On the thermal degradation of poly(vinyl chloride). II. The effect of atmosphere

The early stages of the thermal degradation of PVC were studied. Two commercial, suspension-polymerized resins were thermally treated at different temperatures and oxygen contents. Dehydrochlorination kinetics were followed by conductometric measurements and the formation of polyene sequences by ultraviolet-visible spectroscopy. Crosslinking and chain scission were followed by gel chromatography (GPC) and viscometry. No chain scission was observed in nitrogen atmosphere and no crosslinking in oxygen. Degradation in air proceeded by both reactions. The rate of dehydrochlorination for one of the investigated polymers increased linearly with the logarithm of the oxygen pressure. In nitrogen, an increasing degradation temperature was found to give both an increasing crosslinking and less discoloration. In oxygen, chain scission reactions showed a slight temperature dependence. The temperature effect on the discolorations was similar to that in nitrogen. The main difference between the investigated resins was the amount of internal doubled bonds in the original polymers, the ratio being 2:1. The higher amount resulted in a higher rate of dehydrochlorination, a larger extent of chain scission in oxygen, and a lower extent of crosslinking in nitrogen. Both in oxygen and nitrogen, the obtained results are consistent with allylic mechanisms. In nitrogen, the polyene formation supposedly proceeds by a unimolecular reaction and crosslinking by an intermolecular nonradical dehydrochlorination. In oxygen, radical reactions are superposed and may lead to chain rupture via β-scissions of alkoxy radicals.     

On the thermal degradation of poly(vinyl chloride). III. Structural changes during degradation in nitrogen

The structural changes in poly(vinyl chloride) during thermal degradation in nitrogen at 190°C have been investigated. From gel permeation chromatography analyses no chain scission, but only crosslinking reactions were observed. An increase in the molecular weight was measured even at 0.3% conversion. For longer polyene sequences and at higher conversions, a crosslinking reaction competed with the “zipper” propagation. The secondary reactions, were more extensive at longer polyene sequence lengths. The growing polyene sequences can be terminated not only by branching reactions but also at existing pendent chloromethylene groups. A decrease in the amount of short chain branching with conversion also indicated other types of secondary reactions. Such a decrease was also observed during thermomechanical degradation in a Brabender Plastograph. The average polyene sequence length was calculated to be around 10, depending somewhat on the type of analysis used. Although allylic chlorine atoms seem to be the main points of initiation, other sites cannot be excluded as the number of initiation points increases appreciably during the early stages of the degradation. Such an increase is, of course, also consistent with a radical mechanism.     

Degradation of poly(vinyl chloride). III. Kinetics of thermal dehydrochlorination catalyzed by slow-diffusing HCl

The dehydrochlorination reaction of poly(vinyl chloride) was investigated by subjecting molded polymer discs to thermal treatments at comparatively low temperatures and for low degradation extents, such as to maintain practically unchanged the sample's composition and physical state. The HCl evolution-versus-time curves exhibited accelerating behaviors to be ascribed to the catalytic action of HCl accumulating in the samples owing to a hindered diffusion. By assuming a catalyzed dehydrochlorination reaction occurring independently from the uncatalyzed one and being first order with respect to HCl, a kinetic equation describing satisfactorily the experimental evidence was deduced.     

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.     

On the thermal degradation of poly(vinyl chloride). I. An apparatus for investigation of early stages of thermal degradation

A dehydrochlorination apparatus is described for studies of the early stages of the thermal degradation of poly(vinyl chloride) (PVC), combining good reproducibility, high accuracy, and a low detection limit. The evolved hydrogen chloride is absorbed in water and the electrical conductivity is continuously recorded. Measurements of the rate of dehydrochlorination repeated over an extended period of time showed a standard deviation of 2% of the mean value. The activation energies for the dehydrochlorination in nitrogen for two commercial suspension-polymerized samples were found to be 27.9 ± 1.5 and 26.2 ± 0.6 kcal/mole.     

Photosensitized dehydrochlorination of poly(vinyl chloride). I. Effect of commercial additives

A commercial formulation of thermal antioxidant has been shown to photosensitize the dehydrochlorination of poly(vinyl chloride). The species responsible was shown to be a p-alkyl-substituted phenol, and this was confirmed using p-cresol as a model compound.     

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.     

Degradation of poly(vinyl chloride). I. Kinetics of thermal and radiation-induced dehydrochlorination reactions at low temperatures

The dehydrochlorination reaction arising thermally and from exposure to γ-radiation has been followed, under vacuum, in the temperature range from 80° to 130°C by measuring the pressure of the evolved volatiles. The catalytic action of HCl, which was recently established, has been observed also at these low temperatures. In agreement with previous data, a free-radical mechanism has been accepted to be operating in the radiation-induced reaction, which has been found to be linearly dependent on dose rate and essentially independent of temperature. Assuming the thermal dehydrochlorination to proceed according to the same mechanism, its activation energy, lying within the range of values reported in the literature, represents the activation energy for the thermal process of radical formation by dissociation of normal and anomalous structures in PVC macromolecular chains. Since this value appears to be substantially constant in the temperature range from 90° to 240°C, it can be established whether the dissociation reactions of all the PVC structures are regulated by the same activation energy or, more simply, only one of these structures is concerned.     

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).     

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.     

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.     

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.     

