Ethylene-styrene-propylene terpolymers

Whilst the ASA materials are of European origin, the AES polymers have been developed in Japan and the US. The rubber used is an ethylene-propylene terpolymer rubber of the EPDM type (see Chapter 11) which has a small amount of a diene monomer in the polymerisation recipe. The residual double bonds that exist in the polymer are important in enabling grafting with styrene and acrylonitrile. The blends are claimed to exhibit very good weathering resistance but to be otherwise similar to ABS. 

NATURAL RUBBER(Polyisoprene) POLYBUTADIENE STYRENE-BUTADIENE RUBBER ETHYLENE/PROPYLENE TERPOLYMER... 

Several terpolymers of ethylene, propylene, and CO, and also of ethylene, styrene and CO were studied using Py-GC/MS [4]. 

Styrene-butadiene-styrene (SBS) Styrene-ethylene-butadiene-styrene (SEBS) Ethylene-vinyl acetate/polyvinylidene chloride (EVA/PVDC) Thermoplastic polyurethane (TPU) Polyetherblock polyamide (PEBA) Copolyester, Polyetherester (TEEE) Polypropylene/ethylene- propylene terpolymers (PP-EPDM) Polypropylene/nitrile rubber (PP-NBR)... 

Figure 9.1. Phase-contrast micrographs of blends of chloroprene (CR), nitrile rubber (NBR), ethylene-propylene terpolymer (EPDM), and chlorobutyl rubber with styrene-butadiene rubber (SBR). The SBR phase appears white for the blends with CR and NBR, and dark for the blends with EPDM and chlorobutyl rubber. At low concentrations, the admixed rubber is the dispersed phase at higher concentrations, a phase inversion occurs and the admixed rubber becomes the matrix. (Callan et al, 1971.)...

The process may easily be transformed for the synthesis of other elastomers and copolymers with a double bond in the backbone of the monomer unit. Therefore, the range of elastomers is extensive isoprene, butadiene, butadiene-styrene rubbers, ethylene-propylene terpolymer, and so on. 

From about 1980, there have been extensive investigations of the shear viscosity of rubber-carbon black compounds and related filled polymer melts. Yield values in polystyrene-carbon black compounds in shear flow were found by Lobe and vhiite [L15] in 1979 and by Tanaka and White [Tl] in 1980 for polystyrene with calcium carbonate and titanium dioxide as well as carbon black. From 1982, White and coworkers found yield values in compounds containing butadiene-styrene copolymer [Ml, M37, S12, S18, T7, W29], polyiso-prene [M33, M37, S12, S18], polychloroprene [S18], and ethylene-propylene terpolymer [OlO, S18]. Typical shear viscosity-shear stress data for rubber-carbon black compounds are shown in Figs. 5(a) and (b). White et al. [S12, S18, W28] fit these data with both Eq. (56) and die expression... 

Figure 1 Polymer interpretation chart. PAI, polyamideimide PC, polycarbonate UP, unsaturated polyester PDAP, diarylate phtalate resin VC-VAc, vinyl chloride-vinyl acetate copolymer PVAc, polyvinyl acetate PVFM, polyvinyl formal PUR, polyurethane PA, polyamide PMA, methacrylate ester polymer EVA, ethylene-vinyl acetate copolymer PF, phenol resin EP, epoxide resin PS, polystyrene ABS, acrylonitrile-butadiene-styrene copolymer PPO, polyphenylene oxide P-SULFONE, poly-sulfone PA, polyamide UF, urea resin CN, nitrocellulose PVA, polyvinyl acetate MC, methyl cellulose MF, melamine resin PAN, polyacrylonitrile PVC, polyvinyl chloride PVF, polyvinyl fluoride CR, polychloroprene CHR, polyepichlorohydrin SI, polymethylsiloxane POM, polyoxy-methylene PTFE, polytetrafluoroethylene MOD-PP, modified PP EPT, ethylene-propylene terpolymer EPR, ethylene-propylene rubber PI, polyisoprene BR, butyl rubber PMP, poly(4-methyl pentene-1) PE, poly(ethylene) PB, poly(butene-l). (Adapted from Ref. 22, p. 50.)...

