A study of the degradation of ester-modified epoxy resins obtained by cationic copolymerization of DGEBA with γ-lactones initiated by rare earth triflates

The thermal degradation of new thermosetting materials prepared by cationic copolymerization of mixtures with different proportions of diglycidylether of bisphenol A (DGEBA) with γ-valerolactone (γ-VL) or α-methyl-γ-butyrolactone (γ-MBL) initiated by scandium, ytterbium or lanthanum triflate and a complex of boron trifluoride was investigated. To study the thermal degradation thermogravimetry (TGA) was used. The materials are more degradable than conventional epoxy resins due to the presence of ester groups in the polymer chain, which are broken at the beginning of degradation. The degradability increased with the proportion of linear ester groups and the Lewis acidity of the initiator used in the polymerization and when the proportion of lactone in the initial mixture increased. The kinetic parameters of the degradation were calculated from TGA data by applying isoconversional procedures.     

Thermal degradation of linear polyurethanes and model biscarbamates

Thermal degradation of model biscarbamates, polyurethanes and poly(urethane-ureas) has been investigated by pyrolysis at atmospheric pressure. The biscarbamates were prepared from phenyl, benzyl, and cyclohexyl isocyanate and ethylene glycol. The polyurethanes and poly(urethane-ureas) were prepared from tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), and 4,4′-dicyclohexylmethane diisocyanate (H₁₂-MDI) and poly(oxyethylene glycols) of various molecular weights. Rate constants for thermal degradation were obtained by measuring carbon dioxide evolution. The thermal degradation of all materials showed that the stability increased in the following manner: aromatic < aralkyl < cycloaliphatic. The separation and identification of the products of the thermal degradation gave an insight into the mechanisms involved in the pyrolysis of aromatic, aralkyl, and cycloaliphatic biscarbamates and the influence of temperature on these mechanisms.     

Cationic copolymerization of diglycidyl ether of bisphenol A with phthalide or 3,3′‐diphtalide catalyzed by lanthanide triflates

Mixtures of the diglycidylether of bisphenol A (DGEBA) and phthalide (PT) or 3,3′‐diphthalide (DPT) were cured using ytterbium or lanthanum triflate as catalyst. The curing was studied by differential scanning calorimetry (DSC) and Fourier transform infrared in attenuated‐total‐reflection mode (FTIR/ATR). FTIR/ATR was used to monitor the competitive reactive processes and quantify the evolution of the epoxide and lactone groups. The T_g of the crosslinked materials increased when the proportion of lactone in the curing mixture decreased. The kinetics was studied with DSC experiments and isoconversional procedures. The differences in the reactivity of the systems were related to the Lewis acidity of the lanthanide salt used as initiator. The increase in the proportion of lactone leads to an increase in the reaction rate. The shrinkage was determined from the densities before and after curing and its evolution was studied by thermomechanical analysis. The materials obtained were characterized by thermogravimetry and dynamic mechanical thermal analysis. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1711–1721, 2006     

Products of low-temperature pyrolysis of nanocellulose esters and implications for the mechanism of thermal stabilization

Esterification was used to improve the thermal stability of nanocellulose to extend its application as reinforcing filler to polymer matrices with high melting point. The effect of the structure of ester groups on thermal stability was studied in detail. Various types of nanocellulose esters (straight-chain, C2–C14; cyclic adamantoyl, ADM; aromatic benzoyl, BNZ; and branched pivaloyl, PIV) with degree of substitution values in the range of 0.40–0.47 were prepared from bacterial cellulose nanofibers and nanocrystals. The reaction conditions used to prepare the esters maintained the viscosity-average degree of polymerization (DPv) and crystallinity of the starting materials. Thermogravimetric analysis showed that the temperature at maximum weight loss rate (T_max) increased after esterification. The structure of the ester groups and the DPv, however, showed no varying effect on T_max. The 5 % weight loss temperature (WLT) which was used to assess the thermal stability at the onset of thermal degradation varied with the type of ester. Lower 5 % WLT was observed in straight-chain esters than those of the bulky esters of ADM, BNZ and PIV; which also showed high resistance to weight loss when subjected to isothermal heating. To understand the event at the onset of thermal degradation, low temperature pyrolysis was conducted. The evolved gases were separated and identified by gas chromatography–mass spectrometry technique. Results showed that at the onset of thermal degradation, levoglucosan (LG) is produced from the untreated BC nanocrystals. After esterification, LG formation was inhibited. The removal of the ester groups or deprotection is the main event at the onset of thermal degradation of nanocellulose esters. From the structure of the pyrolysis products, the mechanism of thermal deprotection of nanocellulose esters is proposed for the first time.     