On the influence of HCl on the thermal degradation of poly(vinyl chloride)

The thermal degradation of PVC was studied at 190°C in pure nitrogen and nitrogen containing 10, 20, and 40% HCl (by volume). The rate of dehydrochlorination was determined by gravimetry. Degradations in nitrogen were followed with conductometry in addition. Changes in molecular weight distribution and degree of long-chain branching (LCB) were determined by gel permeation chromatography–viscometry and polyene sequence distribution by UV spectroscopy. The rate of dehydrochlorination increases with the HCI content of the atmosphere. The rate of molecular enlargement also increases but only as a result of the increased dehydrochlorination rate. The increase in M _w and LCB are thus related to the extent of conversion only. Changes in the UV spectra indicate that the increase in rate of dehydrochlorination is mainly due to increased propagation rate in atmospheres containing less than 10% HCI. At higher HCI contents an increase in initiation rate is noted. It is suggested that this, at least in part, is due to the fact that HCI, by forming a cyclic transition state, catalyzes the random elimination of HCI. This process, in turn, is promoted by the presence of polyene sequences.     

Basic principles of thermal degradation and thermal stabilization of poly(vinyl chloride). Synergism of stabilizer action

Changes in the quantities of active stabilizing components during thermal aging of plasticized poly(vinyl chloride) containing a mixture of calcium and zinc stearates were analyzed. A mathematical model of the stabilization process by using the stabilizer mixture and a computer program for analyzing the process of PVC thermal degradation after the beginning of HCl evolution are given.     

Modification of poly(vinyl chloride). XIX. Electroplating of poly(vinyl chloride)

As a preliminary treatment in the PVC-electroplating procedure, treatment with dimethylformamide followed by sensitization leads to a finely roughened and a highly hydrophilic surface with reducing power. This is caused by the formation of an ionic complex compound between dimethylformamide and tin(II) chloride absorbed in the PVC surface. A much more finely and deeply etched surface which exhibits higher adhesion through the mechanical interlocking effect is obtained with the PVC blends containing the plasticizer with a low value of interaction parameter and with a solubility parameter approximate to that of PVC. Adhesion of the metal layer to the PVC surface thus obtained is improved about 1.5 times by thermal aging at 120°C for 20 min.     

Stabilization of poly(vinyl chloride). IV. Color changes on heating poly(vinyl chloride)–dye systems

The stabilization of poly(vinyl chloride) (PVC) involving complementary colors has been previously reported. Obliterating polyene color with various dyes containing complementary colors with the polyene color is studied on the basis of colorimetry. The changes in the color of heated PVC containing Thren Blue IRN, Ceres Blue GN, Oplas Violet 730, Macro-Lex Violet 3R, Macro-Lex Green 5B, or Macro-Lex Red 5B were investigated using a differential colorimeter. When the PVCs containing various dyes were heated, the discoloration from the color of each dye to the color mixture of each dye and polyene color was observed with increased heating times for all systems. In particular, an achromatic color has been observed, during the heat treatments, in PVC containing blue dyes such as Thren Blue IRN or Ceres Blue GN, which set up complementary color relationship with the polyene color. Thus the color of polyenes, which appears with advancing dehydrochlorination of PVC, is masked by the blue dyes. It is also apparent that the obliteration of polyene color does not depend on the chemical influences of the dyes added, but by color mixing of polyenes and the dyes. Cool-color dyes markedly slow down the appearance of polyene colors.     

Photothermal imaging of dehydrochlorination in poly(vinyl chloride) films

Impulse (time domain) laser photopyroelectric effect spectrometry uses the time dependence of heat diffusion in an irradiated sample to infer optical and thermal property depth distributions in the sample. This method was used in conjunction with a recently reported method of inverse problem theory to recover the depth dependence of optical absorption in photodegraded thin films of poly(vinyl chloride) (PVC) on a depth scale of a few tens of microns. The thin films were photodegraded under broadband ultraviolet light prior to photothermal analysis to induce subsurface profiles of visible absorption arising from the depth dependence of light initiated dehydrochlorination reactions in the films. Optical depth profile reconstructions could be made in samples that had undergone mild degradation only and where the absence of significant thermal effusivity changes accompanying degradation could be confirmed. Reconstructed optical transmission profiles were compared with optical transmission micrographs and were shown to resolve features that arise from the depth dependence of photo-induced dehydrochlorination reactions in the films. The extent of these latter reactions is controlled by the depth dependence of the oxygen concentration in the films.     

Modification of poly(vinyl chloride). XXXIV. Crosslinked poly(vinyl chloride) via paste-processing

A novel PVC-crosslinking technique using 6-dibutylamino-1,3,5-triazine-2,4-dithiol (DB) was applied for a paste processing to produce a crosslinked PVC product. The paste formulation recommended in the present study consisted of 100 parts of PVC (Zeon 121), 60 parts of dioctyl phthalate, 0.2 parts of MgO, and 6 parts of a 50% solution of DB-Na in butylcarbitol, which gave a highly crosslinked and transparent sheet with an excellent stability for thermal discolouring. The increasing viscosity behaviour of the paste during storage is explained by the effect of interparticle attracting forces of DB-Na which coordinates to the ether oxygen atoms in the glycol derivatives adsorbed on the surface of PVC particles. The increased viscosity can be reduced by addition of 3 parts of N-butyl-benzene-sulfonamide. The tension-distortion properties at elevated temperatures were remarkably improved at the crosslinked product compared with the uncrosslinked. The mechanical properties of the two crosslinked products produced via paste processing and roll-blending are compared in regard to the differences of the uniformity of crosslinking units.     

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.