Poly commercial elastomer

Poly(aryloxyphosphazene) elastomers can be cured with peroxides, sulfur and radiation. The resulting vulcanizates are resistant to attack by moisture and oils and have been found to have desirable characteristics for electrical insulation applications where fire safety is a concern (Table II) (12). Fire resistant, low smoke, closed cell foams with excellent properties (Table III) have also been developed from poly(aryloxyphosphazene) elastomers (13). Applications for these foams, which can be produced as either slabstock or tube stock, are being developed for military, aerospace and commercial uses. (See Table II and III.)... 

Two commercial phosphazene elastomers were developed and marketed in the mid-1980s, namely, poly(fluoroalkoxyphosphazene) elastomer (ASTM International designation FZ) and poly(aryloxyphosphazene) elastomer (ASTM International designation PZ) [109]. The structure of the fluorinated product is as follows [110] ... 

In the early 1950 s, B.F. Goodrich introduced the first commercial elastomer based on ionic interactions, a poly(butadiene-co-acry-lon1trile-co-acrylic acid). Typically less than 6% of carboxylic monomer 1s employed in order to preserve the elastomeric properties inherent in these systems. When neutralized to the zinc salt, these elastomers display enhanced tensile properties and improved adhesion compared to conventional copolymers. This enhancement of properties can be directly attributed to ionic associations between the metal carboxylate groups. 

Commercially, the poly(styrene- -elastomer- -styrene) materials are made by anionic polymerization (7,45—47). An alkj thium initiator (RLi) first reacts with styrene [100-42-5] monomer ... 

The first poly sulphide elastomer was discovered in 1924 by Patrick during an attempt to prepare ethylene glycol by hydrolysis of ethylene dichloride. Commercial production was begun in 1929 by the Thiokol Chemical Corp. (U.S.A.). The current consumption of polysulphide elastomers, compared to that of other elastomers, is very small, use being restricted mainly to special applications involving resistance to oils and solvents. 

With this initiator, Vandenberg was also able to find a route to sulfur-vulcanizable poly ether elastomers through the copolymerization of propylene oxide with allyl glycidyl ether (71, 94), which Hercules sold commercially under the trademark PAREL. Both of these useful elastomers were amorphous— that is, atactic—polymer structures. 

As the demand for rubber increased so did the chemical industry s efforts to prepare a synthetic sub stitute One of the first elastomers (a synthetic poly mer that possesses elasticity) to find a commercial niche was neoprene discovered by chemists at Du Pont in 1931 Neoprene is produced by free radical polymerization of 2 chloro 1 3 butadiene and has the greatest variety of applications of any elastomer Some uses include electrical insulation conveyer belts hoses and weather balloons... 

Applications. Among the P—O- and P—N-substituted polymers, the fluoroalkoxy- and aryloxy-substituted polymers have so far shown the greatest commercial promise (14—16). Both poly[bis(2,2,2-trifluoroethoxy)phosphazene] [27290-40-0] and poly(diphenoxyphosphazene) [28212-48-8] are microcrystalline, thermoplastic polymers. However, when the substituent symmetry is dismpted with a randomly placed second substituent of different length, the polymers become amorphous and serve as good elastomers. Following initial development of the fluorophosphazene elastomers by the Firestone Tire and Rubber Co., both the fluoroalkoxy (EYPEL-F) and aryloxy (EYPEL-A) elastomers were manufactured by the Ethyl Corp. in the United States from the mid-1980s until 1993 (see ELASTOLffiRS,SYNTHETic-PHOSPHAZENEs). 

Noncrystalline aromatic polycarbonates (qv) and polyesters (polyarylates) and alloys of polycarbonate with other thermoplastics are considered elsewhere, as are aHphatic polyesters derived from natural or biological sources such as poly(3-hydroxybutyrate), poly(glycoHde), or poly(lactide) these, too, are separately covered (see Polymers, environmentally degradable Sutures). Thermoplastic elastomers derived from poly(ester—ether) block copolymers such as PBT/PTMEG-T [82662-36-0] and known by commercial names such as Hytrel and Riteflex are included here in the section on poly(butylene terephthalate). Specific polymers are dealt with largely in order of volume, which puts PET first by virtue of its enormous market volume in bottie resin. 

Polymers account for about 3—4% of the total butylene consumption and about 30% of nonfuels use. Homopolymerization of butylene isomers is relatively unimportant commercially. Only stereoregular poly(l-butene) [9003-29-6] and a small volume of polyisobutylene [25038-49-7] are produced in this manner. High molecular weight polyisobutylenes have found limited use because they cannot be vulcanized. To overcome this deficiency a butyl mbber copolymer of isobutylene with isoprene has been developed. Low molecular weight viscous Hquid polymers of isobutylene are not manufactured because of the high price of purified isobutylene. Copolymerization from relatively inexpensive refinery butane—butylene fractions containing all the butylene isomers yields a range of viscous polymers that satisfy most commercial needs (see Olefin polymers Elastomers, synthetic-butylrubber). 

Many random copolymers have found commercial use as elastomers and plastics. For example, SBR (62), poly(butadiene- (9-styrene) [9003-55-8] has become the largest volume synthetic mbber. It can be prepared ia emulsion by use of free-radical initiators, such as K2S20g or Fe /ROOH (eq. 18), or in solution by use of alkyl lithium initiators. Emulsion SBR copolymers are produced under trade names by such companies as American Synthetic Rubber (ASPC), Armtek, B. F. Goodrich (Ameripool), and Goodyear (PHoflex) solution SBR is manufactured by Firestone (Stereon). The total U.S. production of SBR in 1990 was 581,000 t (63). 

