Natural rubber chemical structure

A detailed discussion of the history structure and applications of natural rubber appears in the May 1990 issue of the Journal of Chemical Education... 

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. 

Figure 13 Chemical structures of trans and cis isomers of 1,4 polyisoprene (gutta-percha and natural rubber, respectively).

Staudinger, like Pickles in 1910, chemically modified rubber and noted its failure to lose colloidal properties as evidence of chain structure (49). His experimental proof was impressive for he had catalytically hydrogenated natural rubber and then thoroughly studied the properties of the saturated product. He reasoned that the disappearance of the double bonds of natural rubber should result in a loss of "residual valence", and failure to do so was conclusive. 

When we compared the viscosities of solutions of natural rubber and of guttapercha and of other elastomers and later of polyethylene vs.(poly)cis-butadiene, with such bulk properties as moduli, densities, X-ray structures, and adhesiveness, we were greatly helped in understanding these behavioral differences by the studies of Wood (6) on the temperature and stress dependent, melting and freezing,hysteresis of natural rubber, and by the work of Treloar (7) and of Flory (8) on the elasticity and crystallinity of elastomers on stretching. Molecular symmetry and stiffness among closely similar chemical structures, as they affect the enthalpy, the entropy, and phase transitions (perhaps best expressed by AHm and by Clapeyron s... 

The new absorptions in the spectra of crosslinked rubber are assigned on the basis of 13C solution NMR chemical shifts for a variety of model compounds, such as pentenes and mono-, di- and tri-sulfidic compounds, by using the 13C chemical shift substituent effect. From the calculated values for particular structural units, the experimental spectra of a sulfur vulcanized natural rubber 194,195,106), natural rubber cured by accelerated sulfur vulcanization 197 y-irradiation crosslinked natural rubber198 and peroxide crosslinked natural rubber and cis-polybutadiene 193 1991 are assigned. 

By using this method, the chemical shifts of the resonances in the spectra of a sulfur vulcanized natural rubber (Fig. 32 expanded aliphatic region in shown in Fig. 33 [top]) are assigned to various units of the polymer network, which arise from structural modifications induced by the vulcanization 194,196 200). Different sulfidic structures are found for unaccelerated and accelerated sulfur vulcanizations, respectively. With increasing amount of accelerator (as compared to the sulfur), the network structure exhibits less crosslinking, fewer main chain structural modifications, and fewer cyclic sulfide structures 197). 

Polymers for membrane preparation can be classified into natural and synthetic ones. Polysaccharides and rubbers are important examples of natural membrane materials, but only cellulose derivatives are still used in large scale for technical membranes. By far the majority of current membranes are made from synthetic polymers (which, however, originally had been developed for many other engineering applications). Macromolecular structure is crucial for membrane barrier and other properties main factors include the chemical structure of the chain segments, molar mass (chain length), chain flexibility as well as intra- and intermolecular interactions. 

A critical requirement for obtaining engineering properties from a rubbery material is its existence in a network structure. Charles Goodyear s discovery of vulcanization changed natural rubber from a material that became sticky when hot and brittle when cold into a material that could be used over a wide range of conditions. Basically, he had found a way to chemically connect the individual polymer chains into a three-dimensional network. Chains that previously could flow past one another under stress now had only limited extensibility, which allowed for the support of considerable stress and retraction upon release of the stress. The terms vulcanization, rubber cure, and cross-linking all refer to the same general phenomenon. 

Natural and synthetic rubbers are used as linings or as structural components for equipment in the chemical industries. By adding the proper ingredients, natural rubbers with varying degrees of hardness and chemical resistance can be produced. Hard rubbers are chemically saturated with sulfur. The vulcanized products are rigid and exhibit excellent resistance to chemical attack by dilute sulfuric acid and dilute hydrochloric acid. 

When only spectroscopic methods are used, they are able to identify polymer components with respect to their chemical nature. However, in many cases, they are unable to answer the question whether two chemical structures are combined to yield a copolymer or a blend or both. For example, analyzing a rubber mixture one is able to identify styrene and butadiene as the monomer units. However, using FTIR or NMR it is impossible to decide if the sample is a mixture of polystyrene (PS) and polybutadiene (PB),or a copolymer of styrene and butadiene, or a blend of a styrene-butadiene copolymer and PB. For the latter case, even the copolymer composition cannot be determined just by running a FTIR or NMR spectrum. 

Natural rubber with its natural structure is a sticky substance with low elasticity which isn t very useful to the chemical industry. However, when natural rubber is heated with sulfur, it becames harder, less soluble and more durable and so much more useful. This process is known as vulcanization. 

As in any other chemical compound, different geometrical arrangements of substituent groups are possible in a polymer where rigid molecular units are involved. This gives rise to trans- and cis-configurational isomerism in polymers containing double bonds in their repeat units, as in polyacetylene and natural and synthetic rubbers. The structures of the trans- and m-isomers of polyacetylene and polybutadiene are illustrated in Fig. 1.8. 

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