Thermal degradation of mixtures of poly(methyl methacrylate) and silver acetate

The degradation behavior of silver acetate—PMMA blends at salt/polymer ratios of 1:1, 1:5, and 1:10 has been studied by using thermal volatilization analysis (TVA) as the principal technique. Degradation of the salt has also been examined; it gives a variety of products best explained by a series of reactions resulting from an initial cleavage of CH₃COO. radicals and silver atoms. Silver acetate, when present with PMMA during degradation, results in a severe destabilization of the polymer, which breaks down to monomer at a high rate at temperatures as low as 200°C. This effect is explained by diffusion of radicals from silver acetate decomposition into the polymer phase, in which they initiate chain scission and depolymerization.     

Thermal degradation of phenyl methacrylate-methyl methacrylate copolymers

The degradation behaviours of poly(phenyl methacrylate), four phenyl methacrylate-methyl methacrylate copolymers which span the composition range, and poly(methyl methacrylate) have been compared by using thermogravimetry in dynamic nitrogen and thermal volatilisation analysis (TVA) under vacuum, with programmed heating at 10°C/min. Volatile products have been separated by subambient TVA and identified and the cold ring fraction and partially degraded polymer have been examined by ir spectroscopy. Poly(phenyl methacrylate) resembles poly(methyl methacrylate) in degrading completely to monomer. Copolymers of phenyl methacrylate and methyl methacrylate are more stable than the homopolymers. On degradation, the major products are the two monomers. Minor products from all the copolymers include carbon dioxide, dimethylketene, isobutene and formaldehyde. Copolymers with low and moderate phenyl methacrylate contents show the formation of anhydride ring structures in the cold ring fraction and partially degraded copolymer, together with small amounts of methanol in the volatile products. Carbon dioxide is a more significant product at lower phenyl methacrylate contents.The mechanism of degradation is discussed.     

Analysis of degradation products by thermal volatilization analysis at subambient temperatures

In the subambient thermal volatilization analysis (TVA) technique, degradation products initially at ?196°C are allowed to warm up to ambient temperature in a controlled manner under vacuum conditions, and volatilization from the sample tube to a trap at ?196°C is monitored by means of a Pirani gauge. The technique is discussed in relation to earlier TVA work in which volatilization from a heated polymer sample was followed. Design and operation of a subambient TVA system are described, and examples of the application of the technique to the study of the degradation products of seven polymers are considered.     

Thermal degradation of poly(vinyl bromide), vinyl bromide-methyl methacrylate copolymers,and poly(vinyl bromide)-poly(methyl methacrylate) blends

Degradation behavior has been compared for PVB, five VB-MMA copolymers which span the composition range, PMMA, and PVC by using thermogravimetry in dynamic nitrogen and thermal volatilization analysis (TVA) under vacuum for programmed heating at 10°C/min. Volatile products have been separated by subambient TVA and identified. PVB is substantially less stable than PVC but shows inmost respects analogous degradation behavior. The introduction of VB into the PMMA chain leads to intramolecular lactonization with release of methyl bromide at temperatures a little above 100°C; after this reaction is complete, however, the polymer is more stable toward volatilization than PMMA. Copolymers with moderate and high VB contents also lose hydrogen bromide. Carbon dioxide is a significant product at intermediate compositions. The variation of product distribution with copolymer composition is discussed in relation to the several reactions involved and comparisons are made with VC-MMA copolymers. PVB-PMMA blends snow some features of degradation behavior in common with the PVC-PMMA system but also very important differences. The effect of PVB is only to stabilize the PMMA; the mechanism is discussed. The role of PVB as an additive and VB as a comonomer for fire-retardant PMMA compositions is briefly considered in relation to earlier studies.     

