Polybutadiene-1-ethylene

The IR spectrum of amorphous alternating polybutene-1-ethylene copolymer shows absorptions at 13.3 pm (characteristic of methylene sequences of two units) and at 9 pm (characteristic of the structure). 

Absorption at 10.8 pm, also found in hydrogenated poly 2,3-dimethyl-butadiene, confirms the above structure. 

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Figure 4 Plot of degree of crystallinity (XDSC) from DSC against crystallinity (Xp) determined by density measurements. (A), hydrogenated polybutadienes ( ), ethylene 1-butene copolymers ( ), ethylene 1-octene copolymers. Reprinted with permission from Ref. [72]. Copyright 1984 American Chemical Society. 

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. 

Composition (type of polymeric components). The base polymer (which is to be modified) may be an amorphous polymer [e.g., polystyrene (PS), styrene-acrylonitrile copolymer, polycarbonate, or poly(vinyl chloride)], a semicrystalline polymer [e.g., polyamide (PA) or polypropylene (PP)], or a thermoset resin (e.g., epoxy resin). The modifier may be a rubber-like elastomer (e.g., polybutadiene, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, or ethylene-propylene-diene copolymer), a core-shell modifier, or another polymer. Even smaller amounts of a compatibilizer, such as a copolymer, are sometimes added as a third component to control the morphology. 

A variety of synthetic rubbers are commercially used styrene-butadiene rubber (SBR), polybutadiene, ethylene-propylene rubber, butyl and halobutyl rubber, etc. The most important is SBR, which is mainly used as a major component of all passenger tyres and in significant amounts in most tyre products. 

Figure 3. Spectrum of cis-po 1 ybutadiene, polybutadiene, ethylene/propylene/diene terpolymer.

Acetone oxime 1,4-Butylene qlycol diacrylate Chlorodiphenyl (54% Cl) Epoxidized polybutadiene Ethylene/methacrylic acid copolymer... 

Fig. 108. Degree of crystallinity calculated from the enthalpy of fusion of 9% PE gels vs mole percent of branches hydrogenated polybutadiene ( ) ethylene-vinyl acetate (A). Reproduced from Macromolecules [Ref. 338] by the courtesy of the authors and of The American Chemical Society...

Figure 7. Scanning electron micrographs of polyethylene copolymers, (a) Hydrogenated polybutadiene (ethylene-butene)...

Synthetic polymers that are commercially manufactured in the quantity of billions of pounds may be classified in three categories (1) plastics, which include thermosetting resins (e.g., urea resins, polyesters, epoxides) and thermoplastic resins (e.g., low-density as well as high-density polyethylene, polystyrene, polypropylene) (2) synthetic fibers, which include cellulosics (such as rayon and acetate) and noncellulose (such as polyester and nylon) and (3) synthetic rubber (e.g., styrene-butadiene copolymer, polybutadiene, ethylene-propylene copolymer). 

The general reaction chemistry used in the synthesis of common rubbers and elastomers mentioned in Table 21.1 is described in the following. The discussion covers four types of rubbers styrene-butadiene rubbers (SBRs), polybutadiene, ethylene-propylene-diene rubbers, and thermoplastic polyurethanes. 

Polybutadiene Ethylene-co-vinyl acetate Ethylene-co-vinyl acetate polymer Polybutadiene Polybutadiene... 

Acrylonitrile—Butadiene—Styrene. ABS is an important commercial polymer, with numerous apphcations. In the late 1950s, ABS was produced by emulsion grafting of styrene-acrylonitrile copolymers onto polybutadiene latex particles. This method continues to be the basis for a considerable volume of ABS manufacture. More recently, ABS has also been produced by continuous mass and mass-suspension processes (237). The various products may be mechanically blended for optimizing properties and cost. Brittle SAN, toughened by SAN-grafted ethylene—propylene and acrylate mbbets, is used in outdoor apphcations. Flame retardancy of ABS is improved by chlorinated PE and other flame-retarding additives (237). 

Pubhcations on curing polymers with TAIC include TEE—propylene copolymer (135), TEE—propylene—perfluoroaHyl ether (136), ethylene—chlorotrifluoroethylene copolymers (137), polyethylene (138), ethylene—vinyl acetate copolymers (139), polybutadienes (140), PVC (141), polyamide (142), polyester (143), poly(ethylene terephthalate) (144), sdoxane elastomers (145), maleimide polymers (146), and polyimide esters (147). 