Thermal stability and degradation kinetics of novel organic/inorganic epoxy hybrid containing nitrogen/silicon/phosphorus by sol-gel method

Hybrids containing silicon, phosphorous and nitrogen were prepared by the sol-gel method and compared with pure epoxy. The silicon, phosphorous and nitrogen components were successfully incorporated into the networks of polymer. Thermogravimetric analysis (TGA) was used for rapid evaluation of the thermal stability of different materials. The integral procedure decomposition temperature (IPDT) has been correlated the volatile parts of polymeric materials and used for estimating the inherent thermal stability of polymeric materials. The IPDT of pure epoxy was 464 °C and the IPDTs of hybrids were higher than that of pure epoxy. The thermal stability of hybrids increased with the contents of inorganic components. The inorganic components can improve the thermal stability of pure epoxy.Two methods have been used to study the degradation of hybrids containing silicon, phosphorous and nitrogen hybrid during thermal analysis. These investigated methods are Kissenger, Ozawa's methods. The activation energies (E_a) were obtained from these methods and compared. It is found that the values of E_a for modified epoxy hybrids are higher than that of pure epoxy. The hybrids of high activation energy possess high thermal stability.     

Novel flame‐retardant thermosets: Phosphine oxide‐containing diglycidylether as curing agent of phenolic novolac resins

Phosphorus‐containing novolac–epoxy systems were prepared from novolac resins and isobutyl bis(glycidylpropylether) phosphine oxide (IHPOGly) as crosslinking agent. Their curing behavior was studied and the thermal, thermomechanical, and flame‐retardant properties of the cured materials were measured. The T_g and decomposition temperatures of the resulting thermosets are moderate and decrease when the phosphorous content increases. Whereas the phosphorous species decrease the thermal stability, at higher temperatures the degradation rates are lower than the degradation rate of the phosphorous‐free resin. V‐O materials were obtained when the resins were tested for ignition resistance with the UL‐94 test. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3516–3526, 2004     

Mechanism and kinetics of thermal degradation of insulating materials developed from cellulose fiber and fire retardants

The mechanism and kinetics of thermal degradation of materials developed from cellulose fiber and synergetic fire retardant or expandable graphite have been investigated using thermogravimetric analysis. The model-free methods such as Kissinger–Akahira–Sunose (KAS), Friedman, and Flynn–Wall–Ozawa (FWO) were applied to measure apparent activation energy (E_α). The increased E_α indicated a greater thermal stability because of the formation of a thermally stable char, and the decreased E_α after the increasing region related to the catalytic reaction of the fire retardants, which revealed that the pyrolysis of fire retardant-containing cellulosic materials through more complex and multi-step kinetics. The Friedman method can be considered as the best method to evaluate the E_α of fire-retarded cellulose thermal insulation compared with the KAS and FWO methods. A master-plots method such as the Criado method was used to determine the possible degradation mechanisms. The degradation of cellulose thermal insulation without a fire retardant is governed by a D3 diffusion process when the conversion value is below 0.6, but the materials containing synergetic fire retardant and expandable graphite fire retardant may have a complicated reaction mechanism that fits several proposed theoretical models in different conversion ranges. Gases released during the thermal degradation were identified by pyrolysis–gas chromatography/mass spectrometry. Fire retardants could catalyze the dehydration of cellulosic thermal insulating materials at a lower temperature and facilitate the generation of furfural and levoglucosenone, thus promoting the formation of char. These results provide useful information to understand the pyrolysis and fire retardancy mechanism of fire-retarded cellulose thermal insulation.

