Stepwise thermal degradation of a polybenzimidazole foam

The stepwise thermal degradation of a polybenzimidazole (PBI) foam, prepared from 3,3′-diaminobenzidine and isophthaldiamide, has been studied under conditions of pyrolysis and nonflaming oxidative degradation in a thermal analyzer using gas and liquid chromatographic separation and mass spectrometric and infrared detection techniques. The recoveries of sample weight, as degradation products, were quantitative over the entire temperature ranges studied (100–300, 300–570, 570–700, and 700–1000°C for pyrolysis; and 100–570 and 570–900°C for nonflaming oxidation). In pyrolysis, 17 volatile compounds were identified with NH₃ and CH₄ accounting for 94 and 57 mole % of the total mass loss between 300–570 and 570–700°C, respectively. Above 700°C, HCN and H₂ were formed from degradation of arylnitrile-containing oligomers. The thermal and oxidative degradation of three substituted benzimidazole monomers was also studied, and the relative ratios of N₂, NH₃, and HCN that were produced from each, when compared with PBI, support a mechanism for degradation that favors cleavages that least alter the conjugation of the polymer backbone. In the presence of air, PBI formed stable oxygen-containing residues that decomposed at high temperatures to N₂, CO₂, and H₂O almost exclusively. Large quantities of H₂ and N₂ from model compounds support results from PBI that suggest that degradation begins with total erosion of the imide ring at 570°C and the formation of more condensed heterocyclic species. These quantitative techniques are generally applicable to the study of all polymeric materials.     

Thermal degradation of copolymers based on selected alkyl methacrylates

The thermal stability and thermal degradation of copolymers based on selected alkyl methacrylates at temperatures between 250 and 400?°C have been studied using pyrolysis?Cgas chromatography. The type and composition of thermal degradation products gave useful information about the mechanism of pyrolysis of copolymers synthesized by using typical commercially available alkyl methacrylates. It was observed that the main thermal degradation products from alkyl methacrylate copolymers are monomers of alkyl methacrylates using by synthesis. Other pyrolysis by-products formed during thermal degradation were carbon dioxide, carbon monoxide, methane, ethane, methanol, ethanol, and propanol-1.     

Thermal behaviour of copolymers of acrylonitrile with haloalkyl acrylates or methacrylates

Thermal stabilities of copolymers of acrylonitrile with 4–14 mol% of 3-chloro-2-hydroxypropyl acrylate or methacrylate, 2-chloroethyl acrylate or methacrylate and 2-bromoethyl acrylate or methacrylate were studied by TGA in air. A two-step degradation between 300 and 350° and 600 and 650° is observed for both PAN and the copolymers. Initially, the degradation is slow up to 350° for the copolymers (8–23% wt loss) compared with PAN (27% wt loss); the trend reverses after 350°. A mechanism of the degradation has been proposed on the basis of i.r. studies of the residue of the copolymers isothermally heated at 300° for 10 min. The influence of the haloalkyl comonomers on the flammability of acrylic copolymers in terms of limiting oxygen index is also reported.     

Pendant functional group copolyether sulfones: III. Modified copolyether sulfones with bisphenolic copper chelate

New copolyether sulfones having copper(II) chelate units as pendant groups were synthesized by a chemical modification reaction of chloromethylated polysulfones with the sodium salt of copper(II) bis(2,4‐dihydroxybenzaldehyde) in dichloromethane/dimethyl sulfoxide as solvent system, at room temperature. The resulting copolymers were confirmed by IR absorption spectra and characterized by softening points, solubilities, differential scanning calorimetry and thermogravimetric analysis measurements. A slow increase of glass transition temperature values was observed in comparison with the starting chloromethylated polysulfones, and the thermal stability in air showed a slow, but insignificant, decrease. A significant increase in solvent resistance was observed. The glass transition temperature values, which do not exceed 200 °C, provide processing possibilities. Copyright © 2003 John Wiley & Sons, Ltd.     

Copolymers of 2-Hydroxyethyl Methacrylate and Alkyl Methacrylates. Part III. Thermal Behavior

The relative thermal stability of copolymers of 2-hydroxyethyl methacrylate-ethyl methacrylate (HEMA-EMA) and HEMA-n-butyl methacrylate (HEMA-BMA) was investigated by thermogravimetry in an air/nitrogen atmosphere. The effect of molecular weight on thermal degradation was evaluated by taking five fractions of HEMA-EMA and four of HEMA-BMA copolymers. The enthalpic changes associated with the endothermic transition were evaluated by differential scanning calorimetry. The structural changes taking place in these copolymers during thermal degradation in air at 200°C were investigated by IR.     

