Oxidation natural rubber

Protective Systems. As in the case of sulfur vulcanization, there have been many research workers in the field of natural rubber oxidation and its protection (39,40). The principal problem has always been to find an antioxidant that provides protection against flex-cracking, and yet does not stain. None has been found as of the mid-1990s, hence it is best to categorize the various types according to their capabilities. 

When squalene has been used as a model compound for studying natural rubber oxidation the addition of a sulphide before oxidation tends to give one of two patterns of response. Either (a) there is little effect on oxidation or (b) there is marked retardation of oxidation. 

Cure Characteristics. Methods of natural rubber production and raw material properties vary from factory to factory and area to area. Consequentiy, the cure characteristics of natural mbber can vary, even within a particular grade. Factors such as maturation, method and pH of coagulation, preservatives, dry mbber content and viscosity-stabilizing agents, eg, hydroxylamine-neutral sulfate, influence the cure characteristics of natural mbber. Therefore the consistency of cure for different grades of mbber is determined from compounds mixed to the ACSl formulation (27). The ACSl formulation is as follows natural mbber, 100 stearic acid, 0.5 zinc oxide, 6.0 sulfur, 3.5 and 2-mercaptobenzothiazole (MBT), 0.5. 

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. 

Manganese, copper, iron, cobalt and nickel ions can all initiate oxidation. Untinned copper wire can have a catastrophic effect on natural rubber compounds with which it comes into contact. Inert fillers for use in rubbers are usually tested for traces of such metal ions, particularly copper and manganese. The problem is perhaps less serious in saturated hydrocarbon polymers but still exists. 

Antioxidants may be assessed in a variety of ways. For screening and for fundamental studies the induction period and rate of oxidation of petroleum fractions with and without antioxidants present provide useful model systems. Since the effect of oxidation differs from polymer to polymer it is important to evaluate the efficacy of the antioxidant with respect to some property seriously affected by oxidation. Thus for polyethylene it is common to study changes in flow properties and in power factor in polypropylene, flow properties and tendency to embrittlement in natural rubber vulcanisates, changes in tensile strength and tear strength. 

The proximity of the methyl group to the double bond in natural rubber results in the polymer being more reactive at both the double bond and at the a-methylenic position than polybutadiene, SBR and, particularly, polychlor-oprene. Consequently natural rubber is more subject to oxidation, and as in this case (c.f. polybutadiene and SBR) this leads to chain scission the rubber becomes softer and weaker. As already stated the oxidation reaction is considerably affected by the type of vulcanisation as well as by the use of antioxidants. 

Like NR, SBR is an unsaturated hydrocarbon polymer. Hence unvulcanised compounds will dissolve in most hydrocarbon solvents and other liquids of similar solubility parameter, whilst vulcanised stocks will swell extensively. Both materials will also undergo many olefinic-type reactions such as oxidation, ozone attack, halogenation, hydrohalogenation and so on, although the activity and detailed reactions differ because of the presence of the adjacent methyl group to the double bond in the natural rubber molecule. Both rubbers may be reinforced by carbon black and neither can be classed as heat-resisting rubbers. 

Spandex fibres, because of their higher modulus, tensile strength and resistance to oxidation, as well as their ability to be produced at finer deniers, have made severe inroads into the natural rubber latex thread market. They have also enabled lighter weight garments to be produced. Staple fibre blends with non-elastic fibres have also been introduced. 

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.)... 

The author is unaware of any commerical polymers that are specifically designed to degrade oxidatively, although oxidation may be involved in association with hydrolytic and biological degradation. It may be of interest to note that before World War II products known as rubbones were produced by degrading natural rubber with cobalt linoleate in the presence of cellulosic materials to produce low molecular weight, fluid oxidised natural rubber (Section 30.4). 

If polypropylene is too hard for the purpose envisaged, then the user should consider, progressively, polyethylene, ethylene-vinyl acetate and plasticised PVC. If more rubberiness is required, then a vulcanising rubber such as natural rubber or SBR or a thermoplastic polyolefin elastomer may be considered. If the material requires to be rubbery and oil and/or heat resistant, vulcanising rubbers such as the polychloroprenes, nitrile rubbers, acrylic rubbers or hydrin rubbers or a thermoplastic elastomer such as a thermoplastic polyester elastomer, thermoplastic polyurethane elastomer or thermoplastic polyamide elastomer may be considered. Where it is important that the elastomer remain rubbery at very low temperatures, then NR, SBR, BR or TPO rubbers may be considered where oil resistance is not a consideration. If, however, oil resistance is important, a polypropylene oxide or hydrin rubber may be preferred. Where a wide temperature service range is paramount, a silicone rubber may be indicated. The selection of rubbery materials has been dealt with by the author elsewhere. ... 

Geon and Seo [47] also determined the effect of vulcanization time on the adhesion of natural rubber to brass-plated steel. For relatively short times, there was a peak at the end of the copper profile that corresponded well with a peak in the sulfur profile. Similarly, peaks in the zinc and oxygen profiles corresponded well. These results showed that copper sulfide and zinc oxide mostly formed at short times but some evidence for formation of zinc sulfide was also obtained. For long times, the peak in the sulfur profile no longer corresponded with that in the copper profile. Instead, the peak in the sulfur profile corresponded to the peak in the zinc profile. It was concluded that the formation of zinc sulfide increased substantially at long times. An increase in vulcanization time correlated well with a decrease in the force required to pull brass-plated steel wires out of rubber blocks. 

