Thermal degradation of cinnamoylated poly(vinyl alcohol)

Thermogravimetry and pyrolysis in combination with gas chromatography and infrared spectroscopy were the experimental techniques applied to the thermal degradation of cinnamoylated poly(vinyl alcohol) samples, constituted from vinyl alcohol-vinyl cinnamate photocrosslinkable copolymers. The thermal decomposition products include gases, liquids and solids. The gases are formed from saturated and unsaturated volatile hydrocarbons C₁? C₄, carbon monoxide and carbon dioxide. The liquid fraction includes aromatic hydrocarbons and some oxygenated organic compounds. The solid product identified in the greatest amount was cinnamic acid. The content in the thermal decomposition products varies considerably both with copolymer composition and temperature.     

Temperature and atmosphere influences on smoke composition during thermal degradation of poly(ethylene terephthalate)

The less‐volatile compounds forming a smoke emitted during the thermal degradation of poly(ethylene terephthalate) (PET) in different conditions were studied. Thermal degradation of PET was carried out within the temperature range of 200–700°C in both a nitrogen and an air atmosphere. The less‐volatile thermal degradation products were trapped on a glass‐fiber filter and analyzed by capillary gas chromatography with mass selective detector (GC‐MS) and high performance liquid chromatography (HPLC). The results are collected in tables and presented on plots as a function of the degradation temperature. The temperature and atmosphere effects on the emission and composition of the smoke during PET thermal degradation were considered. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3064–3068, 2001     

真菌降解光-氧氧化内蒙古胜利褐煤产物分析

为掌握黄孢原毛平革菌降解光-氧氧化内蒙古胜利褐煤固体残渣的成分、结构和热稳定性的变化规律,以及降解液的主要物质构成,为降解工艺的改进以及降解产物的分离和利用提供参考,对降解所得的固体和液体产物进行了检测分析.结果表明:光-氧氧化煤被黄孢原毛平革菌作用后,煤残渣的水分、灰分和挥发分的质量分数均增加,固定碳的质量分数降低,...     

Thermal degradation behaviour of aromatic poly(ester–imide) investigated by pyrolysis–GC/MS

The thermal degradation behaviours of a novel aromatic poly(ester–imide) (PEI) derived from pyromellitic dianhydride and 2,7-bis(4-aminobenzoyloxy)naphthalene have been investigated by thermogravimetric analysis (TGA) and by pyrolysis–gas chromatography/mass spectrometry (pyrolysis–GC/MS). The weight of PEI fell slightly in the temperature range of 350–450 °C in the TGA analysis, but the major weight loss occurred at 520 °C. Evolve gas analysis (EGA) of the PEI showed maximum release of pyrolyzates at 550 °C. The chemical structure of the volatile products resulted from the PEI pyrolysis at different temperatures was identified by pyrolysis–GC/MS. The cleavage of the ester linkage within the polymer chain initiated at 350 °C, and bond scission in the partially hydrolyzed pyromellitimide unit occurred in the temperature range of 450–500 °C. The bonds within the pyromellitimide unit started to cleave at 550 °C. The extensive decomposition of the pyromellitimide segment within the polymer backbone occurred at 600 °C. The possible thermal degradation pathways of this PEI are proposed on the basis of the pyrolysis products.     

Analysis of autoxidized fats by gas chromatography-mass spectrometry. IX. Homolytic vs. Heterolytic cleavage of primary and secondary oxidation products

To elucidate the genesis of volatile lipid oxidation products, thermal homolytic and acid heterolytic decomposition processes were compared. Secondary oxidation products were decomposed thermally (200 C), and the volatiles formed were identified by capillary gas chromatography-mass spectrometry (GC-MS). Oxidation products also were decomposed in the presence of HCl-methanol, and the resulting dimethyl acetals were identified by GC-MS. The volatile thermal decomposition products were those expected by homolytic β-scission on both sides of the hydroperoxide group. No dialdehydes were identified under our thermal decomposition conditions. In contrast, the acetals formed by acid decomposition were those expected by selective heterolytic scission between the hydroperoxide group and the allylic double bond. Dialdehydes identified from acid decomposition of cyclic peroxides and dihydroperoxides included malonaldehyde and 2,4-hexadienedial.     

