions and its major benefits in rigid PVC injection molding are described. Some guidelines for selecting appropriate processing aid products for applications are provided.     

Computational prediction of PVC degradation during injection molding in a rectangular channel

A computational model has been developed to calculate the degradation of PVC during injection molding. The results in this work are for the flow in a rectangular geometry. The effects of the injection speed, melt temperature, and material properties were examined. It was determined that the principal factor influencing PVC degradation is the injection speed. Very good agreement between computational and experimental results was obtained. Furthermore, it was calculated that the materials are more thermally sensitive during processing, with activation energy of 65 kcal/mol. Finally, it was calculated that the degradation becomes significant when the melt temperature is above 250°C, independent of the material studied. The model could be used to design the process to avoid degradation. Polym. Eng. Sci. 44:1295–1312, 2004. © 2004 Society of Plastics Engineers.