A heterogeneous model for the thermal oxidation of solid polypropylene from chemiluminescence analysis

From an analysis of chemiluminescence (CL) curves from the isothermal oxidation of polypropylene powder and film, it is proposed that the usual homogeneous kinetic analysis of the sigmoidal increase in apparent oxidation rate with time is inappropriate and should be considered instead as a statistical accumulation of rapidly oxidizing centres. Over the temperature range 90–150°C it is found that the CL curves up to the maximum emission intensity may be reduced to a single sigmoidal master curve by plotting the data after the induction period in relative coordinates. Identical activation energies are observed for the initial emission and the maximum emission intensities, which suggests that throughout the oxidation there is no change in the CL mechanism, which requires the occurrence of a degenerately branched chain reaction within the oxidizing centres. The induction period shows a different temperature dependence and in the heterogeneous model is interpreted as the time required for the oxidation to spread from the initially localized centres. This model is able to explain the observations of volatile formation in the earliest stages of oxidation and the rapid crack formation at the end of the induction period as well as other anomalies which cannot be rationalized in a homogeneous kinetic model.     

A model for non-linear creep in polypropylene

Measurements of the creep behaviour of a polypropylene polymer under uniaxial tension have been modelled using a stretched exponential function with four parameters. Non-linear behaviour arises because one of the parameters, related to a mean retardation time for the relaxation process responsible for creep, is dependent on stress. Creep curves measured under a uniaxial tensile stress and a uniaxial compressive stress of the same magnitude are different. The differences can be described by relating the retardation time parameter to an effective stress that is determined by the magnitude of both the shear component of the stress and the hydrostatic component. This analysis has then been generalised to enable expressions to be formulated for creep behaviour under an arbitrary multiaxial stress state. This requires an assumption that either the Poisson's ratio or the bulk modulus is independent of time. The validity of this assumption has been evaluated through comparisons of predictions of creep under a pure shear stress with measurements, which show that a time-independent Poisson's ratio is the better approximation. Although not the main theme of the paper, examples are given illustrating the dependence of model parameters on the structure of the crystalline and amorphous regions of the polymer. This is particularly relevant to the application of the model to the analysis of the creep behaviour of welded polypropylene where properties will, in general, be influenced by the heat treatment.     

Thermal oxidation of clay-nanoreinforced polypropylene

The thermo-oxidation process at low temperatures for a montmorillonite-nanoreinforced polypropylene (PP) was studied. Experimental aging kinetic data at 100, 80 and 60 °C have been obtained and compared with a computational simulation in which a kinetic model based on the closed loop approach was used. As a result, it has been found that the montmorillonite role is not limited to a role of inert filler in the polymer matrix but induces a slight catalytic effect leading to induction period reduction. This effect has been well simulated by increasing initial hydroperoxyde concentration. The consequences of kinetic control by oxygen diffusion have also been investigated by using micro ATR-FTIR mapping to assess concentration profiles of the oxidation products across the sample thickness. It has been found that the oxidized layer thickness is close to 17 μm for the pure polypropylene whereas it is around 10 μm for the nanocomposite at 100 °C. These profile variations have been attributed to differences in oxygen diffusion coefficient values. Simulations based on the kinetic model including diffusion-reaction coupling describe these profiles well.     

A kinetic model for limonene oxidation

The kinetic regularities of the autooxidation of R(+)−limonene (LH) were experimentally studied at various temperatures. A kinetic model including the main elementary reactions and the corresponding rate constants was developed. The degenerate chain branching during limonene oxidation proceeds via bimolecular reactions and involves hydroperoxide LOOH + LH → L· + LO· + H₂O and LOOH + LOOH → LO· + LO₂ · + H₂O. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 80–86, January, 2008.     

Surfactant-modified polypropylene as a catalyst for oxidation of mercaptans

Surface modification of polypropylene by soluble metallophthalocyanine was performed. The effect of pretreatment of polypropylene on the degree of surface anchoring of the macrocycle was shown. The catalytic activity of the hybrid materials produced in the oxidation reaction of sodium diethyldithiocarbamate was determined.     

Analysis of the nonvolatile oxidation products of polypropylene I. Thermal oxidation

The nonvolatile products in thermal-oxidized polypropylene sheet have been quantitatively identified by infrared analysis and chemical reaction. The molecular weight changes with oxidation have been studied by gel-permeation chromatography. It was determined that there is a functional group at each end of a chain. A general oxidation mechanism scheme for polypropylene is presented. The discovery of γ-lactone is an indication of the importance of an intramolecular backbiting process. The overall functional group distribution is found to differ from that found in a polyethylene sheet.     

