Natural rubber, structure vulcanization

Individual polymer chains in an ensemble can also be covalently joined to other chains around it at discrete points along it. This yields a 3D network of chains (or open-tree structures of chains or a mix of both). Cross-linking is desirable where insolubility and high mechanical strength are demanded of aplastic. Ideally, each and every chain will be linked to each other so that the entire ensemble of chains is a single giant molecule (this actually does occur in natural rubber when vulcanized or cross-linked.) An automobile or aircraft tire is an example of a fully cross-linked polymer. On heating, cross-linked polymers do not convert into a viscous liquid melt as the molecules are chemically linked to one another and cannot flow independently. 

Two quaternary phosphonium salts (aromatic and aliphatic) have been used as intercalants for Na -MMT, as reported by Avalos et al. and the effect of intercalant structure on clay morphology and natural rubber (NR) vulcanization kinetics was investigated. A higher interlayer space was achieved with aliphatic intercalant and the corresponding diagram is given in Figure 8.2. 

Natural rubber latex, obtained from rubber trees, is converted to its final form by a process known as vulcanization, first discovered by Charles Goodyear in 1839. Vulcaiuzation is basically a crosslinking reaction of double bonds in the latex structure with sulfur. The polymerization of butadiene with itself or with other vinyl monomers results in a material that like natural latex, still contains double bonds. Thus, synthetic rubber made from butadiene can be processed and vulcanized just like natural rubber. 

Now the lone chlorine atom has found itself isolated since the zinc only extracts two adjacent chlorines. Such a result is called reactant isolation, and one wishes to predict the chlorine concentration left in the polymer as a function of time. It was shown by Flory76 that the fraction of chlorines unreacted should approach e 2, and this was used in fact by Marvel77 to determine the structure of polyvinyl chloride. Other examples are the condensation of the polymer of methyl vinyl ketone76 and the vulcanization of natural rubber.78 The vulcanization studies supply another example where a molecular structure was determined by a kinetic scheme. The complete time dependence of the process was recently derived by Cohen and Reiss24 using a novel method of multiplets, which will now be outlined. 

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. 

Linear and carbon-filled, sulfur vulcanized natural rubber were investigated using the eight-pulse sequence MREV-8, which has the following structure 182,183) ... 

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). 

Andreis M, Liu J, Koenig JL (submitted to J. Polym. Sci., Polym. Phys. Edn. for publ.) Solid state carbon-13 NMR studies of vulcanized elastomers. V. Observation of new structures in sulfur vulcanized natural rubber... 

Unsaturated and Vulcanized Rubbers. Oxidation occurs most readily at polymers with structural double bonds, such as natural rubber, polybutadiene, or polyisoprene. Aromatic amines and sterically hindered phenols are effective antioxidants. From the rubber antioxidants, 96.8 million pounds were amines, and 20 million pounds were phenols. Amines act also as antiozonants whereas phenols are not effective. Furukawa shows that amines have a lower oxidation potential which is a prerequisite for antiozonant action. 

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. 

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. 

On the other hand, if the cross-link density is low (the length of the chains between cross-links is large) and the mobility of the chains is high, the cross-linked material is called an elastomer. An example of a typical elastomer is cw-l,4-polyisoprene (natural rubber), which, by means of a cross-linking reaction with sulfur (vulcanization), gives rise to a network structure (see Fig. 1.4). 

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