Ethylene-propylene copolymer thermoplastic elastomers

Organic peroxides are used in the polymer industry as thermal sources of free radicals. They are used primarily to initiate the polymerisation and copolymerisation of vinyl and diene monomers, eg, ethylene, vinyl chloride, styrene, acryUc acid and esters, methacrylic acid and esters, vinyl acetate, acrylonitrile, and butadiene (see Initiators). They ate also used to cute or cross-link resins, eg, unsaturated polyester—styrene blends, thermoplastics such as polyethylene, elastomers such as ethylene—propylene copolymers and terpolymers and ethylene—vinyl acetate copolymer, and mbbets such as siUcone mbbet and styrene-butadiene mbbet. 

FIGURE 13.13 Schematic representation of thermoplastic elastomers obtained through reaction of maleated ethylene-propylene copolymer (EPM) with polyamide-6 (PA-6). 

Applications of ethylene-propylene copolymers and terpolymers include automotive (the major use area), thermoplastic olefin elastomers, single-ply roofing, viscosity index improvers for lube oils, wire and cable insulation, hose, appliance parts, and polymer modification. 

Ethylene propylene copolymers and their blends exhibit diverse degradation behavior under the influence of light, heat and radiation. In spite of many papers in this area, little, if any, mechanistic data on degradation and stabilization of this important class of materials is available in the literature. The present paper reviews the published literature in this area organised under five distinct class of materials, namely, thermoplastic, elastomeric, and heterophasic copolymers, thermoplastic elastomer and blends. Of this, elastomeric ethylene-propylene copolymers appears to have been most exhaustively studied. Very few studies have reported on thermoplastic copolymers, both random as well as heterophasic as well as thermoplastic elastomers and blends. Specific mechanisms of degradation and stabilization of each of these classes of materials are discussed. 

Copolymers of ethylene and propylene have come to stay as important materials with diverse practical applications. They span the full range of polymeric properties, from soft elastomers to hard thermoplastics depending on the relative composition of the two monomers and the manner of their enchainment. Ethylene-propylene copolymers are manufactured commercially using Ziegler-Natta catalysts [1]. For the purposes of this discussion, we will treat these copolymers in terms of three distinct classes of materials ... 

With the high-temperature solution polymerization processes, various ethylene homo- and copolymers with different average molecular mass and copolymer compositions are produced. The product portfolio comprises PE-HD, PE-LLD, PE-VLD, and the ethylene/propylene elastomers (EPM, EPDM) (see Figure 2). The thermoplastic products have a wide range of applications [1]. The elastomeric ethylene/propylene copolymers can also be applied widely in the automotive industry, for plastics modification, in industrial applications such as seals, in electrical cables, and in tires [2], Uncured ethylene/propylene copolymers are applicable as viscosity index improvers for lubricant oils [5]. 

ADK Stab LA 77 Bis(2,2,6,6-tetramethyl-4-piperidinyl) decanedioate Bis(2,2,6,6-tetramethyl-4-piperidinyl)-sebacate Decanedioic acid, bis 2,2,6,6-tetramethyl-4-piperidinyl) ester EINECS 258-207-9 HALS 1 HALS 770 Lowilite 77 LS 770 Mark LA 77 Sanol Sanol 770 Sanol LS 700 Sanol LS 770 Sumisorb 577 T 770 TIN 770 Tinuvin 770 Tinuvin 770DF Tinuvin 770LS TK-10665 Uvaseb 770. Light stabilizer for polyolefins, ABS, PUR acrylics, PS and styrene copolymers, thermoplastic elastomers, ethylene-propylene copolymers, polyamides. Ciba-Geigy Corp. En/Chem SpA bowi. 

Nowadays commercial mixtures of bitumens with uncured synthetic elastomers are produced, e.g. ethylene-propylene-diene terpolymers (EPDM), styrene-butadiene sequence copolymers (SBS), and ethylene-acrylic ester-acrylic acid terpolymers (AECM). Mixtures with some thermoplastics are also commercial products, e.g. polyethylene (PE), ethylene-propylene copolymers (EPM), alpha-olefinic copolymers, atactic polypropylene (aPP), and ethylene-vinyl acetate copolymers (EVA). 

Ethylene/propylene/dicyclopentadiene terpolymer Ethylene-propylene-ethylidene norbornene elastomer, adhesives Epichlorohydrin elastomer Epichlorohydrin/ethylene oxide/allyl glycidyl ether terpolymer Epichlorohydrin/ethylene oxide copolymer Polyisoprene Polyurethane, thermoplastic... 