Chemiluminescence and inhibited oxidation of polypropylene

The efficiency of mixtures of the commercial antioxidants, Hostanox OSP 1, Irganox 1010 and distearylthiodipropionate was examined by chemiluminescence and oxygen uptake methods. Lower induction periods of oxidation, observed by the chemiluminescence method at 190°C, were found with samples which contain more of the less volatile additives. In accordance with earlier findings this is due to the surface nature of chemiluminescence which yields results close to those of the kinetic region.     

Hydroperoxide build-up in the thermal oxidation of polypropylene - A kinetic study

The thermal oxidation of unstabilised polypropylene (PP) was studied at 80 °C under various oxygen pressures: 0.02, 0.5 and 5.0 MPa, and, under 5.0 MPa oxygen pressure at various temperatures: 60, 80, 100 and 120 °C. Hydroperoxides were titrated using a chemical titration method and modulated DSC (taking an enthalpy of −325 kJ mol⁻¹). Starting from a previous kinetic analysis of carbonyl growth in same exposure conditions, we have tried to simulate experimental results by a model based on the classical mechanistic scheme in which initiation results from POOH (mainly bimolecular) decomposition. The model, which takes into account substrate consumption and does not rely on usual simplifying assumptions (steady state for radicals, long kinetic chains, interrelations between termination rate constants), generates kinetic curves with the same shape as experimental ones and predicts well the effect of O₂ pressure and temperature on hydroperoxide and carbonyl concentrations.     

Thermal oxidation of ester-modified isotactic polypropylene

The relationship between the thermal oxidation of isotactic PP samples modified by esters miscible and immiscible with the polymer and the structure of these samples has been studied. An analysis of kinetic features of oxygen uptake, buildup of oxidation products, and changes in the mechanical properties and structural parameters of PP in the course of oxidation has shown that the effect of a modifier on the kinetics of thermal oxidation of the polymer depends on compatibility of an additive and a polymer matrix. The addition of ester that is partially miscible with PP accelerates oxidation. In the case of an immiscible ester, the effect is quite the reverse. This phenomenon is rationalized by the fact that the phase state of the system determines changes in the initial structure of the polymer matrix and, hence, manifestation of structural effects in the reaction kinetics and the participation of additives in chain reactions of cooxidation with PP.     

Role of polymer morphology in the oxidation of polypropylene

The γ-initiated oxidation and presensitized photooxidation of polypropylene films and fibers are shown to be insensitive to sample thickness (if <150 μm) and a range of morphological parameters such as molecular orientation (in drawn samples) and fibrillar and void content. The relevance of these observations is discussed in the light of the many previous assertions as to the influence of morphological effects on oxidation rates. The γ-initiated oxidation was studied in preference to conventional thermal or photoinitiated oxidation because of the greater control over the rate of radical production available by this method.     

Vacuum-ultraviolet induced oxidation of the polymers polyethylene and polypropylene

The emission from low-pressure microwave plasmas in the vacuum-ultraviolet (VUV) region (λ < 200 nm) was investigated in order to use these plasmas as light sources for the study of the VUV photochemistry of polyethylene (PE) and polypropylene (PP) as part of the study of plasma-polymer interaction. These polymers, immersed in low-presure oxygen, were exposed to radiation with wavelengths down to 112 nm, the cut off of magnesium fluoride used as a window to separate the polymer specimen from the plasma light source. Total oxygen incorporation in the surface [O], and the formation of hydroxyl, carbonyl, and carboxyl groups were measured using XPS in combination with chemical derivatizations, particularly their dependence upon the radiation spectrum and the oxygen pressure around the sample. In most experiments the surface oxygen concentration [O] attained a constant value that appears to be related to the initial oxidation rate; this suggests a competition between oxygen incorporation and chain scission reactions, followed by the removal of volatile oxidation products. PE is usually oxidized to a higher level than PP, the latter appearing to be more susceptible to reaction with atomic oxygen than PE. A general initiation mechanism for the VUV experiments is proposed that allows us to explain the observed differences in behavior between PE and PP, and the results obtained under different irradiation conditions. The nature of oxidation products is in both cases very similar to what is observed after direct plasma treatment of the polymers. We conclude that short wavelength radiation contributes very appreciably to the observed surface modification effects during plasma treatment of PE and PP. © 1995 John Wiley & Sons, Inc.     