Thermal degradation of butyl acrylate-methyl acrylate-acrylic acid-copolymers

The thermal degradation of copolymers based on butyl acrylate-methyl acrylate-acrylic acid used as acrylic pressure-sensitive adhesives, especially for bonding of plasticizer containing materials, has been investigated using thermogravimetry and pyrolysis-gas chromatography at 250°C. It was observed that during the pyrolysis of butyl acrylate-methyl acrylate-acrylic acid copolymers unsaturated monomers as methyl acrylate, methyl methacrylate, butyl acrylate and butyl methacrylate were formed. During the side-chain butyl acrylate-methyl-acrylate-acrylic acid-copolymer degradation the presence of methyl alcohol and butyl alcohol was observed.     

Thermal Degradation of Trioxane-Dioxqlane Copolymers Obtained with Boron Trifluoride-Acrylonitrile Complex as Initiator

The thermal degradation of certain trioxane-dioxolane copolymers obtained with boron trifluoride-acrylonitrile complex as initiator has been investigated. The thermal stability of samples, discussed in terms of topoenergetic values, was related both to copolymer composition and conversion. The most thermostable copolymers (～5% weight loss at 300°C in air), having 5–8% dioxolane units, had the highest intrinsic viscosity in the series and were isolated at 35–50% conversion. The results obtained were compared with similar data for a commercial tri-oxane-ethylene oxide copolymer containing 95% formal units.     

Thermal degradation of copolymers of methyl methacrylate and 2,6-dimethoxycarbonyl-1,6-heptadiene

The thermal degradation under vacuum of copolymers of methyl methacrylate and 2,6-dimethoxycarbonyl-1,6-heptadiene of different compositions has been investigated. It has been found that the presence in the polymer chains of small amounts of cyclic structural units from the diene monomer considerably reduces the amount of degradation which occurs in poly(methyl methacrylate) at temperatures lower than 300°C. On the basis of the results of the analysis of the degradation products, a mechanism is suggested which accounts for this effect.     

Synthesis of methacrylic copolymers with nona‐1‐butoxy trititanosiloxane as side groups and its application as a thermosetting resin

Methacrylic copolymers with a hydroxyl group on one end of the main chain and nona‐1‐butoxytrititanosiloxane as side groups (called methacrylic hybrid copolymers) were synthesized for use as baked‐finish‐type coating resins. The chemical structures of the side groups in the methacrylic hybrid copolymers were confirmed with the ash weight of the copolymers after combustion, the elemental ratio analysis of Si and Ti in the ash determined by inductively coupled plasma emission spectrometry, and the characteristic absorption band determined by Fourier transform infrared spectrophotometry. The methacrylic hybrid copolymers were cured at temperatures less than 150 °C in the absence of a curing accelerator. The cured copolymers exhibited a high thermal stability. The curing temperature of the copolymers was determined by the change in the absorption peak strength (peak area) of the 1655 cm⁻¹ band in the IR difference spectrum. The thermal stability of the copolymers was evaluated as the thermal‐degradation temperature measured by thermogravimetric analysis. The methacrylic hybrid copolymers were then be used as effective curing resins. The mixture, consisting of thermoplastic methacrylic terpolymer with hydroxyl and carboxyl groups and the methacrylic hybrid copolymers, were cured at less than 150 °C in the absence of a curing accelerator and exhibited a higher thermal‐degradation temperature than the copolymers. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1090–1098, 2001     

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.     

The thermal degradation of copolymers of methyl methacrylate with methacrylic acid

The degradation has been studied using thermogravimetry and thermal volatilization analysis; product analysis has been carried out by GLC and spectroscopy. The copolymers yield water and methanol below 300°; at higher temperatures, the products also include methyl methacrylate, carbon monoxide, carbon dioxide and methane. Quantitative comparison of the yields of methanol and methyl methacrylate has been made with predicted yields based upon sequence distribution calculations. Methanol is believed to result by two routes (i) intramolecular cyclization of adjacent ester and acid chain units at low temperatures, and (ii) fragmentation of ester units, in competition with depolymerization, at higher temperatures. Methyl methacrylate yields are substantially lower than the MMA content of the copolymer, as a result of these processes; some MMA units also appear in the product fraction volatile at degradation temperatures but not at ambient temperature. The partially-degraded copolymers develop anhydride ring structures in the chain as a result both of dehydration and of methanol production. The mechanisms of the various reactions are discussed.     

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.     

Thermal degradation of copolymers of butadiene and acrylonitrile

Ten copolymers of butadiene and acrylonitrile have been prepared covering the composition range 100-25 mole % butadiene; reactivity ratios are r_butadiene = 0?50, r_{acrylonitrile} = 0?07. The thermal analysis techniques (TVA, TGA and DSC) have been applied to determine the general features of the thermal degradation of these copolymers. The fractions of products comprising permanent gases, products volatile at 20°, chain fragment material and residue have been separated and analysed. The constituent parts of the overall reaction have been discussed and the whole represented in the form of an integrated reaction mechanism.     

