Title of Invention

CATALYTIC COMPOSITION FOR DIMERISING CO-DIMERISING AND OLIGOMERISING OLEFINS

Abstract This invention relates to catalytic composition comprising at least one nickel compound mixed or complexed with at least one tertiary phosphine or a phosphite carrying a functional group, at least partly dissolved in a non-aqueous medium with an ionic nature resulting from bringing at least one aluminum halide into contact with at rleast one quaternary ammonium halide and/or at least one quaternary phosphonium halide, is usefu.1 for dimerizing, co-dimerizing and oligomerizig olefms. Functional groups include, but are not limited to, an amine, a cyclic amine, a nitrogen-containing heterocycle, an ester, an acid, an alcohol, a quaternary ammonium, a quaternary phosphonium, a sulfonium, a sulfonate, a phosphonate group.
Full Text The present invention relates to a catalytic composition used for dimerising, co-dimerising and oligomerising olefins. More particularly, it relates to a composition resulting from at least partly dissolving at least one nickel compound mixed or complexed with a tertiary phosphine or a phoshite carrying a functional group, in a liquid mixture of ionic nature of at least one quaternary ammonium halide and/or at least one quaternary phosphonium halide, at least one aluminium halide and optionally at least one organometallic aluminium compound.
French patent FR-B-2 611 700 describes the use of liquids of ionic nature formed from aluminium halides and quaternary ammonium halides as solvents for organometaUic nickel complexes to catalyse olefin dimerisation. The use of such media, which are not miscible with aliphatic hydrocarbons, in particular with the products from olefin dimerisation, enables homogeneous catalysts to be used more effectively. French patent FR-B-2 659 871 describes a liquid composition with an ionic nature resulting from bringing quaternary ammonium halides and/or quaternary phosphonium halides into contact with alkylaluminium dihalides and optionally also an aluminium trihalide. That same patent describes the use of such media as solvents for transition metal complexes, in particular nickel complexes containing no nickel-carbon bond, which are transformed into catalysts for olefin oligomerisation. In the present text, such media will henceforth be termed "molten salts", as they are liquid at moderate temperatures.
During those studies, it was shown that the most active and most stable nickel catalysts are obtained in "molten salts" constituted by one molar equivalent of an ammonium halide and/or a phosphonium halide with one equivalent and more of an aluminium trihalide, and optionally any quantity of an alkyl aluminium dihalide. That formulation has been shown to be particularly interesting as nickel complexes dissolved in it have high catalytic activity.
It has been shown that under such conditions and when the reaction is carried out in a semi-open system with a continuous olefin supply and continuous separation of the products after decanting, a small but non negligible proportion of the nickel is extracted in the organic phase.

Further, it has been shown that under the conditions described in French patent FR-B-2 611 700, the "phosphine effect", as described by G. Wilke et al., in Ind. Eng. Chem., 1970, 62, No. 12, p. 34, and in United Kingdom patent GB-B-1 058 680, which reports the influence of substituents carried by the phosphorus atom on the mode of enchainment of propylene molecules during catalytic dimerisation by nickel, rapidly disappears over time. That unexplained phenome¬non has deleterious consequences since it does not produce the desired selectivities.
Further, FR-B 2 710 280 shows that adding an aromatic hydrocarbon to a "molten salt" can overcome this problem and result in catalysts with high activity which are more stable and which have a high selectivity for the most highly branched isomers. However, the aromatic hydrocarbon is continuously extracted in the organic phase constituted by the products, which implies that it must be separated and recycled to the reactor.
It has now been discovered that the use of a tertiary phosphine carrying a functional group or a phosphite carrying a functional group or a nickel complex formed with a tertiary phosphine or a functionalised phosphite that is soluble in the "molten salt" results in catalysts with high activity which are stable over time and wherein the extraction of nickel from the reaction products is reduced to a minimum. This has the result of reducing the consumption of the catalyst and thus of improving the economics of the process.
The invention provides a catalytic composition comprising at least one nickel compound mixed or complexed with at least one tertiary phosphine or a phosphite carrying a functional group, aLleast partly dissolved in a non aqueous medium with an ionic nature ("molten salt" type medium), resulting from bringing at least one aluminium halide (product B) into contact with at least one quaternary ammonium halide and/or at least one quaternary phosphonium halide (product A), the "molten salt" type medium possibly further comprising at least one organometallic aluminium compound (product C).

