Diene rubbers synthetic polyisoprene

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). 

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 discovery by Ziegler that ethylene and propylene can be polymerized with transition-metal salts reduced with trialkyl aluminum gave impetus to investigations of the polymerization of conjugated dienes (7—9). In 1955, synthetic polyisoprene (90—97% tij -l,4) was prepared using two new catalysts. A transition-metal catalyst was developed at B. E. Goodrich (10) and an alkaU metal catalyst was developed at the Ekestone Tke Rubber Co. (11). Both catalysts were used to prepare tij -l,4-polyisoprene on a commercial scale (9—19). 

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. 

Diene polymers refer to polymers synthesized from monomers that contain two carbon-carbon double bonds (i.e., diene monomers). Butadiene and isoprene are typical diene monomers (see Scheme 19.1). Butadiene monomers can link to each other in three ways to produce ds-1,4-polybutadiene, trans-l,4-polybutadi-ene and 1,2-polybutadiene, while isoprene monomers can link to each other in four ways. These dienes are the fundamental monomers which are used to synthesize most synthetic rubbers. Typical diene polymers include polyisoprene, polybutadiene and polychloroprene. Diene-based polymers usually refer to diene polymers as well as to those copolymers of which at least one monomer is a diene. They include various copolymers of diene monomers with other monomers, such as poly(butadiene-styrene) and nitrile butadiene rubbers. Except for natural polyisoprene, which is derived from the sap of the rubber tree, Hevea brasiliensis, all other diene-based polymers are prepared synthetically by polymerization methods. 

As of this date, there is no lithium or alkyl-lithium catalyzed polyisoprene manufactured by the leading synthetic rubber producers- in the industrial nations. However, there are several rubber producers who manufacture alkyl-lithium catalyzed synthetic polybutadiene and commercialize it under trade names like "Diene Rubber"(Firestone) "Soleprene"(Phillips Petroleum), "Tufdene"(Ashai KASA Japan). In the early stage of development of alkyl-lithium catalyzed poly-butadiene it was felt that a narrow molecular distribution was needed to give it the excellent wear properties of polybutadiene. However, it was found later that its narrow molecular distribution, coupled with the purity of the rubber, made it the choice rubber to be used in the reinforcement of plastics, such as high impact polystyrene. Till the present time, polybutadiene made by alkyl-lithium catalyst is, for many chemical and technological reasons, still the undisputed rubber in the reinforced plastics applications industries. 

Elastomers, synthetic -acrylic elastomers [ELASTOMERS, SYNTHETIC - ACRYLIC ELASTOMERS] (Vol 8) -butyl rubber [ELASTOMERS, SYNTHETIC - BUTYL RUBBER] (Vol 8) -chlorosulfonated polyethylene [ELASTOMERS, SYNTHETIC - CHLOROSULFONATED POLYETHYLENE] (Vol 8) -ethylene-acrylic elastomers [ELASTOMERS, SYNTHETIC - ETHYLENE-ACRYLIC ELASTOMERS] (Vol 8) -ethylene-propylene-diene rubber [ELASTOMERS,SYNTHETTC - ETHYLENE-PROPYLENE-DIENE RUBBER] (Vol 8) -fluorocarbon elastomers [ELASTOMERS, SYNTHETIC - FLUOROCARBON ELASTOMERS] (Vol 8) -nitrile rubber [ELASTOMERS, SYNTHETIC - NITRILE RUBBER] (Vol 8) -phosphazenes [ELASTOMERS, SYNTHETIC - PHOSPHAZENES] (Vol 8) -polybutadiene [ELASTOMERS, SYNTHETIC - POLYBUTADIENE] (Vol 8) -polychloroprene [ELASTOMERS, SYNTHETIC - POLYCHLOROPRENE] (Vol 8) -polyethers (ELASTOMERS, SYNTHETIC - POLYETHERS] (Vol 8) -polyisoprene [ELASTOMERSSYNTHETTC - POLYISOPRENE] (Vol 9) -survey [ELASTOMERS, SYNTHETIC - SURVEY] (Vol 8)... 

Elastomers include natural rubber (polyisoprene), synthetic polyisoprene, styrene-butadiene rubbers, butyl rubber (isobutylene-isoprene), polybutadiene, ethylene-propylene-diene (EPDM), neoprene (polychloroprene), acrylonitrile-butadiene rubbers, polysulfide rubbers, polyurethane rubbers, crosslinked polyethylene rubber and polynorbomene rubbers. Typically in elastomer mixing the elastomer is mixed with other additives such as carbon black, fillers, oils/plasticizers and accelerators/antioxidants. 

The most widely used elastomers are natural rubber [17], synthetic polyisoprene and butadiene rubbers, styrene-butadiene copolymers, ethylene-propylene rubber (specifically EPDM), butyl and halobutyl elastomers, polyurethanes, polysiloxanes, polychloroprenes, nitrile rubber, polyacrylic rubbers, fluorocarbon elastomers, and thermoplastic elastomers [18-20]. The examples which have unsaturation present in the repeat units (such as, the diene elastomers) have the advantage of easy cross-linkability, but the disadvantage of increased vulnerability to attack by reactants, such as oxygen and ozone. 