Fig. 15. Oxygen permeability versus 1/specific free volume at 25 °C (30). 1. Polybutadiene 2. polyethylene (density 0.922) 3. polycarbonate 4. polystyrene 5. styrene-acrylonitrile 6. poly(ethylene terephthalate) 7. acrylonitrile barrier polymer 8. poly(methyl methacrylate) 9. poly(vinyl chloride) 10. acrylonitrile barrier polymer 11. vinyUdene chloride copolymer 12. polymethacrylonitrile and 13. polyacrylonitrile. See Table 1 for unit conversions.

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. 

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. 

Commercially, anionic polymerization is limited to three monomers styrene, butadiene, and isoprene [78-79-5], therefore only two useful A—B—A block copolymers, S—B—S and S—I—S, can be produced direcdy. In both cases, the elastomer segments contain double bonds which are reactive and limit the stabhity of the product. To improve stabhity, the polybutadiene mid-segment can be polymerized as a random mixture of two stmctural forms, the 1,4 and 1,2 isomers, by addition of an inert polar material to the polymerization solvent ethers and amines have been suggested for this purpose (46). Upon hydrogenation, these isomers give a copolymer of ethylene and butylene. 

I indicates compatible with polyisoprene segments B, compatible with polybutadiene seg-ments EB, compatible with poly (ethylene—butylene) segments and S, compatible with poly-styrene segments. 

The cis-polybutadiene, cis-polyisoprene, and ethylene-propylene rubbers are close duphcates of natural rubber. The newer eth)aene-propylene rubbers (EPR) have excellent resistance to heat and oxidation. 

Hydrogenated SBS triblock polymers have become increasingly important (Kraton G by Shell). With the original polybutadiene block comprised of 65% 1,4-and 35% 1,2-structures the elastomeric central block is equivalent to that of a high-ethylene ethylene-butene rubber. 

The minimum service temperature is determined primarily by the Tg of the soft phase component. Thus the SBS materials ctm be used down towards the Tg of the polybutadiene phase, approaching -100°C. Where polyethers have been used as the soft phase in polyurethane, polyamide or polyester, the soft phase Tg is about -60°C, whilst the polyester polyurethanes will typically be limited to a minimum temperature of about 0°C. The thermoplastic polyolefin rubbers, using ethylene-propylene materials for the soft phase, have similar minimum temperatures to the polyether-based polymers. Such minimum temperatures can also be affected by the presence of plasticisers, including mineral oils, and by resins if these become incorporated into the soft phase. It should, perhaps, be added that if the polymer component of the soft phase was crystallisable, then the higher would also affect the minimum service temperature, this depending on the level of crystallinity. 

The polyols used are of three types polyether, polyester, and polybutadiene. The polyether diols range from 400 to about 10,000 g/mol. The most common polyethers are based on ethylene oxide, propylene oxide, and tetrahydrofuran or their copolymers. The ether link provides low temperature flexibility and low viscosity. Ethylene oxide is the most hydrophilic and thus can increase the rate of ingress of water and consequently the cure rate. However, it will crystallize slowly above about 600 g/mol. Propylene oxide is hydrophobic due to hindered access to the ether link, but still provides high permeability to small molecules like water. Tetrahydrofuran is between these two in hydrophobicity, but somewhat more expensive. Propylene oxide based diols are the most common. 

Bi.4Bmv 1,4-Polybu ta diene (low vinyl) 1,2-Polybutadiene (medium vinyl) (30-60%) Polyethylene Poly(ethylene-co- butylene) Improved stress-strain properties... 

IBI 1,4-Polyisoprene 1,4-Polybutadiene Poly(ethylene-co- propylene Polyethylene Inverse block polymer— properties dependent on composition... 

Random SBR Polystyrene 1,4-Polybutadiene (-20% 1,2) Polystyrene Poly(ethylene-co- butylene) ... 

AA Natural rubber, styrene butadiene, butyl, ethylene propylene, polybutadiene, Polyisoprene... 

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