Thus the "molten salt" type medium, in which the nickel compound mixed or complexed ~ with at least one tertiary phosphine carrying a functional group or at least one phosphite carrying a function group is dissolved, is constituted by mixing:
a) at least one quaternary ammonium and/or quaternary phosphonium halide, more particularly a chloride and/or bromide (product A);
b) at least one aluminium halide (product B); and
c) optionally, at least one organometallic aluminium compound (product C).
Preferred quaternary ammonium and/or phosphonium halides that can be used within the
context of the invention (product A) are:
• those with general formula NR"R^R^R"^X (with the exception of NH4X), PR"R^R^R^X, R"R^N=CR^R^X or R"R2p=CR^R^X, where X represents CI or Br and R\ R^ R^ and R^ which may be identical or different, each represent hydrogen or a hydrocarbyl residue containing 1 to 12 carbon atoms, for example saturated or unsaturated alkyl, cycloalkyl or aromatic groups, aryl groups or aralkyl groups, containing 1 to 12 carbon atoms, it being understood that preferably, only one of substituents R\ R^, R^ and R"^ represents hydrogen; ^
• or one of the following general formulae:

where the nitrogen-containing or phosphorus-containing heterocycles containing 1, 2 or 3 nitrogen and/or phosphorus atoms are constituted by 4 to 10 atoms and X, R and R are defined as above.

Examples which can be cited are tetrabutyl phosphonium chloride, N-butyl pyridinium - chloride, ethylpyridinium bromide, 3-butyl-l-methyl imidazolium chloride, diethylpyrazolium chloride, pyridinium hydrochloride, trimethylphenyl ammonium chloride and 3-ethy 1-1-methyl imidazolium chloride. These salts can be used alone or as a mixture.
The aluminium haUdes used as products B of the invention are essentially aluminium chloride and bromide.
The organometallic aluminium compounds used as optional products C of the invention have general formula AlRxXs.x in which R is a linear or branched alkyl residue containing 2 to 8 carbon atoms, X is chlorine or bromine and the value of x is 1, 2 or 3. Examples of organometallic aluminium compounds that can be used are isobutylaluminium sesquichloride, ethylaluminium sesquichloride, dichloroisobutyl aluminium, dichloroethyl aluminium and chlorodiethylaluminium.
The components of the "molten salts" as defined above are generally used in A:B mole ratios of 1:0.5 to 1:3, preferably 1:1 to 1:2; product C is used in a mole ratio of at most 100:1 with product B, preferably 0.005:1 to 10:1. However, the components and their proportions must be such that the mixture is liquid at the temperature at which the nickel compound and the functionalised tertiary phosphine or functionalised phosphite are introduced, although the catalytic dimerisation reaction can be carried out at a temperature that is lower than or higher than the fusion temperature of the catalytic composition.
Examples of nickel compounds used in the catalytic compositions of the invention are the chloride, bromide, sulphate, carboxylates (for example the 2-ethylhexanoate), phenates and acetyl acetonate. It is also possible to use organometallic nickel complexes which may or may not contain phosphines or phosphites. These nickel complexes are used as a mixture with a functionalised tertiary phosphine or a functionalised phosphite. It is also possible to use nickel complexes that are already complexed with a tertiary phosphine carrying a function or a phosphite carrying a function.

