Elastomers importance

The synthetic fiber industry as we know it began m 1928 when E I Du Pont de Nemours Company lured Professor Wallace H Carothers from Harvard University to direct their research department In a few years Carothers and his associates had pro duced nylon the first synthetic fiber and neoprene a rubber substitute Synthetic fibers and elastomers are both products of important contemporary industries with an economic influence far beyond anything imaginable m the middle 1920s... 

Since entropy plays the determining role in the elasticity of an ideal elastomer, let us review a couple of ideas about this important thermodynamic variable ... 

Acrylonitrile (AN), C H N, first became an important polymeric building block in the 1940s. Although it had been discovered in 1893 (1), its unique properties were not realized until the development of nitrile mbbers during World War II (see Elastomers, synthetic, nitrile rubber) and the discovery of solvents for the homopolymer with resultant fiber appHcations (see Fibers, acrylic) for textiles and carbon fibers. As a comonomer, acrylonitrile (qv) contributes hardness, rigidity, solvent and light resistance, gas impermeabiUty, and the abiUty to orient. These properties have led to many copolymer apphcation developments since 1950. 

Polymer systems have been classified according to glass-transition temperature (T), melting poiat (T ), and polymer molecular weight (12) as elastomers, plastics, and fibers. Fillers play an important role as reinforcement for elastomers. They are used extensively ia all subclasses of plastics, ie, geaeral-purpose, specialty, and engineering plastics (qv). Fillets are not, however, a significant factor ia fibers (qv). 

Low Temperature Properties. The property of solvent resistance makes fluorosihcone elastomers usefiil where alternative fluorocarbon elastomers cannot function. The abiHty to retract to 10% of their original extension after a 100% elongation at low temperature is an important test result. Eluorosihcones can typically pass this test down to —59°C. The brittle point is approximately —68°C. 

Elastomers. Elastomers are polymers or copolymers of hydrocarbons (see Elastomers, synthetic Rubber, natural). Natural mbber is essentially polyisoprene, whereas the most common synthetic mbber is a styrene—butadiene copolymer. Moreover, nearly all synthetic mbber is reinforced with carbon black, itself produced by partial oxidation of heavy hydrocarbons. Table 10 gives U.S. elastomer production for 1991. The two most important elastomers, styrene—butadiene mbber (qv) and polybutadiene mbber, are used primarily in automobile tires. 

Butyl mbber, a copolymer of isobutjiene with 0.5—2.5% isoprene to make vulcanization possible, is the most important commercial polymer made by cationic polymerization (see Elastomers, synthetic-butyl rubber). The polymerization is initiated by water in conjunction with AlCl and carried out at low temperature (—90 to —100° C) to prevent chain transfer that limits the molecular weight (1). Another important commercial appHcation of cationic polymerization is the manufacture of polybutenes, low molecular weight copolymers of isobutylene and a smaller amount of other butenes (1) used in adhesives, sealants, lubricants, viscosity improvers, etc. 

Most of the phosphate esters are used in the production of hydrauHc fluids (qv), plastic and elastomer additives, flame retardants (qv), oil stabilizers, pesticides (qv), and medicinal intermediates (see Surfactants). Some trialkyl phosphates, OP(OR)2, are outstanding solvents for nitrates, especially (UO2) (N02)2, and therefore are important in uranium processing (see Extraction). 

Manufacturers. The main suppHers of polyesterether elastomers and the trade names of their products are as follows. An important end use... 

Diarylamiaes fuactioa as mbber antioxidants by breaking the peroxidative chain reactions leading to mbber deterioration. Nearly all commercial synthetic mbbers (see Elastomers, synthetic), including neoprene, butyl, styrene—butadiene, and the acrylonitrile—butadiene mbbers, can be protected with about 1—2% of an alkylated diphenylamine. DPA itself is not used as a mbber antioxidant. An objectionable feature of these antioxidants is that they cause discoloration and staining which limits their use to applications where this is not important. 

Vulcani2ation is a chemical process for improving an elastomer compound s performance. However, in most cases not all of the desired properties reach their optimum levels simultaneously. One of the mbber compounder s key responsibiHties is to achieve a balance of the most important property requirements by the proper selection of cure system (chemical) and time—temperature cure cycle (physical). 

Amine Cross-Linking. Two commercially important, high performance elastomers which are not normally sulfur-cured are the fluoroelastomers (FKM) and the polyacrylates (ACM). Polyacrylates typically contain a small percent of a reactive monomer designed to react with amine curatives such as hexamethylene-diamine carbamate (Diak 1). Because the type and level of reactive monomer varies with ACM type, it is important to match the curative type to the particular ACM ia questioa. Sulfur and sulfur-beating materials can be used as cure retarders they also serve as age resistors (22). Fluoroelastomer cure systems typically utilize amines as the primary cross-linking agent and metal oxides as acid acceptors. 