N nylon, PO polyolefin, elastomer, TPU thermoplastic urethane, GF glass fiber, NBR nitrile rubber, MAH maleic anhydride, EPR ethylene-propylene copolymer, l ionomer, M- mineral, ABS acrylonitrile-butadiene-styrene copolymer, PPE poly (phenylene ether), R reinforcement, PTFE poly(tetrafluoroethylene), CF° carbon fiber, PEBA poly(etherblockamide), S silicone, RIPP D reaction injection molding plastic, and ASA acrylate-styrene-acrylonitrile copolymer. 

Thermoplastic polyolefin (TPO) elastomers are typically composed of ethylene propylene rubber (EPR) or ethylene propylene diene M (EPDM) as the elastomeric segment and polypropylene thermoplastic segment. LDPE, HDPE, and LLDPE copolymers ethylene vinyl acetate (EVA), ethylene ethylacrylate (EEA), ethylene, methyl-acrylate (EMA) and polybutene-1 can be used in TPOs. Hydrogenation of polyisoprene can yield ethylene propylene copolymers, and hydrogenation of 1,4- and 1,2-stereoisomers of S-B-S yields ethylene butylene copolymers. ... 

Block copolymers made from ethylene and propylene are valuable industrial materials. They can be used as thermoplastic elastomers and as compatibOizing agents for homopolymer blends. The properties of this type of copolymer depend on the microstructure of the blocks, the relative lengths of the blocks, and the overall molecular v eight. An ABA triblock copolymer structure containing crystalline A blocks and an amorphous B block can exhibit elastomeric behavior. The crystalline "hard" blocks can consist of isotactic or syndiotactic polypropylene (iPP or sPP) units or linear polyethylene (PE). The amorphous "soft" blocks can consist of atactic polypropylene (aPP) or ethylene-propylene copolymer (ethylene-propylene rubber, EPR). 

Thermoplastic elastomers Ethylene-propylene copolymer W. Germany 2,646,480 1981 Mitsui Petrochemical... 

In the early stages of development of polypropylene rubbers, particularly butyl rubber, were used to reduce the brittleness of polypropylene. Their use declined for some years with the development of the polypropylene copolymers but interest was greatly renewed in the 1970s. This interest has been centred largely around the ethylene-propylene rubbers which are reasonably compatible in all proportions with polypropylene. At first the main interest was with blends in which the rubber content exceeded 50% of the blend and such materials have been designated as thermoplastic polyolefin elastomers (discussed in Section 11.9.1). There is also increasing interest in compounds with less than 50% rubber, often referred to as elastomer-modified thermoplastics. It is of interest to note... 

Compatibilization along with dynamic vulcanization techniques have been used in thermoplastic elastomer blends of poly(butylene terephthalate) and ethylene propylene diene rubber by Moffett and Dekkers [28]. In situ formation of graft copolymer can be obtained by the use of suitably functionalized rubbers. By the usage of conventional vulcanizing agents for EPDM, the dynamic vulcanization of the blend can be achieved. The optimum effect of compatibilization along with dynamic vulcanization can be obtained only when the compatibilization is done before the rubber phase is dispersed. 

Currently, important TPE s include blends of semicrystalline thermoplastic polyolefins such as propylene copolymers, with ethylene-propylene terepolymer elastomer. Block copolymers of styrene with other monomers such as butadiene, isoprene, and ethylene or ethylene/propy-lene are the most widely used TPE s. Styrene-butadiene-styrene (SBS) accounted for 70% of global styrene block copolymers (SBC). Currently, global capacity of SBC is approximately 1.1 million tons. Polyurethane thermoplastic elastomers are relatively more expensive then other TPE s. However, they are noted for their flexibility, strength, toughness, and abrasion and chemical resistance. Blends of polyvinyl chloride with elastomers such as butyl are widely used in Japan. ... 

Thermoplastic Olefin. These thermoplastic elastomers are primarily blends, or block or graft copolymers, of ethylene/propylene rubber with polypropylene. 

The following TPs are the main thermoforming materials processed high-impact and high-heat PS, HDPE, PP, PVC, ABS, CPET, PET, and PMMA. Other plastics of lesser usage are transparent styrene-butadiene block copolymers, acrylics, polycarbonates, cellulosics, thermoplastic elastomers (TPE), and ethylene-propylene thermoplastic vulcanizates. Coextruded structures of up to seven layers include barriers of EVAL, Saran, or nylon, with polyolefins, and/or styreneics for functional properties and decorative aesthetics at reasonable costs.239-241... 

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