Thermal and metal-catalyzed decomposition of methyl linolenate hydroperoxides

Much work has been reported on the volatile oxidative products of fats and their impact on flavor deterioration, cellular damage and the decrease in safety of fatcontaining foods. However, relatively little information is available on the mechanism of hydroperoxide decomposition. Pure methyl linolenate hydroperoxides were decomposed thermally at 150 C and catalytically with ferric chloride-ascorbic acid at room temperature. The volatile decomposition products were collected on porous polymer (Tenax) traps and concentrated by gel permeation chromatography. The total volatile products showed significant differences in composition by capillary gas chromatography-mass spectrometry (GC-MS). Thermal decomposition produced much more methyl octanoate (60.1%) and less 2,4-heptadienal (0.5%) than catalytic decomposition (13.2 and 60.8%, respectively). The volatiles from the ferric chloride-ascorbic acid system also contained unique products tentatively identified by GC-MS as isomers of chloromethyl butene. These results may have important implications in evaluating precursors of flavor deterioration in vegetable oils containing linolenate and in understanding better the biological significance of lipid peroxidation.     

Analysis of autoxidized fats by gas chromatography-mass spectrometry: X. Volatile thermal decomposition products of methyl linolenate dimers

High-molecular weight compounds previously were found to be important secondary products from autoxidation of polyunsaturated fatty esters. The contribution of dimers to oxidative deterioration was investigated by analyzing their volatile thermal decomposition products by capillary gas chromatography-mass spectrometry. Dimers were isolated by gel permeation chromatography from autoxidized linolenate and from the corresponding monohydroperoxides, cyclic peroxides and dihydroperoxides. Major volatile decomposition products identified from these oxidative dimers were similar to those formed from the corresponding monomeric hydroperoxides. However, dimers from linolenate hydroperoxides produced more propanal and methyl 9-oxononanoate than the corresponding monomers but less methyl octanoate and much less or no 2,4-heptadienal and 2,4,7-decatrienal. Significant differences in minor volatile products also were observed between dimeric and monomeric products of methyl linolenate oxidation compounds. Mechanisms are suggested for the formation of volatile decomposition products from different dimeric structures. These dimers are believed to be important sources of volatile compounds contributing to flavor and oxidative deterioration of fats.     

Thermal degradation of EVA and EBA—A comparison. I. Volatile decomposition products

This is the first in a series of papers in which structural changes during thermal degradation of ethylene-vinyl acetate (EVA) and ethylene-butyl acrylate (EBA) copolymers are compared. EVA, containing 11.4 mol% vinyl acetate (VA) and EBA, containing 5.4 mol% butyl acrylate (BA), were pyrolyzed at 280°C in nitrogen for 30 min. In another series of pyrolysis, EVA containing 1.2, 2.2, and 11.4 mol% VA were treated at 150–190°C for 3 h. The volatile decomposition products were collected in cooled traps respectively gas bags and then analysed with GC-MS and ion-chromatography. EVA is rather labile. The main volatile decomposition product is acetic acid. A linear decomposition rate was found already at the lowest investigated pyrolysis temperature, 150°C. After 30 min at 280°C every 15th of the acetate side groups had been eliminated. EBA is much more stable to pyrolysis. Thirty minutes at 280°C resulted in a decomposition of one out of 1500 BA groups. Butene is the main volatile decomposition product. Ester pyrolysis is supposed to account for the degradation of both types of polymers. The big difference in reactivity is presumably due to conformational differences. The ester pyrolysis mechanism will result in random unsaturations in EVA and carboxylic groups in EBA. To a minor extent acetaldehyde is formed when EVA is degraded. According to the mechanisms suggested, carbonyl groups remain in the main chain. Contrary to what is reported for poly(butyl acrylate), no alcohol was formed when pyrolysing EBA. This indicates that adjacent acrylate groups are needed for alcohol formation. For both types of polymer, scissions of the main chain results in hydrocarbon fragments mainly. In addition, acrylate containing fragments are observed when EBA is degraded. EVA, however, does not give any acetate-containing fragments.     

