Effect of thermal stabilizers on the photo-oxidative degradation of solid poly(vinyl chloride)

It has been found that metal (Ba, Ca, Cd and Pb) stearates and pure stearic acid have stabilizing effects on the photodehydrochlorination of poly(vinyl chloride) (PVC) and the formation of polyene structures. On the other hand the same compounds accelerate photo-oxidation of PVC. From oxygen uptake measurements at different temperatures we calculated the energy of activation of photo-oxidation. It was found that metal stearates decrease the energy of activation of photo-oxidation processes of PVC, whereas stearic acid increases it. A synergistic effect of an equimolecular mixture of Ba and Cd stearates has also been observed.     

Effect of the combination of a benzotriazole‐type ultraviolet absorber with thermal stabilizers on the photodegradation of poly(vinyl chloride)

The effect of the combination of a benzotriazole type of UV absorber (UV326) with different types of thermal stabilizers, including an organic calcium complex and an organotin mercaptide, on the photodegradation of poly(vinyl chloride) (PVC) was investigated by color difference measurements, UV‐vis spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and viscosity‐average molecular weight (M_η) determinations. Films of PVC containing 0.5 phr of UV326, with or without 2 phr of thermal stabilizer, were prepared by solution casting and subjected to accelerated UV weathering under xenon light with an irradiance of 0.51 W/(m² nm) at 65°C. The results revealed that both UV326 and the mixture of UV326 with the organic calcium complex displayed good performance in inhibiting the photodehydrochlorination and photooxidation of PVC. In contrast, the combination of UV326 and the methyltin mercaptide remarkably accelerated the discoloration of PVC when the irradiation time increased from 300 to 400 h because of the UV sensitivity of the organotin. However, carbonyl index data indicated that a hydrogen abstraction reaction did not take place between UV326 and the methyltin mercaptide, so that the photooxidation of the PVC film was prevented effectively during the whole period of exposure, a result which may be attributed to the strong steric hindrance effect of the tert‐butyl group at the 3‐position of the phenyl ring in UV326. The changes of M_η were in good accordance with the results obtained from other characterizations. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

Effect of the combination of a benzophenone‐type ultraviolet absorber with thermal stabilizers on the photodegradation of poly(vinyl chloride)

The effect of the combination of a UV absorber (Chimassorb 81) with different types of thermal stabilizers, including an organic calcium complex and an organotin mercaptide, on the photodegradation of poly(vinyl chloride) (PVC) was investigated by color difference measurements, UV–Vis spectroscopy, Fourier‐transform infrared spectroscopy, thermogravimetric (TG) analysis, and viscosity‐average molecular weight determination. Films of PVC containing 0.5 phr of Chimassorb 81, with and without 2 phr of a thermal stabilizer, were prepared by solution casting. Then the accelerated UV weathering of the films was carried out under xenon light with an irradiance of 0.51 W/(m² · nm) at 65°C. The results showed that both Chimassorb 81 and the mixture of Chimassorb 81 with the organic calcium complex showed good behavior in inhibiting the photodehydrochlorination and photooxidation of PVC. In contrast, the combination of Chimassorb 81 and methyltin mercaptide significantly accelerated initial color development during the final 200 h of exposure because of the UV sensitivity of the organotin. Moreover, when Chimassorb 81 and the methyltin mercaptide were used together to stabilize PVC films, the expected antioxidant effect of the mixture was not observed, in contrast to the behavior found with other stabilized systems, perhaps because the Chimassorb 81 had been depleted by the methyltin mercaptide during the UV irradiation. The TG analysis revealed that ultraviolet irradiation had caused severe destruction of the PVC chains. However, addition of Chimassorb 81 or the combination of Chimassorb 81 with the organic calcium complex effectively prevented the destruction, as was demonstrated by changes in the activation energies for thermal degradation. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

Influence of additional thermal stabilizers on the reprocessing of postconsumer poly(vinyl chloride) bottles