Mass spectral and pyrolysis/gas-chromatographic studies of the monomer and polymer of bis(p-toluenesulfonate) of 2,4-hexadiyne-1,6-diol

The thermal degradation of the monomer and polymer of bis(p-toluenesulfonate) of 2,4-hexadiyne-1,6-diol has been investigated. Decomposition during the latter stages of solid-state thermal polymerization at 80°C and of 100% polymer at 112°C was observed by mass spectrometry and the decomposition fragments identified. Mechanisms for this low-temperature degradation are suggested. Pyrolysis of the monomer and polymer between 400 and 1000°C was studied by gas chromatography and mass spectrometry. The principal pyrolysis products are triacetylene and p-toluenesulfonic acid. The fragmentation routes leading to and derived from these products are discussed.     

Investigation of the thermal degradation process of polystyrene brominated on the ring

The results of investigation of the degradation process of polystyrene brominated on the ring via an ionic route have been presented. Using thermogravimetric (TG) and differential thermal analysis (DTA) methods, the course of degradation of polymer samples with different bromine content has been described. Introducing of bromine on the aromatic ring influenced the initial decomposition temperature (IDT) and the temperature corresponding to the maximum of decomposition rate (T _m). The samples have been pyrolyzed at 300°C and some pyrolysis products were identified by means of gas chromatography/mass spectrometry. Finally, the possible mechanism of degradation was presented.     

Poly(Aryl ethers) by nucleophilic aromatic substitution. II. Thermal stability

The thermal stability and degradation process for a specific poly(aryl ether) system have been studied. In particular, the polymer which is available from Union Carbide Corporation as Bakelite polysulfone has been examined in detail. Polysulfone can be prepared from 2,2-bis(4-hydroxyphenyl)propane and 4,4′-dichlorodiphenyl sulfone by nucleophilic aromatic substitution. Because of a low-temperature transition at ? 100°C. and a glass transition at 195°C., polysulfone retains useful mechanical properties from ?100°C. to 175°C. A number of experimental methods were utilized to study the thermal decomposition process for this polymer system. Polysulfone gradually degraded in vacuum above 400°C. as demonstrated by mass spectrometry. Thermogravimetric analysis in argon, air, or high vacuum indicated that rapid decomposition began above 460°C. From gas chromatography, mass spectrometry and repeated laboratory pyrolyses, a number of products from polymer decompositions were identified. The most important degradation process in vacuum or inert atmosphere was loss of sulfur dioxide. Several model compounds representative of portions of poly(aryl ether) molecules were synthesized and the relative thermal stabilities determined. Possible mechanisms for pure thermal decomposition of polysulfone were derived from the product analyses, model studies, and consideration of bond dissociation energies.     

Application of pyrolysis-capillary gas chromatography with NPD detection in thermal degradation of polyphosphazenes study

Polyphosphazenes represent a unique class of polymers with a backbone composed of alternating phosphorous and nitrogen atoms. The thermal behaviour and decomposition of a variety of polyphosphazenes depends on the type of side groups present. Especially those that bear aryloxy side groups, possess a high temperature stability as well as excellent flame resistance. Pyrolysis-capillary gas chromatography has been used in a study of three polyphosphazene samples for thermal stability characterisation. Degradation products were detected with three single detectors for flame ionisation (FID), nitrogen-phosphorous sensitivity (NPD) and mass spectrometry (MSD) at different pyrolysis temperatures ranging from 300°C up to 800°C. The NPD responses for phosphorous or nitrogen fragments of polyphosphazenes have been used for the construction of degradation product schemes and the examination of the thermal stability of the polyphosphazene’s backbone. Partial identification of the degradation products present in the gaseous phase was achieved by MSD. The polyphosphazenes thermal degradation conversion rates were at a maximum at 450–500°C. At various pyrolysis temperatures, the calculated N/P peak area ratio is a function of the degree of polyphosphazene-N=P-chain degradation, and reflective of the nitrogen — phosphorous detector sensitivity. NPD proved to be suitable tool for characterization of polyphospazene thermal stability.     