Effect of photochemical oxidation on polypropylene phosphorescence

Phosphorescence from polyolefins was studied from the aspects of excitation and emission wavelength and lifetime. Effects of photochemical oxidation on polypropylene phosphorescence are discussed in contrast to the effects of thermal oxidation.     

A model for explosions during carbon monoxide oxidation

During the oxidation of carbon monoxide containing a trace of water, ten well-known atomic and molecular species can be identified as of potential significance. All conceivable reactions of these species in their ground electronic states were considered, and rate constants for all those that are of potential importance are either known or can be estimated with considerable confidence. For compositions and temperatures of experimental interest an isothermal system goes to a single steady state that is stable to perturbation and will neither explode nor oscillate. These steady-state computations also predict that as the temperature is raised above about 1000 K most of the water is converted to H, OH, and HO₂ radicals. Under such conditions, exothermic reactions would be so rapid that strong thermal gradients would develop in any real system of plausible dimensions. A simple model based on these calculations predicts explosion limits consistent with those observed experimentally. Simultaneous behavior in time and in space must be calculated in detail before it is clear whether or not this model based on ground electronic states can model the oscillations that are sometimes observed in this system.     

Carboxylate clays: A model study for polypropylene/clay nanocomposites

Sodium-montmorillonite was intercalated by carboxylate salts to prepare carboxylate clays. The intercalation of sodium acetate doubles the clay basal spacing and no degradation of the carboxylate clay is noticed in the extrusion temperature range. These carboxylate clays were used to synthesize polypropylene-graft-maleic anhydride (PP-g-MA)/clay nanocomposites. Nanocomposites were also produced by a one-pot process using in situ prepared carboxylate clay. The carboxylate salts within the clay layers partially neutralize the maleic anhydride groups of the PP-g-MA matrix, in situ during the melt compounding. The ionic groups of the partially neutralized polymer offer favourable interactions with the clay, hence reinforcing the interfacial bond between the polymer and the clay and improving the composite properties. The use of carboxylate clay clearly improves the clay dispersion into the PP-g-MA matrix and improves the nanocomposite’s thermal and rheological properties.     

Study of the thermal oxidation of polyolefines—VIII: Volatile products of polypropylene thermal oxidation

In the oxidation of isotactic polypropylene, qualitative and quantitative studies were made of organic volatile products by gas chromatographic methods. Experimental results and further data have been compared. Most of the products formed during degradation are acetone, and other ketones and aldehydes. Propylene, acetic acid and 2.4-dimethyl furane have also been identified.The products are formed in an accelerating kinetic process. There was linear relationship between the volatile products measured and the amount of oxygen consumption: approximately 2% of the oxygen absorbed is built into low molecular weight organic carbonyl compounds.     

Effect of oxygen pressure on the oxidation kinetics of unstabilised polypropylene

The thermal oxidation of unstabilised polypropylene films at 80 °C and various oxygen pressures ranging from 0.02 MPa to 5 MPa has been studied by FTIR spectrophotometry (carbonyl growth). The induction time decreases and the maximum oxidation rate increases quasi-hyperbolically when the oxygen pressure increases. The asymptotic behaviour (corresponding to the regime of oxygen excess) is not reached at the highest pressure under study. A kinetic model derived from a classical mechanistic scheme but free of simplifying hypotheses, has been used to simulate the observed behaviour and to determine the elementary rate constants. It is shown that a good simulation of kinetic curves of carbonyl build-up in the whole pressure interval under study can be obtained with a set of physically reasonable rate constant values. The “inverse problem” cannot be, however, totally solved because certain constants are interdependent so that some rate constant values have to be arbitrarily chosen or taken from the literature.     

Photothermal oxidation of squalane: A model compound for polyolefins

Photothermal oxidation of squalane has been studied by oxygen uptake measurements in a quartz glass reaction cell. The activation energy for oxidation has been found to be ∼ 12·7 kcal/mole which supports the intramolecular hydrogen abstraction at the tertiary CH bond site. Hydroperoxy groups are formed during the induction period, which on decomposition (OO bond scission) leads to accelerated degradation and results in the formation of carbonyl and unsaturated groups.