Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1998-06-09
2001-07-24
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S139000, C526S141000, C526S145000, C526S147000, C526S161000, C526S171000, C526S281000, C502S155000
Reexamination Certificate
active
06265506
ABSTRACT:
BACKGROUND OF THE INVENTION
This invention is directed to a method of copolymerizing ethylene with cycloolefin monomers, often referred to as norbornene-type, or NB-type. More specifically, the method employs cationic palladium catalysts and the polymers obtained by the method of this invention are amorphous addition copolymers which may be random or alternating in character. Said catalysts also yield novel polymers from functional NB-type monomers.
Addition copolymers of ethylene and norbornene-type monomers are well known and can be prepared using a variety of catalysts disclosed in the prior art. This general type of copolymers can be prepared using free radical catalysts disclosed in U.S. Pat. No. 3,494,897 (Reding et al.); titanium tetrachloride and diethylaluminum chloride as disclosed in East German Patents 109,224 and 222,317 (VEB Leuna); or a variety of vanadium compounds, usually in combination with organoaluminum compounds, as disclosed in European Patent Application No. 156464 (Kajiura et al.). The copolymers obtained with these catalysts are random copolymers. U.S. Pat. No. 4,948,856 issued to Minchak et al. (B. F. Goodrich) discloses preparing generally alternating copolymers by the use of vanadium catalysts which are soluble in the norbornene-type monomer and a co-catalyst which may be any alkyl aluminum halide or alkyloxy aluminum halide. European Patent Application No. 0 504 418 A1 (Matsumoto et al.) discloses copolymerization of said monomers in the presence of catalysts such as transition metal compounds, including nickel compounds, and a compound which forms an ionic complex with the transition metal compound or a catalyst comprising said two compounds and an organoaluminum compound. More recently, metallocene catalysts were used to prepare copolymers of cycloolefins and &agr;-olefins as disclosed in EP 283,164 (1987) issued to Mitsui Petrochemicals and EP 407,870 (1989), EP 485,893 (1990) and EP 503,422 (1991) issued to Hoechst AG. Most recently PCT published application WO96/23010 discloses processes of polymerizing ethylene, aryl olefins and/or selected cyclic olefins which are catalysed by selected transition metal compounds, including nickel complexes of diimine, and sometimes also a cocatalyst. This disclosure provides, however, that when norbornene or a substituted norbornene is used, no other olefin can be present.
SUMMARY OF THE INVENTION
It is a general object of the invention to provide a novel method of preparing generally amorphous copolymers of ethylene and at least one norbornene (NB)-type comonomer. These polymers may be random or alternating, depending on the choice of catalyst and/or the relative ratio of the monomers used. This method comprises polymerizing said monomers in a diluent or in bulk in the presence of a cationic palladium catalyst resulting from reacting a chelating ligand with a palladium (II) compound. If a weak chelating ligand is used, it is necessary to carry out the polymerization in the presence of excess chelate ligand.
Another object is to obtain novel copolymers of ethylene and at least one functional norbornene-type monomer.
DETAILED DISCLOSURE OF THE INVENTION
This invention is directed to a new method of preparing substantially amorphous copolymers of ethylene and one or more norbornene (NB)-type comonomers using cationic palladium catalysts. The resulting copolymers may be alternating or random, depending on the relative proportion of each type of monomer used and on the choice of the catalyst. This method comprises polymerizing said monomers in the presence of a cationic palladium catalyst in a diluent or in bulk.
The catalysts employed in the method of this invention are cationic palladium catalysts which are obtained from (i) a palladium compound, (ii) a neutral chelating ligand containing two heteroatoms, other than 2,2-bipyridine, (iii) a compound able to form an ionic complex when reacted with a palladium compound, and (iv) optionally, an organometallic cocatalyst, provided that when the palladium catalyst is devoid of the palladium-carbon sigma (&sgr;) bond the cocatalyst must be employed.