Influence of the fire retardant,ammonium polyphosphate,on the thermal degradation of poly(methyl methacrylate)

The thermal degradation of ammonium polyphosphate (APP), a commercial fire retardant, and its blends with poly(methyl methacrylate) (PMMA) have been studied by thermal volatilization analysis (TVA) and the degradation products identified. APP degrades under vacuum in three stages. Initially it condenses to an ultraphosphate (<260°C) with release of ammonia and water. Fragmentation follows (260–370°C), giving high-boiling ammonium salts of phosphate fragments and further ammonia and water. The polyphosphoric acid (PPA) which remains then undergoes extensive Fragmentation (>370°C). In the presence of APP, the normal depolymerization of PMMA to monomer competes with degradation reactions which form high-boiling chain fragments, methanol, carbon monoxide, dimethyl-ether, carbon dioxide, hydrocarbons, and char. These additional reactions are initiated principally by the PPA. Intramolecular cyclization occurs, resulting in the formation of anhydride, and ester groups are eliminated, methanol and carbon monoxide being evolved. Further degradation of the modified polymer leads to the other volatile products and the char.     

Primary thermal degradation processes occurring in poly(phenylenesulfide) investigated by direct pyrolysis–mass spectrometry

The thermal degradation Processes which occur in poly(phenylenesulfide) (PPS) have been studied by direct pyrolysis-mass spectrometry (DPMS). The structure of the compounds evolved in the overall temperature range of PPS decomposition (400–700°C) suggests the occurrence of several thermal decomposition steps. At the onset of the thermal degradation (430–450°C) this polymer decomposes with the formation of cyclic oligomers, generated by a simple cylization mechanism either initiated at the—SH end groups or by the exchange between the inner sulfur atoms along the polymer chain. At higher temperature (> 500°C) another decomposition reaction takes over with the formation of aromatic linear thiols. The formation of thiodibenzofuran units by a subsequent dehydrogenation reaction occurs in the temperature range of 550–650°C; in fact, pyrolysis products with a quasi-ladder structure have also been detected. Ultimately, above 600°C, extrusion of sulfur from the pyrolysis residue occurs with the maximum evolution at the end of decomposition (about 700°C). It appears, therefore, that the residue obtained at high temperature tends to have a crosslinked graphite-like structure from which the bonded sulfur is extruded. © 1994 John Wiley & Sons, Inc.     

HCN evolution from thermal and oxidative degradation of poly(diphenyl methane pyromellitimide) at high temperatures

HCN evolution from thermal and oxidative degradation of poly(diphenyl methane pyromellitimide) has been investigated over a range of temperatures from 500 to 1000°C; rate constants and Arrhenius equations have been determined. Kinetics and mechanisms have been proposed and quantitatively evaluated. They account well for the experimental results. The rate determining steps are C? N scission for thermal degradation and H abstraction from the methylene bridge by O₂ for oxidative degradation, respectively. At high temperatures, oxidation and thermal decomposition of the evolved HCN take place on its passage through the hot zone of the furnace in the highest range of temperatures (800–1000°C). Additional HCN is produced (>800°C) from the char obtained during thermal and oxidative degradation.     

Degradation of polymer blends—Part XI. Blends of polystyrene with polyisoprene

The degradation behaviour of polystyrene and cis-1,4-polyisoprene when both are present in the same film as a 1:1 blend has been compared with that when the polymers are degraded separately. Degradations have been studied under programmed heating conditions using TG, TVA, DTA and DSC and also under isothermal conditions at 340 and 360°C. Volatile products of degradation have been studied and separated by sub-ambient TVA and also identified by spectroscopic methods. The volatile products from the blend are the same as those from the constituent polymers. Volatile production occurs less readily for each polymer than when it is degraded alone. Stabilisation of PS is especially marked and under isothermal conditions at the above temperatures, PS does not evolve volatiles until PI degradation is completed. Chain scission in PS, prior to volatilisation, is increased, however, in the presence of PI. It is concluded that the increased scission results from attack on PS by PI radicals of short chain length and that the stabilisation effect on the PS is due to an inhibiting action of dipentene evolved by the PI. Both these reactions follow diffusion of mobile species of rather low volatility from the PI phase into the PS phase.     

