Synthetic Elastomer

Styrene butadiene rubber (SBR) is, quantitatively, the most important synthetic rubber. It is a copolymer of styrene and butadiene in such a ratio that its rubbery nature predominates, vulcanization is carried out with sulphur, reinforcement with carbon black. It is used at a very large scale in tyres for passenger cars, thanks to its excellent combination of abrasion resistance and friction on the road. In large tyres it can not replace natural rubber because of its heat development (hysteresis losses). 

Butadiene rubber (BR) or Polybutadiene has an excellent abrasion resistance and a very low damping, but is, undiluted, too jumpy for use in tyres. In blends with SBR or natural rubber a good compromise of properties can be obtained. 

Isoprene rubber (IR) or Polyisoprene is a synthetic copy of natural rubber (NR) and approaches NR in its properties. Besides for tyres, IR is, because of its good flow properties, suitable for injection moulding. 

Butyl rubber (IIR) is derived from polyisobutylene, a polymer which is not further mentioned in this chapter, which has a rubbery nature, but which can not be vulcanised in the conventional way with sulphur. This objection is taken away by copolymerisation with a small amount of isoprene. Butyl rubber has a very low resilience, but outrivals all other rubbers in resistance to gas permeation for that reason it is generally used for tyre inner tubes. 

Chloroprene rubber (CR) is a synthetic rubber with very high chemical resistance, and is, therefore, applied in cable protection, oil transport tubes etc. 

The elastomer must exhibit a low value of Tg. Among polymers that might be regarded as engineering elastomers the following should be mentioned—butadiene-styrene copolymer (GR-S or SBR), butyl, neoprene, EPR (copolymer ethylene-propylene), nitrile, polybutadiene, thiokol, polyiso-prene, silicon, polyurethane, Hypalon, and EPDM. The internal breakdown by consumption is about 75% synthetic versus 25% natural rubber. Within the family of synthetic elastomers a typical breakdown is about 46% SBR, 19% polybutadiene, 9% EPR, 4% neoprene and 3% nitrile. 

Natural rubber itself is a polyisoprene (cis). By the addition of carbon black, it reaches excellent mechanical properties however, natural rubber suffers from relatively low resistance to heat, oxygen from the atmosphere (mainly to ozone), and various oils or solvents. The synthetic polyisoprene and SBR are typical rubber substitutes, resembling mbber in general performance. 

The primary need for a substitute arose in the Second World War, when 

EPR is currently replaced by EPDM, a modification with a diene monomer, due to its improved workability. A novel type of elastomer (called a thermoplastic elastomer) exhibits quite revolutionary behavior. Here cross-linking is temporary (at room temperature) while it can flow at higher temperatures, like thermoplastics. The typical one (SBS) is a strictly ordered block copolymer of styrene and butadiene, made by an anionic polymerization. The butadiene chains (at a controlled MW of 70,000) are embedded in a rigid phase of polystyrene spheres (MW of 15,000) thus providing temporary cross-linking at ambient conditions, while being processible at high temperatures like thermoplastics. 

1500 series Cold nonpigmented emulsion SBR (polymerized below 10°C) 

1600 series Cold polymerized/carbon black master batch/14 phr oil (max) SBR 1700 series Oil-extended cold emulsion SBR 

1800 series Cold emulsion-polymerized/carbon black master batch/more than 14 phr oil SBR 

1900 series Emulsion resin rubber master batches 

Passenger tires Retread rubber Truck tires 

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Acroleiu, iu lARC Monographs on the Evaluation of Carcinogenic Risk of Chemicals to Humans. Some Monomers, Plastics and Synthetic Elastomers andMcrolein, Vol. 19, International Agency for Research on Cancer, Lyon, France, 1979, pp. 479—494. 

Gaskets in both dry gas and Hquid chlorine systems are made of mbberi2ed compressed asbestos. Eor wet chlorine gas, mbber or synthetic elastomers are acceptable. PTEE is resistant to both wet and dry chlorine gas and to Hquid chlorine up to 200°C. Tantalum, HasteUoy C, PTEE, PVDE, Monel, and nickel are recommended for membranes, mpture disks, and beUows. 