The functional phosphines used as a mixture with (or to complex) the nickel compounds of the invention have general formulae PR1iR"2R3s and R1iR"2P-R"-PR"1R"2, where R"l, R"2 and R"3, which may be identical or different, are alkyl, cycloalkyl, aryl or aralkyl radicals containing 1 to 10 carbon atoms at least one of which carries a functional group such as an amine, a cyclic amine, a nitrogen-containing heterocycle, an ester, an acid, an alcohol, a quaternary ammonium, a quaternary phosphonium, a sulphonium, a sulphonate or a phosphonate and R" is a divalent aliphatic residue containing 1 to 6 carbon atoms.
The functional phosphines can be selected from compounds containing pyridine or imidazole substituents or their quaternised derivatives containing pyridinium or imidazoUum substituents that satisfy formulae 1 to 7 defined below.
Examples of functional phosphines carrying a pyridine substituent are 2-dicyclopentyl-phosphinoethyl-4-pyridine with formula (1), 2-dicyclopentylphosphinoethyl-2-pyridine with formula (2), 2-diisobutylphosphinoethyl-4-pyridine with formula (lb), 2-diisopropylphosphinoethyl-4-pyridine with formula (4) and their quaternisation derivatives with formula (3), where R is an aUcyl group containing 1 to 10 carbon atoms and X is a weakly co-ordinating anion. Examples of weakly co-ordinating anions which can be cited Eire tetrafluoroborate, hexafluorophoshate, tetrachloroaluminate, hexafluoroantimonate, carboxylate anions such as acetate, trifluoroacetate, trifluorosulphonate, and the anions N(CF3S02)2" and C(CF3S02)3". Examples of quaternisation derivatives are 2-dicyclopentylphosphinoethyl-N-ethyl pyridinium tetrafluoroborate with formula (3a), or 2-dicyclopentylphosphinoethyl-N-ethyl pyridinium chloride with formula (3b).
Examples of functional phosphines carrying an imidazole substituent which can be cited are 2-dicyclopentylphosphinoethyl-N-iniidazole with formula (5), 2-diisopropylphosphinoethyl-N-imidazole with formula (7), 2-diisobutylphosphinoethyl-N-imidazole with formula (7b) and their quaternisation derivatives with formula (6), where R is an alkyl group containing 1 to 10 carbon

atoms and X is a weakly co-ordinating anion (as defined above), such as 2-dicyclopentyl-phosphinoethyl-1-methyl imidazolium tetrafluoroborate with formula (6a).
The functionalised phosphites used as a mixture with (or to complex the nickel compounds of the invention) have general formulae P(OR"i) (0R"2) (0R"3) and (-0-R"5-0-)P(OR"2), where R"i, R"2, R"3 and R"5, which may be identical or different, are aryl or aralkyl radicals at least one of which carries a functional group such as an amine, a cyclic amine, a nitrogen-containing heterocycle, an ester, an acid, an alcohol, a quaternary ammonium, a quaternary phosphonium, a sulphonium, a sulphonate or a phosphonate.
The functional phosphites can be selected from compounds with formulae 9 to 11 described below.
It is possible to use phosphites represented by general formula (9) (where x is 0 to 2), where Y"^ can be an organic cation such as a quaternary anunonium or quaternary phosphonium with general formula NR"R^R^R^ and PR^R^R^R^ where R", R^ R^ and R\ which may be identical or different, each represent hydrogen, an aliphatic (saturated or unsaturated) or aromatic hydrocarbon group containing 1 to 12 carbon atoms; the quaternary ammonium and/or phosphonium ions can also be derivatives of heterocycles containing 1, 2 or 3 nitrogen and/or phosphorus atoms or an alkaline cation such as Li"^, Na"^ or K"^ [formula (9b)].

As examples of quaternary ammonium or phosphonium cations that can be found in formulae (9) and (10), can be cited tetrabutylammonium, as in formula (9a) or formula (10a), tetrabutylphosphonium, N-butylpyridinium, ethylpyridinium, 3-butyl-l-methylimidazolium, diethyl-pyrazolium and trimethylphenylammonium.
Finally, it is possible to use phosphites represented by general formula (11), where anion X is a weakly co-ordinating anion. Examples of weakly co-ordinating anions which can be cited are tetrafluoroborate or hexafluorophosphate, as in formula (11a), tetrachloroaluminate, hexafluoro-antimonate, carboxylate anions such as acetate or trifluoroacetate, trifluorosulphonate, the N(CF3S02)2~ and C(CF3S02)3" and the tetraphenylborate anion and tetraphenylborate anions where the aromatic rings are substituted.