Thermal and pyrolysis studies of copolyesters

Random copolyesters of dimethyl terephthalate (DMT), ethylene glycol (EG), and butane-1,4-diol (BD) and the homopolyesters poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) have been subjected to degradation and pyrolysis studies. Differential thermal analysis (DTA) showed that the decomposition temperature is dependent on the percentage of EG and BD present in the copolyesters. Thermal volatilization analysis (TVA) also showed that the decomposition temperature is dependent on the percentage of EG and BD present in the copolyesters. The trend for the decomposition temperatures obtained from TVA studies for these copolyesters is similar to such other thermal properties as melting temperature T_m, ΔH_f, ΔH_c, etc. The subambient thermal volatilization analysis (SATVA) curves obtained for these polymers are also presented. The SATVA curve is the fingerprint of the total volatile products formed during the degradation in high vacuum. The isothermal pyrolysis of these materials was carried out in high vacuum at 450°C. The products formed were separated in a gas chromatograph and were subsequently identified in a mass spectrometer. The major pyrolysis products from PBT were butadiene and tetrahydrofuran, whereas those from PET were ethylene and acetaldehyde. The ratio of acetaldehyde to ethylene increases with the EG content in the copolyester, suggesting a different decomposition mechanism compared to the decomposition mechanism of PBT and PET.     

Thermal degradation of styrene-butadiene diblock copolymer: Part 1—Characteristics of polystyrene and polybutadiene degradation

Polystyrene, polybutadiene and diblock styrene-butadiene copolymer have been prepared, using sec-butyllithium as initiator, and characterised. Techniques required in an investigation of the degradation of the copolymer have first been applied to the two homopolymers. Degradations have been carried out under temperature programmed conditions at a heating rate of 10°/min, using TG and DSC in dynamic nitrogen and TVA (vacuum), and also isothermal TG and TVA at 380°C. The volatile product fractions have been separated by subambient TVA to facilitate identification of the various products. Volatile and cold ring fractions from isothermal degradation have been measured quantitatively by an improved gravimetric technique using the TVA system. Infra-red and nuclear magnetic resonance spectroscopy and mass spectrometry have been used to characterise the main product fractions. A new adsorption TVA method has allowed methane and hydrogen to be identified as constituents of the small amount of non-condensable gases formed in polybutadiene degradation.     

Thermal degradation of copolymers of 2-hydroxyethyl methacrylate and alkyl methacrylates

Thermal degradation of homopolymers of ethyl methacrylate (I), n-butyl methacrylate (II), 2-hydroxyethyl methacrylate (III), and copolymers of III with I and II were carried out by thermal volatilization analysis (TVA) up to 440°C with subsequent subambient thermal volatilization analysis (SATVA). An on-line mass spectrometry coupled with TVA and SATVA was employed to identify the products of thermal degradations. Isothermal pyrolyses of the polymers were carried out separately at 400°C in vacuum for 30 min and the liquid products of decomposition were collected and analysed by gas chromatography. The relationship between the amounts of I and II obtained from pyrolysis and the amounts of these components actually present in the copolymer samples was determined. Also the amount of III and ethyleneglycol dimethacrylate obtained from pyrolysis increases with the amount of III in the copolymer. The polymers were also characterized by differential thermal analysis.     

Thermal behavior of poly-p-xylylene-m-carborane

Thermal analysis, infrared spectroscopy, and gel-permeation chromatography studies were undertaken to determine the behavior of poly(p-xylylene-m-carborane) at elevated temperature. Results show that the polymer softened at about 200°C, probably because of polymorphism. Chlorine atoms from chain ends also ruptured at this temperature. This initiated subsequent hydrogen abstraction and thermal oxidation reactions that resulted in the decomposition of the polymer. The process of degradation closely parallels the thermal oxidation of polybenzyl and other polymers with readily activated methylene groups. The volatile products that formed at 300 and 400°C were produced because of the cleavage of methylene groups and their oxidation products. Larger polymer segments containing phenylene and m-carborane groups were evolved at higher temperatures. Some crosslinking occurred when the polymer was heated in air at temperatures above 200°C. The degree of polydispersity of the polymer fraction that remained soluble in organic solvents increased with corresponding increase of temperature.     

