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

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

Thermal degradation of poly(alkyl acrylates). I. Preliminary investigations

A qualitative survey of the thermal degradation reactions which occur in poly(ethyl acrylate), poly(n-propyl acrylate), poly(isopropyl acrylate), poly(n-butyl acrylate) and poly(2-ethylhexyl acrylate) has been made by using three thermal analytical methods: thermogravimetric analysis (TGA), thermal volatilization analysis (TVA), and the dynamic molecular still (DMS), all combined with infrared and mass spectrometry. Degradation in poly(isopropyl acrylate), which is a secondary ester, becomes discernible at 260°C and proceeds in two stages. The other four polymers, which are all primary esters, are more stable. They degrade in a single-stage process starting at 300°C. The principal volatile products from the primary esters are carbon dioxide and the olefin and alcohol corresponding to the alkyl group. A roughly equivalent quantity of short-chain fragments is also formed. From poly(isopropyl acrylate), carbon dioxide and propylene are the only volatile products in the first phase of the reaction.     

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 analysis of blends of low density polyethylene, poly(ethyl acrylate) and ethylene ethyl acrylate copolymer with polydimethylsiloxane

The thermal stability of blends of polyethylene, poly(ethyl acrylate) and ethylene ethyl acrylate (EEA) copolymer with polydimethylsiloxane has been investigated in inert atmosphere using TG-DTC and TVA. The condensable volatile degradation products from the TVA experiments were separated by subambient TVA and investigated by FT-IR spectroscopy, GC., MS and GCMS techniques. The cold ring fraction was characterised by FT-IR spectroscopy and GC. Most of the degradation products from the blends were similar to the degradation products from polydimethylsiloxane and the corresponding polyolefin when degraded alone, but the presence of some additional products indicated interactions during degradation as a result of blending. The mechanisms of formation of degradation products from the blends are discussed in detail.     

Thermotropic liquid crystal behaviour of alkaline-earth-metal dihexadecyl phosphate salts

Alkaline-earth-metal dihexadecyl phosphate salts were synthesized, and their thermal stability was evaluated by thermogravimetry. Their thermotropic liquid crystal behaviour was investigated by differential scanning calorimetry, polarizing optical microscopy, dilatometry, and X-ray diffraction. On heating, the calcium, strontium, and barium salts exhibit columnar liquid crystal phases, whereas the less ionic beryllium and magnesium salts melt directly into isotropic liquids.     

Thermotropic liquid crystal behaviour of alkaline-earth-metal dihexadecyl phosphate salts

Alkaline-earth-metal dihexadecyl phosphate salts were synthesized, and their thermal stability was evaluated by thermogravimetry. Their thermotropic liquid crystal behaviour was investigated by differential scanning calorimetry, polarizing optical microscopy, dilatometry, and X-ray diffraction. On heating, the calcium, strontium, and barium salts exhibit columnar liquid crystal phases, whereas the less ionic beryllium and magnesium salts melt directly into isotropic liquids.     

Thermal degradation of the polyurethane from 1,4-butanediol and methylene bis(4-phenyl isocyanate)

A polyurethane prepared from 1,4-butanediol (BD) and methylene bis(4-phenyl isocyanate) begins to evolve volatile degradation products at approximately 240°C. By a combination of thermal analysis methods (TVA, TG, and DSC) and examination of the volatile and involatile products by using a combination of GLC and infrared and mass spectrometric analysis, it is shown that the total reaction comprises a primary depoly-condensation process in which the two monomers are formed, followed by the subsequent reaction of these monomers to form the volatile products, tetrahydrofuran, dihydrofuran, carbon dioxide, water, butadiene, hydrogen cyanide, and carbon monoxide and residual carbodiimide and urea structures. A mechanism, which accounts for all these products, has been formulated and tested.     

Additional purification of alkali or alkaline earth salts by using silica gel modified with pyrocatechol violet as a sorbent

Sorption of 14 metal ions on silica gel impregnated with a mixture of Aliquat 336 and Pyrocatechol Violet was investigated. It was found that alkali metals and calcium are not retained on the sorbent, magnesium is retained from solutions of pH > 6, contrary to other metal ions. The sorbent was used for purification of some salts from trace amounts of heavy metals and magnesium. Some metals ion mixtures have also been separated by using column extraction chromatography stepwise elution with perchloric acid solutions.     

