Polyisoprene, oxidation

Thus, a mechanism of cis-l,4-polyisoprene oxidation could be that shown in reactions (234)—(237)... 

Mayo et al. [404] found that phenylhydrazine catalysed markedly the degradation of polyisoprene in solution with oxygen. The effect increases with the amount of phenylhydrazine. Considering the above results it seems possible that hydrazines formed during the photolysis of DPPH catalyse the polyisoprene oxidation [508]. It was also found that the addition of hydrazine hydrate accelerated the thermal oxidation of polyimides [187]. 

Elastomers. Elastomers are polymers or copolymers of hydrocarbons (see Elastomers, synthetic Rubber, natural). Natural mbber is essentially polyisoprene, whereas the most common synthetic mbber is a styrene—butadiene copolymer. Moreover, nearly all synthetic mbber is reinforced with carbon black, itself produced by partial oxidation of heavy hydrocarbons. Table 10 gives U.S. elastomer production for 1991. The two most important elastomers, styrene—butadiene mbber (qv) and polybutadiene mbber, are used primarily in automobile tires. 

The cis-polybutadiene, cis-polyisoprene, and ethylene-propylene rubbers are close duphcates of natural rubber. The newer eth)aene-propylene rubbers (EPR) have excellent resistance to heat and oxidation. 

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. 

In a similar manner polyisoprene-polyethylene oxide block copolymers can prepared301. It is surprising that the poly(methyl methacrylate) anion can be successfully used for the polymerization of ethylene oxide without chain transfer302. Graft copolymers are also prepared by successive addition of ethylene oxide to the poly-... 

In the paper by Ptschelintsev et al. [28] on the oxidation of polyisoprene, it was reported that one recombination event of free radicals leads to scissions of... 

Figure 3 shows how the elementary structure of the polymer affects the observed patterns of chemiluminescence response in oxygen at 120°C. As expected, the oxidizability decreases in the order polyisoprene < polybutadiene < polypropylene < polyethylene. However, it is difficult to understand why the maximum light emission is almost 2x lower for polybutadiene than for PP. The oxidation of polybutadiene occurs via secondary peroxyl radicals, while in... 

The comparison of measurements for oxidation of polyisoprene indicates that the increase of chemiluminescence precedes that of oxygen uptake (Figure 12) and that a maximum of chemiluminescence is situated around an inflexion point of the oxygen absorption curve. 

Figure 12 Chemiluminescence intensity and absorption of oxygen [43] scans for oxidation of polyisoprene in oxygen, temperatures 90°C and 100°C.

Figure 16 Relaxation changes of chemiluminescence intensity for oxidized polyisoprene during replacement of oxygen by nitrogen and vice versa.

Figure 2.21 Most probable hydrogens attacked by oxidation a) PP resin segment, b) polypropylene glycol segment, and c) trans polyisoprene segment. The arrows point to the hydrogens that are the most susceptible to attack and removal...

Based on the results obtained to date, which have been summarized above for several different semicrystalline polymers— linear and low density (branched) polyethylene, polytrimethylene oxide, polyethylene oxide and cis polyisoprene—it is concluded that the relatively fast segmental motions, as manifested in Tq, are independent of all aspects of the crystallinity and are the same as the completely amorphous polymer at the same temperature. Furthermore, it has previously been shown that for polyethylene, the motions in the non-crystalline regions are essentially the same as those in the melts of low molecular weight ii-alkanes. (17)... 

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. 

---