Thermal degradation of polymers. II. Mass spectrometric thermal analysis of phenol-formaldehyde polycondensates

The degradation of phenol–formaldehyde polycondensates has been investigated by mass spectrometric thermal analysis to 800°C. The thermal oxidative mechanism proposed by Conley and co-workers has been confirmed. Direct analysis of products at frequent intervals of a temperature-programmed heating cycle demonstrates the existence of postcuring, general degradation, and char-forming stages. Activation energies for formation of each product and for degradation of the polymer have been determined. Phenolic homologs, products of thermal scission of methylene–phenyl bonds, show high activation energies; oxidation products have activation energies comparable to or slightly higher than that for oxidation of methylene bridges to carbonyl groups. The tarry high molecular weight products found on pyrolysis at atmospheric pressure are not formed in high vacuum because recombination reactions of phenols and formaldehyde are minimized. Otherwise, no major change in product composition, as compared to the high heating rate pyrolysis–gas chromatographic investigation of Jackson and Conley, was observed.     

Characteristics of hemicellulose,cellulose and lignin pyrolysis

The pyrolysis characteristics of three main components (hemicellulose, cellulose and lignin) of biomass were investigated using, respectively, a thermogravimetric analyzer (TGA) with differential scanning calorimetry (DSC) detector and a pack bed. The releasing of main gas products from biomass pyrolysis in TGA was on-line measured using Fourier transform infrared (FTIR) spectroscopy. In thermal analysis, the pyrolysis of hemicellulose and cellulose occurred quickly, with the weight loss of hemicellulose mainly happened at 220–315 °C and that of cellulose at 315–400 °C. However, lignin was more difficult to decompose, as its weight loss happened in a wide temperature range (from 160 to 900 °C) and the generated solid residue was very high (∼40 wt.%). From the viewpoint of energy consumption in the course of pyrolysis, cellulose behaved differently from hemicellulose and lignin; the pyrolysis of the former was endothermic while that of the latter was exothermic. The main gas products from pyrolyzing the three components were similar, including CO₂, CO, CH₄ and some organics. The releasing behaviors of H₂ and the total gas yield were measured using Micro-GC when pyrolyzing the three components in a packed bed. It was observed that hemicellulose had higher CO₂ yield, cellulose generated higher CO yield, and lignin owned higher H₂ and CH₄ yield. A better understanding to the gas products releasing from biomass pyrolysis could be achieved based on this in-depth investigation on three main biomass components.     

Pyrolysis gas chromatographic analysis of polyacrylonitrile

Pyrolysis gas chromatographic analysis of polyacrylonitrile under an inert atmosphere was made in a temperature region of 500–900°C. It was confirmed that the main degradation products are various kinds of lower nitriles that include CH₂CHCN, CH₃CN, and HCN. In addition, lower hydrocarbons such as CH₄ and C₂H₄, which are related to secondary decomposition, were detected. Various thermo‐analytical data were obtained, including those concerning the relation between retention time and the polarity of nitriles, and the dependence of the products' limiting yield on pyrolysis temperature. Based on the above results, specific applications of the pyrolysis gas chromatographic analysis and the utility of this procedure in the study of thermal degradation of polyacrylonitrile are described. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 473–478, 2001     

Thermal Stability of Polymer Additives: Comparison of Decomposition Models Including Oxidative Pyrolysis

The thermo‐oxidative stability of widely used polymer additives has been investigated. A comparative analytical approach with classic and innovative decomposition models for polymer additives was conducted and the results supported using quantum‐chemical calculations. Unique pyrolysis products of the analytes were compiled utilizing pyrolysis online coupled to gas chromatography followed by mass spectrometric detection (Pyr‐GC–MS). The pyrolysis was either performed under inert conditions or in an oxygen‐containing atmosphere. Squalane was applied as polymer‐mimicking liquid next to low density polyethylene (LDPE) and polyamide 6 (PA 6) as matrices for 10 selected additives. The additives included in this study range from antioxidants and plasticizers to processing aids. These were selected to address a range of application in consumer products and to cover different chemical classes. The toxicological relevance of additives and potential breakdown products was considered. Consequently, degradation of sterically hindered antioxidants, diarylamines, and a trimellitic acid derivative was investigated. The findings were used to predict the behavior of consumer products made of polymeric materials entailing additives. The level of Antioxidant 2246 [2‐tert‐butyl‐6‐[(3‐tert‐butyl‐2‐hydroxy‐5‐methylphenyl)methyl]‐4‐methylphenol] and one of its predicted decomposition products was determined in baby bottle nipples made of natural rubber [2‐tert‐butyl‐4‐methylphenol] utilizing the complementary technique of gas chromatography coupled to tandem mass spectrometry (GC–MS/MS). This study provides a comprehensive characterization of important polymer additives and enables the prioritization of degradation products for further risk assessment. J. VINYL ADDIT. TECHNOL., 25:E12–E27, 2019. © 2018 The Authors. Journal of Vinyl and Additive Technology published by Wiley Periodicals, Inc. on behalf of Society of Plastics Engineers     

