The effect of aromatic plasticisers on the photo‐dehydrochlorination of poly(vinyl chloride)

Biggin, I. S.; Gerrard, D.L.; Williams, Grant

doi:10.1002/vnl.730040407

Cited by 30 publications

(4 citation statements)

References 11 publications

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“…A slight increase of MW from 9.52 × 10 4 to 9.98 × 10 4 is detected for UPVC as the aging time reaches 4 h, namely, about a 4.8% increment of MW. It can be accounted for the fact that UPVC degradation is initiated by the scission of CCl bond, and then the crosslinking reaction between two macromolecular free radicals, derived from the dehydrochlorination reaction, is likely to occur,16 which directly lead to the increase of MW. However, MW sharply reduces by about 22% when the aging time increases to 8 h. In the case of PPVC, its MW steadily decreases by about 4% at the aging time of 4 h, and then reduces again by about 14% at the aging time of 8 h. Combining the trend MW changing with the corresponding morphologies, it evidently reveals that an accelerating aging process is prone to occur once microvoids or microcracks are formed in the surface layer, namely the formation of a relatively rough topology.…”

Section: Resultsmentioning

confidence: 99%

Formation mechanism of microvoids and microcracks of poly(vinyl chloride) under an artificial aging environment

Xiang

Wang

Chen

et al. 2011

J of Applied Polymer Sci

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Degradation behaviors of both the unplasticized and plasticized poly(vinyl chloride) (UPVC and PPVC) under an artificial accelerating aging condition were extensively studied. The dependence of mechanical properties, average molecular weight (MW), and surface morphology of the earlier PVC on aging time was investigated by tensile tests, gel penetrate chromatogram (GPC), and scanning electron microscope (SEM), respectively. Fourier transform infrared and ultraviolet (UV)–visible spectroscopy were used to evaluate the probable formation of both the oxygen‐containing groups and the conjugated sequences during aging. The results reveal that UPVC is much easier to be degraded than PPVC under the same testing conditions. The irradiated surface is detected to change from an even topology into a rough topology initially, and then follows the appearance of many voids even cracks in the SEM morphology. During the aging process, oxygen‐containing groups and conjugation of PVC molecular chains around the cracks are observed, and noticeably increase with aging time. However, visible difference of the corresponding MWs of PVC before and after aging is not detected. Moreover, a novel degradation mechanism nearly related to the formation of microvoids and microcracks based on the cohesion energy of groups along PVC molecular chains is developed and semiquantitatively discussed. It is detected that the formation of microvoids and microcracks is attributed to both the thermodynamic changes of PVC backbone during the aging and the aggregation of oxygen‐containing groups with relatively large volumes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

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Section: Resultsmentioning

confidence: 99%

Formation mechanism of microvoids and microcracks of poly(vinyl chloride) under an artificial aging environment

Xiang

Wang

Chen

et al. 2011

J of Applied Polymer Sci

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“…Mathematical models of thermal decomposition reactions make possible the understanding of the whole process and the obtainment of quantitative conclusions from apparent kinetic parameters 3–9. This is the main reason why a mathematical model would be helpful to get a clear vision of the mechanism of plastisols thermal degradation, a subject which has raised some interest during the last years 2, 10–14…”

Section: Introductionmentioning

confidence: 99%

Kinetic analysis of the thermal degradation of PVC plastisols

Jiménez

López‐Martínez²,

Torre

et al. 1999

J. Appl. Polym. Sci.

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ABSTRACT:The thermal degradation of plasticized polyvinyl chloride (plastisol) is reported here. Plastisols used in the present work were prepared with the plasticizer diethylhexyl phthalate in different proportions. Thermogravimetric analysis has been applied to study the behavior of plastisols at high temperatures and to evaluate their degradation kinetics. Several tests were carried out at different heating rates and the variation of the degree of reaction with time and temperature was calculated. The influence of the heating rate in dynamic measurements (5-40°C/min) on kinetic parameters, such as activation energies and reaction orders, has also been studied. These parameters were calculated from dynamic thermogravimetric analysis tests using Friedman analysis and a kinetic model for the degradation of poly(vinyl chloride) and plastisols has been then developed. The obtained model was able to simulate the thermal degradation process of plastisols in dynamic conditions and was used to evaluate the effects of additives in the degradation. The results of this study can be used to optimize the concentration of plasticizers and stabilizers in poly(vinyl chloride) formulations.

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“…The samples were then placed in Petri dishes and heated at 80°C for 72 hours. Samples were taken at 0, 24, 48, and 72 hours and the level of dehydrochlorination determined by laser Raman spectroscopy as described previously (4). After the samples had been heated for 72 hours, they were all extracted with water and the aqueous extracts treated with a solution of silver nitrate acidified with dilute nitric acid.…”

Section: Methodsmentioning

confidence: 99%

The effect of amines on the dehydrochlorination of poly(vinyl chloride)

Bowley

Gerrard

Biggin

1988

J. Vinyl Addit. Technol.

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A study has been made of the effect of amines, particularly those used as catalysts in the preparation of polyurethane foams, on the dehydrochlorination of poly(viny1 chloride) (PVC). It has been shown that when PVC is heated at a temperature of 80°C in the presence of amines the levels of dehydrochlorination produced are considerably greater than those found if no amine is present. This has been attributed to a chemical dehydrochlorination reaction and could well have implications with respect to the physical and mechanical properties of the polymer for certain of its commercial applications.

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The effect of aromatic plasticisers on the photo‐dehydrochlorination of poly(vinyl chloride)

Cited by 30 publications

References 11 publications

Formation mechanism of microvoids and microcracks of poly(vinyl chloride) under an artificial aging environment

Formation mechanism of microvoids and microcracks of poly(vinyl chloride) under an artificial aging environment

Kinetic analysis of the thermal degradation of PVC plastisols

The effect of amines on the dehydrochlorination of poly(vinyl chloride)

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