Thermal Degradation of Poly(Allyl Methacrylate) by Mass Spectroscopy and TGA

Allyl methacrylate, AMA was polymerized in CCl₄ solution by α,α′‐azoisobutyronitrile at 50°C. The thermal degradation mechanism of PAMA was characterized by MS, TGA‐FT‐IR and FT‐IR‐ATR methods. The mass spectrum and TGA thermogram showed two stage degradation. The first stage of degradation was mostly linkage type degradation for the fragmentation of pendant allyl groups at 225–350°C. In the second stage, at 395–515°C, the degradation is random scission and depolymerization types. This was also supported by direct thermal pyrolysis of polymer under vacuum. The degradation fragments of MS and TGA were in agreement. In the degradation process, monomer degraded further to CO, CO₂, allyl and ether groups. No strong monomer peak was observed in mass spectrum.     

Thermal degradation of polymers with phenylene units in the chain. II. Sulfur-containing polyarylenes

Poly(p-phenylene sulfide), a poly(arylene sulfone), and a poly(arylene sulfonate) were subjected to thermal degradation in vacuo, at temperatures between 250 and 620°C. The volatile and solid degradation products were analyzed by mass spectroscopy, infrared spectroscopy, and elemental analysis. The major decomposition product of poly-(phenylene sulfide) is a condensate, which consists of di- and trimeric chain fragments, dibenzothiophene, and possibly thianthrene. The residual polymer loses two thirds of its sulfur as hydrogen sulfide, however, one third is retained even at 620°C. The most characteristic decomposition reaction of the polysulfone and of the polysulfonate is the almost complete removal of the sulfur as sulfur dioxide. The elimination of sulfur dioxide is practically complete at 450°C for the polysulfone and at 350°C for the polysulfonate.     

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.     

Investigation of thermal and catalytic degradation of polystyrene waste into styrene monomer over natural volcanic tuff and Florisil catalysts

Thermal and catalytic degradation of polystyrene waste over two different samples of natural volcanic tuff catalyst comparative with Florisil catalyst has been carried out in order to establish the conversion degree into styrene monomer. The polystyrene waste (PS) was subjected to a thermal degradation process in the range of 380–500°C in presence of studied catalysts in a ratio of 1/10 in mass, catalyst/PS. The catalysts were characterized by N₂ adsorption-desorption isotherms (BET), Scanning Electron Microscopy (SEM) and Fourier-transform infrared spectrometry (FTIR). Influences of temperature and type of catalysts on the yields and on the distribution of end-products obtained by thermal and catalytic degradation of polystyrene waste have been studied. The maximum yields of liquid products were obtained at 460°C degradation temperature and were calculated between 83.45% and 90.11%. The liquid products were characterized by gas chromatography mass spectrometry (GC-MS) and FTIR analytical techniques. The GC-MS results showed that the liquid products contained styrene monomer up to 55.62%. The FTIR spectra of liquid products indicated the specific vibration bands of the functional groups of compounds of liquid products. The amounts of styrene monomer obtained were influenced by structural and textural properties of studied catalyst and the contribution on product distribution is discussed.      

The high-temperature degradation of poly(2,6-dimethyl-1,4-phenylene ether)

The thermal degradation of poly(2,6-dimethyl-1,4-phenylene ether) has been investigated to 1000°C in an inert atmosphere. X-ray diffraction, thermogravimetric analysis, and differential scanning calorimetry were employed to study the physical changes in the polymer, and vapor-phase chromatography, infrared spectroscopy, and mass spectrometric thermal analysis were used to elucidate the chemical aspects of the degradation process. It was found that degradation occurs in two steps: (1) a rapid exothermic process occurs between 430 and 500°C, leading to the evolution of phenolic products, water, and a black, highly crosslinked residue, and (2) a slower, char-forming process occurs above 500°C, characterized by the evolution of methane, carbon monoxide, and hydrogen. The chars formed in process 2 were found by x-ray analysis to be amorphous. The infrared spectrum of a sample heated to 510°C is nearly identical with that of the starting polymer, indicating that oxidative reactions are not important in the first process. The data for the low-temperature process are consistent with a thermal degradation scheme based on the radical-redistribution reaction of polyphenylene ethers and/or the degradation of o-benzylphenols formed by the thermal rearrangement of o-methyl diphenyl ethers. The char-forming process is best explained by simultaneous operation of the Szwarc mechanism of toluene pyrolysis, producing hydrogen and methane and reactions that cleave the aromatic rings and produce carbon monoxide.     