Investigation of polymerization of benzoxazines and thermal degradation characteristics of polybenzoxazines via direct pyrolysis mass spectrometry

Polymerization of benzoxazines and thermal degradation mechanisms of polybenzoxazines were investigated using the direct pyrolysis mass spectrometry (DP‐MS) technique. The benzoxazine structures were based on phenol and aniline and on bisphenol‐A and methylamine or aniline. Polymerizations of the benzoxazines were carried out by curing them at elevated temperatures without addition of initiator or catalyst. DP‐MS data showed the presence of chains generated by opposing polymerization reaction pathways indicating quite complex structures for the polybenzoxazines under investigation. Thermal decomposition of polybenzoxazines was started by the cleavage of methylamine or aniline linkages. It was determined that polybenzoxazines based on phenol were more stable than the corresponding bisphenol‐A‐based polybenzoxazines, while those based on methylamine were more stable than the corresponding polybenzoxazines incorporating aniline. Thus, it can be concluded that the presence of bulky groups decreased the extent of crosslinking which in return decreased the thermal stability. Copyright © 2012 Society of Chemical Industry     

MoO3 additives for PVC: A study of the molecular interactions

The detailed molecular interactions occurring during thermal degradation of PVC polymer formulations containing MoO₃ additives are investigated using laser microprobe techniques coupled with mass analysis of the volatile pyrolysis products. Comparison with Sb₂O₃–PVC compounds indicate that the additive effects exhibited by MoO₃ are fundamentally different from those observed for Sb₂O₃. Thermal decomposition of MoO₃–PVC is characterized by (1) catalyzed dehydrochlorination of PVC at a lower temperature and increased rate; (2) marked reduction in evolution of benzene, the major fuel species from PVC; and (3) decreased evolution of volatile hydrocarbon species from the polymer plasticizer component. Vapor-phase interactions involving volatile molybdenum species are found to be unimportant. The experimental data indicate that condensed-phase mechanisms and heterogeneous reactions involving MoO₃(s) control polymer decomposition processes. Molecular level details of these reactions are presented and their implications to polymer flame retardance and smoke suppression discussed.     

Pyrolysis–molecular weight chromatography–vapor-phase infrared spectrophotometry: An on-line system for analysis of polymers. IV. Influence of cis/trans ratio on the thermal degradation of 1,4-polybutadienes

The influence of the cis/trans ratio of 1,4-polybutadienes on the volatile products formed during temperature-programmed thermal degradation to 15% weight loss has been investigated using a mass chromatograph (a gas chromatograph which directly provides mass numbers of resolved components of a mixture) and an “on the fly” vapor-phase infrared spectrophotometer. In order of amounts, major volatile products were 4-vinyl-1-cyclohexene (dimer), 1,3-butadiene (monomer), cyclopentene, and 1,3-cyclohexadiene. With increasing trans content, the relative quantities of 4-vinyl-1-cyclohexene decreased strongly, cyclopentene increased strongly, 1,3-butadiene decreased moderately, and 1,3-cyclohexadiene increased moderately. For a high-trans polybutadiene, increasing the heating rate produced relatively more monomer and dimer but less cyclopentene. Mass chromatograms from 1,4-polybutadienes which had been heated to 15% weight loss in their prehistory were similar to those obtained from 1,2-polybutadiene, indicating that 1,4-polybutadiene undergoes isomerization prior to degradation. Mechanisms for the formation of the main volatile products of decomposition are discussed.     

Thermal degradation of perfluoropolyphenylenes

The thermal degradation of meta- and para-linked perfluoropolyphenylenes in vacuo and in oxygen has been studied. Rates of breakdown were determined thermogravimetrically and products of breakdown in vacuum analyzed by using a mass spectrometer. The thermal stability in vacuo was comparable with that of polyphenylene, and that in oxygen was rather inferior to that of polytetrafluoroethylene. The higher molecular weight polymers gave as the main volatile degradation products silicon tetrafluoride and carbon dioxide, together with a carbonized residue containing virtually no fluorine.     

Identification of some sulphur species in a high organic sulphur coal

In this paper, a preliminary study is described concerning the characterization of sulphur forms in a subbituminous coal rich with organic sulphur deposited in a lacustrine carbonate environment (Upper Cretaceous, Provence, France). Two American high organic sulphur coals were studied for comparison with the Provence coal. Optical microscopy, scanning electron microscopy and electron microprobe approaches offered a global view of the relations between sulphur, metals and coal petrography. Sulphur occurs in all the macerals and most minerals. Vitrinite contains the major part of organic sulphur and metals. This common occurrence of organic sulphur and metals in vitrinite suggests the presence of organosulphur-metallic species. X-Ray photoelectron spectrometry showed that mineral and organic sulphur is very much reduced (divalent). It would mainly include pyrite, sulphides and thiophenes. Programmed temperature oxidation and programmed temperature reduction (Attar's test) revealed fragile sulphur compounds such as aliphatic thiols and sulphides and thermal stable sulphur compounds such as aromatic and high molecular weight compounds. Curie-point pyrolysis in combination with mass spectrometry, gas chromatography, and gas chromatography-mass spectrometry indicated the absence of free organic sulphur compounds and of elemental sulphur. Pyrolysis yielded large amounts of low molecular weight products (H₂S, COS, etc.) and smaller amounts of thiopenes, benzothiophenes, dibenzothiophenes and their alkylated homologues. These sulphur compounds could result from the thermal degradation of organic sulphur moieties of the coal as well as from secondary reactions.     

