Ethylene/butadiene copolymers, catalytic system and process...

Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...

Reexamination Certificate

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C526S137000, C526S160000, C526S164000, C502S117000, C502S153000

Reexamination Certificate

active

07094854

ABSTRACT:
Disclosed are ethylene and butadiene copolymers and a catalytic system usable for the synthesis of these copolymers. The copolymers have a molar content of units resulting from butadiene of ≧8%, said units comprising trans-1,2 cyclohexane linkages, and a number-average molecular mass Mn of ≧40,000 g/mol. The catalytic system includes:(i) an organometallic complex represented by one of the following formulae A or B:where Ln represents a lanthanide and X a halogen, where, in the formula A, two ligand molecules Cp1and Cp2each consisting of a fluorenyl group, are attached to Ln, where, in the formula B, a ligand molecule consisting of two fluorenyl groups Cp1and Cp2, joined together by a bridge P of formula MR2, where M is an element of column IVa and R is an alkyl with 1 to 20 carbon atoms, is attached to Ln, and(ii) a co-catalyst selected from an alkylmagnesium, an alkyllithium, an alkylaluminium, a Grignard reagent, or a mixture of these constituents. The (co-catalyst/organometallic complex) molar ratio falls within a range of from 1 to 8.

REFERENCES:
patent: 5191052 (1993-03-01), Welborn, Jr.
patent: 6569799 (2003-05-01), Barbotin et al.
patent: 1 092 731 (2001-04-01), None
Llauro, Marie France et al., “Investigation of ethylene/butadiene copolymers microstructure by 1H and 13C NMR”, Macromolecules 2001, 34, pp. 6304-6311, XP002244179, (2001).
Nakamura, Hiroshi et al., “Alternative.eta.5- and eta. 6-Bonding Modes for Bis(fluorenyl)lanthanide Complexes by Reactions with A1R3 and Successive Addition of THF”, Organometallics 2000, 19 (24), pp. 5392-5399 XP002244180 (2000).
Evans, William J. et al., “Copolymerization of Ethylene Carbonate and epsilon.-Caprolactone Using Samarium Complexes”, MACROMOLECULES 1994, 27 (14), pp. 4011-4013, XP002244181 (1994).
CUI, Liqiang et al., “Preliminary Investigations on polymerization catalysts composed of lanthanocene and methylaluminoxane”, Polymer Bulletin, Springer Verlag. Heidenberg, DE, vol. 40, No. 6, pp. 729-734, XP000755393, (Jun. 1, 1998).
Llauro, Marie France et al., “Investigation of ethylene/butadiene copolymers microstructure by 1H and 13C NMR”, Macromolecules 2001, 34, pp. 6304-6311, XP002244179, (2001).
Nakamura, Hiroshi et al., “Alternative.eta.5- and eta. 6-Bonding Modes for Bis(fluorenyl)lanthanide Complexes by Reactions with A1R3 and Successive Addition of THF”, Organometallics 2000, 19 (24), pp. 5392-5399 XP002244180 (2000).
Evans, William J. et al., “Copolymerization of Ethylene Carbonate and epsilon.-Caprolactone Using Samarium Complexes”, MACROMOLECULES 1994, 27 (14), pp. 4011-4013, XP002244181 (1994).
CUI, Liqiang et al., “Preliminary Investigations on polymerization catalysts composed of lanthanocene and methylaluminoxane”, Polymer Bulletin, Springer Verlag. Heidenberg, DE, vol. 40, No. 6, pp. 729-734, XP000755393, (Jun. 1, 1998).
International Search Report issued in Application No. P/EP03/11303.

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