     

Sol–gel doped TiO<Subscript>2</Subscript> nanomaterials: a comparative study

Among the great number of sol–gel prepared nanomaterials, TiO₂ has attracted significant interest due to its high photocatalytic activity, excellent functionality, thermal stability and non-toxicity. The photocatalytic degradation of pollutants using un-doped and doped TiO₂ nanopowders or thin films is very attractive for applications in environmental protection, as a possible solution for water purification. The present work describes a comparative structural and chemical study of un-doped TiO₂ and the corresponding S- and Ag-doped materials. The photocatalytic activity was established by testing the degradation of organic chloride compounds from aqueous solutions. Sol–gel Ag-doped TiO₂ coatings, prepared by co-gelation and sol–gel Ag-doped TiO₂ coatings obtained from nanopowders were also compared. Their structural evolution and crystallization behaviour (lattice parameters, crystallite sizes, internal strains) with thermal treatment were followed by thermal analysis, X-ray diffraction, transmission electron microscopy, atomic force microscopy and specific surface areas measurements. X-ray photoelectron spectroscopy analyses were performed to characterize the surface composition and S or Ag speciation, which was used to interpret the catalytic data.     

Study on the effect of rare earth metal triflates as initiators in the cationic curing of DGEBA/γ-valerolactone mixtures and characterization of the thermosets obtained

The thermal cationic curing of mixtures in different proportions of diglycidylether of bisphenol A (DGEBA) with γ-valerolactone (γ-VL) initiated by scandium, ytterbium and lanthanum triflates or a conventional BF₃·MEA initiator was investigated. The non-isothermal differential scanning calorimetry (DSC) experiments at a controlled heating rate were used to evaluate the evolution of the reactive systems. BF₃·MEA and rare earth metal triflates initiated curing systems follow a different evolution. Among rare earth metal triflates tested, the scandium was the most active initiator. The phenomenological changes that take place during curing were studied and represented in a time-temperature-transformation (TTT) diagram. Some characteristics of the materials were also evaluated.     

The remediation of wastewater containing 4-chlorophenol using integrated photocatalytic and biological treatment

In this work, the performance of integrated photocatalytic and biological treatment was studied for the degradation of 4-chlorophenol (MCP) present in wastewaters. Photocatalysis was used as a pre-treatment to biological degradation. Pollutant removal efficiency was quantified using MCP removal and total organic carbon (TOC) removal. Both photocatalytic as well as biological treatments were carried out in batch reactors, using TiO₂ as the photocatalyst. The inoculum for biological experiments was obtained from paper mill effluent treatment plant and was developed through a process of selection and acclimatization. Effect of TiO₂ concentration on the photocatalytic degradation of MCP was studied along with the effect of the duration of photochemical oxidation and glucose concentrations (0 g/L, 1 g/L and 2 g/L) on the biodegradation of MCP. Integrated biological and photochemical degradation was found to be more effective in treating MCP, especially at higher concentrations (400 mg/L). An initial MCP concentration of 400 mg/L required 96 h for complete mineralization when treated with the process combination, whereas the treatment went on up to 264 h when biodegradation alone was employed.     

Synthesis and thermal properties of cellulose-based polycaprolactones

Cellulose-based polycaprolactone (CAPCL) sheets were prepared from cellulose acetate (CA) and ϵ-caprolactone (CL). Thermal properties of the obtained CAPCL's were studied by differential scanning calorimetry (DSC), thermogravimetry (TG) and TG-Fourier transform infrared spectrometry (TG-FTIR). The glass transition temperatures (T_g 's) of CAPCL decreased with increasing CL/OH ratio, until CL/OH ratio reached 15 and then increased above that ratio. Melting of CAPCL was observed when CL/OH ratio was over 10. The thermal degradation temperatures (T_d 's) of CAPCL increased from ca. 350 °C to 390 °C with increasing CL/OH ratio. The results obtained by TG-FTIR analysis of CAPCL showed that gases with OH, CH, C=O, C-O-C groups evolved by thermal degradation.     