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.     

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.     

Pyrolysis products of untreated and flame retardant-treated α-cellulose and levoglucosan

A typical gas chromatogram of the volatile pyrolysis products of untreated α-cellulose contains 39 peaks; however, mass spectral data indicate that at least 59 compounds, with molecular weights less than about 150, are present. A total of 37 compounds have been identified, 13 of which have not been previously reported. Most of the newly identified compounds contain a benzene ring, indicating that these compounds may be products of reactions between initial volatiles. A comparison of the products generated in the temperature range of 330°–440°C indicates that the formation of pyrolysis products is essential independent of temperature. Comparisons of the chromatograms obtained for untreated levoglucosan and cellulose indicate that most of the decomposition of cellulose probably forms levoglucosan which then decomposes to yield the observed pyrolysis products. In addition, the products of flame retardant-treated levoglucosan are essentially the same as those of cellulose with the same retardant treatment. This suggests that the retardants act on the levoglucosan formed in the decomposition of the cellulose rather than on the cellulose directly.     

Characterization of the volatile decomposition products of oxidized methyl arachidonate

The volatile thermal and oxidative decomposition products of methyl arachidonate were separated by capillary gas chromatography and identified by mass spectrometry. Various aldehydes, ketones, aldehyde esters, hydrocarbons and alcohols were identified. The major products included hexanal, methyl 5-oxopentanoate, pentane, methyl butanoate and 2,4-decadienal, which could be important to off-odor development in oxidized food systems containing arachidonate.     

Studies of temperature influence on volatile thermal degradation products of poly(ethylene terephthalate)

The temperature influence on the thermal degradation products evolved from poly(ethylene terephthalate) (PET) was investigated. The experiments were carried out within the temperature range of 200–700°C in air. The main volatile toxic products and weight losses during thermal degradation of PET were determined. The results are presented on plots as a function of the degradation temperature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2377–2381, 1998     

Thermal and catalytic degradation of waste high-density polyethylene (HDPE) using spent FCC catalyst

Thermal and catalytic degradation using spent fluid catalytic cracking (FCC) catalyst of waste high-density polyethylene (HDPE) at 430 °C into fuel oil were carried out with a stirred semi-batch operation. The product yield and the recovery amount, molecular weight distribution and paraffin, olefin, naphthene and aromatic (PONA) distribution of liquid product by catalytic degradation using spent FCC catalyst were compared with those by thermal degradation. The catalytic degradation had lower degradation temperature, faster liquid product rate and more olefin products as well as shorter molecular weight distributions of gasoline range in the liquid product than thermal degradation. These results confirmed that the catalytic degradation using spent FCC catalyst could be a better alternative method to solve a major environmental problem of waste plastics. This paper is dedicated to Dr. Youn Yong Lee on the occasion of his retirement from Korea Institute of Science and Technology.     

Degradation process of an industrial thermoplastic elastomer polyurethane-coated fabric in artificial weathering conditions

The aging of an industrial thermoplastic elastomer polyurethane (TPU)-coated fabric, based on a polyether diol and an aromatic diisocyanate, is studied in artificial weathering tests. It is noticed that the degradation of this TPU-coated fabric leads to a weight loss, to the formation of a reticulated layer in sample surface, and to a change of surface relief. The degradation layer and the surface relief have been observed by optical microscopy. The weight loss has been followed with aging time. The main degradation products causing weight loss are volatile. Therefore, they have been analyzed by gas chromatography–mass spectroscopy. The weight loss degradation takes place in the exposed part of the reticulated layer by volatile products emission, which implies the urethane and the polyether bonds. Water is involved in degradation process: without external water supply, weight loss is limited; with a permanent contact of vapor or liquid water, the weight loss rate is constant and depends on aging conditions. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2525–2534, 1999