Composition and structure of low-molecular-weight products of thermal oxidative degradation of atactic polypropylene

The composition and structure of low-molecular-weight products of thermal oxidative degradation of atactic polypropylene were studied.     

Structure of products of thermal oxidative degradation of atactic polypropylene

The structure of oxidized atactic polypropylene was studied.     

Copper carboxylate formation in the thermal oxidative degradation of atactic polypropylene on copper oxide films

The thermal oxidation of atactic polypropylene on CuO_0.67 surfaces in air was studied using IR reflection-absorption spectroscopy. Degradative losses of primary, secondary, and tertiary alkyl hydrogens were observed. At 60 and 73°C, carboxylic acids are the primary degradation products, while at 85 and 100°C, copper carboxylate formation predominates and CuO_0.67 is decomposed. The distinct change in the oxidative mechanisms between 73 and 85°C apparently is related to an irreversible thermal transition in the atactic polypropylene films, which may favor carboxylate production by increasing the permeability of the films to oxygen and water vapor.     

Study of the composition of low-molecular products of the thermal oxidative destruction of atactic polypropylene by gas chromatography/mass spectrometry

The paper presents the results of studying the composition of low-molecular products of the thermal oxidative destruction of atactic polypropylene by gas chromatography/mass spectrometry. Special attention has been paid to the investigation of the mass spectra of compounds dominating in the composition of low-molecular products of the incomplete oxidative destruction of the original polymer, carried out for the synthesis of components for composite materials of the new generation. The most probable molecular structures of the studied compounds are determined on the basis of fragmentation patterns.     

The oxidative thermal degradation of polypropylene and the influence of transition metal chelates

Thermoanalytical techniques have been used to investigate the oxidative thermal degradation of polypropylene with special reference to the inhibiting effects of certain metal chelates. The inhibiting efficiency, defined in terms of the difference in temperature between the melting point of the polymer and the temperature of onset of exothermic oxygen uptake, has been determined for each additive using differential thermal analysis (DTA). The exothermicity of polypropylene oxidation has also been estimated.     

Atactic polypropylene thermal degradation test

Atactic polypropylene was subject to thermal treatment the temperature range 200–260°C for 2–4 h. Polymer structure changes assessment was made by derivatograph.     

Reaction of products of thermal and thermal oxidative degradation of polyvinyl chloride with barium hydroxide

The reaction of products of thermal and thermal oxidative degradation of polyvinyl chloride with barium hydroxide was studied. The degree of binding of chlorine and carbon atoms from polyvinyl chloride in reactions of barium hydroxide with hydrogen chloride and carbon dioxide formed by degradation and oxidation of the polymer was studied in relation to the hydroxide/polymer weight ratio and temperature. The activation energies of the reaction and the specific rates of formation of barium chloride and carbonate were calculated.     

Aging and degradation of polyolefins. I. Peroxide-initiated oxidations of atactic polypropylene

Efficiencies of polymer radical production by thermal decomposition of di-tert-butylperoxy oxalate (DBPO) have been measured in bulk atactic polypropylene (PP) at 25–55°C; they range from 1 to 26%, depending on [DBPO], temperature, and presence of oxygen. Most of the polymer radicals thus produced disproportionate in the absence of oxygen but form peroxy radicals in its presence. Most of the pairs of peroxy radicals interact by a first-order reaction in the polymer cage. The fraction that escapes gives hydroperoxide in a reaction that is half order in rate of initiation. In interactions of polymer peroxy radicals, in or out of the cage, about one-third give dialkyl peroxides and immediate chain termination, two-thirds give alkoxy radicals. About one-third of the later cleave at 45°C; the rest abstract hydrogen to give hydroxy groups and new polymer and polymer peroxy radicals. The primary peroxy radicals from cleavage account for the rest of the chain termination. Cleavage of alkoxy radicals and crosslinking of PP through dialkyl peroxides nearly compensate. Up to 70% of the oxygen absorbed has been found in hydroperoxides. The formation of these can be completely inhibited, but cage reactions are unaffected by inhibitors. Concentrations of free polymer peroxy radicals have been measured by electron spin resonance and found to be very high, about 10^?3M at 58–63°C. Comparison with results on 2,4-dimethylpentane indicate that rate constants for both chain propagation and termination in the polymer are much smaller than those for the model hydrocarbon but that the ratio, k_p/(2k_t)^½, is about the same.     

Stabiliser partitioning and oxidative degradation in rubber-toughened polypropylene

Solubility measurements on an antioxidant and a UV stabiliser in polypropylene and an ethylene/propylene rubber are correlated with partitioning between the two bulk polymers and between the phases of a blend. At low concentrations, partitioning concentrates the additive in the rubber; the effect increases with temperature, so that most of the additive will be in this phase at processing temperatures. Calculations suggest that the additives can diffuse between phases fast enough to compensate for consumption in either at service temperatures. At processing temperatures, diffusion of antioxidant from the more stable rubber phase to the polypropylene phase may be slow enough to limit protection from oxidation.     