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. 

Solid SBR is often prefened to natural rubber because of its better thermal oxidative stability, higher abrasion resistance and easier processability. Solid SBRs are generally grouped into three families according to the production method. 

During World War II, polychloroprene was chosen as a replacement for natural rubber because of its availability. Two copolymers of chloroprene and sulphur which contain thiuram disulphide were available (Neoprene GN and CG). One of the first successful applications of these polychloroprene adhesives was for temporary and permanent sole attachment in the shoe industry. However, these polychloroprene cements show a decrease in viscosity on ageing and a black discolouration appears during storage in steel drums. Discolouration was produced by trace amounts of hydrochloric acid produced by oxidation of polychloroprene... 

Most rubbers used in adhesives are not resistant to oxidation. Because the degree of unsaturation present in the polymer backbone of natural rubber, styrene-butadiene rubber, nitrile rubber and polychloroprene rubber, they can easily react with oxygen. Butyl rubber, however, possesses small degree of unsaturation and is quite resistant to oxidation. The effects of oxidation in rubber base adhesives after some years of service life can be assessed using FTIR spectroscopy. The ratio of the intensities of the absorption bands at 1740 cm" (carbonyl group) and at 2900 cm" (carbon-hydrogen bonds) significantly increases when the elastomer has been oxidized [50]. 

Hydrogen fluoride reacts witlr metal carbonates, oxides, and hydroxides. Accumulation of these fluoride compounds can render valves and other close-fitting moving parts inoperable in a process system, causing possible equipment or process failures. Hydrogen fluoride also attacks glass, silicate ceramics, leather, natural rubber, and wood, but does not promote their combustion. 

The pneumatic tire has the geometry of a thin-wallcd toroidal shell. It consists of as many as fifty different materials, including natural rubber and a variety ot synthetic elastomers, plus carbon black of various types, tire cord, bead wire, and many chemical compounding ingredients, such as sulfur and zinc oxide. These constituent materials are combined in different proportions to form the key components of the composite tire structure. The compliant tread of a passenger car tire, for example, provides road grip the sidewall protects the internal cords from curb abrasion in turn, the cords, prestressed by inflation pressure, reinforce the rubber matrix and carry the majority of applied loads finally, the two circumferential bundles of bead wire anchor the pressnrized torus securely to the rim of the wheel. 

Carbon blacks are the most widely used fillers for elastomers, especially vulcanised natural rubber. They cause an improvement in stiffness, they increase the tensile strength, and they can also enhance the wear resistance. Other particulate fillers of an inorganic nature, such as metal oxides, carbonates, and silicates, generally do not prove to be nearly so effective as carbon black. This filler, which comes in various grades, is prepared by heat treatment of some sort of organic material, and comes in very small particle sizes, i.e. from 15 to 100 nm. These particles retain some chemical reactivity, and function in part by chemical reaction with the rubber molecules. They thus contribute to the crosslinking of the final material. 

Oxidation of Natural Rubber (NR) Pale Crepe at 46°C, Accelerated by Ultraviolet (UV) Light... 

FIGURE 26.58 Abrasion of two natural rubber (NR) tread compounds, one unprotected, the other with two parts Nonox ZA on a knurled Aluminum and a knurled steel surface, respectively, in the presence of (a) magnesium oxide (MgO) powder and (b) a dust mix of Fuller s earth and alumina powder. (Deduced from Schallamach, A.,Appl. Pol. Sci., 12, 281, 1968.)... 

Natural rubber is resistant to dilute mineral acids, alkahes, and salts, but oxidizing media, oils, and most organic solvents will attack it. Hard rubber is made by adding 25 percent or more of sulfur to natural or synthetic rubber and, as such, is both hard and strong. Chloroprene or neoprene rubber is resistant to attack by ozone, sunlight, oils, gasoline, and aromatic or halogenated solvents but is... 

The anti-oxidant itself is often consumed in performing its function, although hindered amine light stabilisers (HALS) are self-regenerating. Depending on the polymer, their concentration in the polymer may vary from a few parts per million (e.g., in PE) to several per cent (e.g., in ABS, natural rubber). Because it is impossible to determine all the polymer down-stream end uses, nearly all have food contact approval. 

The action of certain metals (e.g., copper) on unsaturated rubbers, primarily natural rubber, is to catalyse the oxidative degradation of the polymer. The metal must be in an ionic form, i.e., straightforward contact with the metal such as a seal with a copper pipe will not promote such degradation. 

Combination with oxygen. On the basis of the electronic theory of valency the meaning of the term has been extended to include all reactions in which there occurs an increase in the ratio of the electronegative to the electropositive atoms or groups of a substance. The controlled oxidation of natural rubber produces resinous substances called Rubbones. 

Nitrile rubber can be cured by sulphur, sulphur donor systems and peroxides. However, the solubility of sulphur in nitrile rubber is much lower than in NR, and a magnesium carbonate coated grade (sulphur MC) is normally used this is added as early in the mixing cycle as possible. Less sulphur and more accelerator than is commonly used for curing natural rubber is required. A cadmium oxide/magnesium oxide cure system gives improved heat resistance, but the use of cadmium, a heavy metal, will increasingly be restricted. 

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