Exploiting pyrolysis protocols on BTDA-TDI/MDI (P84) polyimide/nanocrystalline cellulose carbon membrane for gas separations

Tubular carbon membranes were fabricated by the blending of BTDA-TDI/MDI (P84) polyimide with nanocrystalline cellulose in a controlled pyrolysis process, specifically the pyrolysis environment (He, Ar, and N₂) and the thermal soak time (30–120 min). The carbon membrane layer on a tubular support is converted to carbon matrix at 800 °C with a heating rate of 3 °C min⁻¹. The effects of these controlled pyrolysis conditions on the gas permeation properties have been investigated. The results revealed that the pyrolysis under Ar gas environment at 120 min of thermal soak time have the best gas permeation performance with the highest CO₂/CH₄ selectivity of 68.2 ± 3.3 and CO₂ permeance of 213.6 ± 2.2 GPU. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46901.     

New method for evaluation of kinetic parameters and mechanism of degradation from pyrolysis–GC studies: Thermal degradation of polydimethylsiloxanes

Thermal degradation of polydimethylsiloxane (PDMS) polymers having hydroxyl (PS) and vinyl (PS‐V) terminals was studied by pyrolysis‐gas chromatography (PGC) in the temperature range from 550 to 950°C. The degradation products were primarily cyclic oligomers ranging from trimer (D₃) to cyclomer D₁₁ and minor amounts of linear products and methane. The product composition varied significantly with pyrolysis temperature and extent of degradation. A new method was developed to derive a mass loss‐temperature curve (pyrothermogram, PTG) and to determine the kinetic parameters of decomposition (k, n, and E_a) from sequential pyrolysis studies. It was shown that isothermal rate constants can be derived from repeated pyrolysis data. Good agreement between the rate constants derived from the two methods validates the methodology adopted. This was further confirmed from thermogravimetric studies. The E_a values for the decomposition of PS and PS‐V derived from sequential pyrolysis were 40 ± 2 and 46 ± 2 kcal mol⁻¹, respectively. Various mechanisms for the degradation of PDMS were reviewed and discussed in relation to the PGC results. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 441–450, 1999     

Pyrolysis of used sunflower oil in the presence of sodium carbonate by using fractionating pyrolysis reactor

Pyrolysis of used sunflower oil was carried out in a reactor equipped with a fractionating packed column (in three different lengths of 180, 360 and 540 mm) at 400 and 420°C in the presence of sodium carbonate (1, 5, 10 and 20% based on oil weight) as a catalyst. The use of packed column increased the residence times of the primer pyrolysis products in the reactor and packed column by the fractionating of the products which caused the additional catalytic and thermal reactions in the reaction system and increased the content of liquid hydrocarbons in gasoline boiling range. The conversion of oil was high (42–83 wt.%) and the product distribution was depended strongly on the reaction temperature, packed column length and catalyst content. The pyrolysis products consisted of gas and liquid hydrocarbons, carboxylic acids, CO, CO₂, H₂ and water. Increase in the column length increased the amount of gas and coke–residual oil and decreased the amount of liquid hydrocarbon and acid phase. Also, increase of sodium carbonate content and the temperature increased the formation of liquid hydrocarbon and gas products and decreased the formation of aqueous phase, acid phase and coke–residual oil. The major hydrocarbons of the liquid hydrocarbon phase were C₅–C₁₁ hydrocarbons. The highest C₅–C₁₁ yields (36.4%) was obtained by using 10% Na₂CO₃ and a packed column of 180 mm at 420°C. The gas products included mostly C₁–C₃ hydrocarbons.     

