Synthetic Natural Rubber Polyisoprene

Materials that are constructed from organic polymers such as polyethylene, polystyrene, polyisoprene (natural rubber and a synthetic elastomer) and poly(vinyl chloride) are common features of our daily lives. Most of these and related organic polymers are generated from acyclic precursors by free radical, anionic, cationic or organometallic polymerisation processes or by condensation reactions. Cyclic precursors are rarely used for the production of organic polymers. 

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

Styrene-Butadiene Random Copolymer, 25% (wt) Styrene (SBR) Styrene-Butadiene Block Copolymer, about 25% Styrene (YSBR) Cis-1,4- Polyisoprene (Natural Rubber NR, Also Made Synthetically IR) Cis-1,4 Polybutadiene (BR) Polychloroprene (CR), Neoprene Butadiene-Acrylonitrile Random Copolymer, Variable % Acrylonitrile (NBR) Reclaimed Rubber (Whole Tires) (Mainly NR and SBR)... 

Silicone, natural, and synthetic rubbers have been used for the fabrication of implants. Natural rubber is made mostly from the latex of the Hevea brasiliensis tree and the chemical formula is the same as that of cw-1,4 polyisoprene. Natural rubber was found to be compatible with blood in its pure form. Also, cross-linking by x-ray and organic peroxides produces rubber with superior blood compatibility compared with rubbers made by the conventional sulfur vulcanization. 

Comparative studies on the thermal degradation of polyisoprene, natural rubber (cis-polyisoprene) and gutta percha (t r tns-polyisoprene) all of which have the same chemical composition have shown that they differ in their thermal degradation characteristics. Studies under vacuum at 290-380 "C have shown that the decomposition of natural rubber (NR) is initiated at comparatively low temperatures at a considerable rate, whereas its decomposition rate at higher temperatures (above 330 "C) is to some extent slower than that of gutta percha and polyisoprene (Figure 2.1). The half-life temperature for synthetic polyisoprene is 320 C [1, 2]. 

U.S. and Western European production figures for polyisoprene, the closest synthetic to natural rubber, appear to be quite small at less than 100 kilotonnes per annum in each area. However, there is a much higher capacity, and presumably greater use, for polyisoprene in Eastern Europe and the former Soviet republics. 

As described in Section 1.1, the first commercial polymers, which were naturally occurring, were polyisoprenes (natural rubber and gutta-percha) and subsequently cellulose derivatives. From the early twentieth century, various totally synthetic polymers were introduced. Farbenfabrrken Bayer introduced bulk polymerized totally synthetic elastomers in 1910. Poly(dimethyl butadiene) synthetic rubber was produced commercially by Bayer in Leverkusen during World War I. The 1920s saw the commercial development of polystyrene (PS) and poly(vinyl chloride) (PVC). In 1934, the IG Farbenindustrie (a combine of Bayer, BASF, Floechst, and other firms) began to commercially manufacture butadiene-acrylonitrile copolymer (N BR) as an oil resistant rubber and in 1937 butadiene-styrene copolymer (SBR) intended for pneumatic tires. 

Synthetic polyisoprene, isoprene rubber (IR), was introduced in the 1950s as odorless rubber with virtually the same properties as natural rubber. Isoprene rubber product and processing properties are better than natural rubber in a number of characteristics. MW and MWD can be controlled for consistent performance and processing properties. 

Medical tapes are the oldest application of pressure-sensitive tapes [203]. Major progress towards skin compatibility was made by introduction of zinc oxide into the rubber-based PSAs [282]. With the development of polyisoprene, polyisobutylene, and other synthetic elastomers, natural rubber was replaced to a certain extent in medical products by synthetic rubbers. These were followed by the styrenic block copolymers [211, pp. 317-373]. 