Polysalt complexes of poly(vinylbenzo-18-crown-6) and of poly(crown acrylate)s with polyanions

Macrocyclic polyether or crown ether ester derivatives of acrylic and methacrylic acid were synthesized and polymerized. The cation binding properties of the polymers determined by extraction of picrate salts were similar to those obtained for poly(crown ether)s derived from styrene. In the presence of a crown-complexable cation both polymers form insoluble polysalt complexes with sodium carboxymethylcellulose, potassium poly(styrene sulfonate), and potassium polyacrylate. The extent of precipitation depends on the type and concentration of cation as well as on the ratio polyanion to poly(crown ether). The precipitate appears to have an equal number of positive and negative charges. An insoluble hydrogen-bonded complex is formed in the absence of salt when poly(vinylbenzo-18-crown-6) and poly(acrylic acid) are mixed in 0.01M HCl. Organic solutes bound to the poly(crown ether)s, which occur in an aqueous mixture of poly(vinylbenzo-18-crown-6) and picrate anions, are precipitated with the poly(crown ether) when the polysalt complex is formed.     

Thermal degradation of metal novolak precursors for high temperature superconductors: thermogravimetric and mass spectroscopy studies

High temperature superconductor (HTS) materials were prepared from novolak metal precursors in a special annealing process. In the present paper the thermal behaviour of pure cresol novolaks and novolak metal salt (nitrate) precursors was investigated by means of simultaneous thermogravimetric analysis and mass spectroscopy in air. The results show significant differences in thermal stability between the pure novolaks and the novolak metal precursors, with respect to the process as well as the products of decomposition. The main volatile products for the precursors are CO₂, H₂O and NO, thus indicating that the thermal degradation results in the formation of metal oxides at a temperature of about 300 °C.     

Preparation and degradation of copolymers of methyl methacrylate with alkali metal methacrylates—II: Thermal analysis of the copolymers,nature of the degradation products and general characteristics of the degradation reaction

Three series of copolymers, each spanning the composition range from alkali metal methacrylate homopolymer to methyl methacrylate homopolymer, have been prepared; their degradations have been studied under programmed heating conditions, by means of simultaneous thermogravimetry and thermal volatilization analysis (TVA) in a vacuum system and by differential thermal analysis in dynamic nitrogen. Total volatile products have been characterised by infrared spectroscopy, subambient TVA and GLC. The thermal analysis data suggest that the two types of monomer unit tend to participate in degradation processes in different temperature ranges. However, in addition to those products characteristic of the degradation of each homopolymer, the copolymers give substantial amounts of methanol; this product must arise from a reaction specific to the copolymer structure.     

Metal complexes of poly(acrylic acid): synthesis, characterization and thermogravimetric studies

Thermogravimetric studies of the sodium salt of poly(acrylic acid), its modified sodium salt and its various metal complexes were made. The thermal stabilities of the various systems decreased in the order: poly(acrylic acid) > Ni(II) > Co(II) > Zn(II) > Fe(III) > Cu(II) > polymeric sodium salt. The higher thermal stabilities of the polymer-metal complexes result from the development of stable ring structures in the polymer matrix upon coordination with metal ions. The metal-ion complexation of carboxylate ligands of linear poly(acrylic acid), optimization of the complexation conditions and infra-red and ultraviolet-visible spectrometric characterizations are also illustrated.     

Preparation and properties of some salts of perfluorooctanoic acid

The sodium, potassium, lithium, caesium, barium, calcium, silver, lead and ammonium salts of perfluorooctanoic acid were prepared. Their thermal stabilities, and some spectroscopic data are reported. An attempt is made to correlate some of these measurements with the properties of the metal ions or metals concerned.     

Thermal degradation behavior of blends of phenyl methacrylate-styrene copolymers with aluminum isopropoxide

Thermal degradation studies were carried out of copolymer phenyl methacrylate-styrene in the presence of aluminum isopropoxide to assess the stability and alteration of degradation mechanism using thermogravimetry-differential thermogravimetry (TG-DTG) in inert atmosphere and under vacuum using thermal volatilization analysis (TVA). After collecting the condensable volatile degradation products from TVA experiments and separating them by sub-ambient TVA, investigation and identification were effected out by IR spectroscopy and gas chromatography-mass spectrometry (GC-MS) techniques. The degradation products from the blends consisted of some additional products, i.e., isopropanol, phenol, methacrylic acid, ethyl benzene, benzene and a cyclic compound apart from similar products obtained from the degradation of pure copolymers. The mechanism of newly formed degradation products has been discussed in detail. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermal degradation of blends of polystyrene and poly-4-methoxystyrene with bisphenol A polycarbonate

Blends of polystyrene (PS) and poly-4-methoxystyrene (PMeS) with bisphenol A polycarbonate (PC) (1:1 by weight) have been studied using thermogravimetry (TG) and thermal volatilisation analysis (TVA). The condensable volatile products obtained in the TVA experiments were separated by subambient TVA and the less-volatile liquids were examined by GC-MS. The cold ring fraction of products was characterised by IR spectroscopy.