Thermal characteristics and pyrolysis of methyl‐di(phenylethynyl)silane resin

Thermal stability of a recently synthesized polymeric methyl‐di(phenylethynyl)silane (MDPES) resin was studied using a number of thermal and spectrometric analytical techniques. The polymer exhibits extremely high thermal stability. Thermogravimetric analysis (TGA) shows that the temperature of 5% weight loss (T_d5) was 615°C and total weight loss at 800°C was 8.9%, in nitrogen atmosphere, while in air, T_d5 was found to be 562°C, and total weight loss at 800°C was found to be 55.8% of the initial weight. Differential thermal degradation (DTG) studies show that the thermal degradation of MDPES resin was single‐stage in air and two‐stage in nitrogen. The thermal degradation kinetics was studied using dynamic TGA, and the apparent activation energies were estimated to be 120.5 and 114.8 kJ/mol in air, respectively, by Kissinger and Coats–Redfern method. The white flaky pyrolysis residue was identified to be silicon dioxide by FTIR and EDS, indicating that the thermal stability of polymer may be enhanced by the formation of a thin silicon dioxide film on the material surface. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 103: 605–610, 2007     

Thermal degradation of cellulose and its phosphorylated products in air and nitrogen

The thermal degradation of cellulose and its phosphorylated products (phosphates, diethylphosphate, and diphenylphosphate) were studied in air and nitrogen by differential thermal analysis and dynamic thermogravimetry from ambient temperature to 750°C. From the resulting data various thermodynamic parameters were obtained following the methods of Broido and Freeman and Carroll. The values of E_a for decomposition for phosphorylated cellulose were found to be in the range 55–138 kJ mol^?1 in air and 85–152 kJ mol^?1 in nitrogen and depended upon the percent of phosphorus contents in the samples. The mass spectrum of cellobiose phosphate indicated the absence of the molecular ion, indicating that the compound was thermally unstable. The IR spectra of the pyrolysis residues of cellulose phosphate gave indication of formation of a compound having C?O and P?O groups. A fire retardancy mechanism for the thermal degradation of cellulose phosphate has been proposed.     

Pyrolysis and thermo‐oxidative degradation of polycyclopentadiene

Thermal degradation of polycyclopentadiene polymer (PCPD) was investigated by pyrolysis gas chromatography (PGC) in the temperature range of 500–950°C. The nature and composition of the pyrolyzates at various temperatures are presented, and the mechanism of degradation is explained. The activation energy of decomposition (E_a) was obtained from an Arrhenius‐type plot using the concentration of the product ethylene (C₂) at different pyrolysis temperatures and the value was found to be 138 kJ mol⁻¹. Thermo‐oxidative degradation of PCPD in the presence of ammonium perchlorate (AP), the most commonly used oxidizer for polymeric fuel binders, was studied at a pyrolysis temperature of 700°C. The compositions of the products with varying amounts of AP are given, and the exothermicity of oxidative decomposition reactions is evaluated. The energetics of the degradation processes are compared with those of polybutadiene type polymers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 635–641, 2000     

Heat Treatment Effect on Lignin and Carbohydrates in Corsican Pine Earlywood and Latewood Studied by PY–GC–MS Technique

Lignin-derived degradation products from non-treated (NT) and heat-treated (T) Corsican pine (Pinus nigra subsp. laricio) obtained by pyrolysis–gas chromatography–mass spectrometry (Py–GC–MS) were investigated, whereby the earlywood (EW) and latewood (LW) parts of the annual ring were considered separately. The data evaluation was done by principal component analysis (PCA) and the Kruskal–Wallis test. There are no differences in the pyrolysis products composition between EW and LW, but NT and T samples were discernible by PCA applied to Py–GC–MS data. Less phenols with longer chains (4-vinylguaiacol, and trans-isoeugenol) than those with shorter chains (guaiacol, 4-methylguaiacol) and an increase of anhydrosugar (AHS) were found among the pyrolysis products after heat treatment. These signs for autocondensation and side chain cleavages in the lignin during heat treatment were more evident in the EW than in the LW and for the crystallization of cellulose. A slight decrease of the carbohydrate/lignin ratio (C/L) after heat treatment indicates a greater degradation of carbohydrates compared to lignin. The relation of pyrolysis products of lignin and mechanical properties of wood was evaluated by regression analysis. An inverse correlation between short-chain phenols and MOE and a direct correlation between long-chain phenols and compression strength was found in case of NT wood, while a weak positive correlation could be observed between short-chain phenols and the density in T wood.     