Crystallization during polymerization of poly-p-xylylene. III. Crystal structure and molecular orientation as a function of temperature

Polymerization of p-xylylene was carried out from the gas phase with monomer produced by the pyrolysis of [2,2]-p-cyclophane. The crystalline form and preferred orientation of as-polymerized polymer deposited at various temperatures (?196 to 80°C) were investigated by x-ray diffraction methods. The melting behavior and other thermal transitions were studied by DSC. At 80°C the polymer film deposit is a mixture of the α and β forms, while between 60 and 0°C the deposit is of the α form. At lower temperature the polymer deposit is mainly of the β form, which shows diffuse reflections. At liquid nitrogen temperature it is of the β form with sharp reflections, contaminated with a small amount of oligomer. It was also found that at low temperatures, fibrillar crystals grow from the substrate in a direction 45° against the gas flow, and at even lower temperature, well-oriented filmlike crystals grow perpendicular to the substrate surface.     

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.     

Oxidative degradation products of irradiated polyethylene

Oxidative thermal degradation products of polyethylenes at various temperatures crosslinked with electron beams have been analyzed with gas chromatography and mass spectrometry techniques. Carbon monoxide and carbon dioxide are determined at a temperature range of 200–340°C, and the activation energies of the unirradiated and the irradiated polyethylene (at 100 Mrad) are 13.5 and 11.4 Kcal/mole, respectively. C₁ to C₈ hydrocarbons produced in air and in nitrogen are determined at temperatures from 400 to 450°C for the polyethylenes. The irradiated polyethylene produces less hydrocarbons in air than the unirradiated polyethylene, contrary to the fact that the crosslinked polymer evolves more hydrocarbons than the unirradiated polymer in a nitrogen atmosphere. Aldehydes and ketones are observed in the volatile oxidative degradation products, and these carbonyl compounds increase quantitatively with increase of temperature up to about 460°C. It is concluded that irradiated polyethylene is thermally more unstable in the absence of oxygen and more easily oxidable at low degradation temperatures in air than unirradiated polyethylene. Irradiated polyethylene, however, is more heat-stable than unirradiated polyethylene from the standpoint of the ignition process.     

Thermal Behavior Analysis of Two Synthesized Flavor Precursors of N‐alkylpyrrole Derivatives

To expand the library of pyrrole‐containing flavor precursors, two new flavor precursors—methyl N‐benzyl‐2‐methyl‐5‐formylpyrrole‐3‐carboxylate (NBMF) and methyl N‐butyl‐2‐methyl‐5‐formylpyrrole‐3‐carboxylate (NUMF)—were synthesized by cyclization, oxidation, and alkylation reactions. Thermogravimetry (TG), differential scanning calorimeter, and pyrolysis–gas chromatography/mass spectrometry were utilized to analyze the thermal degradation behavior and thermal degradation products of NBMF and NUMF. The TG‐DTG curve indicated that the maximum mass loss rates of NBMF and NUMF appear at 310 and 268°C, respectively. The largest peaks of NBMF and NUMF showed by the differential scanning calorimeter curve were 315 and 274°C, respectively. Pyrolysis–gas chromatography/mass spectrometry detected small molecule fragrance compounds appeared during thermal degradation, such as 2‐methylpyrrole, 1‐methylpyrrole‐2‐carboxylic acid methyl ester, limonene, and methyl formate. Finally, the thermal degradation mechanism of NBMF and NUMF was discussed, which provided a theoretical basis for their application in tobacco flavoring additives.     

Thermal Oxidation Products of Nylon 6 Determined by MALDI‐TOF Mass Spectrometry

Matrix‐assisted laser desorption ionisation (MALDI) mass spectrometry was used, in an attempt to find firm evidence for the structure of the species produced in the thermal oxidative degradation of Nylon 6 (Ny6), at 250°C in air. The MALDI spectra of the products showed the presence of polymer chains containing aldehydes, amides, methyl and N‐formamide terminal groups. The aldehydes undergo further oxidation to produce carboxylic end groups. The formation of azomethines, from the further reaction of aldehydes with amino‐terminated Ny6 chains, is also supported by the appearance of specific peaks in the MALDI spectra.     

Synthesis of fully conjugated aromatic polyazomethine from AB-type monomer using soluble precursor method

A new AB-type monomer, N,N-bistrimethylsilylated p-aminobenz-aldehyde diethyl acetal was prepared via three steps from p-bromoaniline as a starting material. The two-stage polymerization involving a soluble precursor polymer process gave a poly(p-phenylenevinylene)-type polyazomethine, poly(1,4-phenylene-nitrilomethylidyne). The first stage of polymerization was carried out in tetrahydrofuran or hexamethylphosphoramide containing water at room temperature. In the second stage, the polymer was thermally converted into the final polyazomethine by heating over 300°C to form a free-standing film. The film was reddish brown and insoluble in common organic solvents. The investigation of the first-stage products by means of MALDI-TOF mass spectroscopy proved the oligomers with 4-11 repeating units per molecule. From the ¹H-NMR analysis of the model reaction, the polymerization mechanism was found to be a stepwise polycondensation of 4-diethoxymethylaniline which was formed by removal of two silyl groups of the monomer.     

