EP Terpolymer

With respect to titanium catalysts for polymerization of ethylene or propylene, Ziegler synthesized the first high-density polyethylene and Natta prepared isotactic polypropylene by means of coordination catalysts about 50 years ago. The preparation methods of catalysts have been studied extensively. These TiCL3 catalysts have very high activity for homopolymerization of ethylene and propylene, whereas, they exhibit low activity for random copolymerization of ethylene with propylene when compared to vanadium catalysts. Refer to Ziegler-Nata Catalyst, Vanadium Catalysts, and EP Terpolymer, (Source Elastomer Technology Handbook, N. P. Cheremisinoff - editor, CRC Press, Boca Raton, Florida, 1993). 

J.J. Harrison and J. Ruhe, William R., Dispersant polysuccinimides derived from terpolymers, EP Patent 0831104, assigned to Chevron Chem. Co., March 25,1998. 

Materials. PVC, Geon 103 EP from B. F. Goodrich Co., and a terpolymer, Elvaloy 741 from E. I. du Pont de Nemours and Co., were used. Blends of the two polymers were mixed on a two-roll mill at 160°C and then pressed into films on a heated press at 150°C. The compositions of the mixtures are reported as weight percentages in our text. 

Although a large share of the EP co-polymers and EPD terpolymers is still manufactured with vanadium-based catalysts at low temperature, metallocene catalysts have added a whole new dimension to EP co-polymerization, and to the range of material properties that can be achieved, as has been the case for the ethylene-based low-density copolymers discussed in the previous section. The subject of EP co-polymerization with group 4 bis(cyclopentadienyl) complexes has been reviewed in detail up to 1998.59... 

There are polymers which have high ozone resistance. ENB terpolymers are but one example. Refer to EP Rubbers for a brief discussion. 

The EP thermoplastic elastomers are distinguished from the crossUnked analogues, which are not thermoplastics since reforming is impossible. A very important thermoplastic elastomer is comprised of a blend of an EP copolymer with an ethylene-propylene-diene (EPDM) terpolymer. This latter material is, of course, a crosslinkable thermoset however, these materials can be processed as thermoplastics if the crosslinkable component is present at low enough concentration to be present as an isolated phase. Melt-processing causes the formation of chemical bonds within the isolated rubber phase, a process called dynamic vulcanization. A commercial example of this type of material is Santoprene [4] manufactured by Advanced Elastomer Systems. Other blends of noncrosslinkable TPEs with crosslinkable materials are used commercially. These materials are classified as elastomer blends and are the subject of Chapter 12. 

Gecet, High-temperature EPS copolymer Huntsman Corp., Headquarters Gelimat, Compounding system, Draiswerke Inc. Geloy, Weatherable ASA terpolymer, GE... 

Fig. 1. CO/ethene-based PK-E. Note Applied notation for perfectly alternating CO/a-olefin polyketones PK-MiM2-re, in which Mi and M2 are abbreviations for the types of a-olefins incorporated in the co- or terpolymer chain [eg M = ethene (E), propene (P), butene (B), pentene (P), hexene (H), octene (0), decene (D), dodecene (Do), tetradecene (Td), hexadecene (Hd), octadecene (Od), icosene (Ic), and styrene (S)] and n, the molar monomer index n = [100 x [M2]/([Mi] + [M2])], is the percentage of M2 (in mol%) on the total amount of a-olefin incorporated in the polymer backbone. For example, PK-E represents a copolymer build up of CO and ethene, while PK-EP-6 represents a terpolymer build up of CO, ethene, and propene in a molar ratio of 100 94 6.

The molecular weight of the various product grades is controlled mainly by the reaction temperature, the overall pressure, and the partial pressure ratio of the monomers. A small amount of water (2 vol%) is added to the reaction mixture to reduce the amoimt of methanol chemically bound to the terpolymer in the form of ketal groups. The initially encountered problems of extensive reactor fouling and low bulk density of the product were overcome simultaneously by introduction of a seed powder (typically 4-10 wt% PK-EP-6) in the reactor prior to the start of the polymerization and the use of an excess of acid in the catalyst solution. Both the seed powder and the excess of acid assist agglomeration of the newly formed terpolymer particles. The required excess of acid depends on the desired molecular weight. 

Much less recognized is the possible influence of tacticity on copolymer properties when a-olefin monomer units are a minor component, and crystallinity is not based on a tactic a-olefin sequence but on a different comonomer such as ethylene. In this chapter, this tacticity effect is shown for ethylene-rich ethylene/propylene (EP) copolymers, where the crystallizable sequences are based on ethylene, that is, a comonomer that does not have tacticity requirements. In particular, this chapter describes in detail the microstructure of EP copolymers having industrially relevant compositions (ethylene content 80-55 mol%), with particular focus on the placement of propylene units along the ethylene-based macromolecular chains and their influence on copolymer properties. This subject is, of course, related to the industrial relevance of EP copolymers and ethylene/propylene/diene monomer terpolymers (EPDMs) (collectively referred to as EP(D)Ms), which presently represent the most widely produced saturated rubbers. ... 

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.)...

SBR - styrene-butadiene rubber EPS - expanded polj tyrene ABS - acrylonitrile-butadiene-styrene terpolymer... 

The ethylene-propylene (EP), ethylene-butadiene (EB) and propylene-butadiene (PB) copolymerizations and ethylene-propylene-butadiene (EPB) terpolymerization with a supported catalyst, TiCl4/MgCl2/ethyl benzoate-AlEt3, are described. The catalytic activities were enhanced in the EP copolymerizations, while the catalytic activities were decreased in the co- and terpolymerizations containing butadiene as compared with the corresponding homopolymerizations. It was found that the butadiene units in these co- and terpolymers are mostly in trans-1,4 configuration and long blocked sequences. 

Fig.15 shows 6PC curves of the EP copolymer and EPB terpolymer with 9.8 mol% Butadiene. The molecular weight distribution of the EPB terpolymer appears as a nonuniform modal and the amount of lower molecular weight fractions increases as compared with the EP copolymer. 

In the early history of polypropylene technology, blends with ethylene propylene copolymer were introduced for toughening polypropylene. Subsequently block copolymers of polypropylene with random ethylene propylene copolymer rubber were produced in the polymerization reaction. Dynamic vulcanization of ethylene propylene terpolymer in blends with polypropylene together with hydrocarbon oils was a third technology. The first TPO was elastomer (ethylene)-modified propylene (EP polymer) marketed to overcome polypropylene s weakness that cold temperature negatively impacts resistance. 

The preparation of ethylene copolymers (or terpolymers) such as linear low-density polyethylenes (LLDPE), ethylene/propylene elastomers (EP), ethylene/ propylene/diene terpolymers (EPDM) is also based on these catalytic systems. Stereoregular polyisoprene and polybutadiene elastomers are also obtained by this method of polymerization the formation of 1,4-m-polydienes requires the prior double coordination of the monomer onto the growing active center ... 

Whdi ethylene is copolymerized with propylene, the amorphous, rubbery material called ethylene propylene rubber PM - from ethylene propylene monomers) results if the ethylene content is high commercial polymers may contain 30 to 50% of ethylene units. In order to obtain a sulfur vul-canisable material, a small percentage of a third monomer (3 to 10% of a diene monomer, for example, ethylidene nor-bornene) is incorporated so as to make a terpolymer, this ter-polymer may be referred to as EPDM. An abbreviation which covers both types of ethylene propylene rubber is EP(D)M usually, all types of this rubber have a propylene content of between 25 and 55% by weight. 

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