Evaluation of cure conditions for polyimide thin films by pyrolysis–mass spectrometry

Films of a BTDA–mPDA–ODA polyimide copolymer (DuPont Pyralin PI-2555) were spincoated onto silicon wafers and cured at either 300 or 350°C. Films cured at each temperature were then analyzed by various pyrolysis mass spectrometric methods. Low-temperature pyrolysis mass spectrometry showed that polyimide films cured at the lower temperature contained more residual water and N-methyl pyrrolidone solvent than did the films cured at the higher temperature. High-temperature pyrolysis mass spectrometry of the two samples showed subtle differences in the mass spectrum of the polyimide pyrolysate under electron impact (EI) ionization conditions. Principal components analysis was used to differentiate between the EI mass spectra of the high-and low-temperature cured films. Several pyrolysis products, primarily aromatic hydrocarbon and heterocyclic fragments, were separated and identified by gas chromatography/mass spectrometry.     

Kinetics of the pyrolysis of cellulose in the temperature range 250–300°C.

Samples of α-cellulose, containing 0.11–0.14% ash, were isothermally pyrolyzed in a fluidized bath in a nitrogen environment at 250–298°C. Results were reported in terms of volatilization (based on weight-loss measurements) and decomposition (in term of glucosan loss). The findings show three distinct stages of pyrolysis: (1) an initial period of rapid decomposition and weight loss; (2) a range in which both the volatilization and decomposition are of zero order; (3) a region in which the volatilization follows a first-order rate, leaving a char deposit which does not undergo further pyrolysis. The degree of decomposition and volatilization occurring during the zero-order phase increases with increasing temperature. A single activation energy of 42 kcal./mole describes both the decomposition and volatilization rates in the zero-order phase over the entire 250–298°C. range.     

Thermogravimetric and differential thermal analysis of cellulose,hemicellulose, and lignin

The thermal degradation of samples of cellulose, hemicellulose, and lignin have been investigated using the techniques of thermogravimetric analysis (TGA) and differential thermal analysis (DTA) between room temperature and 600°C. The results calculated from static and dynamic TGA indicated that the activation energy E for thermal degradation for different cellulosic, hemicellulose, and lignin samples is in the range 36–60, 15–26, and 13–19 kcal/mole, respectively. DTA of all the wood components studied showed an endothermic tendency around 100°C in an atmosphere of flowing nitrogen and stationary air. However, in the presence of flowing oxygen this endothermic effect was absent. In the active pyrolysis temperature range in flowing nitrogen and stationary air atmospheres, thermal degradation of Avicel cellulose occurred via a sharp endothermic and a sharp exothermic process, the endothermic nadir and exothermic peak being at 320° and 360°C, respectively. In the presence of oxygen, combustion of Avicel cellulose occurred via two sharp exothermic processes. DTA studies of different cellulose samples in the presence of air showed that the shape of the curve depends on the sources from which the samples were prepared as well as on the presence of noncellulosic impurities. Potassium xylan recorded a sharp exothermic peak at 290°C in a nitrogen atmosphere, and in a stationary air atmosphere it yielded an additional peak at 410°C, while in the presence of oxygen the curve showed two sharp exothermic peaks. DTA traces of periodate lignin in flowing nitrogen and air were the same and showed two exothermic peaks at 320° and 410°C, while in the presence of oxygen there were two exothermic peaks in the temperature range 200°–500°C.     

Fast pyrolysis of glucose‐based carbohydrates with added NaCl part 2: Validation and evaluation of the mechanistic model

A mechanistic model considering the significant catalytic effects of Na⁺ on fast pyrolysis of glucose‐based carbohydrates was developed in Part 1 of this study. A computational framework based on continuous distribution kinetics and mass action kinetics was constructed to solve the mechanistic model. Agreement between model yields of various pyrolysis products with experimental data from fast pyrolysis of glucose‐based carbohydrates dosed with NaCl ranging from 0–0.34 mmol/g at 500 °C validated the model and demonstrated the robustness and extendibility of the mechanistic model. The model was able to capture the yields of major and minor products as well as their trends across NaCl concentrations. Modeling results showed that Na⁺ accelerated the rate of decomposition and reduced the time for complete thermoconversion of carbohydrates. The sharp reduction in the yield of levoglucosan (LVG) from fast pyrolysis of cellulose in the presence of NaCl was mainly caused by reduced decomposition of cellulose chains via end‐chain initiation and depropagation due to Na⁺ favoring competing dehydration reactions. Analysis of the contributions of reaction pathways showed that the decomposition of LVG made a minor contribution to its yield reduction and contributed less than 0.5% to the final yield of glycolaldehyde from fast pyrolysis of glucose‐based carbohydrates in the presence of NaCl. © 2015 American Institute of Chemical Engineers AIChE J, 62: 778–791, 2016     

Thermal degradation behavior and gas phase flame‐retardant mechanism of polylactide/PCPP blends