The palladium compound may be any palladium (II) salt which contains anionic ligands selected from halides such as chloride, bromide, iodide, or fluoride ions; pseudohalides such as cyanide, cyanate, hydride, alkoxide, aryloxide and the like; carbanions such as branched and unbranched (C
1
-C
40
) alkylanions, phenyl anion; cyclopentadienylide anions; &pgr;-allyl groupings; enolates of &bgr;-dicarbonyl compounds such as acetylacetonate, 2,4-pentadionate; halogenated acetylacetonates such as 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate, 1,1,1-trifluoro-2,4-pentanedionate; anions of acidic oxides of carbon such as carboxylates and halogenated carboxylates (e.g., 2-ethylhexanoate, neodecanoate trifluoroacetate, etc.) and oxides of nitrogen (e.g., nitrated, nitrites, etc.), of bismuth (e.g., bismuthate, etc.), of aluminum (e.g., aluminates etc.), of silicon (e.g., silicates etc.), of phosphorus (e.g., phosphates, phosphites, phosphines, etc.) and of sulfur (e.g., sulfates such as triflate, p-toluene sulfonate, sulfites, etc.); ylides; amides; imides; oxides; phosphides; sulfides; (C
6
-C
24
) aryloxides; (C
1
-C
20
) alkoxides; hydroxides; hydroxy (C
1
-C
20
) alkyl; catechols; oxylate; chelating alkoxides and aryloxides; complex anions such as PF
6
−
, AlF
3
O
3
SCF
3
−
, SbF
6
−
and compounds represented by the formulae Al(R
7
)
4
−
and B(X)
4
−
wherein R
7
and X independently represent a halogen atom selected from Cl, F, I and Br, or a substituted or unsubstituted hydrocarbyl group. Representative of hydrocarbyl groups are (C
1
-C
25
) alkyl such as methyl, ethyl, propyl, butyl, octyl dodecyl, hexadecyl, eicosyl, docosyl, pentacosyl, and isomeric forms thereof; (C
2
-C
25
) alkenyl such as vinyl, allyl, crotyl, butenyl, hexenyl, decenyl, hexadecenyl, pentacosenyl, and isomeric forms thereof; (C
6
-C
25
) aryl such as phenyl, tolyl, xylyl, naphthyl, and the like; (C
7
-C
25
) aralkyl such as benzyl, phenethyl, phenbutyl, phenoctyl and the like; (C
3
-C
8
) cycloalkyl such as cyclopropyl, cyclobutyl, cyclohexyl, cyclooctyl, 2-norbornyl, 2-norbornenyl and the like. In addition to the above definitions X represents the radical:
The term substituted hydrocarbyl means the hydrocarbyl group as previously defined wherein one or more hydrogen atoms have been replaced with a halogen atom such as Cl, F, Br and I (e.g., as in the perfluorophenyl radical); hydroxyl; amino; alkyl; nitro; mercapto and the like.
Illustrative examples of specific palladium compounds include palladium halides such as palladium iodide, palladium bromide and preferably palladium chloride; palladium acetylacetonates such as palladium bis(acetylacetonate); palladium carboxylates where the carboxylate group has up to 24 carbons and preferably from 2 to 12 carbons and may be exemplified by palladium acetate, hexanoate, ethylhexanoate, dodecanoate and the like. The palladium compound may also be a complex adduct of palladium salts bearing neutral donor ligands. It is preferred to use a relatively labile donor ligand such as bis(benzonitrile)palladium dichloride, (cyclooctadiene)palladium dichloride, (cyclooctadiene)palladium(methyl)bromide, (dimethoxyethane)palladium dibromide and the like.
Palladium adducts bearing strong chelating ligands may also be used, but such ligands are not preferred because these ligands may compete with the added chelate ligand (X~Y) to give mixed catalysts (in which there are palladium species present in solution containing either one ligand or the other, depending on the relative strength of the two ligands and the equilibrium conditions) which would yield mixed results, that is, a mixture that contains copolymers of different compositions and molecular weights. However by using an excess of the neutral chelate ligand (X~Y) the replacement of the stronger ligands of the palladium complex adducts will be favored, resulting in a catalyst which will polymerize both types of monomers to yield a copolymer
Goodall Brian Leslie
McIntosh, III Lester Howard
Dunlap Thoburn T.
Rabago R.
Shust Nestor W.
The B. F. Goodrich Company
Wu David W.
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