Polymers oxidative stability

Instrumentation used for polymer oxidative stability (Chapter 11) includes, thermogravimetric analysis, differential scanning calorimetry, evolved gas analysis, infrared spectroscopy and ESR spectroscopy, matrix assisted laser desorption/ionisation mass spectrometry and imaging chemiluminescence is included. 

Impurities in mineral fillers can have serious effects. Coarse particles (grit) will lead to points of weakness in soft polymers which will therefore fail under stresses below that which might be expected. Traces of copper, manganese and iron can affect the oxidative stability whilst lead may react with sulphur-containing additives or sulphurous fumes in the atmosphere to give a discoloured product. 

In terms of processing there is no need for pre-drying PCHE granules, a standard extruder screw as used for polycarbonate may be used and discs are said to release well from the mould. Question marks remain on the oxidative stability of the polymer and on the quality of adhesion of the reflective layer but Dow claim that metallising is possible. 

As with the polysulphones, the deactivated aromatic nature of the polymer leads to a high degree of oxidative stability, with an indicated UL Temperature Index in excess of 250°C for PEEKK. The only other melt-processable polymers in the same league are poly(phenylene sulphides) and certain liquid crystal polyesters (see Chapter 25). 

Oxidative stability is highly important because it deals with the degradation of polymers under actual performance conditions. Oxidative stability, as applied to urethanes, refers to the combination of oxygen and heat or oxygen and light that causes degradation of urethanes. 

A major development in fluoroplastks is the recent small scale production of Teflon AF, a noncrystaUme (amorphous) fluorocarbon polymer with a high glass transition temperature (240 °C) This optically transparent TFE copolymer is soluble m certan fluorocabons and has the same chemical and oxidative stability as crystallme TFE homopolymers [5]... 

DSC helps in determining the glass-transition temperature, vulcanization, and oxidative stability. TG mainly is applied for the quantitative determination of major components of a polymer sample. TMA or DLTMA (dynamic load thermomechanical analysis) measures the elastic properties viz. modulus. 

Physical properties of carbon black-filled EPR and EPDM elastomers have been found to be comparable with the suUur-cured analogues [372]. Aromatic oils increase the optimum dose requirement for these compounds due to the reaction of the transient intermediates formed during radiolysis of the polymer with the oil as well as energy transfer which is particularly effective when the oil contains aromatic groups. The performance and oxidative stability of unfilled EPDM as well as its blend with PE [373], and the thermal stabdity and radiation-initiated oxidation of EPR compounds are reported by a number of workers [374,375]. 

Derivitization reactions have previously been employed to extend the sensitivity and resolution of IR, ultraviolet and X-ray photo-electron spectroscopy (7-13). Yet no proposed method has the range to accommodate the major oxidation products from polyolefins. As part of an ongoing study of polymer oxidation and stabilization, we discuss here a series of reactions with small, reactive gas molecules. The products from these reactions can be rapidly identified and quantified by IR. Some of these reactions are new, others have already been described in the literature, although their products have not always been fully identified. 

Such hybrid molecules and supramolecular solids offer the promise of systems with the flexibility, strength, toughness, and ease of fabrication of polymers, with the high temperature oxidative stability of ceramics, and the electrical or catalytic properties of metals. Polyphosphazene chemistry provides an illustration of what is possible in one representative hybrid system. 

A synthesis of comblike organoboron polymer/boron stabilized imidoanion hybrids was examined via reactions of poly(organoboron halides) with 1-hexylamine and oligo(ethylene oxide) monomethyl ether and subsequent neutralization with lithium hydride (scheme 8). The obtained polymers (10) were amorphous soft solids soluble in common organic solvents such as methanol, THF, and chloroform. In the nB-NMR spectra (Fig. 11), neutralization of the iminoborane unit with lithium hydride... 

Measuring the relative oxidative stability of polymers is important. Measurements can be used to determine dependencies on structural and molecular weight/weight distribution or the effectiveness of an antioxidant, or to perhaps assess the amount present in a polymer sample, etc. The preferred and commonest method consists in raising the sample temperature to a predetermined level, while in an inert atmosphere, then switching the atmosphere to air or oxygen. The time to the onset of exothermic reaction is measured. 

One important point should be stressed here the efficiency of any stabilizing system depends very much on the removal or depletion of the defect structures in the polymer. An example is shown in Figure 1 where the case 5 mechanism vide supra) of a synergistic mixture is theoretically depicted [7]. The line 2 shows that the effect of the synergistic mixture of two antioxidants on thermo-oxidation stability is negligible, if there occurs a relatively significant initiation of oxidation reaction in a way independent from the route taking place via hydroperoxides. 

This research was an attempt to develop new polymers with the mechanical properties of polyarylene ethers and the dielectric properties of fluoropolymers. After initially testing the viability of the [2n+ 2n] cyclodimerization reaction for preparing high-molecular-weight polymers and testing the dielectric properties of these polymers, two polymers (one thermoplastic and one thermoset) were prepared in larger quantities to evaluate the thermal and mechanical performance of these novel compositions. The high Te thermoset was also quantitatively tested for thermal/oxidative stability. 

Figure 3.7. Thermal/oxidative stability of the PFCB thermoset polymer.

Oxidation kinetics of oriented PP was measured under conditions of external priming. The parameter specifying the oxidability of a polymer is slightly dependent on deformation. For instance, at 200°C it only decreases by 1.5 times with X changing from 0 to 10. This unambiguously clarifies that the main reason for increase in thermal-oxidative stability of deformed PP is a sharp drop in the escape of a branching agent (hydroperoxide), i.e. a decrease in hydroperoxide escape. 

The SSP behavior of co-polyesters with rigid or voluminous comonomers, such as the flame retardant additive 9,10-dihydro[2,3-di-9-oxa-(2-hydroxyethoxy)-carbonylpropyl]-10-phosphaphenanthrene-10-oxide, or the ionic compound, sodium 5-sulfoisophthalate, is inhibited. This also occurs in the melt phase and cannot be improved by the use of catalysts [56], The results of studies examining the influence of employed catalysts with respect to stability and quality of the polymer suggest the use of antimony catalysts. The thermal or thermo-oxidative stability is, however, reduced by the interaction of the catalyst with the carboxylic groups of the polymer [57],... 

The phenyl modified polymers possess the optimum combination of high temperature and elastomeric properties and were used in the study of formulation parameters These variables can have an important effect on the thermal stability and property profile of vulcanized systems For example, the use of reinforcing silicas, peroxide content, and oxidative stabilizers have been shown to be important ( 3, 10, in However, polymer-silica interactions had the most pronounced effect on retaining properties during high temperature aging studies ... 

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