Thermal degradation of polyquinoxalines

A systematic investigation of the thermal stability of nine structurally related polyquinoxalines has been conducted. The relative oxidation resistance of these polymers is controlled by two opposing structural effects. Phenyl sidegroup substitution in the heterocycle greatly improves oxidative stability, while the introduction of oxygen into the main polymer chain, in the form of ether groups, produces a negative effect of equal magnitude. These results are discussed from a mechanistic point of view. Simultaneous, dynamic thermal analysis in vacuum up to 1400°C and analysis of volatile and nonvolatile products indicates three major decomposition regions. Between 500 and 640°C, main polymer degradation takes place involving the heterocycle. This event is followed by dehydrogenation of a stable degradation product between 640 and 690°C. Above 1360°C an exothermic reaction takes place to yield highly condensed aromatic residues.     

Temperature effect on conducting polyaniline salts: Thermal and spectral studies

Five different polyaniline salts have been prepared by chemical polymerization of aniline in aqueous solution of different acids. Polyaniline samples have been heat treated at four different temperatures (150, 200, 275, and 375°C) and characterized by electron paramagnetic, electronic absorption, and infrared spectral measurements. Thermal stabilities of the chemically synthesized polyaniline salts have been studied by thermal analysis and spectral methods. Polyaniline salts undergo a three-step weight-loss process in the heating cycle. The first step (up to 110°C) corresponds to the loss of water molecules from the polymer chain. In the second step (110–275°C), a small amount of acid escapes as volatile gas, and after 275°C the polymer undergoes oxidative thermal degradation in the third step. It was found that thermal stability of polyaniline salts depends on the counteranion used and the polymer is apparently stable up to 250°C. No structural changes have taken place up to 200°C and this has been confirmed from infrared and electronic absorption spectra. No definite correlation exists between conductivity and spin concentration. © 1994 John Wiley & Sons, Inc.     

Chemical reactions occurring in the thermal treatment of polymer blends investigated by direct pyrolysis mass spectrometry: Polycarbonate/polybuthyleneterephthalate

The chemical reactions occurring in the thermal treatment of polycarbonate/polybuthyleneterephthalate (PC/PBT) blends have been investigated by gradual heating (10°C/min) using thermogravimetry and direct pyrolysis into the mass spectrometer. Exchange reactions occur already in the temperature range below 300°C but the transesterification equilibrium is affected by the evolution of thermal degradation products. Buthylenecarbonate, was detected in the first decomposition stage (320–380°C), which is evolved together with a series of cyclic compounds containing units of PC and PBT, in varying ratios. The overall thermal reaction evolves towards the formation of the most thermally stable polymer, i.e., a totally aromatic polyester (polymer III , Table I), which was found to be the end-product of the thermal processes occurring in the system investigated. The thermal decomposition products obtained from the PC/PBT blends in the range 320–600°C have mass sufficiently high to be structurally significant, since they contain at least one copolymer repeating unit. The reactions occurring in the thermal treatment of the PC/PBT blend are discussed in detail. © 1993 John Wiley & Sons, Inc.     

Thermal Degradation of Polymers. IV. Poly-2,2′-(m-phenylene)-5,5′-bibenzimidazole

The thermal decomposition of poly-2,2′-(m-phenylene)-5,5′-bibenzimidazole has been investigated at temperatures to 916°C. Mass-spectrometric thermal analysis (MTA), supported by elemental analysis of residues at various stages of a thermogravimetric analysis, was used to determine product distribution as a function of temperature. Below 550°C, the major product is water. Above 550°C, degradation of the heterocyclic structure to hydrogen cyanide, ammonia, carbon monoxide, and water begins. Hydrogen and methane probably are formed from decomposition and condensation of the carbocyclic structure. Activation energies for the formation of each major product were derived from the MTA data. The average of these is somewhat temperature-dependent but agrees within experimental error with the value of 44 ± 11 kcal obtained from isothermal kinetics. A mechanism involving initial hydrolysis of the polymer to an amine-substituted polyamide is postulated. Subsequent homolytic reactions account for formation of the major products.