Natural rubber degradation

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). 

Natural rubber can be viewed as a 1,4-addition polymer of isoprene. In fact, pyrolysis degrades natural rubber to isoprene. Pyrolysis (Greek pyros, a fire, -f lysis) is the heating of a substance in the absence of air until it decomposes. The isoprene units of natural rubber are all linked in a head-to-tail fashion, and all of the double bonds are ds ... 

Table 3 11 Trans and cis epoxides in degraded natural rubbers.

C-NMR studies on oxidative degraded natural rubbers showed the presence of epoxides as part of the by-products, of which the cis configuration was found to be the major product the tram configuration was the minor product, as shown in Table 3.11. This contradicts the prediction that degradation of natural rubber produces tram epoxide groups. ... 

Natural mbber, the other natural hydrocarbon polymer, consisting mainly of cfr-l,4-polyisoprene is relatively resistant to microbial attack in comparison to other natural polymers. A number of micro-organisms have been reported to degrade natural rubber. An enzyme which degrades the mbber was isolated from the extracellular culture medium of Xanthomonas sp., and the erude fractions which are capable of depolymerizing natural mbber in the latex state have been reported.The same authors " reported on a Nocardia strain that used natural mbber as its sole carbon source. 

There is much evidence that weak links are present in the chains of most polymer species. These weak points may be at a terminal position and arise from the specific mechanism of chain termination or may be non-terminal and arise from a momentary aberration in the modus operandi of the polymerisation reaction. Because of these weak points it is found that polyethylene, polytetrafluoroethylene and poly(vinyl chloride), to take just three well-known examples, have a much lower resistance to thermal degradation than low molecular weight analogues. For similar reasons polyacrylonitrile and natural rubber may degrade whilst being dissolved in suitable solvents. 

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. 

Natural rubber is harvested as latex by tapping trees in a manner similar to maple syrup. Tree latex contains about 35 wt% rubber solids, as well as small quantities of carbohydrates, resins, mineral salts and fatty acids. Ammonia should be immediately added to the latex to avoid coagulation by these other ingredients and to prevent bacterial degradation. After collection, the latex can be concentrated to 60-70% solids if the latex product is required for end-use. Otherwise, the latex is coagulated, washed, dried, and pressed into bales for use as dry rubber. 

There were essentially three reasons for this opposition. Firstly, many macromolecular compounds in solution behave as colloids. Hence they were assumed to be identical with the then known inorganic colloids. This in turn implied that they were not macromolecular at all, but were actually composed of small molecules bound together by ill-defined secondary forces. Such thinking led the German chemist C. D. Harries to pursue the search for the rubber molecule in the early years of the twentieth century. He used various mild degradations of natural rubber, which he believed would destroy the colloidal character of the material and yield its constituent molecules, which were assumed to be fairly small. He was, of course, unsuccessful. 

The molecular weight of natural rubber (NR) can be altered by mechanical means. Mastication of NR results in a reduction of molecular weight. In the distant past, NR was commonly subjected to mechanical degradation on open mills for extended periods of time to improve processability. 

Al-Malaika, S. and Amir, E.J., Thermoplastic elastomers Part III—Ageing and mechanical properties of natural rubber-reclaimed rubber/polypropylene systems and their role as solid phase dispersants in polypropylene/polyethylene blends, Polym. Degrad. Stab., 26, 31, 1989. 

Tsuchii, A., Suzuki, T., and Takeda, K., Microbial degradation of natural rubber vulcanizates, Appl. Bnviron. Microbiol., 50, 965, 1985. 

This discussion of the structures of diene polymers would be incomplete without reference to the important contributions which have accrued from applications of the ozone degradation method. An important feature of the structure which lies beyond the province of spectral measurements, namely, the orientation of successive units in the chain, is amenable to elucidation by identification of the products of ozone cleavage. The early experiments of Harries on the determination of the structures of natural rubber, gutta-percha, and synthetic diene polymers through the use of this method are classics in polymer structure determination. On hydrolysis of the ozonide of natural rubber, perferably in the presence of hydrogen peroxide, carbon atoms which were doubly bonded prior to formation of the ozonide... 

Antiozonant additives are employed with unsaturated rubbers such as natural rubber, nitrile rubber, styrene-butadiene rubber, etc., to minimise the atmospheric ozone degradation reaction. Common antiozonant types include the parapheny-lene diamines such as N-(l,3-dimethylbutyl)-AT-phenyl-p-phenylene diamine (6PPD) and N-isopropyl-N7 phenyl-p-phenylene diamine (IPPD). Both these antioxidants can be identified and quantified using GC- or LC-based techniques. 

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. 

A test which is claimed to be a more reliable guide to the condition of a natural rubber latex than the KOH number. The test is performed by steam distillation of the latex and titration of the distillate with standard alkali solution. The VFA number is a measure of the state of degradation of the latex. 

Grinding or milling causes degradation of many polymers. The process of mastication of natural rubber involves a mechanically initiated, autoxidative degradation which lowers the molecular weight to a level where the material is easier to process on a commercial scale. 

Certain elastomeric materials used as gaskets, seals, and hoses can be degraded by aromatic fuel components. Elastomers such as natural rubber, neoprene, Buna-N, and ethylene-propylene will all swell in the presence of aromatic fuel components. 

If the degradation reaction is carried out in the presence of an unpolymerizable species, only one molecule of the monomer adds to the primary radical This is the case for the system natural rubber-maleic anhydride 11,65,71). 

PB. Sulekha, R. Joseph, and K.E. George, Studies on polyisobutylene bound paraphenylene diamine antioxidant in natural rubber, Polym. Degrad. Stab., 63(2) 225-230, February 1999. 

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. 

Neoprene is the generic name for polychloroprene rubber. It has been produced commercially since 1931 and had rapid and wide acceptance because it is much superior to natural rubber for heat and oil resistance. Heat resistance is far better than NR, BR or SBR. but less than EPDM. When heated in the absence of air, neoprene withstands degradation better than other elastomers which are normally considered more heat resistant, and retains its properties fifteen times longer than in the presence of air. Compression set at higher temperature is better than natural rubber and 100°C is typically the test temperature rather than 70°C. Abrasion resistance is not as good as natural rubber but generally better than most heat resistant and oil resistant rubbers. This is also true for tear strength and flex resistance. 

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