A comparative study on thermal and catalytic degradation of polybutylene terephthalate

A comparative study on the thermal and catalytic degradation of polybutylene terephthalate (PBT) at atmospheric pressure was conducted. The weight loss of PBT under thermal degradation was significantly influenced by the temperature between 360 °C and 380 °C, but little affected by the PBT particle size. Four groups of catalysts include metal chloride, metal oxide, metal acetate, and metal copper powder were used to test PBT degradation activity. Copper (II) chloride is the most active one for increasing the percentage PBT weight loss more than 100% in comparison with the result of thermal degradation at a temperature of 360 °C for 30 min. PBT and catalyst mixtures can be prepared by impregnation and physical method, the former resulted in a better PBT degradation. The percentage PBT weight loss in the presence of CuCl₂ increased steadily between 320 °C and 380 °C which was different from the results of thermal degradation. The time for obtaining a same percentage PBT weight loss reduced effectively when compared to the catalytic to thermal degradation. The weight ratio of CuCl₂/PBT was tested between 0 and 0.2 and the optimal ratio was 0.1. The gaseous product distribution analyzed by GC/MS for PBT thermal and catalytic degradation revealed almost the same and the major products were ethane, carbon monoxide, carbon dioxide, 1-butene, 2-butene, 1,3-butadiene, and butadiene dimmer. But the relative abundance of major products was changed, especially for 1,3-butadiene increased dramatically, and a new chlorocompound was produced in catalytic degradation. In condensed liquid product, both the number and the molar mass of components were more and greater than that of in gaseous product and 4-heptylacetophenone was the most abundance product. In PBT catalytic degradation, 4-heptylacetophenone and some products were decreased and some even disappeared completely while the abundance of benzoic acid increased and three new products were generated.     

Thermal properties of microcrystalline cellulose-filled PET–PTT blend polymer composites

Polymer composite materials were prepared from poly(ethylene terephthalate)–poly(trimethylene terephthalate) blends as the matrix and different microcrystalline cellulose (MCC) filler levels (0–40 wt%) using melt compounding followed by compression molding. The composites were analyzed using dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC) and thermogravimetric analysis (TG). The DSC results indicated that there is no consistent or significant influence of the MCC addition on the glass transition (T _g), melting (T _m), and crystallization temperature of the composites. With increasing MCC content, dynamic mechanical properties improved because of the reinforcing effect of the MCC. The tan δ peak values from the DMTA were not significantly changed as the MCC content increased. TG indicated that the onset temperature of rapid thermal degradation decreased with increasing MCC content. It was also found that the thermal stability of the composites slightly decreased as the MCC content increased.     

Synthesis and properties of mono- and bis[2-(dimethylaminomethyl)]cymantrenyl derivatives of ytterbium

The reaction of [2-(dimethylaminomethyl)]cymantrenyl]lithium with ytterbium diiodide affords [2-(dimethylaminomethyl)cymantrenyl]ytterbium iodide or bis[2-(dimethylaminomethyl)cymantrenyl]ytterbium depending on the ratio of the starting reactants. Reactions of these complexes with a series of electrophiles (H₂O, Me₃SiCl, MeCOCl, HgCl₂, PhCOCl) were studied and the corresponding derivatives of cymantrene were prepared in high yields.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No.3, pp. 531–533, March, 1994.     

Effect of auxiliary chemicals on preparation of silica MCM-41

Silica MCM-41 materials were prepared hydrothermally by using 1,3,5-trimethylbenzene (MS) or 1,3,5-triisopropylbenzene (TI) as an auxiliary chemical. The BJH poressize of MCM-41 increased up to 12 nm with increasing amounts of MS. However, MCM-41 materials prepared with MS displayed irregular pore arrangements and a half of these materials exhibited low thermal and hydrothermal stabilities. On the other hand, MCM-41 materials prepared with TI as an auxiliary chemical displayed regular pore arrangements and high thermal and hydrothermal stabilities, but their BJH pore sizes did not go over 4.0 nm (intrinsic value; ca. 5 nm). MCM-41 prepared with TI together with a small amount of MS (TI/MS/SiO₂=1.5/0.5/1) displayed regular pore arrangements and high thermal and hydrothermal stabilities. Its BJH pore size was 4.7 nm (intrinsic value; ca. 6 nm).     

Thermal degradation study of gadolinium and lutetium methanesulfonates

The synthesis, characterization and thermal degradation study of gadolinium and lutetium methanesulfonates is reported. The prepared salts were characterized by elemental analysis and infrared spectroscopy. The thermal degradation study was performed by using thermogravimetry (TG), differential thermal analysis (DTA) and differential scanning calorimetry (DSC). By using thermogravimetric data, a kinetic study of the dehydration of Gd and Lu methanesulfonates is performed employing the Coats-Redfern and Zsakó methods. It is verified that under heating, the gadolinium and lutetium methanesulfonates suffer three main processes: dehydration, thermal degradation and oxide formation. The thermal degradation products were characterized by infrared spectroscopy and X-diffractometry. Furthermore, depending on the atmosphere nature, i.e. inert or oxidant, the thermal degradation process could be endothermic (N₂) or exothermic (air).     