The addition of heat stabilizers is essential for preventing the degradation of poly(vinyl chloride) (PVC) during its processing. The heat stabilizers consumed in the first run have to be made up before the reprocessing of recycled PVC. In this study, solvent‐cast films, which were prepared from granulated postconsumer PVC bottles mixed with plasticizers and thermal stabilizers, were used. The films were subjected to various heat treatments. No considerable structural change upon heat treatments at 140–160°C was found in IR and differential scanning calorimetry analyses. Polyene formation observed through ultraviolet analysis was not severe, indicating that the added stabilizers worked well in preventing degradation. The weight loss during the heat treatments was attributed partly to the decomposition of PVC and the evaporation of volatile components and mainly to the removal of the solvent upon heating. Although this study was conducted with water bottles that were to be recycled, it may be equally well applied to other similarly formulated PVC‐based materials, such as packaging films. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3994–3999, 2003     

Studies on photodegradation of poly(vinyl chloride) (part 1)

Films prepared from emulsion polymerized poly(vinyl chloride) were subjected at 0°C to accelerated photodegradation in air using a weatherometer. Photooxidation and scission of the main chain took place but dehydrochlorination or formation of polyenes was not observed. The absorption of the carbonyl group indicating oxidation was found at 1725cm^?1 in the infrared absorption spectrum. Only when tetrahydrofuran, which had been used for the preparation of films, was left in the films, an absorption was also found at 1770cm^?1. Oxidation occurred at the position of the methylene carbon and the cut end of the main chain. As a result of the X-ray photoelectronic spectrum (ESCA) analysis, it was found that the carbonyl concentration was higher in the surface layer of the sample than in the interior thereof.     

Photodegradation of plasticized poly(vinyl chloride) stabilized by different types of thermal stabilizers

Photodegradation of plasticized poly(vinyl chloride) (PVC) stabilized by different thermal stabilizers including organic calcium complex and mercaptide organotin was investigated. Plasticized PVC sheets prepared by an open twin‐roller mill and plate vulcanizing machine were exposed to xenon‐arc light with the irradiance of 0.51 W/(m²·nm) at 65°C. A much better color stability displayed by mercaptide organotin than organic calcium complex has been confirmed by digital photos and color difference. This can be explained that the more effective mercaptide organotin minimizes the amount of thermal damage from processing thus favours subsequent UV weathering. Carbonyl index and decomposition activation energy (E_a1) obtained from attenuated total refection‐Fourier transform infrared spectra (ATR‐FTIR) and thermogravimetric (TG) analysis, respectively, further indicate that plasticized PVC sheets containing mercaptide organotin have more excellent UV resistance. Mechanical tests reveal that photodegradation of PVC is accompanied by the predominant process of chain scission on the surface of samples. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers.     

Influences of molecular weight on photodegradation of poly(vinyl chloride)

2-Dicyanomethylene-1,3-indandione forms colourless adducts with higher molecular derivatives of N,N-Diethanolaniline which thermally decompose to dark blue dyes. The rate of the dye formation is determined UV-photometrically and is compared with rates for monomeric model compounds. It is shown that reaction rates can be correlated with the solvent polarity parameter E_T′ (r = 0,928). Due to kinetic data a carbanionic mechanism is suggested.     

Lanthanum histidine with pentaerythritol and zinc stearate as thermal stabilizers for poly(vinyl chloride)

Lanthanum histidine [La(His)₂·(NO₃)·2H₂O or La(His)₂] was synthesized via the reaction of histidine and lanthanum nitrate, and it was investigated as a stabilizer for poly(vinyl chloride) (PVC). The results show that La(His)₂ exhibited a stabilizing effect on PVC as a long‐term stabilizer because it prolonged the stability time of PVC to 76 min, which was about 24 times longer than the stability time of the pure PVC. The stabilizing effect of La(His)₂ as a costabilizer with pentaerythritol (Pe) and zinc stearate (ZnSt₂) was also studied. The results show that the use of La(His)₂ with Pe or Pe/ZnSt₂ improved the stability time of PVC. La(His)₂/Pe/ZnSt₂ provided PVC with a good initial color and long‐term stability, and when it was prepared at mass ratios of 0.8:2.4:0.8 and 1.6:1.6:0.8, the stability times of PVC were improved to 86 and 88 min, respectively. As a nontoxic stabilizer, La(His)₂/Pe/ZnSt₂ has the potential to replace the toxic stabilizers widely used in PVC manufacturing. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42878.     