The compounding technique for latex differs from that of dry mbber and is fundamentally simpler. A critical factor of colloidal stabiUty makes necessary that each ingredient is of optimum particle size, pH, and concentration when added as an aqueous dispersion to the latex. Rubber latex is a colloidal aqueous emulsion of an elastomer and natural mbber latex is the milky exudation of certain trees and plants that of greatest commercial importance is the... 

The more important grades of thermoplastic natural mbber, which fall into the olefinic class of thermoplastic elastomers, are prepared with the natural mbber phase partially cross-linked during blending, a process known as dynamic vulcanization. The hardness of the soft blends is controlled by the natural mbber content, and typical properties of those of 50—90 hardness (Shore A) are shown in Table 7. 

These thermoplastic natural mbber elastomers have a place in the modem world, where recycling has become so important, and when excessive heat is not found in service. Thus, footwear, gla2ing seals, sports goods, hose, domestic products, and a whole range of automotive products have already been identified for such use. It must be noted, however, that tines are not a potential market for these materials, because of the high temperatures which result from emergency braking. 

Quahty control testing of siUcones utilizes a combination of physical and chemical measurements to ensure satisfactory product performance and processibihty. Eor example, in addition to the usual physical properties of cured elastomers, the plasticity of heat-cured mbber and the extmsion rate of TVR elastomers under standard conditions are important to the customer. Where the siUcone appHcation involves surface activity, a use test is frequently the only rehable indicator of performance. Eor example, the performance of an antifoaming agent can be tested by measuring the foam reduction when the sihcone emulsion is added to an agitated standard detergent solution. The product data sheets and technical bulletins from commercial siUcone producers can be consulted for more information. 

Rubber-Modified Copolymers. Acrylonitrile—butadiene—styrene polymers have become important commercial products since the mid-1950s. The development and properties of ABS polymers have been discussed in detail (76) (see Acrylonitrile polymers). ABS polymers, like HIPS, are two-phase systems in which the elastomer component is dispersed in the rigid SAN copolymer matrix. The electron photomicrographs in Figure 6 show the difference in morphology of mass vs emulsion ABS polymers. The differences in stmcture of the dispersed phases are primarily a result of differences in production processes, types of mbber used, and variation in mbber concentrations. 

The melt temperature of a polyurethane is important for processibiUty. Melting should occur well below the decomposition temperature. Below the glass-transition temperature the molecular motion is frozen, and the material is only able to undergo small-scale elastic deformations. For amorphous polyurethane elastomers, the T of the soft segment is ca —50 to —60 " C, whereas for the amorphous hard segment, T is in the 20—100°C range. The T and T of the mote common macrodiols used in the manufacture of TPU are Hsted in Table 2. 

Polymeric isocyanates or PMDI ate cmde products that vary in exact composition. The main constituents are 40—60% 4,4 -MDI the remainder is the other isomers of MDI, trimeric species, and higher molecular weight oligomers. Important product variables are functionaHty and acidity. Rigid polyurethane foams are mainly manufactured from PMDI. The so-called pure MDI is a low melting soHd that is used for high performance polyurethane elastomers and spandex fibers. Liquid MDI products are used in RIM polyurethane elastomers. 

Poly(butadiene- (9-acrylonitrile) [9008-18-3] NBR (64), is another commercially significant random copolymer. This mbber is manufactured by free-radical emulsion polymerization. Important producers include Copolymer Rubber and Chemical (Nysyn), B. F. Goodrich (Hycar), Goodyear (Chemigum), and Uninoyal (Paracdl). The total U.S. production of nitrile mbber (NBR) in 1990 was 95.6 t (65). The most important property of NBR mbber is its oil resistance. It is used in oil well parts, fuels, oil, and solvents (64) (see Elastomers, synthetic— nitrile rubber). 

Impact polystyrene (IPS) is one of a class of materials that contains mbber grafted with polystyrene. This composition is usually produced by polymerizing styrene (by mass or solution free-radical polymerization) in the presence of a small amount (ca 5%) of dissolved elastomer. Some of the important producers of impact-resistant polystyrenes are BASE (Polystyrol), Dow (Styron), and Monsanto (Lustrex). The 1988 U.S. production of impact polystyrene was more than 1 million t (92). 

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. 

Elastomers. Ethylene—propylene terpolymer (diene monomer) elastomers (EPDM) use a variety of third monomers during polymerization (see Elastomers, ethyiene-propylene-diene rubber). Ethyhdenenorbomene (ENB) is the most important of these monomers and requires dicyclopentadiene as a precursor. ENB is synthesized in a two step preparation, ie, a Diels-Alder reaction of CPD (via cracking of DCPD) with butadiene to yield 5-vinylbicyclo[2.2.1]-hept-2-ene [3048-64-4] (7) where the external double bond is then isomerized catalyticaHy toward the ring yielding 5-ethyhdenebicyclo[2.2.1]-hept-2-ene [16219-75-3] (ENB) (8) (60). 

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