Thermal degradation of polyvinyl-trimethyl-silane by pyrolysis gas chromatography

Pyrolysis Gas Chromatographic investigations have been carried out on a vinyl polymer containing silicon in the side-group. Comparison of the mechanism of degradation of isotactic polyvinyl-trimethyl-silane with those of other vinyl polymers indicates the importance of the side-group in the thermal decomposition of polymers of this type.We have identified the volatile pyrolysis products and studied the effect of pyrolysis conditions on their production. From the point of view of thermal degradation, polyvinyl-trimethyl-silane behaves like polypropylene but unlike polystyrene. During the degradation, random initiation is followed by intramolecular hydrogen abstraction, mainly leading to trimer. This reaction is faster than monomer formation by depropagation. We conclude that, in thermal degradation, the most important property of the side-group is not its size but its chemical nature.     

Thermal degradation of poly-2-hydroxyethyl methacrylate by pyrolysis gas chromatography

The thermal degradation of linear poly-2-hydroxyethyl methacrylate and of its acetyl and methoxy derivatives was investigated by the Curie-point pyrolysis gas chromatography. The kinetic parameters of pyrolysis were determined and the formation of crosslinks during degradation, due to the hydroxyl groups present in the polymer, was proved.     

Thermal degradation of copolymers of styrene and 4-nitrostyrene

The thermal degradation of styrene-4-nitrostyrene copolymers (SNS) has been studied using differential thermal analysis (DTA) and thermogravimetry (TGA) under isothermal and dynamic conditions in dynamic nitrogen. The apparent activation energy of the degradative process was determined following several methods of thermogravimetric analysis. The stability decreases as the nitrostyrene content in the copolymer increases. Fourier-transform infra-red spectroscopy has been used to analyze the degradation products at various degrees of conversion.     

Thermal decomposition of polybutadienes by pyrolysis gas chromatography

The thermal decomposition of cis-1,4-, trans-1,4-, and 1,2-polybutadienes (PBD) in the temperature range 450–900°C was investigated by pyrolysis gas chromatography (PGC). The cis- and trans-PBDs have closely similar product distribution and can be readily distinguished at lower temperatures of pyrolysis from the 1,2-PBD by the low amount of vinyl cyclohexene (VCH) produced by the 1,2 species. The amount of butadiene (BD) produced by 1,2-PBD varies with the tacticity of the polymer; the greater syndiotactic yields a lesser amount of BD. A method of determining the 1,4 and the 1,2 contents of PBD based on the ratios of peak heights of ethylene (C2) to VCH, propylene (C3) to VCH, and BD to VCH is presented. The advantages of this method are discussed. The nature and composition of the products of pyrolysis in the temperature range 540–900°C are presented and the mechanism of degradation at these elevated temperatures is explained.     

Identification of acrylate copolymers using pyrolysis and gas chromatography

A combination of pyrolysis and gas chromatography were used to investigate thermal degradation products formed from acrylic copolymers containing alkyl acrylate and methacrylate. The method provided an analytical tool for characterizing the chemical composition and structure of the degradation products. Thermal degradation of the synthesized copolymers was analyzed using isothermal (250 °C) pyrolysis–gas chromatography. The degradation process, and the nature and amount of pyrolysis products, provides relevant information about the thermal degradation of acrylic copolymers and the mechanism of pyrolysis. During pyrolysis, the formation of corresponding olefins, alcohols, acrylates and methacrylate was observed.     

Thermal degradation mechanism of methacrylonitrile-styrene copolymers on flash pyrolysis

The thermal degradation mechanisms of random copolymers of methacrylonitrile (MAN) and styrene (St) have been investigated by pyrolysis gas chromatography in the temperature range of 358 to 920?C using a Curie point pyrolyzer (JHP-2) and comparing results with the results from TG/DTA-FTIR apparatus (SII-6200, JASCO-320). The amount of St monomer from decomposition of the copolymer is higher than that from P(St) alone; whilst that of MAN monomer from copolymer is lower than that from P(MAN). This phenomenon reflects the boundary effect in the pyrolysis of copolymer. The thermal degradation mechanisms of copolymers are discussed in terms of the competition between the depolymerization and the back biting reaction on the basis of bond dissociation energies of C-C and C-H bonds in the copolymer chain.     