Plastics and Elastomers. Common plastics and elastomers (qv) show exceUent resistance to hydrochloric acid within the temperature limits of the materials. Soft natural mbber compounds have been used for many years as liners for concentrated hydrochloric acid storage tanks up to a temperature of 60°C (see Rubber, natural). SemUiard mbber is used as linings in pipe and equipment at temperatures up to 70°C and hard mbber is used for pipes up to 50°C and pressures up to 345 kPa (50 psig). When contaminants are present, synthetic elastomers such as neoprene, nitrile, butyl. 

Nickel dialkyldithiocarbamates stabili2e vulcani2ates of epichlorhydrinethylene oxide against heat aging (178). Nickel dibutyldithiocarbamate [56377-13-0] is used as an oxidation inhibitor in synthetic elastomers. Nickel chelates of substituted acetylacetonates are flame retardants for epoxy resins (179). Nickel dicycloalkyldithiophosphinates have been proposed as flame-retardant additives for polystyrene (180—182) (see Flame retardants Heat stabilizers). 

Chloroprene (2-chloro-1,3-butadiene), [126-99-8] was first obtained as a by-product from tbe synthesis of divinylacetylene (1). Wben a mbbery polymer was found to form spontaneously, investigations were begun tbat prompdy defined tbe two methods of synthesis that have since been the basis of commercial production (2), and the first successbil synthetic elastomer. Neoprene, or DuPrene as it was first called, was introduced in 1932. Production of chloroprene today is completely dependent on the production of the polymer. The only other use accounting for significant volume is the synthesis of 2,3-dichloro-l,3-butadiene, which is used as a monomer in selected copolymerizations with chloroprene. 

Rubber and Synthetic Elastomers. For many years nondecorative coated fabrics consisted of natural mbber on cotton cloth. Natural mbber is possibly the best all-purpose mbber but some characteristics, such as poor resistance to oxygen and ozone attack, reversion and poor weathering, and low oil and heat resistance, limit its use to special appHcation areas (see Elastomers, synthetic Rubber, natural). 

The economic importance of copolymers can be cleady illustrated by a comparison of U.S. production of various homopolymer and copolymer elastomers and resins (102). Figure 5 shows the relative contribution of elastomeric copolymers (SBR, ethylene—propylene, nitrile mbber) and elastomeric homopolymers (polybutadiene, polyisoprene) to the total production of synthetic elastomers. Clearly, SBR, a random copolymer, constitutes the bulk of the entire U.S. production. Copolymers of ethylene and propylene, and nitrile mbber (a random copolymer of butadiene and acrylonitrile) are manufactured in smaller quantities. Nevertheless, the latter copolymers approach the volume of elastomeric butadiene homopolymers. 

Fig. 5. U.S. production of synthetic elastomers (thousands of metric tons) versus production year (63). A, Total B, SBR C, polybutadiene D,...

L. E. Eorman, in J. P. Kennedy and E. G. Tomquist, eds.. Polymer Chemistry of Synthetic Elastomers II, High Polymers, Vol. 23, Wiley-Interscience, New York, 1969. 

The purpose of this article is to provide a brief overview of the materials designated synthetic elastomers and the elastomeric or mbbery state. Subsequent entries describe the individual classes of elastomers in detail. Table 1 provides a fundamental description of the principal classes of synthetic elastomers. Table 2 gives the widely accepted ASTM abbreviations for synthetic mbbers. 

Nitrile Rubber (NBR). This is the most solvent-resistant of the synthetic elastomers, except for Thiokol, which, however, has rather severe limitations. NBR was developed both in Germany and the United States by private industry prior to World War II. It is a copolymer of butadiene, CH2=CH—CH=CH2, and acrylonitrile, CH2=CHCN, corresponding to the molecular stmcture shown in Table 1. 

Thermoplastic Elastomers. These represent a whole class of synthetic elastomers, developed siace the 1960s, that ate permanently and reversibly thermoplastic, but behave as cross-linked networks at ambient temperature. One of the first was the triblock copolymer of the polystyrene—polybutadiene—polystyrene type (SheU s Kraton) prepared by anionic polymerization with organoHthium initiator. The stmcture and morphology is shown schematically in Figure 3. The incompatibiHty of the polystyrene and polybutadiene blocks leads to a dispersion of the spherical polystyrene domains (ca 20—30 nm) in the mbbery matrix of polybutadiene. Since each polybutadiene chain is anchored at both ends to a polystyrene domain, a network results. However, at elevated temperatures where the polystyrene softens, the elastomer can be molded like any thermoplastic, yet behaves much like a vulcanized mbber on cooling (see Elastomers, synthetic-thermoplastic elastomers). 