The use of alkaU metals for anionic polymerization of diene monomers is primarily of historical interest. A patent disclosure issued in 1911 (16) detailed the use of metallic sodium to polymerize isoprene and other dienes. Independentiy and simultaneously, the use of sodium metal to polymerize butadiene, isoprene, and 2,3-dimethyl-l,3-butadiene was described (17). Interest in alkaU metal-initiated polymerization of 1,3-dienes culminated in the discovery (18) at Firestone Tire and Rubber Co. that polymerization of neat isoprene with lithium dispersion produced high i7j -l,4-polyisoprene, similar in stmcture and properties to Hevea natural mbber (see ELASTOLffiRS,SYNTHETic-POLYisoPRENE Rubber, natural). 

The revolutionary development of stereospecific polymerization by the Ziegler-Natta catalysts also resulted ia the accomplishment ia the 1950s of a 100-year-old goal, the synthesis of i7j -l,4-polyisoprene (natural mbber). This actually led to the immediate termination of the U.S. Government Synthetic Rubber Program ia 1956 because the technical problem of dupHcating the molecular stmcture of natural mbber was thereby solved, and also because the mbber plantations of the Far East were again available. 

Between the 1920s when the initial commercial development of mbbery elastomers based on 1,3-dienes began (5—7), and 1955 when transition metal catalysts were fkst used to prepare synthetic polyisoprene, researchers in the U.S. and Europe developed emulsion polybutadiene and styrene—butadiene copolymers as substitutes for natural mbber. However, the tire properties of these polymers were inferior to natural mbber compounds. In seeking to improve the synthetic material properties, research was conducted in many laboratories worldwide, especially in the U.S. under the Rubber Reserve Program. 

The latex of the Sapota achras yields a thermoplastic material, chicle, consisting of about 17.4% hydrocarbon, 40% acetone soluble resin and 35% occluded water. The hydrocarbon appears to contain both trans- and c/s-polyisoprene. Although originally introduced as gutta pereha and natural rubber substitutes, deresinated chicle has become important as the base for chewing gum. Like other polyisoprenes, it is meeting competition from synthetic polymers. 

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. 

The standard polymers used for rubber linings consist of materials that are cross-linkable macromolecules which, on mixing with suitable reactants that form strong chemical bonds, change from a soft deformable substance into an elastic material. These polymers include natural rubber and its corresponding synthetic, c/s-polyisoprene, styrene-butadiene rubber, polychloroprene, butyl rubber, halogenated butyl rubbers, acrylonitrile-... 

Isoprene may be the naturally occurring alkene with the greatest economic impact. This compound, a major component of the sap of the rubber tree, is used to make the long-chain molecules of natural rubber (polyisoprene). As we describe in Chapter 13. the synthetic rubbers that make up most of today s tires are made from other alkenes. 

The infrared spectra of hevea (natural rubber), balata (or guttapercha), the latter both in the crystalline (a) and the amorphous forms, and of synthetic polyisoprene are compared in Fig. 32. The hevea and balata (amorphous) spectra offer calibrations for cfs-1,4 and irans-1,4 structures, respectively, in the synthetic polymer. Owing to the presence of the methyl substituent, however, the spectral difference between the as and trans forms is slight both absorb at about 840... 

Figure 15. Behavior under strain of an unvulcanized tire ply (conventional recipe) based on NR (natural rubber 100%), 1R (synthetic cis-7,4-polyisoprene 100%), BP/1R (a 50/50 blend of IR and txans-butadiene-piperylene copolymer).

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. 

Other polymeric binders, natural and synthetic, may be found as paints or varnishes in modern artworks and installations. Artists very easily adopt resins developed as industrial coatings or for specialized applications, and use them according to their creative needs. Natural rubber latex is a water dispersion of 1,4-ds-polyisoprene particles where pigments can be added to give coloured paints. By means of Py-GC/MS the presence of these paints can be easily assessed. As shown in Figure 12.13, the principal marker peaks in the pyrogram are those of isoprene, limonene and other cyclic dimers. 

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