Oxygen effect, poly polymerization

In 1991, Deming and Novak reported the pronounced effect of molecular oxygen on the polymerization process [16]. Under anaerobic conditions, isocyanides underwent only slow polymerization in the presence of NiCl2, even in ethanol, affording poly(isocyanide)s in only moderate yields of 50-60% after 20 h. When the polymerization was carried out in air at 1 atm, the polymerization was completed within 1 h. Air at 1 atm was sufficient to main-... 

A hindered amine light stabiliser has been found to enhance the light stability of blends of low and linear low density polyethylene with the latter contributing linearly to the overall stability of the blend. In coatings hindered piperidine light stabilisers are also effective especially when used in conjunction with a benzotriazole absorber while surface protection of styrene copolymers with 2-(2-hydroxy-5-vinylphenyl)benzotriazole requires a small amount of a hindered piperidine stabiliser. Polymeric hindered piperidine compounds on the other hand have been found to inhibit the singlet oxygen attack on poly(butadiene). ... 

An important question to be explained by the chemical mechanism is why base catalysis often leads to condensed structures. In 1950, Aelion et al. (13) pointed out that the condensation reaction in base-catalyzed systems was faster than with acid catalysis and that the microstructure of the final product was different. Many of these facts are due to the opposite effects of, for example, substituents, on silicon on the stabilization of the transition state in base- and acid-catalyzed reactions (15). For the base-catalyzed condensation reaction to take place, a silicon atom has to be attacked by a deprotonated silanol oxygen the nucleophile. The acidity of the silanol proton increases as the basicity of the other groups bonded to the silicon decreases. This feature implies that poly silicic acid is a stronger acid than Si(OH)4 (20). Therefore, monomers react preferentially with higher polymerized species. 

The growing concern over the toxicity of residual ethylene oxide after sterilization of polymers for use in the field of medicine has led to the rapid growth of the field of radiation sterilization. The medical industry consumes a massive volume of polymeric material in both equipment and implants. As a consequence there is much interest in the effects of radiation on the physical properties and stability of irradiated polymers. The standard dose for radiation sterilization is 25 kGy, which is sufficient to alter the properties of many polymers, being for example close to or above the gel dose of many elastomers. There is also interest in the reaction of oxygen with long-lived radical species formed during irradiation. A common polymer used in medical equipment, poly(propylcne) is susceptible to oxidative degradation, and must be blended with appropriate stabilizers before radiation sterilization. 

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