Oxidative stability temperatures

In the first step cumene is oxidized to cumene hydroperoxide with atmospheric air or air enriched with oxygen ia one or a series of oxidizers. The temperature is generally between 80 and 130°C and pressure and promoters, such as sodium hydroxide, may be used (17). A typical process iavolves the use of three or four oxidation reactors ia series. Feed to the first reactor is fresh cumene and cumene recycled from the concentrator and other reactors. Each reactor is partitioned. At the bottom there may be a layer of fresh 2—3% sodium hydroxide if a promoter (stabilizer) is used. Cumene enters the side of the reactor, overflows the partition to the other side, and then goes on to the next reactor. The air (oxygen) is bubbled ia at the bottom and leaves at the top of each reactor. 

The absence of both secondary and tertiary C—H bonds leads to a high measure of oxidative stability. Oxidation does take place when thin films are heated in air to temperatures above 300°C and causes cross-linking but this is of little practical significance. The absence of double bonds gives a very good but not absolute resistance to ozone. 

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). 

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]... 

Bismuth oeeurs mainly as bismite (a-Bi203), bismuthinite (Bi2S3) and bismutite [(Bi0)2C03] very oeeasionally it oeeurs native, in assoeiation with Pb, Ag or Co ores. The main eommereial souree of the element is as a byproduet from Pb/Zn and Cu plants, from whieh it is obtained by special processes dependent on the nature of the main product. Sulfide ores are roasted to the oxide and then reduced by iron or charcoal. Because of its low mp, very low solubiUty in Fe, and fairly high oxidative stability in air, Bi can be melted and cast (like Pb) in iron and steel vessels. Like Sb, the metal is too brittle to roll, draw, or extrude at room temperature, but above 225°C Bi can be worked quite well. 

Figure 4 The effect of stabilizer concentration on the induction period of polypropylene thermal oxidative breakdown (temperature 200°C P02 = 300 Tor). 1-polyamineani-line disulfide 2-polydiiminodiphenyloxide disulfide 3-polythiosemicarbazide disulfide 4-Santanox 5-hydroru-beanic polydisulfide 6-thiocarbamidepoly disulfide 7-po-lydisulfide.

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. 

An ATE requires high lubrication performance, high levels of oxidation stability to withstand the locally high operating temperatures, a degree of fluidity that ensures... 

Hydraulic oils need to be of the highest oxidation stability, particularly for high-temperature operations, because... 

The stringent requirements covering oxidation stability are defined by the test method DIN 51352, Part 2, known as the Pneurop Oxidation Test (POT). This test simulates the oxidizing effects of high temperature, intimate exposure to air, and the presence of iron oxide, which acts as catalyst - all factors highly conducive to the chemical breakdown of oil, and the consequent formation of deposits that can lead to fire and explosion. 

Type 1 and 2 resins Refers to SBA resins. Type 1 resins are either standard (particularly good temperature and oxidation stability) or porous (higher capacity and resistance against organic fouling). The structure of type 2 resins is similar to type 1 but provides for maximum capacity and resistance to fouling. 

Phenolic networks are well known for their excellent thermal and thermo-oxidative stabilities. The mechanisms for high-temperature phenolic degradation include dehydration, thermal crosslinking, and oxidation, which eventually lead to char. 

The most commonly used siloxane modifiers are those having phenyl, trifluoro-propyl and cyanopropyl substituents. Introduction of phenyl units into the polydimethylsiloxane backbone either in the form of methylphenylsiloxane or diphenyl-siloxane increases the thermal and oxidative stability, glass transition temperature and the organic solubility characteristics of the resulting copolymers. At low levels (5-10 percent by weight) of incorporation, bulky phenyl groups also break up the regularity of polydimethylsiloxane chains and inhibit the crystallization (Tc... 

Thermoanalytical techniques such as differential scanning calorimetry (DSC) and thermogravi-metric analysis (TGA) have also been widely used to study rubber oxidation [24—27]. The oxidative stability of mbbers and the effectiveness of various antioxidants can be evaluated with DSC based on the heat change (oxidation exotherm) during oxidation, the activation energy of oxidation, the isothermal induction time, the onset temperamre of oxidation, and the oxidation peak temperature. 

Polyalphaolefin hydraulic fluids have many advantages over the mineral oil counterparts including low temperature flow characteristics, lower volatility, and oxidative stability (Chrisope and Landry 1993 Shubkin 1993). Certain polyalphaolefins maintain good operational characteristics and have been proposed for use in hydraulic systems in U.S. military aircraft (Kinkead et al. 1992b). 

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. 

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. 

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