Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2001-03-23
2003-06-10
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...
C526S134000, C526S141000, C526S157000, C526S161000, C526S169100, C526S171000, C526S172000, C502S121000, C502S123000, C502S124000, C502S164000, C502S167000
Reexamination Certificate
active
06576724
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to the catalytic dimerization, codimerization and oligomerization of olefins.
It has as its object a new catalytic composition, the codimerization or result of the dissolution of at least one nickel complex that contains at least one heterocyclic carbene ligand, in the liquid mixture, of ionic type, at least one ammonium halide and/or quaternary phosphonium halide, at least one aluminum trihalide and optionally at least one alkylaluminum halide. This invention also has as its object the use of this catalytic composition in processes of dimerization, codimerization and/or oligomerization of olefins.
BACKGROUND OF THE INVENTION
Some organometallic nickel complexes that contain heterocyclic carbene ligands have been described in the prior art (International Application WO-A-99/6004, U.S. Pat. No. 5,728,839 and Patent Application EP-A-0 798 041). Application WO-A-99/6004 also describes the use of these complexes for the polymerization of acrylates and the hydrocyanation of olefins. Such complexes have the advantage of being very stable. More particularly, these monocarbene or bicarbene ligands lead to nickel complexes that are thermally and chemically stable primarily with regard to oxidation.
Some of these nickel complexes, however, exhibit the drawback of being very non-soluble in standard organic solvents, which limits use thereof. International Patent Application WO-A-99/6004 describes the preparation of carbenic cationic nickel complexes that are water-soluble. The use of water, however, cannot become general in reactions whose active catalytic radical involves a metal-carbon bond, which deteriorates in quality in the presence of protons. This is the case of the dimerization or oligomerization of the olefins.
French Patent FR-B-2 611 700 describes the use of ionic liquids that are formed by aluminum halides and quaternary ammonium halides as solvents of organometallic nickel complexes for the catalysis of dimerization of olefins. The use of such immiscible media with the aliphatic hydrocarbons, in particular with the products that are obtained from the dimerization of olefins, makes possible a better use of homogeneous catalysts. French Patent FR-B-2 659 871 describes a liquid ionic composition that results from bringing into contact at least one quaternary ammonium halide and/or quaternary phosphonium halide with at least one alkylaluminum dihalide and optionally in addition at least one aluminum trihalide. This patent also describes the use of these media as solvents of transition metal complexes, in particular nickel complexes that do not contain a nickel-carbon bond, which are transformed into catalysts for oligomerization of olefins. Below, these media will be called “molten salts” because they are liquid at moderate temperature.
During these works, it was shown that the most active nickel catalysts are obtained in “molten salts” that consist of a molar equivalent of quaternary ammonium halide and/or quaternary phosphonium halide with an equivalent (or more) of aluminum trihalide and optionally any amount of alkylaluminum dihalide. This formulation has proven particularly advantageous because the nickel complexes that are dissolved in it have a high catalytic activity.
The neutral ligands that are described in these works and optionally associated with nickel are tertiary phosphines. The drawback of the alkylphosphine ligands is that these are expensive compounds that oxidize easily in the presence of air.
SUMMARY OF THE INVENTION
It has now been found that the nickel complexes that carry at least one monocarbene or bicarbene ligand that correspond, for example, to formulas (I) and (II) that are provided below are soluble and stable in the “molten salts” media and that they make it possible to catalyze the dimerization, codimerization or oligomerization of olefins. These carbene ligands were the object of a survey in Angew. Chem. Int. Ed. Engl. 1997, 36, 2162. These are &sgr;-donor ligands and &pgr;-acceptor ligands that form very stable bonds with the transition metals. Their electronic properties can be compared to those of basic trialkylphosphines.
The invention therefore has as its object a catalytic composition that results from the dissolution of a nickel compound that contains at least one heterocyclic mono- or bicarbene ligand in a “molten salt” medium that consists of at least one quaternary ammonium halide and/or at least one quaternary phosphonium halide (Product A), at least one aluminum halide (Product B), and optionally at least one organic aluminum compound (Product C).