The oxidation of diene rubbers proceeds under the influence of atmospheric oxygen even at room temperature, and results in the hardening and fragility of the surface layer. In its initial stages, the oxidative degradation of natural rubber is characterised by softening of the material and the appearance of stickiness rubber elasticity then decreases and it cracks [2]. Non-vulcanised synthetic polyisoprene is oxidised extensively even at room temperature [47]. The oxidation of rubber proceeds at its double bonds and at the single bond a to the tertiary carbon atom. 

Ziegler-Natta catalysts can also be used for preparation of stereoregular polymers from 1,3-dienes. For example, polyisoprene with 96-97 per cent cw-1,4 content (i.e. synthetic natural rubber ) can be prepared using catalysts obtained from TiCU-f Ai Bu3. 

A number of different synthetic rubbers are produced commercially by diene polymerization. Both cis- and frrms-polyisoprene can be made, and the synthetic rubber thus produced is similar to the natural material. Chloroprene (2-chloro-l,3-butadiene) is polymerized to yield neoprene, an excellent, although expensive, synthetic rubber with good weather resistance. Neoprene is used in the production of industrial hoses and gloves, among other things. 

The coordination catalysts were quickly extended to dienes and found to produce the long-sought objective of a "synthetic natural rubber, i.e., cis-1,4-polyisoprene. cis-1,4-Polybutadiene was also quickly produced. These were, and still are, erroneously referred to as stereo rubbers. They are actually unique geometric isomers rather than stereoisomers, but the name stereo rubber became established probably because of the relationship in time and catalyst usage to stereo olefin polymerization. 

At the end of the 19th century, rubber, with gutta-percha, was used mainly as an electrical insulator on wires and cables. Demand was limited, and the supply of natural rubber at a reasonable price (about 1.00/lb in 1900) was ensured. Some work was done during these years on practical syntheses of isoprene and on the replacement of isoprene by its simpler homolog, butadiene, which had been known since 1863. However, advent of the automobile and accelerated use of electric power rapidly increased the demand for rubber, thus raising its price to about 3.00/lb in 1911. These circumstances focused new attention on the production of a synthetic rubber. S. B. Lebedev polymerized butadiene in 1910, and Carl Dietrich Harries, between 1900 and 1910 established qualitatively the structure of rubber as a 1,A-polyisoprene and synthesized larger quantities of rubberlike materials from isoprene and other dienes. 

The first attempts to prepare synthetic rubber were made ivith isoprene, which was known to be a building unit of the natural products, hevea, gutta percha, and others. The difficulty of producing isoprene economically, the poor properties of the early polyisoprene, and finally the realization that a successful synthetic rubber, unlike other natural substitutes, would not necessarily be an exact duplication of the natural product encouraged research with other monomers. Some of the first synthetic diene polymers produced commercially, the Neoprenes, a class of poly-2-chloro-butadienes, were superior to natural rubber in resistance to aging, chemical attack, and wear. ... 

Hydrocarbon Solvents One of the most important synthetic and commercial aspects of anionic polymerization is the ability to prepare polydienes [poly(l,3-dienes)] with high 1,4-microstructure using lithium as the counterion in hydrocarbon solutions [3, 156]. The key discovery was reported in 1956 by scientists at the Firestone Tire and Rubber Company that polyisoprene produced by lithium metal-initiated anionic polymerization had a high (>90%) cm-1,4-microstructure similar to natural rubber [47], In general, conjugated 1,3-dienes [CH2=C(R)-CH=CH2] can polymerize to form four constimtional isomeric microstructures as shown below. The stereochemistry of the anionic polymerization of isoprene and... 

Orientations in elongated mbbers are sometimes regular to the extent that there is local crystallization of individual chain segments (e.g., in natural rubber). X-ray diffraction patterns of such samples are very similar to those obtained from stretched fibers. The following synthetic polymers are of technical relevance as mbbers poly(acrylic ester)s, polybutadienes, polyisoprenes, polychloroprenes, butadiene/styrene copolymers, styrene/butadiene/styrene tri-block-copolymers (also hydrogenated), butadiene/acrylonitrile copolymers (also hydrogenated), ethylene/propylene co- and terpolymers (with non-conjugated dienes (e.g., ethylidene norbomene)), ethylene/vinyl acetate copolymers, ethyl-ene/methacrylic acid copolymers (ionomers), polyisobutylene (and copolymers with isoprene), chlorinated polyethylenes, chlorosulfonated polyethylenes, polyurethanes, silicones, poly(fluoro alkylene)s, poly(alkylene sulfide)s. 

Rubber fibers from natural sources have been known for over 100 years. Natural rubber in commerce is derived from coagulation of Hevea brasilien-sis latex and is primarily cis-polyisoprene, a diene polymer. Most synthetic rubbers were developed during and following Worid War 11. They are crosslinked diene polymers, copolymers containing dienes, or amorphous polyolefins. Both the natural and synthetic rubbers must be crossl inked (vulcanized) with sulfur or other agents before true elastomeric properties are introduced. hi addition, accelerators, antioxidants, fillers, and other materials are added to the polymeric rabber prior to fiber formation. 

Addition of butadiene to ethene polymerizations gives cross-linked material, but dienes are themselves important substrates for polymerization reactions. Natural rubber is an all-ds polymer of isoprene (Figure 21.10), which we encountered in Chapter 11, as an important precursor of the terpenes. Synthetic rubber made by radical polymerization is a mixture of cis- and trans-polyisoprene, (21.10). The material produced by metal-catalyzed polymerization is, however, all-ds and essentially identical to natural rubber. 

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