The thermal degradation behavior of the blend based on polylactide (PLA) and poly(1,2‐propanediol 2‐carboxyethyl phenyl phosphinate) (PCPP) was investigated by the thermogravimetric analysis (TGA). Thermal degradation activation energies (E_a) of neat PLA and PLA/15% PCPP blend were calculated via the Flynn–Wall–Ozawa method. The E_a of the blends increased with the addition of PCPP increasing when the conversion was higher than 10%. In addition, the appropriate conversion models for the thermal degradation process of PLA and PLA/15% PCPP were studied via the Criado method. At the same time, the main gaseous decomposition products of PLA and its blend were identified by TGA/infrared spectrometry (TGA–FTIR) analysis. And it revealed that the PCPP improved the flame‐retardant property of PLA via altering the release of the flammable gas and nonflammable gas. Moreover, the PCPP improved the flame‐retardant property of PLA by inhibiting exothermic oxidation reactions in the combustion, which was further proved by pyrolysis–gas chromatography–mass spectrometry analysis. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40480.     

Thermal degradation of polymers. part IV. Vacuum pyrolysis of poly(m-aminostyrene). The residue and the fraction volatile at pyrolysis temperature involatile at room temperature

The effect of the extent of degradation of poly(m–aminostyrene) on the quantity and composition of the residue and the effect of pyrolysis temperature on the fraction volatile at pyrolysis temperature are discussed. The behavior of poly(m–aminostyrene) is compared to that of polystyrene; a significant difference has been found for the behavior of the residue from poly(m–aminostyrene), which is ascribed to a crosslinking reaction involving the amino substituent. Mechanisms to acount for the observed products of degradation have been suggested and are discussed. Relative thermal stability studies have also been made and compared with results from polystyrene.     

Fast pyrolysis of glucose‐based carbohydrates with added NaCl part 1: Experiments and development of a mechanistic model

Sodium ions, one of the natural inorganic constituents in lignocellulosic biomass, significantly alter pyrolysis behavior and resulting chemical speciation. Here, experiments were conducted using a micropyrolyzer to investigate the catalytic effects of NaCl on fast pyrolysis of glucose‐based carbohydrates (glucose, cellobiose, maltohexaose, and cellulose), and on a major product of cellulose pyrolysis, levoglucosan (LVG). A mechanistic model that addressed the significant catalytic effects of NaCl on the product distribution was developed. The model incorporated interactions of Na⁺ with cellulosic chains and low molecular weight species, reactions mediated by Na⁺ including dehydration, cyclic/Grob fragmentation, ring‐opening/closing, isomerization, and char formation, and a degradation network of LVG in the presence of Na⁺. Rate coefficients of elementary steps were specified based on Arrhenius parameters. The mechanistic model for cellulose included 768 reactions of 222 species, which included 252 reactions of 150 species comprising the mechanistic model of glucose decomposition in the presence of NaCl. © 2015 American Institute of Chemical Engineers AIChE J, 62: 766–777, 2016     

The pyrolysis of cellulose derivatives

The thermal degradation in vacuo of ethyl cellulose and cellulose acetate in the form of very thin films or bulk material between 230° and 320°C has been studied. With the ethyl cellulose films, volatilization (as measured by weight loss) was a first-order process up to about 50% reaction, with an activation energy of 208 kJ/mole. This is about the same as that associated with the initial drop in intrinsic viscosity of the solid during bulk pyrolysis, in which very high molecular weight material, probably crosslinked, was formed at a later stage. The volatile products from ethyl cellulose included H₂O, CO, CO₂, C₂H₄, C₂H₆, C₂H₅OH, CH₃CHO, unsaturated aliphatic compounds, and furan derivatives. Acetic acid and acetyl derivatives of D -glucose were produced from cellulose acetate. It is suggested that the polymers degrade by radical chain mechanisms, and a number of possible elementary steps are proposed.     

CO2 gasification of wood charcoals derived from vacuum and atmospheric pyrolysis

The gasification of biomass derived char obtained via vacuum and atmospheric pyrolysis of Populus tremuloides has been studied in the ranges of 725–960°C and 0.1 to 6 MPa. CO₂ was used as the oxidizing gas. The results show that char reactivity is influenced by the preheating rates and that pressure effects are significant between 850°C and 950°C. A correlation based on the expression: df/dt = k₀{exp(-E/RT)}(1 - f)^af^βP^yCO₂ was used to fit the experimental data. In general, vacuum pyrolysis derived char showed a higher reactivity than atmospheric pyrolysis chars. An explanation based on a higher oxygen content of the vacuum pyrolysis char is suggested.