Effect of the remaining lanthanide catalysts on the hydrolytic and enzymatic degradation of poly-(ϵ-caprolactone)

Poly-(ϵ-caprolactone) is a biodegradable polymer, which can be used for both medical and environmental applications. Due to its multiple applications the synthesis of such a polymer has been attracting an increasing attention in the past few decades. In our work, the polymers were synthesised by bulk polymerisation, using different lanthanide halides as initiators. The lanthanide derivatives are known as very active catalysts in the ring-opening polymerisation of cyclic esters. Moreover, they are not toxic in comparison of catalysts, which are usually used for this synthesis. In this paper, the influence of the lanthanides on both the hydrolytic and enzymatic degradation of the PCL obtained by ring-opening polymerization of ϵ-caprolactone with different lanthanide-based catalysts such as: lanthane chloride (LaCl₃), ytterbium chloride (YbCl₃) and samarium chloride (SmCl₃) was assessed. Samarium seems to slightly accelerate the hydrolytic degradation of the polymer and to slow down or inhibit its enzymatic degradation, mainly when the molecular weight of the polymer is high. The behaviour of PCL containing another lanthanide like lanthane is dependent on the nature of the metallic ion. Complete degradation, by the Lipase PS from Pseudomonas cepacia, is achieved only with Ytterbium.     

The catalytic role of oxide in the thermooxidative degradation of poly(methyl methacrylate)-TiO2 nanocomposites

The influence of TiO₂ nanoparticles on the thermal degradation of poly(methyl methacrylate) (PMMA) was investigated by TGA. The studied materials were characterized by Py-GC-MS, TEM, SEM, TGA, DSC and TGA-MS. The PMMA-TiO₂ nanocomposites were prepared by melt blending with different (5, 10, 15 and 20 wt% TiO₂) loadings. According to TGA results and to the activation energy (determined by the model-free isoconversional method of Vyazovkin), the incorporation of 5 wt% of TiO₂ nanoparticles into PMMA stabilizes it by more than 40 °C. However, for higher loading contents, a catalytic effect on the thermal decomposition was observed which increased with the oxide content. The results obtained by Py-GC-MS showed clearly that TiO₂ increases the formation of methanol, methacrylic acid and propanoic acid methyl ester during the degradation of PMMA. This catalytic effect could be explained through the interaction of the methoxy group of the methacrylate function with the hydroxyl groups present at the surface of the oxide particles.     

Understanding of thermal/thermo-oxidative degradation kinetics of polythiophene nanoparticles

The polythiophene nanoparticles (nano-PT) were prepared with average diameter of 20–35 nm. The nanostructurals of polythiophene were confirmed by TEM and SEM analyzes. The kinetics of the thermal degradation and thermal oxidative degradation of nano-PT were investigated by thermogravimetric analysis. Kissinger method, Flynn–Wall–Ozawa method, and advanced isoconversional method have been used to determine the activation energies of nano-PT degradation. The results showed that the thermal stability of nano-PT in pure N₂ is higher than that in air atmosphere. The analyzes of the solid-state processes mechanism of nano-PT by Criado et al. method showed: the thermal degradation process of nano-PT goes to a mechanism involving second-order (F ₂ mechanism); otherwise, the thermo-oxidative degradation process of nano-PT is corresponding to a phase boundary controlled reaction mechanism (R ₂ mechanism).     

Synthesis and optical properties of non-stoichiometric lanthanide (Sm,Eu, Tm,Yb) fluorides

Nonstoichiometric samarium, europium, ytterbium, and thulium fluorides were prepared by reduction of the corresponding trifluorides with the same lanthanide metal or silicon. Crystal lattice type and lattice parameters of the compounds were determined by powder X-ray diffraction. In the synthesis of ytterbium fluoride, the formation of cubic superstructure Yb₂₇F₆₄ was detected. Data reflecting the relationship between the structure and optical characteristics of the phases (IR spectra, electronic diffuse reflectance spectra) were obtained and the spectral bands were assigned.