DETAILED DESCRIPTION OF THE INVENTION
The nickel compounds that are used according to the invention are salts of nickel or organometallic compounds that may or may not be charged and that correspond to the general formula (already described in Patent Application EP-A-0 798 041):
(Ni
a
X
b
Y
d
L
c
)
n
(A)
n
in which:
a, b, c, d and n are integers with a equal to 1, 2 or 3; b equal to 0 to 2 times a; d equal to 0 to 2 times a; c is at least 1; n equal to 0, 1 or 2;
X and Y, identical or different, each represent a mono- or multidentate ligand that may or may not be charged; by way of examples, it is possible to cite halides, carboxylates (for example ethyl-2-hexanoate), acetylacetonate, sulfate, phenates, mono- and di-olefins, &pgr;-aromatic compounds, alkyl or aryl radicals, phosphines, phosphites and carbon monoxide;
L is a heterocyclic mono- or bi-carbene that corresponds to, for example, one of general formulas (I) and (II) above, in which R
1
, R
2
, R
3
, R
4
, R
5
and R
6
, identical or different, each represent hydrogen, a hydrocarbon-containing group, aliphatic group, saturated or unsaturated group, or aromatic group, comprising 1 to 12 carbon atoms, and Q represents an aliphatic bivalent radical with 1 to 4 carbon atoms; and
A is a sparingly coordinating anion; by way of examples, it is possible to cite tetrafluoroborate anions, hexafluorophosphate anions, tetraphenylborate anions and derivatives thereof, tetrachloroaluminate anions, hexafluoroantimonate anions, trifluoroacetate anions, trifluoromethylsulfonate anions and acetate anions.
Heterocyclic carbenes L can be generated from corresponding imidazolium or bis(azolium) salts by deprotonation. The transition metal can play the role of reducing agent.
By way of nonlimiting examples of heterocyclic mono- or bicarbene ligands, the carbene ligands that are described by formulas (1), (2) and (3) that are given below will be cited.
By way of nonlimiting examples of nickel compounds that can be used according to the invention, it is possible to cite the complexes of NiCl
2
, [dimethyl-1,3-imidazolylidene-2]
2
; NiI
2
, [dimethyl-1,3-imidazolylidene-2]
2
; &pgr;-allyl nickel chloride (dimethyl-1,3-imidazolylidene-2); NiCl
2
, [dimethyl-1,1′-imidazole-diylidene-2,2′-methylene-3,3′]
2
; NiCl
2
, [dimethyl-1,1′-imidazole-diylidene-2,2′-ethylene-3,3′]
2
; NiI
2
[dimethyl-1,1′-imidazole-diylidene-2,2′-methylene-3,3′]
2
and NiI
2
[dimethyl-1,1′-imidazole-diylidene-2,2′-methylene-3,3′]
2
.
The “molten salts” that are employed according to the invention consist of:
a) at least one halide, more particularly a chloride and/or a bromide, quaternary ammonium and/or quaternary phosphonium (A);
b) at least aluminum trichloride and/or aluminum tribromide (B); and
c) optionally an organic aluminum compound (C).
The quaternary ammonium and/or phosphonium halides that can be used within the scope of the invention (Product A) preferably correspond to
one of general formulas NR
1
R
2
R
3
R
4
X (with the exception of NH
4
X), PR
1
R
2
R
3
R
4
X, R
1
R
2
N—CR
3
R
4
X or R
1
R
2
P=CR
3
R
4
X, in which X represents Cl or Br and R
1
, R
2
, R
3
and R
4
, identical or different, each represent hydrogen or a hydrocarbyl radical with 1 to 12 carbon atoms, for example alkyl groups, saturated or unsaturated groups, cycloalkyl or aromatic groups, aryl or aralkyl groups compri
Commereuc Dominique
Harry Stephane
Olivier-Bourbigou Helene
Institut Francais du Pe'trole
Lee Rip A
Millen White Zelano & Branigan P.C.
Wu David W.
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