Acrylic rubbers, as is the case for most specialty elastomers, are characterized by higher price and smaller consumption compared to general-purpose mbbers. The total mbber consumption ia 1991 was forecast (55) at 15.7 million t worldwide with a 66% share for synthetic elastomers (10.4 x 10 t). Acryhc elastomers consumption, as a minor amount of the total synthetic mbbers consumption, can hardly be estimated. As a first approximation, the ACM consumption is estimated to be 7000 t distributed among the United States, Western Europe, and Japan/Far East, where automotive production is significantly present. 

Isobutjiene was first polymerized ia 1873. High molecular weight polymer was later synthesized at I. G. Farben by decreasiag the polymerization temperature to —75°, but the saturated, unreactive polymer could not be cross-linked iato a useful synthetic elastomer. It was not until 1937 that poly(isobutylene- (9-isoprene) [9010-85-9] or butyl mbber was iavented at the Standard Oil Development Co. (now Exxon Chemical Co.) laboratories (1). 

The first sulfur curable copolymer was prepared ia ethyl chloride usiag AlCl coinitiator and 1,3-butadiene as comonomer however, it was soon found that isoprene was a better diene comonomer and methyl chloride was a better polymerization diluent. With the advent of World War II, there was a critical need to produce synthetic elastomers in North America because the supply of natural mbber was drastically curtailed. This resulted in an enormous scientific and engineering effort that resulted in commercial production of butyl mbber in 1943. 

Prior to butyl mbber, the known natural and synthetic elastomers had reactive sites at every monomer unit. Unlike natural mbber, polychloroprene, and polybutadiene, butyl mbber had widely spaced olefin sites with aHyUc hydrogens. This led to the principle of limited functionahty synthetic elastomers that was later appHed to other synthetic elastomers, eg, chlorosulfonated polyethylene, siUcone mbber, and ethylene—propylene terpolymers. 

C. A. Hargreaves II inj. P. Keimedy and E. G. Tomqvist, eds., Pofymer Chemistry of Synthetic Elastomers Wiley-Interscience, New York, 1986, pp. 227-252. 

The ability to bond natural rubber to itself and to steel makes it ideal for lining tanks. Many of the synthetic elastomers, while more chemically resistant than natural rubber, have veiy poor bonding characteristics and hence are not well suited for hning tanks. 

Besides the higher volume pressure sensitive adhesives discussed above, the industry also uses other synthetic elastomers as the base component for PSA formulation. Most of these elastomers require some form of tackification to make the materials tacky. However, a few materials are low enough in Tg and sufficiently compliant to be useful without requiring compounding with tackifiers. 

Some rubber base adhesives need vulcanization to produce adequate ultimate strength. The adhesion is mainly due to chemical interactions at the interface. Other rubber base adhesives (contact adhesives) do not necessarily need vulcanization but rather adequate formulation to produce adhesive joints, mainly with porous substrates. In this case, the mechanism of diffusion dominates their adhesion properties. Consequently, the properties of the elastomeric adhesives depend on both the variety of intrinsic properties in natural and synthetic elastomers, and the modifying additives which may be incorporated into the adhesive formulation (tackifiers, reinforcing resins, fillers, plasticizers, curing agents, etc.). 

During World War II, several new synthetic elastomers were produced and new types of adhesives (mainly styrene-butadiene and acrylonitrile copolymers) were manufactured to produce adequate performance in joints produced with new difficult-to-bond substrates. Furthermore, formulations to work under extreme environmental conditions (high temperature, resistance to chemicals, improved resistance to ageing) were obtained using polychloroprene (Neoprene) adhesives. Most of those adhesives need vulcanization to perform properly. 

Tackifiers and modifiers are generally added to improve the adhesive performance of synthetic elastomers. All resins added to an adhesive formulation modify their properties (viscosity, open time, tack) and therefore these resins are also called... 

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. 

Sealing rings that are inert to most chemical corrosives and solvents are usually manufactured from PTFE or one of the synthetic elastomers. 

Prior to 1940, the use of synthetic elastomers in linings was negligible, but the advent of the Second World War, and the consequent loss of natural rubber sources to the Allies, led to the use of synthetic rubber, namely a styrene-butadiene copolymer which, whilst not having all the properties of natural rubber, proved to have adequate anti-corrosive performance. 

RUBBER AND SYNTHETIC ELASTOMERS Table 18.6 Summary of elastomer properties... 

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