NMR spectroscopy is capable of distinguishing between the different types of NMR unsaturation that can occur in a polymer. NMR spectroscopy has been used to determine unsaturation in acrylonitrile-butadiene-styrene terpolymers (ABS) [33, 34], 1,2-polybutadiene [34, 35], ethylene-propylene terpolymers [35], and vinyl chloride-vinylidene chloride copolymers [10, 36, 37]. 

Rubbers and elastomeric products for practical applications are usually blends of different elastomer types that develop specific domain morphologies at the microscale, and, therefore, they are a part of this chapter. The most common representatives of the ruhher family are natural ruhher (NR) and the synthetic polyhutadiene ruhher (PB). There are various copolymers of butadiene with styrene (styrene butadiene rubber, SBR) or acrylonitrile (acrylonitrile-butadiene rubber, NBR). Several elastomers have been developed for special purposes, such as EVA (ethylene vinyl acetate copolymer), PU (polyurethane), EPDM (ethylene propylene terpolymer), and siUcone rubber. 

Krishen [42] obtained the products listed in Table 4.10 by pyrolysis of ethylene-butadiene rubber and ethylene-propylene-diene terpolymer. He showed that the 2-methyl-2-butene peak was linear with the natural rubber content of the sample. Styrene-butadiene rubber was determined from the peak area of the 1,3-butadiene peak. The ethylene-propylene-terpolymer content was deducted from the 1-pentane peak area of the pyrolysis products. 

With the onset of World War II, immediate work was started to find a commercial substitute for natural rubber because of the restrictions on world movement of goods and likelihood of the loss of rubbergrowing areas in the Far East to the Japanese. Some commercial quantities of GRS, a styrene-butadiene copolymer, became available and modern forms of this make up the rubber type in most popular use, especially in car tyres. After World War II renewed interest in the field of fundamental polymerization technology soon produced a number of new synthetic rubbers, many of which required special additives to assist their processing, whilst others such as ethylene-propylene terpolymer allowed very large volumes of petroleum oil to be used as extenders rather than in limited quantities as plasticizers. Work in the field of natural rubber also enabled large volumes of oil to be used with this polymer. 

Figure 3.20 shows a pyrogram of polymethylmethacrylate copolymerised to contain 1 and 10% of acrylic or methacrylic acid. By this procedure, copolymerised acrylic or methacrylic acid has been identified in terpolymers with (a) butyl acrylate and styrene, (b) methylmethacrylate and ethyl acrylate and, (c) ethylene and propylene. A methyl methacrylate - methylstyrene - maleic acid terpolymer, when examined by this propylation - pyrolysis procedure, yielded dipropyl fumerate and a smaller amount of dipropyl maleate. 

Amines can add to C50. An early paper showed that up to 15 amine molecules may be added to the fullerene, but the hexa-adduct with the chains attached to the central double bond of the six pyracyclene unit constituting the Qo seems favored [32]. This addition has been used to graft Qo on poly(ethylene imine) and poly(4- [(2-aminoethyl)imino]methyl styrene) [33] or amine functionalized ethylene propylene terpolymer [34] to obtain sidefullerene polymers. Amino-terminated polystyrene with very narrow molar mass distributions, synthesized using amonic polymerization followed by end functionalization, can add to Coo to form multiarm stars (Scheme 5.7). Even, if a ratio C60/PS-NH2 of 2 1 is used in order to favor the mono-adduct, about 20% of di-adducts as well as small amounts of higher adducts are obtained [35]. 

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. 

