Polymer-reactive antioxidant 1,3-addition reaction

Another polymer reactive antioxidant which can be combined with rubber during vulcanization involves the 1,3 addition reaction of nitrones to the double bond in rubbers, reaction 4 (11). 

A second mechanism in the. aging of CTPB propellants also exists and proceeds concurrently with the reactions proposed above. It consists of an attack at the reactive points of unsaturation in the backbone polymer, which causes additional crosslinking and hence an increase in propellant modulus, particularly at the surface. The exposed surface of CTPB propellants changes, as indicated by an increase in hardness. Heavy metal ions are particularly harmful, and it was found that an increase from 10 to 80 p.p.m. of iron caused a significant increase in surface hardening by catalytic attack on the double bonds. Antioxidants in general provide sufficient protection for polymer storage. In CTPB propellants the antioxidant selected to protect the double bond is very important. Amine-type antioxidants have provided better surface stability than phenolic compounds. 

The above approach of mechanochemically initiated addition of reactive antioxidants on different polymers, such as rubbers and unsaturated thermoplastics such as ABS is illustrated here for thiol-containing antioxidants. For example, using thiol compounds (37) and (38) as the reactive antioxidants, Kharasch-type addition of the thiol function to the polymer double bond takes place during melt processing to give bound antioxidant adduct (see reaction 7) the polymer becomes much more substantive under aggressive environments. 

Polyolefins such as polyethylene and polypropylene contain only C—C and C—H bonds and may be considered as high molecular weight paraffins. Like the simpler paraffins they are somewhat inert and their major chemical reaction is substitution, e.g. halogenation. In addition the branched polyethylenes and the higher polyolefins contain tertiary carbon atoms which are reactive sites for oxidation. Because of this it is necessary to add antioxidants to stabilise the polymers against oxidation Some polyolefins may be cross-linked by peroxides. 

The use of a reactive di- or poly-functional comonomer (non-antioxidant) which can co-graft with a monofunctional polymerisable antioxidant on polymers can improve the grafting efficiency from as low as 10-40% to an excess of 80-90%. This strategy, however, presents immense challenges due to the presence of more than one polymerisable group in the comonomer which could lead to additional undesirable (competing) side reactions com-... 

In the case of BR or SBR, the efficiency can be much greater than 1.0, especially if all antioxidant materials are removed. A chain reaction is indicated here. It might be explained by steric considerations. In butadiene-based rubbers, double bonds are quite accessible. Radical addition to double bonds could give highly reactive radicals, which would be likely to add to other polymer double bonds. A chain of additions might be more likely in butadiene rubber than in the presence of hindering methyl groups in isoprene rubbers. 

Chem. Descrip. Triphenyl phosphite CAS 101-02-0 EINECS/ELINCS 202-908-4 Uses Costabilizer for PVC and other polymers such as PP vise, modifier, reactive diluent for a variety of resin systems, esp. epoxies antioxidant for syn. rubbers, butyrates flame retardant for PU foams in transesterification reactions lubricant oil additive chem. intermediate for prod, of other phosphite esters and phosphonates Features Improves adhesion, elec, props., dimensional stability Properties Colorless mobile liq. 10% P Albrite Tributyl Phosphate [Huntsman Surf. Sciences]... 

A combination of heat and oxygen will cause oxidation in the polymer, resulting in degradation. The mechanism is the formation of free radicals, which are highly reactive chemical species. This reaction can be observed, as the products will tend to show a discoloration to yellow or brown. Additives called antioxidants can be used to interrupt this mechanism. The chemicals most commonly employed are hindered phenols, which act as peroxide radical decomposers. 

---