Thermal degradation of copolymers of styrene and acrylonitrile. III. Chain-scission reaction

The chain-scission reaction which occurs in copolymers of styrene and acrylonitrile has been studied at temperatures of 262, 252, and 240°C. Under these conditions volatilization is negligible, and chain scission can be studied in virtual isolation. At 262°C three kinds of chain scission are discernible, namely, at weak links which are associated with styrene units, “normal” scission in styrene segments of the chain and scission associated with the acrylonitrile units. The rate constants for normal scission and scission associated with acrylonitrile units are in the ratio of approximately 1 to 30. The molecular weight of the copolymer has no effect on the rates of scission. At 252°C the same general behavior is observed for the copolymers containing up to 24.9% acrylonitrile. The 33.4% acrylonitrile copolymer is anomalous, however. At 240°C the trends observed at 262°C appear to break down completely although individual experiments are quite reproducible. This behavior at the lower temperatures is believed to be associated with the fact that the melting points of the various copolymers are in this temperature range. Thus the viscosity of the medium, which should be expected to have a strong influence on the chain scission reaction, will be changing rapidly with temperature, copolymer composition, and molecular weight in this temperature range.     

Thermal degradation of copolymers of styrene and acrylonitrile. II. Reaction products

Hydrogen cyanide is a minor product of degradation of copolymers of styrene and acrylonitrile. The liquid products have been separated and identified by combined gas chromatography and mass spectrometry (GC-MS), as styrene, acrylonitrile, toluene, and benzene. The ratio of styrene to acrylonitrile monomers in the products is approximately twice that of the monomer units in the copolymers, and the ratios of styrene to toluene and benzene are the same as are obtained from pure polystyrene. These ratios were determined by using infrared spectral methods. The fraction of products volatile at the temperature of degradation but involatile at ambient temperature was also analyzed by using GC-MS. A series of four dimers and four trimers were fairly reliably identified. The residual material from copolymers containing up to 33.4% acrylonitrile is always soluble in toluene. The 50/50 copolymer and its residues are insoluble in toluene. Yellow coloration develops in the residues from high acrylonitrile copolymers at advanced stages of degradation. Infrared and ultraviolet spectra suggest that this is due to conjugated unsaturation in the polymer chain backbone which may be associated with the liberation of hydrogen cyanide from the acrylonitrile units.     

Compositional characterization of styrene copolymers by non-exclusion liquid chromatography

Recent advances in high-performance liquid chromatography enable us to separate synthetic copolymers according to composition. Several techniques for non-exclusion liquid chromatography (NELC) for polymers and copolymers are reviewed, focusing on the technique developed in our laboratory. Size exclusion chromatography in combination with NELC makes possible the accurate determination of both molecular weight distribution and chemical composition distribution of copolymers at the same time.     

The examination of some vinyl acetate/olefin copolymers by pyrolysis gas chromatography mass spectrometry.

A study of the thermal degradation of some vinyl acetate/olefin copolymers reveals that side chain scissions at the backbone and scissions within the side chains themselves yield fragments which are apparently characteristic of the parent olefin.     

Pyrolysis-gas chromatography of some crosslinked copolymers of styrene

The thermal degradation of copolymers of styrene, ethylstyrene and divinylbenzene with acrylonitrile and other acrylic monomers has been studied by pyrolysis-gas chromatography at 420, 570 and 790°. The thermal degradation products were identified and determined at 570°. The thermal degradation of some chloromethylated copolymers with the same composition was also followed. It has been ascertained that the chloromethylated copolymers show characteristic behaviour in thermal degradation. This is explained by modification of the degradation mechanism of the chloromethylated copolymers with respect to the development of crosslinking processes.     

Thermal degradation of graft copolymers of PVC prepared by mastication with styrene and methyl methacrylate,and of further PVC mixtures and vinyl chloride copolymers

Graft copolymers prepared by mastication of PVC in the presence of styrene or of a styrene/ methyl methacrylate mixture, have been studied by thermogravimetry, estimation of hydrogen chloride, thermal volatilization analysis, and flash pyrolysis/g.l.c. The degradation behaviour of PVC/ polystyrene mixtures, vinyl chloride/styrene random copolymers, a random copolymer of methyl methacrylate and styrene, and PVC/poly-α-methylstyrene mixtures has also been studied. The graft copolymers resemble the PVC/methacrylate graft copolymers previously studied in showing retardation of the dehydrochlorination reaction, but contrast with them in yielding chain fragments but no monomer during HCl production. Some stabilization of the second component at higher temperatures is also found. PVC/polystyrene mixtures behave in the same way as the corresponding graft copolymers, but vinyl chloride/styrene copolymers show reduced stability towards both dehydrochlorination and monomer production compared with the homopolymers. PVC/poly-α-methylstyrene mixtures yield some monomer concurrently with HCl loss, and display marked retardation of the latter reaction. Stabilization of the second polymer at higher temperatures is again observed. Many of these results add further strong support to the view that chlorine atoms are involved as chain carriers in the thermal dehydrochlorination of PVC.     