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.     

Glycidyl methacrylate–tert-butyl acrylate copolymers: Synthesis,characterization, and thermal studies

Glycidyl methacrylate was copolymerized with tert-butyl acrylate in bulk at 60°C using benzoyl peroxide as free radical initiator. The copolymer composition was determined by chemical analysis as well as from ¹³C-NMR data. The monomer reactivity ratios were calculated by using the YBR method. The number average sequence length of the copolymers was determined from ¹³C-NMR data and compared with those obtained from reactivity ratios. The intrinsic viscosity of the copolymers was determined in DMF, and thermal stability as well as mechanism of thermal degradation of the copolymers were evaluated.     

Pyrolysis/Gas chromatography/mass spectrometry of polymers: Polyisopropenylcyclohexane and copolymers with its aromatic counterpart, α-methylstyrene

Flash pyrolyses at 400, 650, and 900°C of polyisopropenylcyclohexane (PIC) and copolymers, produced by partial hydrogenation of poly-α-methylstyrene (PAMS), have shown that the decomposition of the PIC or IC sequences is complex. In comparison, PAMS and AMS sequences give only depolymerization to monomer at the two lower temperatures but a more complex degradation at 900°C, based on the products identified. It is interesting to note that traces of decalin solvent initiated the depolymerization of PAMS and the AMS sequences in the copolymers at 400°C. The products identified by copolymer pyrolyses indicated that no reaction occurred between S and IC units during decomposition. Average sequence data on the copolymers could not be determined because of the facile unzipping of the AMS sequences and the greater thermal stability of the IC sequences. The fragmentation pattern did indicate that partial hydrogenation of PAMS had produced random copolymer and not a blend of two homopolymers.     

Radiation degradation of copolymers of ethylene and α-olefins: The temperature dependence of yields of volatile products

γ-Irradiation of polyolefins produces small amounts of volatile hydrocarbons. Their yields have been measured for irradiation of homopolymers of ethylene and copolymers with propene, 1-butene and 1-hexene at temperatures from 30 to 175°C. The alkane distribution was characteristic for each type of polymer, and dependent on the frequency of the alkyl substituents. The distribution for a particular polymer was similar at all temperatures, although the yields of alkanes increased rapidly above 100°C. The yields of alkenes, which were mainly ethylene and butene, increased proportionately more rapidly from almost nil at 30°C. The ethylene yields from all the polymers fitted a common Arrhenius relationship with an activation energy of 40 kJ mol^?1 and are attributed to radiation-induced thermal depolymerization. Detection of alkyl short branches in polyolefins is more sensitive at higher temperatures, but corrections for radiation-induced thermal degradation are more significant, whereas morphological differences can apparently affect the radiation sensitivities at 30°C.     

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.     

Thermal degradation of copolymers of 36Cl-vinyl chloride and methyl methacrylate

The degradation of copolymers of vinyl ³⁶Cl-chloride and methyl methacrylate has been studied using film samples, slow heating rate and high vacuum conditions. Volatilization has been followed using thermal volatilization analysis and radioactive assay of methyl chloride and hydrogen chloride. By carrying out duplicate experiments with and without an ice trap at ? 100°, it is possible to measure methyl chloride alone and both products, respectively, so that each product can be estimated. Yields have been found to agree well with those predicted from sequence distribution calculations. Some differences in behaviour compared with earlier work using powder samples and nitrogen flow conditions are discussed.     

Photodegradation of copolymers of methyl methacrylate and methyl acrylate at elevated temperatures

Four methyl methacrylate—methyl acrylate copolymers with molar ratios, MMA/MA, of 112/1, 26/1, 7·7/1, and 2/1 have been photodegraded at 170°C by 2537 Å radiation. The changes which occur in the molecular weight of the copolymers are typical of a random scission process and from these and volatilization data the extent of chain scission during the course of the reaction has been calculated. The pattern of volatile products is the same as that previously obtained in the thermal reaction at 300°C although there are a number of differences in detail. For example, only one in ten of the methyl acrylate units is liberated as monomer compared with one in four in the thermal reaction and the ratio CO₂/chain scissions is considerably greater than the strict 1/1 ratio observed in the thermal reaction. Zip lengths are also very much greater in the photo reaction. These minor differences between the two reactions have been accounted for in terms of the mechanism previously presented to account for the thermal reaction, bearing in mind the differences in the temperature (170 and 300°C) at which the two investigations were carried out.