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). 

The earliest study describing vulcanised polymers of esters of acryUc acid was carried out in Germany by Rohm (2) before World War I. The first commercial acryUc elastomers were produced in the United States in the 1940s (3—5). They were homopolymers and copolymers of ethyl acrylate and other alkyl acrylates, with a preference for poly(ethyl acrylate) [9003-32-17, due to its superior balance of properties. The main drawback of these products was the vulcanisation. The fully saturated chemical stmcture of the polymeric backbone in fact is inactive toward the classical accelerators and curing systems. As a consequence they requited the use of aggressive and not versatile compounds such as strong bases, eg, sodium metasiUcate pentahydrate. To overcome this limitation, monomers containing a reactive moiety were incorporated in the polymer backbone by copolymerisation with the usual alkyl acrylates. 

Mihtary interest in the development of fuel and thermal resistant elastomers for low temperature service created a need for fluorinated elastomers. In the early 1950s, the M. W. Kellogg Co. in a joint project with the U.S. Army Quartermaster Corps, and 3M in a joint project with the U.S. Air Force, developed two commercial fluorocarbon elastomers. The copolymers of vinyUdene fluoride, CF2=CH2, and chlorotrifluoroethylene, CF2=CFC1, became available from Kellogg in 1955 under the trademark of Kel-F (1-3) (see Fluorine compounds, ORGANic-POLYcm.OROTRiFLUOROETHYLENE Poly(vinylidene) fluoride). In 1956, 3M introduced a polymer based on poly(l,l-dihydroperfluorobutyl acrylate) trademarked 3M Brand Fluorombber 1F4 (4). The poor balance of acid, steam, and heat resistance of the latter elastomer limited its commercial use. 

Epichlorohydrin Elastomers without AGE. ECH homopolymer, polyepichlorohydrin [24969-06-0] (1), and ECH—EO copolymer, poly(epichlorohydrin- (9-ethylene oxide) [24969-10-6] (2), are linear and amorphous. Because it is unsymmetrical, ECH monomer can polymerize in the head-to-head, tail-to-tail, or head-to-tail fashion. The commercial polymer is 97—99% head-to-tail, and has been shown to be stereorandom and atactic (15—17). Only low degrees of crystallinity are present in commercial ECH homopolymers the amorphous product is preferred. 

In the case of poly(alkoxyphosphazenes) (IV) or poly(aryloxyphos-phazenes) (V) a dramatic change in properties can arise by employing combinations of substituents. Polymers such as (NP CHjCF ) and (NP CgH,).) are semicrystalline thermoplastics (Table I). With the introduction of two or more substituents of sufficiently different size, elastomers are obtained (Figure 4). Another requirement for elastomeric behavior is that the substituents be randomly distributed along the P-N backbone. This principle was first demonstrated by Rose (9), and subsequent work in several industrial laboratories has led to the development of phosphazene elastomers of commercial interest. A phosphazene fluoroelastomer and a phosphazene elastomer with mixed aryloxy side chains are showing promise for military and commercial applications. These elastomers are the subject of another paper in this symposium (10). 

The Material of the Example. Poly(ether ester) (PEE) materials are thermoplastic elastomers. Fibers made from this class of multiblock copolymers are commercially available as Sympatex . Axle sleeves for automotive applications or gaskets are traded as Arnitel or Hytrel . Polyether blocks form the soft phase (matrix). The polyester forms the hard domains which provide physical cross-linking of the chains. This nanostructure is the reason for the rubbery nature of the material. 

Many other crosslinking reactions are used in commercial applications. A variety of halogen-containing elastomers are crosslinked by heating with a basic oxide (e.g., MgO or ZnO) and a primary diamine [Labana, 1986 Schmiegel, 1979]. This includes poly(epichlorohydrin) (Sec. 7-2b-6) various co- and terpolymers of fluorinated monomers such as vinylidene fluoride, hexafluoropropene, perfluoro(methyl vinyl ether), and tetrafluoroethylene (Sec. 6-8e) and terpolymers of alkyl acrylate, acrylonitrile, and 2-chloroethyl vinyl ether (Sec. 6-8e). 

For polyurethane production, Donnelly [109] has carried out the synthesis of copolyurethanes based on mixtures of commercial poly(THF diol)s with glucose. Complex products resulted, which can be represented by mono- or bis(glucoside) structures. From a variety of polyol blends, solid polyurethanes were prepared which ranged from linear, soluble, weak elastomers to polymers of higher transition temperature and stiffness, low solubility, and low extension under tensile load [110]. 

Of all the commercially available organic and inorganic polymeric materials, RTV silicone elastomer has proved to he one of the most effective encapsulants used for mechanical and moisture protection of the Integrated Circuitry (1C) devices. A general overview of the RTV silicone elastomer and its commercial preparation and cure mechanism are described. Improved electrical performance of the RTV silicone encapsulant, by immobilizing the contaminant ions, such as Na, K" , Cl , with the addition of the heterocyclic poly-ethers as the contaminant ion scavengers seems to have a potential application as the contaminant ionic migration preventor in the electronic applications. 

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