Studies on photodegradation of poly(vinyl chloride) accelerated by α-hydroperoxy-tetrahydrofuran

A study of the role of THF, THFO₂ charge-transfer complex and α-hydroperoxy-tetrahydrofuran (HOOTHF) in the photodecomposition of poly(vinyl chloride) (PVC) film cast from THF is presented. Detailed e.s.r. studies show that during u.v. irradiation (254 nm), THF and/or HOOTHF, oxyTHF free radicals are formed, which participate in the dehydrochlorination of PVC. The final products of photooxidation of THF are α-hydroxy-tetrahydrofuran (HOTHF) and butyrolactone, which give strong i.r. absorption bands at 1735 and 1789 cm^?1, respectively. The presence of THF residues in PVC films cast from this solvent should always be considered when thermal or photochemical studies are made.     

Mechanism of action and effectiveness of ester thiols as thermal stabilizers for poly(vinyl chloride)

Organic thiols containing at least one carboxylate ester group (ester thiols) are excellent thermal stabilizers for both rigid and plasticized poly(vinyl chloride) (PVC). Their mechanism of action is shown to involve the deactivation of unstable structural defects by nucleophilic chloride displacement, the retardation and removal of coloration through thiol additions to polyene double bonds, and the prevention of autoacceleration during thermal dehydrochlorination through polyene shortening reactions and the scavenging of free radicals formed from polyenes and HCl. An unusually facile displacement of labile chloride that is favored by thiol acidity can account, at least in part, for the relatively high effectiveness of dipentaerythritol hexakis(mercaptoacetate) as a stabilizer. J. VINYL ADDIT. TECHNOL., 13:170–175, 2007. © 2007 Society of Plastics Engineers     

Photostabilizing effect of some thermal stabilizers for poly(vinyl chloride) in the presence of filler

The commercial stabilizers Ca‐Zn stearate and dibutyltin‐S,S′‐di(isooctyl thioglycolate) have been investigated as photostabilizers for rigid poly(vinyl chloride) (PVC) in the presence of two types of CaCO₃ as filler (natural and modified). The results reveal the costabilizing efficiency of CaCO₃, especially the natural type, when it is used in concentrations of 1–30% by weight. The stabilizing efficiency of CaCO₃ is indicated by the longer induction period and the lower rate of dehydrochlorination. The stabilizing effect of CaCO₃ may be attributed because of its opacity and action as a screening agent by reflecting ultraviolet light, thereby hindering the penetration of the light into the polymer matrix. In addition, CaCO₃ has the ability to absorb the HCl evolved during processing. The slight difference in the stabilizing effect of natural CaCO₃ compared to that of the modified one can be attributed to the modification process, that may decrease the number of active sites on the surface of CaCO₃, that in turn are responsible for the absorption of the evolved HCl. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

Studies on photodegradation of poly(vinyl chloride), part 4

Various PVC films containing a thermal stabilizer selected from three kinds of metal stearates and three kinds of organotin compounds were irradiated with ultraviolet rays and the unirradiated samples were subjected to the ESR analysis. Further, these PVC films were subjected to the photodegradation test using a weatherometer at a sample surface temperature of 0°C. By tracing the conversion of methyl radicals to alkoxy radicals or peroxy radicals with the lapse of time according to the ESR, effects of the foregoing stabilizers for stabilizing PVC against actinic rays could be evaluated. Results of the ESR were well in agreement with the results obtained at the photodegradation test using the weatherometer.     