Study of the mechanism of polysulfone decomposition by pyrolysis/gas chromatography and pyrolysis/gas chromatography/mass spectrometry

Both co- and terpolysulfones have been flash-pyrolyzed at high temperature followed by separation and identification of the products by gas chromatography and/or gas chromatography/mass spectrometry. As expected, most of the products were the corresponding olefin and SO₂. Additionally, higher molecular weight products, including aromatics, and olefin isomerization products, were produced. Mechanisms for initiation and formation of the higher molecular weight products are presented which include the back reaction of intermediate free radicals to abstract hydrogen or to form C? C bonds followed by expulsion of SO₂. The free-radical intermediates formed by the SO₂ expulsion undergo transformations to give the aromatic products. No breakdown products were found with either O or S present, nor was SO₂H found.     

Thermal decomposition of copolymers of styrene and halogenated monomers

Copolymers of 1,2,2,2-tetrachloroethyl esters of unsaturated acids and halogenated N-phenyl maleimides with styrene were pyrolyzed; volatile products were analyzed with a mass spectrometer combined with a gas chromatograph. Hydrogen halide and carbon dioxide in the volatile products were determined during the thermal decomposition of copolymers in glass ampoules; the acyl chloride groups were determined in the residues. The thermal decomposition of copolymers of tetrachloroethyl esters with styrene sets in at ca. 230° by the release of chloral from the copolymer and splitting of some of the CCl bonds in the copolymer. The decomposition of copolymers of styrene with halogenated N-phenyl maleimides starts above 300° by depolymerization of the polystyrene chain sections and by splitting of some of the carbon-halogen bonds. At 310 and 500° for copolymers of tetrachloroethyl esters and at 500° for halogenated N-phenyl maleimides, there is radical dehydrohalogenation of the copolymers, with depolymerization of polystyrene blocks and splitting of carbon-carbon bonds in the main chain.     

Thermal studies of copolymers of styrene and maleic anhydride

Copolymers of styrene and maleic anhydride prepared by a charge transfer mechanism have been studied thermally by thermogravimetry and differential scanning calorimetry. The copolymers degrade in two stages; the first stage accounts for about 85% of the degradation. Incorporation of maleic anhydride to styrene decreases the thermal stability of the later. Differential scanning calorimetric studies show two exotherms between 300° to 500 °C. Glass-transition temperatures for the copolymers are lower than that of polystyrene.     

Pyrolysis—gas chromatography of methyl methacrylate—styrene and methyl methacrylate—α-methylstyrene copolymers

The pyrolysis—gas chromatographic behaviour of methyl methacrylate copolymers with styrene or α-methylstyrene was investigated with a Curie-point pyrolyzer. Monomer yield from each copolymer was very high as a result of the high probability of unzipping. Though only small quantities of dimers and or trimers are formed on the pyrolysis of two copolymers, they reflect the sequence distribution of copolymers. Under some assumption, the run number of each copolymer is calculated using the amounts of dimer and or trimer formed.     

Characterization of substituted polyacetylene microstructure by pyrolysis gas chromatography

A series of substituted acetylenes has been polymerized with WOC14/Ph4Sn metathesis catalyst and [Rh(cod)OMe]2 insertion catalyst, and the thermal degradation of the polyacetylenes prepared has been studied using pyrolysis capillary gas chromatography (Py-GC) with flame ionization and mass spectrometric detection to obtain information on the effect of the catalyst on the head-tail (H-T) isomerism of polyacetylenes (poly(phenylacetylene), poly[(4-methylphenyl)acetylene], poly(benzylacetylene), poly((2-fluorophenyl)acetylene], poly[(3-fluorophenyl)acetylene], and poly[(4-fluoro-phenyl)acetylenel). Cyclotrimers have been found to be the main pyrolysis products in all cases. Direct Py-MS connection was used to determine the temperature profiles of the released pyrolysis products. 1,3,5-Trisubstituted benzenes were found to be the predominant pyrolysis products of the polymers prepared with the insertion catalyst, which proves the presence of long head-to-tail sequences of monomeric units in these polyacetylenes. On the other hand, both 1,2,4- and 1,3,5-trisubstituted benzenes are present in significant amounts in the pyrolysis products of polymers prepared with the metathesis catalyst, which proves the presence of a significant content of the head-to-head (HH) and tail-to-tail (TT) linkages in these isomers of polyacetylenes. Contents of the regular (HT) and inverse (HH-TT) monomer linkages (RML and IML, respectively) in polymer chains were determined from the relative amounts of di-, tri-, and tetrasubstituted benzenes found in the Py-GC products.