1,4-Polyisoprene degradation

In tlie study, the nature of tlie latex, the phenylhydrazine concentrations, temperature and air flow were tlie parameters investigated in detail. As shown in Table 1, the degree of polyisoprene degradation depends on the concentration of phenylhydrazine relative to rubber. The other reaction conditions were found to be not very sensitive and thus the reaction conditions adapted were ... 

As with c -polyisoprene, the gutta molecule may be hydrogenated, hydro-chlorinated and vulcanised with sulphur. Ozone will cause rapid degradation. It is also seriously affected by both air (oxygen) and light and is therefore stored under water. Antioxidants such as those used in natural rubber retard oxidative deterioration. If the material is subjected to heat and mechanical working when dry, there is additional deterioration so that it is important to maintain a minimum moisture content of 1%. (It is not usual to vulcanise the polymer.)... 

Other polymers used in the PSA industry include synthetic polyisoprenes and polybutadienes, styrene-butadiene rubbers, butadiene-acrylonitrile rubbers, polychloroprenes, and some polyisobutylenes. With the exception of pure polyisobutylenes, these polymer backbones retain some unsaturation, which makes them susceptible to oxidation and UV degradation. The rubbers require compounding with tackifiers and, if desired, plasticizers or oils to make them tacky. To improve performance and to make them more processible, diene-based polymers are typically compounded with additional stabilizers, chemical crosslinkers, and solvents for coating. Emulsion polymerized styrene butadiene rubbers (SBRs) are a common basis for PSA formulation [121]. The tackified SBR PSAs show improved cohesive strength as the Mooney viscosity and percent bound styrene in the rubber increases. The peel performance typically is best with 24—40% bound styrene in the rubber. To increase adhesion to polar surfaces, carboxylated SBRs have been used for PSA formulation. Blends of SBR and natural rubber are commonly used to improve long-term stability of the adhesives. 

Used tires create serious environmental problems, because they do not degrade easily and they release noxious contaminants when they bum. Recently, a process has been developed that breaks tires down into a polyisoprene oil that can then be further decomposed into limonene. The yield of limonene is only a few percent, but if this process can be made more efficient it may become possible to turn ugly, smelly old tires into fragrant oil of lemon. 

While polymers that contain sites of unsaturation, such as polyisoprene and the polybutadienes, are most susceptible to oxygen and ozone oxidation, most other polymers also show some susceptibility to such degradation including NR, PS, PP, nylons, PEs, and most natural and naturally derived polymers. 

Natural rubber is a polymer of isoprene- most often cis-l,4-polyiso-prene - with a molecular weight of 100,000 to 1,000,000. Typically, a few percent of other materials, such as proteins, fatty acids, resins and inorganic materials is found in natural rubber. Polyisoprene is also created synthetically, producing what is sometimes referred to as "synthetic natural rubber". Owing to the presence of a double bond in each and every repeat unit, natural rubber is sensitive to ozone cracking. Some natural rubber sources called gutta percha are composed of trans-1,4-poly isoprene, a structural isomer which has similar, but not identical properties. Natural rubber is an elastomer and a thermoplastic. However, it should be noted that as the rubber is vulcanized it will turn into a thermoset. Most rubber in everyday use is vulcanized to a point where it shares properties of both, i.e., if it is heated and cooled, it is degraded but not destroyed. 

In other applications the pattern of evolution of styrene, butadiene and acrylonitrile as a function of temperature has provided a unique way for classifying different types of ABS. The loss of the antioxidant butylated hydroxytoluene (BHT) was also detected by MS preceding EVA copolymer degradation [165] BHT was identified at a concentration level of 20 ppm. Lehrle and co-workers [52] have described a successful controlled release system for the stabilisation of rubber by encapsulating efficient but rather mobile antioxidants to prevent loss from the host polymer. The performance of the controlled-release of the antioxidant BHT from alginate matrix particles was studied by means of DSC, TG and TG-MS. Polyisoprene rubber is more resistant to oxidation when protected in this way than by the equivalent concentration of unencapsulated antioxidant. 

Figure 14.27 Degradation of polyisoprene by photolysis (a), and ozonol-ysis (6).

EPTMs are suffidently reactive toward firee radicals (see previous Section), even when they contain low amounts of conjugated unsaturation (0.1 M or less). Thus degradation phenomena are practically avoided during their radical curing. We have verified the po ibility of codicumyl peroxide-based formulations. Figure 13 shows that with 0 J—1.5 % peroxide... 

Figure 7. Upper curve, IR spectra of stress-ozone-degraded polyisoprene lower curve, results from subtraction of reference polyisoprene curve from the upper...

This reaction was reported for the benzophenone photosensitized degradation of polypropylene (92),polystyrene (95), poly(vinyl alcohol) (94),polyisoprene (95,96),polyurethane (97) and polyadenylic acid (98) In solid state benzophenone also produce an extensive crosslinking of polyethylene (99-105) It has also been found that benzophenone and its derivatives caused an initial rapid oxidation,increasing with ketone concentration (70) Currently the relative importance of singlet oxygen formation in energy transfer reaction between excited benzophenone and molecular oxygen is discussed (92,104) ... 

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