Studies on photodegradation of poly(vinyl chloride), part 3

PVC films were degraded by outdoor exposure, irradiation by a weatherometer and heating by an electric oven. In PVC films subjected to outdoor exposure and to irradiation by the weatherometer at a low temperature, e. g. sample surface temperature of 0°C, photo-oxidation and scission of the main chain were caused, but dehydrochlorination or formation of solvent-insoluble substances were not observed. In contrast, PVC subjected to irradiation by the weatherometer at a high temperature, e. g. sample surface temperature of 80°C, showed a degradation tendency similar to that of PVC heated at 200°C in the electric oven, and decomposition of the thermal degradation type characterized by dehydrochlorination, formation of polyenes and formation of solvent-insoluble substances were observed.     

Effect of poly(epichlorohydrin) on the thermal and mechanical properties of poly(vinyl chloride)

Five kinds of polyepichlorohydrin (PECH) of different molecular weights were synthesized and characterized by gel permeation chromatography (GPC). Mechanical blending was used to mix PECH and poly(vinyl chloride) (PVC) together. The blends of different PVC/PECH ratios were characterized by thermogravimetric analysis (TGA), tensile tests, differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). TGA results show the thermal stability of PVC/PECH blends is desirable. Tensile tests indicate elongation at break is raised by increasing both the amount and the molecular weight of PECH. DSC is used to determine the glass transition temperature of PECH, and a quite low T_g is obtained. DMA results indicate that PECH has a perfect compatibility with PVC, when PECH concentration is below 20 wt %. There is only one peak in each tan δ curve, and the corresponding T_g decreases as PECH amount increases. However, above 20 wt %, phase separation takes place. The molecular weight of PECH also has a great influence on the glass transition temperature of the blends. This study shows that PECH is an excellent plasticizer for PVC, and one can tailor the glass transition temperature and tensile properties by changing the amount and the molecular weight of PECH. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The influence of stabilizers on the fusion of rigid poly(vinyl chloride)

It is known that the fusion rate of rigid PVC in an extruder partly depends upon the lubricants that are used. In the present study it is shown that different stabilizers have a great influence upon the rate of fusion of rigid PVC. Results from extrusion experiments and the Brabender Plastograph strongly indicate that a correlation exists between rapid melting in the extruder and the melt viscosity-temperature relation of the polymer blend. The reason why certain stabilizers cause a more rapid fusion of the PVC is attributed to the chemical structure of the stabilizers.     

Effect of compatibility between solvent and poly(vinyl chloride) on dechlorination of poly(vinyl chloride)

In this study, the use of diethylene glycol (DEG), triethylene glycol (TEG), n-C₁₀H₂₁OH, and ethylene glycol (EG) as solvents for NaOH in the dechlorination of poly(vinyl chloride) (PVC) was investigated. In the early reaction time, the degrees of dechlorination for DEG, TEG, and n-C₁₀H₂₁OH were notably higher than that for EG. Further, the high compatibility between PVC and the solvents was considered to result in the easy penetration of the solvent and OH⁻ into PVC particles, leading to the acceleration of dechlorination in the early reaction stage. An improvement of the dechlorination was actually observed for DEG and TEG compared with EG. The solvent with the best compatibility to PVC, n-C₁₀H₂₁OH, however, showed little improvement due to the formation of a protective polyene layer on the surface of the PVC particles.     

Effect of thermal decomposition on dielectric relaxation process of poly(vinyl chloride)

Dielectric absorption caused by the molecular relaxation of thermally decomposed poly(vinyl chloride) in air was studied on samples in the form of thin films. It was found that, with the progress of thermal decomposition, the magnitude of α dielectric absorption changes in three stages: (1) initial decrease in magnitude corresponding to the process of the formation of polyene sequences caused by dehydrochlorination; (2) ensuing increase corresponding to the deformation of polyene sequences attributed to oxidation; (3) final decrease corresponding to the formation of crosslinks.     

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.     

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.