On degradation, both PS-PC and PMeS-PC blends show an interaction which is observed as a destabilisation. It is suggested that in the degrading blends, the PC component is destabilised as a result of transport of small radical species from the other polymer phase. These radicals may abstract hydrogen atoms, leading to an increase in backbone scission reactions and consequently a lower degradation temperature than when the polymer is degraded alone.     

Vaporization and thermal decomposition of transition metal salts in flameless atomic absorption spectrometry with a carbon tube atomizer

Vaporization and thermal decomposition of Cr, Mn, Fe, Co, Ni and Cu salts were investigated by measuring the absorption spectra observed when aqueous solutions of these salts were heated in the carbon tube atomizer. Gaseous metal halides are vaporized in the atomizer at temperatures above 300–500° C. SO₂ and NO are produced by thermal decomposition of metal sulfates and nitrates, respectively. The vaporization of metal halides is also confirmed by the spectra for solutions of metals in hydrochloric acid and for mixtures of metal nitrates and ammonium halides.     

Thermal degradation of chlorinated rubber: Evidence for an alternative cyclic structure for chlorinated rubber

The thermal degradation under vacuum or in nitrogen of commercial chlorinated rubber (ICI Alloprene, 64.5 wt.-% chlorine) was studied by isothermal thermogravimetry and by simultaneous TG/TVA with programmed heating by using a Cahn RG thermobalance built into a thermal volatilization analysis (TVA) system. Analysis of volatile products was performed by titration and by spectroscopic methods. The only major degradation product is hydrogen chloride; five-sevenths of the total available hydrogen chloride is lost with great ease, and complete dehydrochlorination is very much easier than in poly(vinylidene chloride). Conjugation develops early in the degradation, but the minor products methane, ethylene, and hydrogen are observed in the later stages of reaction. These features cannot be reconciled with the previously proposed cyclic structure for chlorinated rubber, and an alternative structure which accounts well for the degradation behavior is suggested.     

Thermal degradation of ammonium polymethacrylate and polymethacrylamide

The degradation of ammonium polymethacrylate and polymethacrylamide has been studied by a combination of thermal analysis methods (TVA and TG) and examination of volatile and involatile products by infrared analysis. It is shown that total reaction comprises an initial cyclization and further fragmentation of the modified chain at higher temperatures to yield gaseous volatiles. The partially degraded NH₄PMA contains anhydride ring and cyclic imide structures in the chain. Quantitative comparison of yields of isocyanic acid and carbon dioxide has shown that imidization is the major reaction and anhydride formation is of less importance. The mechanisms of the various reactions are discussed.     

Polymerization of 4-vinylpyridinium salts. III. A clarification of the mechanism of spontaneous polymerization

The mechanism of the spontaneous polymerization of 4-vinylpyiridine on quaternization or protonation has been investigated. Results indicate that initiation is caused by the nucleophilic attack of 4-vinylpyridine on the double bond of 4-vinylpyridinium ion. It was shown that halide ions do not contribute significantly to the initiation. In the case of acid salts of 4-vinylpyridine a hydrogen-transfer polymerization occurred to give an ionene polymer with pyridinium units in the main chain. The “matrix” polymerization of 4-vinylpyridine on poly(phosphoric acid) or poly(acrylic acid) also resulted in ionene formation. Conditions under which stable 4-vinylpyridinium salts can be obtained are discussed.     

Thermoanalytical properties of monobasic nitrilotriacetate salts of alkaline earth metals and zinc

Monobasic metal nitrilotriacetate hydrated salts, MH[N(CH₂COO)₃].xH₂O, have been prepared by the reaction of nitrilotriacetic acid with metal carbonate. DTA studies of these salts both in N₂ and air reveal that these salts initially undergo dehydration and then, through acetate intermediates, decompose to oxycarbonates or oxides.