Natural rubber or polyisoprene

In 1826, Faraday established the chemical formula of the monomer unit of natural rubber or polyisoprene. 

A comparison of polychloroprene and natural rubber or polyisoprene molecular structures shows close similarities. However, while the methyl groups activates the double bond in the polyisoprene molecule, the chlorine atom has the opposite effect in polychloroprene. Thus polychloroprene is less prone to oxygen and ozone attack than natural rubber is. At the same time accelerated sulfur vulcanization is also not a feasible proposition, and alternative vulcanization or curing systems are necessary. 

Natural rubber or polyisoprene (NR or IR) Ethylene propylene diene rubber (EPDM) Isobutylene-isoprene (butyl) rubber (HR)... 

Thermodynamic Analysis. As reported previously, the storage modulus G of PDMS networks with tetrafunctional crosslinks is independent of frequency between 10 3 and 1 Hz (21). This behaviour which is entirely different from that of vulcanized natural rubber or synthetic polyisoprene networks, was attributed to the lack of entanglements, both trapped and untrapped, in these PDMS networks. Figure 4 shows that G of a network with comb-like crosslinks is also frequency independent within an error of 0.5%. For comparison, two curves for PDMS having tetrafunctional crosslinks are also shown. The flat curves imply that slower relaxations are highly unlikely. Hence a thermodynamic analysis of the G data below 1 Hz can be made as they equal equilibrium moduli. 

Chemically, natural rubber or dr-polyisoprene, has a broad molecular-weight distribution, ranging from several million to about one hundred thousand. 

The system Cl-buty 1-natural rubber (or cw-polyisoprene) could not be resolved by differential solvent techniques because the polymeric solubility parameters were too similar. At one end of the spectrum—i.e., with styrene at — 25 °C—natural rubber could be highly swollen while restricting the chlorobutyl swell, but the reverse was not possible, as indicated by the swelling volumes in the trimethylpentane. As displayed in Table II, attempts to use a highly symmetrically branched hydrocarbon with a very low solubility parameter, served only to reduce both the swelling of natural rubber and chlorobutyl. (Neopentane is a gas above 10°C and a solid below — 20°C). Therefore, for this report the use of differential solvents in the study of interfacial bonding in blends was limited to systems of Cl-butyl and cw-polybutadiene or SBR. 

Cis-1,4 polyisoprene (natural rubber or synthetic isoprene rubber) and trans-1,4 polyisoprene (balata or guttah-percha) show strongly different properties. 

Polyisoprene (R = CH3) with a c/s-1,4 configuration is common in nature in different species of piants and is known as natural rubber. Trans-polyisoprene is found in two naturai resins known as gutta-percha and balata. Natural or synthetic polyisoprenes, as well as polybutadiene, are among the most common elastomers with many practical uses. Other elastomers with extensive practical applications are copolymers, many of them using butadiene or isoprene in the starting monomer mixture. 

Synthetic natural rubber, cw-polyisoprene, is an example of a stereospecific polymer made possible by this means. There are five types of stereo specific (or stereoregular) structures cis, trans, isotactic, syndi-otactic, and tritactic. 

Finite chain extensibility is the major reason for strain hardening at high elongations (Fig. 7.8). Another source of hardening in some networks is stress-induced crystallization. For example, vulcanized natural rubber (cw-polyisoprene) does not crystallize in the unstretched state at room temperature, but crystallizes rapidly when stretched by a factor of 3 or more. The extent of crystallization increases as the network is stretched more. The amorphous state is fully recovered when the stress is removed. Since the crystals invariably have larger modulus than the surrounding... 

Natural Rubber Natural rubber, also called India rubber or caoutchouc, is an elastomer that is derived from latex, a milky colloid mainly extracted from rubber trees (Figure 5.1.35). The purified form of natural rubber is polyisoprene, which can also be produced synthetically. Natural rubber is used extensively in many applications and products, as is synthetic rubber. Today, the global annual production of natural rubber is 10 Mio. tonnes, which is about 40% of the total rubber production (natural and synthetic). The three largest producing countries of natural rubber are Thailand, Indonesia, and Malaysia. 

Representative diene-based polymers include natural rubber (NR), polyisoprene (PIP), PBD, styrene—butadiene rubber (SBR), and acrylonitrile-butadiene rubber (NBR), which together compose a key class of polymers widely used in the rubber industry. These unsaturated polyolefins are ideal polymers for chemical modifications owing to the availability of parent materials with a diverse range of molecular weights and suitable catalytic transformations of the double bonds in the polymer chain. The chemical modifications of diene-based polymers can be catalytic or noncatalytic. The C=C bonds of diene-based polymers can be transformed to saturated C—C and C—H bonds (hydrogenation), carbonyls (hydrofbrmylation and hydrocarboxylation), epoxides (epoxidation), C—Si bonds (hydrosilylation), C—Ar bonds (hydroarylation), C—B bonds (hydroboration), and C—halogen bonds (hydrohalogenation). ... 

Reactions on natural rubber or cis-l,4-polyisoprene, in the presence of various OA catalysts such as c -camphorsulfonic acid, percamphoric acid or sodium or barium active-isoamyl-alcoholate were reported by Minoura [189]. Optically active polymers, after hydrolysis of the optically active group, were only obtained with barium alcoholate. The rotatory powers are very small, even for the best reported value of the addition (20%). With other catalysts, there was no asymmetric induction. The mechanism producing the active adduct polymer was thought by the author to be as follows (Scheme LXXI) ... 

NR, IR Natural rubber, Isoprene Polyisoprene Most moderate wet or dry chemicals, organic acids, alcohols, ketones, aldehydes Ozone, strong acids, fats, oils, greases, most hydrocarbons... 

Where high c/.s-polyisoprene is required as the base polymer for the manufacture of rubber articles, either natural rubber or the synthetic counterpart can be used almost without exception. 

High shear testing machines such as the Wallace rapid plastimeter, the Monsanto processability tester and extrusion viscometers may better differentiate between natural rubber and polyisoprene, and even between polyisoprenes from different suppliers. None of these machines alone, however, will accurately predict the behaviour of the polymer or batch for all processing operations. Thus Mooney viscosity plus practical experience remain the principal factors in categorising factory processing. 

Several other elastic materials may be made by copolymerising one of the above monomers with lesser amounts of one or more monomers. Notable amongst these are SBR, a copolymer of butadiene and styrene, and nitrile rubber (NBR), a copolymer of butadiene and acrylonitrile. The natural rubber molecule is structurally a c/i -1,4-polyisoprene so that it is convenient to consider natural rubber in this chapter. Some idea of the relative importance of these materials may be gauged from the data in Table 11.14. 

A number of high molecular weight polyisoprenes occur in nature which differ from natural rubber in that they are essentially non-elastic. As with natural rubber they are obtained from the latex of certain plants but they differ in that they are either frani-l,4-polyisoprenes and/or are associated with large quantities of resinous matter. 

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. 

FIGURE 19.17 The gray cylinders in the small inset represent polyisoprene molecules, and the beaded yellow strings represent disulfide (—S—S—) links that are introduced when the rubber is vulcanized, or heated with sulfur. These cross-links increase the resilience of the rubber and make it more useful than natural rubber. Automobile tires are made of vulcanized rubber and a number of additives, including carbon. 

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