Oxygen reaction + polymers

Such copolymers of oxygen have been prepared from styrene, a-methylstyrene, indene, ketenes, butadiene, isoprene, l,l-diphen5iethylene, methyl methacrjiate, methyl acrylate, acrylonitrile, and vinyl chloride (44,66,109). 1,3-Dienes, such as butadiene, yield randomly distributed 1,2- and 1,4-copolymers. Oxygen pressure and olefin stmcture are important factors in these reactions for example, other products, eg, carbonyl compounds, epoxides, etc, can form at low oxygen pressures. Polymers possessing dialkyl peroxide moieties in the polymer backbone have also been prepared by base-catalyzed condensations of di(hydroxy-/ f2 -alkyl) peroxides with dibasic acid chlorides or bis(chloroformates) (110). 

B. Ranby and J. F. Rabek (eds.) Singlet Oxygen Reactions with Organic Compounds and Polymers, Wiley, Chichester, 1978, 331 pp. 

The above-mentioned mode of reactions changes when the irradiation is carried out in the presence of gases such as oxygen. In this case, energy transfer, the reaction of oxygen with polymer radicals [32] (leading to the formation of peroxy radicals) and other reactions may affect the type and concentration of products formed [33]. The same can be said for certain additives mixed into the elastomer for one or the other purpose. 

Oxidative Reactions Caused by Ozone and Atomic Oxygen on Polymer Surfaces... 

PMMA - Red Phosphorus System. The initial reaction that was investigated was that between PMMA and red phosphorus (4-51. Phosphorus was chosen since this material is known to function as a flame retardant for oxygen-containing polymers (1 2). Two previous investigations of the reaction of PMMA with red phosphorus have been carried out and the results are conflicting. Raley has reported that the addition of organic halides and red phosphorus to PMMA caused moderate to severe deterioration in flammability characteristics. Other authors have reported that the addition of chlorine and phosphorus compounds are effective flame retardant additives (12). 

When diffusion of oxygen in the polymer occurs rapidly (Ak 1), we observe the kinetic regime of polymer oxidation (see Equation [13.16]). When penetration of oxygen into polymer is slow, the reaction rate v KXp02. 

The fact that functionalization of polymers and small molecules is observed to occur predominately on terminal (methyl) carbon atoms does not imply that the oxyfluorination reaction is truly selective. Although the reaction mechanism has not been studied in detail, it is undoubtedly a free-radical process. Molecular oxygen reacts spontaneously with the fluorocarbon—hydrogen radicals generated by fluorine during the fluorination process. Acid fluorides are retained on terminal carbon atoms because they are stable in 1 atm of elemental fluorine. Hypofluorites, which may be short-lived intermediates of oxygen reactions with methylene radical sites along the carbon chain, are not observed in the functionalized polymers. It is probable that, if they are intermediates, they are cleaved and removed by the excess elemental fluorine. 

Singlet-oxygen studies have being reported to such diverse areas as chemiluminescence [14], photocarcinogenity [15], ozonolysis [16], photodynamic action [17], peroxide decomposition [7], photosynthesis [14], air pollution [18], metallocatalyzed oxygenation reactions [19,20], synthetic applications [21], and polymer degradation [10]. 

Ranby, B. Rabek, J. F. Singlet Oxygen Reactions with OrganicCompounds and Polymers, Wiley Chichester, 1979. 

Brunow, G. Forssk hl, I. Gr6nlund,A.C. LindstrOm, G. Nyberg, K. In Singlet Oxygen Reactions with Organic Compounds and Polymers RAnby, B. Rabek, J.F. Eds. John Wiley Sons, New York, New York, 1978. 

The main by-products are 1-chlorobutadiene, produced from the residual dichloro 2-butenes or formed during the reaction, polymers, sodium chloride and monochloro-butenes (l-chloro 1-butene, 2-diloro 2-butenes, 2-chloro 1-butene, etc.) To control the undesirable polymerizations, the reaction takes place in an oxygen-free environment, at the lowest possible temperature, and with an inhibitor. Also effective is the presence of a solvent (methanol, ethanol) or a catalyst In this case, however, it is necessary to raise the caustic soda concentrations (30 per cent) or to employ other bases (liquid ammonia, ion exchange resins, etc.). In the absence of catalyst, the residence time is 3 to 5 h. and selectivity exceeds 95 molar percent for a once-through conversion of nearly 95 per cent... 

Apart from the commonly used NaOCl, urea—H2O2 has been used/ With this reaction, simple alkenes can be epoxi-dized with high enantioselectivity. The mechanism of this reaction has been examined.Radical intermediates have been suggested for this reaction, polymer-bound Mn -salen complex, in conjunction with NaOCl, has been used for asymmetric epoxidation. Chromium-salen complexes and ruthenium-salen complexes have been used for epoxidation. Manganese porphyrin complexes have also been used. Cobalt complexes give similar results. A related epoxidation reaction used an iron complex with molecular oxygen and isopropanal. Nonracemic epoxides can be prepared from racemic epoxides with salen-cobalt(II) catalysts following a modified procedure for kinetic resolution. 

In macroscale reduction of unsubstituted phenylarsonic acid at a mercury pool electrode, the final product is an oxygen-containing polymer, which contains As—As as well as As—O—As bonds . Precipitation of PhAsH2 was also observed during the electrolysis , and it was suggested that products were formed by the following reactions ... 

This paper includes results from our research programs on photooxidation and photo-stabilization of polymers supported by the Swedish National Board for Technical Development (STU) and a project in the NORDFORSK program on singlet oxygen reactions. 

SCHEME 16.11 Singlet oxygen oxidation of aromatic ring. (Adapted from Golnick, K., In Ranby, B., and Rabek, J.F., Eds. Singlet Oxygen Reactions with Organic Compounds and Polymers. New York, John Wiley and Sons, 111-134, 1978.)... 

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