The isoprene units in the copolymer impart the ability to crosslink the product. Polystyrene is far too rigid to be used as an elastomer but styrene copolymers with 1,3-butadiene (SBR rubber) are quite flexible and rubbery. Polyethylene is a crystalline plastic while ethylene-propylene copolymers and terpolymers of ethylene, propylene and diene (e.g., dicyclopentadiene, hexa-1,4-diene, 2-ethylidenenorborn-5-ene) are elastomers (EPR and EPDM rubbers). Nitrile or NBR rubber is a copolymer of acrylonitrile and 1,3-butadiene. Vinylidene fluoride-chlorotrifluoroethylene and olefin-acrylic ester copolymers and 1,3-butadiene-styrene-vinyl pyridine terpolymer are examples of specialty elastomers. 

Figure 14.9 Effect of various impact modifiers (25wt%) on the notched Izod impact strength of recycled PET (as moulded and annealed at 150°C for 16 h) E-GMA, glycidyl-methacrylate-functionalized ethylene copolymer E-EA-GMA, ethylene-ethyl acrylate-glycidyl methacrylate (72/20/8) terpolymer E-EA, ethylene-ethyl acrylate EPR, ethylene propylene rubber MA-GPR, maleic anhydride grafted ethylene propylene rubber MBS, poly(methyl methacrylate)-g-poly(butadiene/styrene) BuA-C/S, poly(butyl acrylate-g-poly(methyl methacrylate) core/shell rubber. Data taken from Akkapeddi etal. [26]...

Terpolymerization, the simultaneous polymerization of three monomers, has become increasingly important from the commercial viewpoint. The improvements that are obtained by copolymerizing styrene with acrylonitrile or butadiene have been mentioned previously. The radical terpolymerization of styrene with acrylonitrile and butadiene increases even further the degree of variation in properties that can be built into the final product. Many other commercial uses of terpolymerization exist. In most of these the terpolymer has two of the monomers present in major amounts to obtain the gross properties desired, with the third monomer in a minor amount for modification of a special property. Thus the ethylene-propylene elastomers are terpolymerized with minor amounts of a diene in order to allow the product to be subsquently crosslinked. 

Sulfonation is very useful chemical modification of polymer, as it induces high polarity in the polymer changing its chemical as well as physical properties. Sulfonated polymers are also important precursors for ionomer formation [75]. There are reports of sulfonation of ethylene-propylene diene terpolymer (EPDM) [76, 77], polyarylene-ether-sulfone [78], polyaromatic ether ketone [79], polyether ether ketone (PEEK) [80], styrene-ethylene-butylene-styrene block copolymer, (SEBS) [81]. Poly [bis(3-methyl phenoxy) phosphozene] [82], Sulfonated polymers show a distinct peak at 1176 cm"1 due to stretching vibration of 0=S=0 in the -S03H group. Another peak appears at 881 cm 1 due to stretching vibration of S-OH bond. However, the position of different vibrational bands due to sulfonation depends on the nature of the cations as well as types of solvents [75, 76]. 

Acrylonitrile-Ethylene/Propylene-Styrene Copolymer AES is a terpolymer obtained by grafting styrene-acrylonitrile copolymer to ethylene-propylene or ethylene-propylene-diene monomer rubber. Similar to ABS except with improved weathering resistance. 

Studies of ethylene-vinyl aromatic monomer polymerizations continue to be published. Chung and Lu reported the synthesis of copolymers of ethylene and P-methylstyrene [28] and the same group extended these studies to produce and characterize elastomeric terpolymers which further include propylene and 1-octene as the additional monomers [29,30]. Returning to the subject of alternative molecular architectures for copolymers, Hou et al. [31] has reported the ability of samarium (II) complexes to copolymerize ethylene and styrene into block copolymers. 

Fig. 1. Grafting efficiency vs. termonomer content for some ethylene-propylene based terpolymers. Conditions styrene-acrylonitrile (molar ratio 1.5 1) -2.6 mol/1 terpoiymer 25 -s- 30 g/i BPO = 8.67 mmol/1 solvent = n-hep-tane-benzene (1 I by wt) T =...

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