Autoxidation kinetics of atactic polypropylene in bulk

The kinetics of the reaction between atactic polypropylene (APP) and oxygen in bulk at temperatures ranging from 170 to 210°C and oxygen partial pressures from 160 to 760 torr have been studied by thermal differential analysis. The reaction takes place in two successive steps, both giving hydroperoxide groups as product. Partial reaction orders with respect to APP and oxygen for the first step, which corresponds to the uncatalyzed attack of a C? H tertiary bond to give a hydroperoxide, are one and two, respectively. In the second step, interpreted as another attack on a tertiary C? H by oxygen, catalyzed by a neighboring hydroperoxide group, reaction orders are one and one-half for APP and oxygen, respectively. Activation parameters have been determined and a reaction sequence is proposed. Hydroperoxidated APP subsequently decomposes via a zero-order process giving methylketone groups as its main product. An interpretation of this process is also given.     

Miscibility of isotactic polypropylene with atactic polystyrene

The miscibility of isotactic polypropylene-atactic polystyrene blends using dilatometric, TOA, DAT and stress-strain methods were studied. It appears that the blends are heterogeneous, having two glass transition temperatures. However, some interactions between components are evident to change theTgs of their amorphous phases and theTm of isotactic polypropylene crystals. The results are discussed on the basis of the blends' thermal and tensile properties.     

Kinetic study of anhydride formation during thermal degradation of isotactic and atactic polymethacrylic acid

A kinetic study of anhydride formation in isotactic and atactic polymethacrylic acids (PMA) has been performed at about 200° using a vacuum thermobalance. The results obey first order kinetics and show that the rate of water loss is about four times higher for the isotactic PMA than for the atactic isomer. The activation energies are almost identical (42 ± 1 kcal per mole); it is concluded that the arrangement of neighbouring carboxyl groups is more favourable for the formation of a cyclic anhydride by intramolecular reaction in the case of the isotactic PMA.     

Kinetics of styrene homogeneous polymerization to atactic polypropylene

The rate of polymerization of styrene initiated by hydroperoxidized atactic polypropylene in a homogeneous toluene solution has been measured at 60 and 70°C. The reaction is first-order with respect to styrene concentration and independent of the polymeric hydroperoxide concentration above 2 × 10^?5N hydroperoxide. The individual rate constants, length and frequency of the grafted polystyrene chains along the polypropylene backbone have been calculated and their significance discussed. The initiation rate constant compares closely with values reported for the analogous tert-butyl hydroperoxide-initiated polymerization. The rate constant for the chain transfer termination elementary step at 70°C., however, is 18 times the value reported for the tert-butyl hydroperoxide-initiated polymerization of styrene. This high constant accounts for the relatively low rates of polymerization observed and high termination rates. Chain deactivation is presumably accelerated by increased collisions between growing styrene chains and inactive propylene hydroperoxide and polystyrene molecules. Distribution of polystyrene grafts on polypropylene is estimated from knowledge of effects of styrene concentration, polymeric hydroperoxide concentration, and temperature upon the rate of polymerization.     

The origins of volatile oxidation products in the thermal degradation of polypropylene, identified by selective isotopic labeling

Making use of polypropylene samples that are selectively labeled with carbon-13 at each of the three unique positions within the repeating unit, we are conducting mass spectral analyses of the volatile organic oxidation products that are produced when the polymer is subjected to elevated temperature in the presence of air. By examination of both the parent and fragmentation ion peaks in the mass spectrum, we are able to identify the positioning of the C-13 labels within the volatile compounds, and thereby map each compound onto its site of origin from within the macromolecular structure of polypropylene. Most of the organic oxidation products are remarkably specific in terms of their genesis from the polymer. The structural results are discussed in terms of the oxidation chemistry of the macromolecule.     

Temperature dependence of free volume in atactic polypropylene

Positron annihilation lifetime spectroscopy data are often used to get information on the typical sizes of sub nanometric holes forming the free volume in polymers. To this purpose, the cavities are modelled as spheres or, more generally, using geometries which assume an isotropic expansion with the temperature. However, this guess could be unrealistic owing to the irregular shape of holes and the constrained movements of the macromolecules.In this work positron and dilatometric data are used to estimate the free volume fraction in atactic polypropylene. Comparison with the prediction of the Simha–Somcynsky theory supplies information on the thermal dependence of the volume of holes, whose behaviour can be interpreted in terms of anisotropic expansion.     

Kinetics of thermal degradation and thermal oxidative degradation of poly(p-dioxanone)

The kinetics of the thermal degradation and thermal oxidative degradation of poly(p-dioxanone) (PPDO) were investigated by thermogravimetric analysis. Kissinger method, Friedman method, Flynn-Wall-Ozawa method and Coats-Redfern method have been used to determine the activation energies of PPDO degradation. The results showed that the thermal stability of PPDO in pure nitrogen is higher than that in air atmosphere. The analyses of the solid-state processes mechanism of PPDO by Coats-Redfern method and Criado et al. method showed: the thermal degradation process of PPDO goes to a mechanism involving random nucleation with one nucleus on the individual particle (F₁ mechanism); otherwise, the thermal oxidative degradation process of PPDO is corresponding to a nucleation and growth mechanism (A₂ mechanism).     

Kinetic of pyrite thermal degradation under oxidative environment

Journal of Thermal Analysis and Calorimetry - Pyrite is the most common mineral in polymetallic sulphides ores. In order to apply the combustion group theory to the pyrometallurgical processes that...