Synthesis and characterization of ordered polyurethanes from nonsymmetric diisocyanate and ethylene glycol

An ordered polyurethane with a head‐to‐head (H‐H) or tail‐to‐tail (T‐T) content over 95% was prepared by polyaddition reaction of a nonsymmetric monomer, p‐isocyanatobenzyl isocyanate (1) with a symmetric monomer, ethylene glycol (2). The model reactions were studied in detail to demonstrate the feasibility of polymer formation. The polymerization was conducted in THF in the presence of triethylamine (TEA) at 0 °C by slow addition of a half amount of 2 to 1, followed by removing THF and then adding the rest of 2 in DMF at once at 30 °C in the presence of dibutyltin dilaurate (DBTL). The microstructure of the polymer obtained was investigated by ¹³C NMR spectroscopy, and it was found that the polymer had the expected structural regularity. The constitutional regularity of polymers influenced their thermal properties. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2106–2114, 2000     

Preparation and degradation of salts of poly(methacrylic acid). I. Lithium,sodium, potassium,and caesium salts

The polymers of lithium, sodium, potassium, and caesium salts of methacrylic acid have been prepared by free radical polymerization of the respective monomers in methanol solution. The degradation behavior of the polymers has been investigated by thermal volatilization analysis, thermogravimetry, and product analysis. These materials are stable to about 350°C under programmed heating at 10°C/min in vacuo. The principal degradation products are monomer, the corresponding isobutyrate, carbonate, oxide, carbon dioxide, and a fraction of liquid volatiles that is complex and contains a variety of aldehydes and ketones. The mechanism of degradation is discussed in detail.     

Synthesis and structure of the p-hydroxybenzoic acid polymer

The synthesis and structure of the p-hydroxybenzoic acid polymer is described. The polymer was successfully prepared from either the phenyl ester of p-hydroxybenzoic acid or from p-acetoxybenzoic acid. With highly purified acetoxybenzoic acid, single crystals of the polymer could be prepared. The structure of the polymer was determined and shown to consist of a double helix where the two chains are in a reversed head-to-tail order. The unit cell dimensions are: a = 17.8 Å and c = 18.4 Å, where c corresponds to the chain length with a repeat distance of three units. The mechanism of polymerization and formation of the single crystal is discussed. The polymer displays a reversible high-temperature crystalline transition at 325–360°C (not a melting point). The transition was characterized by differential thermal analysis, differential calorimetry, thermal expansion coefficient measurements, high-temperature x-ray scans, and dielectric constant determinations. Orientation of the polymer chains during fabrication and changes in the mechanism of oxidative degradation above the crystal transition are described.     

Polymerization of 2-hydroxyethyl methacrylate by hydro/solvothermal technique in presence of nanographene: electrical and thermal degradation characterization

Nanocomposites of poly(2-hydroxyethyl methacrylate) (PHEMA) loaded with 1.7 mass%, 6.5 mass% and 9.0 mass% nanographene were prepared by hydro/solvothermal technique. The main peaks of the nanographene and amorphous polymer structure were revealed by X-ray diffraction (XRD) analysis. Nanocomposites were characterized by SEM, DSC and TGA techniques. The dielectric constant (ε?), the dielectric loss factor (ε?), the loss tangent (tanδ) and the conductivity (σ_ac) were measured using a dielectric analyzer in a frequency range from 100 Hz to 2 kHz. Also, current (I)–voltage (V) measurements were carried out. It is well known that nanocomposite formation causes an improvement of many properties for a polymer, providing enhanced properties such as conductivity and thermal stability. This investigation was done to understand whether the presence of nanographene causes changes in the degradation pathway of poly(HEMA) prepared by hydro/solvothermal technique. For this aim, pure poly(HEMA) and nanocomposites were heated from room temperature to 500 °C. The characterization of degradation products for the cold ring fractions (CRFs) and trapped at???196 °C (in liquid nitrogen) was investigated by means of FT-IR, ¹H, ¹³C-NMR spectroscopic and GC–MS techniques. The FT-IR, NMR and GC–MS data showed that depolymerization corresponding to monomer (2-hydroxyethyl methacrylate) was the most important product trapped at CRF and???196 °C in the thermal degradation of nanocomposites. As the nanographene loading increased in composite systems, the rate of depolymerization of poly(HEMA) increased compared to pure poly(HEMA). The nanographene particles in the composite systems acted as a mass barrier that retards the escape of the volatile products

     

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.     

