聚烯烃（聚乙烯）低温热氧化与降解

综述了近年来聚烯烃特别是聚乙烯的低温热氧化机理，动力学以及氧化降解研究现状及发展，指出现今低温热氧化与降解研究意义。     

Photo- and thermal-oxidation of polyethylene: Comparison of mechanisms and influence of unsaturation content

The behaviour of polyethylene with different contents in vinyl and t-vinylene groups have been studied by photooxidation with λ ≥ 300 nm light or by thermooxidation at a temperature of 100 °C. The oxidation was studied by infrared spectroscopy and it was shown that the same oxidation products were obtained, but with different relative concentrations depending on the conditions of ageing, i.e. photochemical or thermal conditions. The mechanisms by which the oxidation products are formed were recalled. The differences between photo- and thermo-oxidation were evidenced on the basis of the stability of ketones that do not accumulate in photochemical conditions, as a result of Norrish reactions. The influence of the initial amount of unsaturated groups on the rates of oxidation was characterized. It was shown that the concentration of unsaturations had no effect on the rate of photooxidation but dramatically influenced the stability in thermooxidative conditions.     

Effect of multiple extrusion on molecular structure of polypropylene impact copolymer

Neat and multiple processed polypropylene impact-copolymer (ICPP) were fractionated using series of hydrocarbon solvents with increasing solvent power. The analyses of the fractions obtained in successive extractions showed significant decrease in weight-average molecular weight (Mw) and narrowing the molecular weight distribution (MWD) of investigated samples after extrusions. Although the changes due to thermooxidation were observed in all phases of the system, the most intensive degradation was found in the prevailing PP homopolymer phase.     

Dielectric properties of a filled epoxy resin: Effect of thermal treatments

Dielectric measurements have been performed at several frequencies on samples of a cycloaliphatic epoxy resin filled with aluminum hydroxide. The samples were thermally treated at three different temperatures for times up to 2,000 hours. At low aging temperatures and times an improvement of the characteristics is observed due perhaps to an assessment of the bulk of the polymer and more precisely to a change in the free volume. At high temperatures and times a thermo-oxidation involving layers deeper and deeper becomes the predominant mechanism responsible of the decrease in the properties with respect to the virgin material. T _g, tan and versust _a, generalized curves are finally presented useful to predict the behaviour for aging times not easily experienced.Thanks are due to Magrini-Galileo, Italy, for supplying the samples and to C.N.R., Italy, for financial support.     

Rate of thermooxidation and polymer morphology

A model of the thermooxidation of semicrystalline polymers involving two processes simultaneously is described. The first process is initiated by oxygen dissolved in the interspherulitic amorphous pahse. The second is related to a slower rate of polymer chain scission m the interlamellar amorphous pahse, which is controlled by oxygen diffusion into the spherulite. The presented model describes an exampble of isotactic polypropylene and predicts the effect of polymer morphology on the process of thermooxidation. It leads to the conclusion that the initial rate of polymer chain scission depends on the amount of interspherulitic amorphous phase fraction but the slower rate, considered in steady state conditions of oxygen diffussion into the interlamellar amorphous phase, depends depends on spherulite size according to the derived equation.     

Thermooxidation rate of diacetate terminated polyoxymethylene with various morphological structures

Thermooxidative degradation of POM films with different morphological structures was investigated in air in the temperature range of 145–160C.The various degrees of crystallinity and different morphologies of POM films were obtained by quenching molten samples to different temperatures. The studies of thermooxidation by IR absorption and weight loss measurements have shown that the process is influenced by sample morphology. The induction period and the advanced states of, chain scission depend on oxygen diffusion into the samples. This process is strongly dependent upon the degree of crystallinity and morphological structure of the polymer.