Thermooxidation

LARC-TPI is a linear thermoplastic PI which can be processed ia the imide form to produce large-area, void-free adhesive bonds. Mitsui Toatsu Chemicals, Inc., has obtained Hcense to produce this product commercially for appHcations such as adhesives, films, mol ding compounds, etc. These are thermooxidatively stable and show essentially no loss ia weight at 300°C ia air. Weight loss does not exceed 2—3% after isothermal aging ia air at 300°C for 550 h. 

Polyphenylquinoxalines (PPQ) are easier to make than the polyquinoxalines and offer superior solubiHty, processibiHty, and thermooxidative stabiHty (65). The PPQs exhibit excellent high temperature adhesive, composite, and film properties. However, to increase the use temperature of PPQs, acetylene... 

Thermal, Thermooxidative, and Photooxidative Degradation. LLDPE is relatively stable to heat. Thermal degradation starts at temperatures above 250°C and results in a gradual decrease of molecular weight and the formation of double bonds in polymer chains. At temperatures above 450°C, LLDPE is pyrolyzed with the formation of isoalkanes and olefins. 

Thermal, Thermooxidative, and Photooxidative Degradation. Polymers of a-olefins have at least one tertiary C-H bond in each monomer unit of polymer chains. As a result, these polymers are susceptible to both thermal and thermooxidative degradation. Reactivity in degradation reactions is especially significant in the case of polyolefins with branched alkyl side groups. For example, thermal decomposition of... 

Both thermooxidation and photooxidation of polyolefins can be prevented by using the same antioxidants as those employed for the stabilization of polypropylene, ie, alkylated phenols, polyphenols, thioesters, and organic phosphites in the amount of 0.2—0.5% (22,25). 

Fig. 6. The initial degradation pathway for thermooxidation and photooxidation. The free radical X is generated by the effect of heat or light on impurities,...

The cleavage of dicyclopentadiene into cyclopentadiene can be accomplished at temperatures above 160°C, producing the heterocycHc Diels-Alder maleic addition product, which opens to the diacid. This product can be esterified with propylene glycol to produce resins that demonstrate enhanced resihence and thermooxidative resistance suitable for molded electrical components. 

TriaUyl cyanurate is used as a comonomer in small amounts with methacrylate esters and unsaturated polyesters. The addition of 5% or more of TAC to MMA in castings improves heat and solvent resistance as weU as thermooxidative stabUity (99). For optical appUcations, up to 20% TAC has been suggested. Reactivity ratios for TAC and methacrylate esters have been reported (100). 

Fig. 9. Thermal and thermooxidative degradation of PS. Viscosity is for a 10% solution in toluene at 25°C.

Methods for recycling used plastic materials are reviewed. Emphasis is placed on the research projects into chemical recycling methods for used plastics at the Leuna location. These include development of a process for the thermaL thermooxidative pretreatment of used plastic materials, utilisation of pretreated used plastic materials in the visbreaker by gasification and by hydrogenation and the production of wax oxidates from pretreated used plastics. The results are discussed. 

Since the utility of these materials is improved by the incorporation of these reactive functionalities without severely decreasing other favorable properties such as thermooxidative stability and solvent resistance the chemistry of the isoimide isomerization and acetylene crosslinking reactions is of considerable interest. Previous work in our laboratory has shown that these materials, when loaded with metal powders, provide a convenient and effective method of optimizing the electrical conductance and thermal stability of aluminum conductor joints. 

Sundar and Keller have reported the synthesis of linear boron-silicon-diacetylene polymers (31) (Fig. 21) using phenylboron dichloride (PBD) as the source for boron.50 The compositions of the thermally stable boron-silicon-diacetylene copolymers 31a-d are summarized in Figure 21. These polymers were observed to possess exceptional thermooxidative stabilities. 

Figure 66 The thermooxidatively stable silyl-carborane hybrid diethynylbenzene-silylene polymer 108 containing various carbon-carbon unsaturations. (Adapted from ref. 136.)...

A typical synthetic route to the incorporation of pendent carboranyl units into a polymer chain is shown in scheme 3. Poly(o-carboranyl-organo-siloxane)s have been successfully prepared through hydrolysis of dimethyldichlorosilane in the presence of carboranedichloromethylsilane. The polymer has some of the elastomeric characteristics of the parent poly(siloxane) however, the thermal-oxidative cleavage of the o-carboranyl pendent group is reported to occurat lower temperatures than that for the thermooxidative cleavage of Si—O and Si—C bonds.10 Thermal studies have... 

L. Matisova-Rychla and J. Rychly, Inherent relations of chemiluminescence and thermooxidation of polymers, In R.L. Clough, N.C. Billingham and K.T. Gillen (Eds.), Advances in Chemistry, Series 249 Polymer Durability, Degradation, Stabilization and Lifetime Prediction. American Chemical Society, Washington, DC, 1996, p. 175. 

L. Rychla and J. Rychly, New concepts in chemiluminescence at the evaluation of thermooxidative stability of polypropylene from isothermal and non-isothermal experiments. In A. Jimenez and G.E. Zaikov (Eds.), Polymer Analysis and Degradation, Nova Science Publishers, New York, 2000 p. 124. 

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