The utilization of TG/GC/MS in the establishment of the mechanism of poly(styrene) degradation

General purpose poly(styrene) is a large volume commodity polymer used in a variety of applications. It is widely used in food packaging, particularly for baked goods. In this application, the presence of styrene monomer, which has a distinctive taste and aroma, cannot be tolerated. Processing of the polymer and forming of the food container at an unacceptably high temperature leads to the formation of styrene monomer and finished articles with unacceptable aroma characteristics. An examination of the thermal degradation of poly(styrene) has revealed the origin of monomer formation. The thermal decomposition of poly(styrene) has been widely studied. However, most studies have been carried out at high temperature (>300°C) where many processes are occurring simultaneously. Degradation at lower temperature, 280°C, occurs in two well-defined steps. The first is thermolysis of a head-to-head bond present in the mainchain as a consequence of polymerization termination by radical coupling. This generates macroradicals which smoothly depolymerize to expel styrene monomer. The nature of the degradation is readily apparent from kinetic analysis of the isothermal thermogravimetry (TG) data and the identity of the single volatile product may be readily established by gas chromatography/mass spectrometry (GC/MS) analysis of the effluent from the TG analysis.     

Structure and properties of poly-2,5-distyrylpyrazine

Poly-2,5-distyrylpyrazine (poly-DSP) was investigated by differential thermal analysis (DTA), thermogravimetric analysis (TGA), and measurements of dynamic viscoelastic and electrical properties. From DTA and TGA studies it was confirmed that poly-DSP melts at 321°C and depolymerizes rapidly to the monomer at temperatures between 335°C and 345°C in helium. The polymer is affected by oxygen above 200°C. The E′ value from dynamic viscoelasticity measurements on amorphous film is 2 × 10¹¹ dyne/cm² at room temperature. It decrease abruptly in the temperature range 140–150°C; but the net decrease of E′ within this temperature range is relatively small. The electrical properties of amorphous poly-DSP are characterized by a small temperature dependence of the dielectric constant between room temperature and 100°C. The dielectric loss tangent was observed to be small, and the dc conductivity was extremely small. It is concluded that rotation of the phenyl branches in the polymer occurs above ?30°C and the glass transition occurs at about 150°C. These properties are discussed in some detail in relation to the polymer structure.     

Synthesis of novel tri‐benzoxazine and effect of phenolic nucleophiles on its ring‐opening polymerization

A trifunctional benzoxazine, 1,3,5‐tris(3‐phenyl‐3,4‐dihydro‐2H‐benzo[1,3]oxazin‐6‐yl)benzene (T‐Bz) was synthesized and in an effort to reduce its curing temperature (curing maxima at 238 °C), it was mixed with various phenolic nucleophiles such as phenol (PH), p‐methoxy phenol (MPH), 2‐methyl resorcinol (MR), hydroquinone (HQ), pyrogallol (PG), 2‐naphthol (NPH), 2,7‐dihydroxy naphthalene (DHN), and 1,1'‐bi‐2‐naphthol (BINOL). The influence of these phenolic nucleophiles on ring‐opening polymerization temperature of T‐Bz was examined by DSC and FTIR analysis. T‐Bz undergoes a complete ring‐opening addition reaction in the presence of bi‐ and trifunctional phenolic nucleophiles (MR/HQ/PG/DHN) at 140 °C (heated for 3 h) and forms a networked polybenzoxazine (NPBz). The NPBzs showed a high thermal stability with T_d20 of 350–465 °C and char yield of 67–78% at 500 °C; however, a diminutive weight loss (6.9–9.8%) was observed at 150–250 °C (T_d5: 215–235 °C) due to degradation of phenolic end groups. This article also gives an insight on how the traces of phenolic impurities can alter the thermal properties of pure benzoxazine monomer as well as its corresponding polymer. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2811–2819     

Synthesis and thermochemistry of phenylmaleimide- and phenylnadimide-terminated bisphenol A polycarbonates

Phenylmaleimide (PMI)- and phenylnadimide (PNI)-terminated bisphenol A polycarbonates (PCs) were prepared by solution or interfacial phosgenation processes, and their thermal crosslinking, both with and without a free radical initiator, and the thermal stability of the resultant network polymers were investigated. m-PMI PCs were prepared by interfacial phosgenation of bisphenol A and m-hydroxyphenylmaleimide, but p-hydroxyphenylmaleimide caused rapid phosgene hydrolysis under interfacial conditions and PCs from it could only be made by solution phosgenation. The degree of crosslinking of PMI PCs, as measured by their gel fraction, heated in the absence of a free radical initiator was generally higher at 250°C than at 300°C and increased with the concentration of PMI end groups. m- and p-PMI PCs form thermosets having nearly complete gel fractions by radical initiated curing at 150–200°C. The gel fraction of these thermosets decreases with exposure to higher temperatures (300°C). This behavior is attributed to BA PC chain degradation induced by nitrogen-containing maleimide reaction products. p-PNI PC was prepared by solution phosgenation and the thermal reaction of it in the presence of the initiator produced only a small increase in molecular weight. © 1997 John Wiley & Sons, Inc.