As examples of nickel compounds that can be used to constitute the catalytic compositions of the invention can be cited the complexes [NiCli, 1.5P(2-dicyclopentylethyl-4-pyridine)]2, [NiCla, 2P(2-dicyclopentylethyl-N-ethyl pyridinium tetrafluoroborate)], [Ni2Cl4, (2-dicyclopentyl-phosphinoethyl-N-ethyl pyridinium tetrafluoroborate)3, I.5CH2CI2], NiCl2, 2 pyridine mixed with at least one equivalent of fiinctionalised tertiary phosphine or functionalised phosphite, nickel chloride mixed with at least one equivalent of 2-dicyclopentylphosphinoethyl-4-pyridine, nickel acetate mixed with at least one equivalent of 2-dicyclopentylphosphinoethyl-4-pyridine, nickel (2-ethyl hexanoate) octoate mixed with at least one equivalent of 2-dicyclopentylphosphinoethyl-4-pyridine and 2-dicyclopentylphosphinoethyl-4-pyridine Tt-allyl nickel chloride.
The compounds forming part of the catalytic composition of the invention can be mixed in any order. The mixture can be produced by simply bringing them into contact followed by agitation until a homogeneous liquid is formed. This mixture can be produced outside the dimerisation or oligomerisation reactor or, as is preferable, in the reactor.
More particular olefins that can be dimerised, co-dimerised or oligomerised using the catalytic compositions of the invention are ethylene, propylene, n-butenes and n-pentenes, used alone or as a mixture (co-dimerisation), pure or diluted in an alkane, such as those found in cuts from oil refining processes, such as catalytic cracking or steam cracking.
The catalytic olefin dimerisation or oligomerisation reaction can be carried out in a closed system, in a semi-open system or continuously, with one or more reaction stages. Vigorous agitation must be carried out to ensure good contact between the reactant or reactants and the catalytic mixture. The reaction temperature can be from -40°C to +70°C, preferably -20°C to +50""C. It is possible to operate above or below the fusion temperature of the medium, the dispersed solid state not being a limitation to the proper conduct of the reaction. The heat engendered in the reaction can be eliminated using any means known to the skilled person. The pressure can be from atmospheric pressure to 20 MPa, preferably atmospheric pressure to 5 MPa. The reaction products

and the reactant or reactants which has/have not reacted are separated from the catalytic system simply by decanting, then fractionation.
The following examples illustrate the invention without limiting its scope. EXAMPLE 1: Preparation of ionic solvent
17.5 g (0.1 mole) of l-butyl-3-methyl imidazolium chloride, 16.3 g (0.122 mole) of sublimed aluminium chloride, 1.6 g (0.0126 mole) of dichloroethyl aluminium were mixed at ambient temperature. A liquid was obtained.
EXAMPLE 2: Preparation of the complex [NiCIi, 1.5 P(2-dicyclopentyIethyl-4-pyridine)]2
2.37 g of NiCla, 6H2O and 10 ml of absolute methanol were introduced into a Schlenk tube maintained under an argon atmosphere. After the nickel salt had dissolved, 20 ml of pentane was added. The 2 phases were agitated and 5.33 g of tertiary phosphine with formula (1) (20 mmoles) was added. After 2 hours agitation, the red precipitate was filtered. 5.82 g was obtained. Elemental analysis corresponded to the complex with formula [NiCl2, 1.5 P(2-dicyclopentylethyl-4-pyridine)]2 (M = 1085 g; 10.7% by weight of Ni).
EXAMPLE 3 Quatemisation of pyridine in the complex described in Example 2
3.72 g of the complex described in Example 2 was placed in a Schlenk tube and dichloromethane was added. Then a solution of tetrafluoroborate oxonium in dichloromethane (2.14 g of Et30^BF4") was added dropwise. It was agitated for 4 hours, at the end of which period a red solution was obtained. The solvent was evaporated off and 20 ml of ether was added. The red crystalline solid obtained was filtered off 4.56 g was obtained. Elemental analysis corresponded to the complex with formula: Ni2Cl4(P-N*EtBF4")3, I.5CH2CI2, where P-N is the ligand with formula (1).
EXAMPLE 4: Propylene dimerisation
A glass reactor provided with a temperature sensor, a magnetic bar in the lower stage (20 ml volume) to ensure proper agitation and a double envelope for circulating a cooling liquid was purged

of air and moisture and maintained at an atmospheric pressure of 99% pure propylene. 0.03 mmole of the complex prepared in Example 2 (0.06 mmole of Ni) was introduced then the temperature was reduced to 10°C and 5 ml of the liquid composition prepared above (Example 1) was injected using a syringe, along with 7 ml of heptane. Agitation was commenced and immediately, propylene absorption was observed. When the non agitated upper stage was full of liquid, the major portion of the hydrocarbon phase had been extracted. The reaction was stopped after 7 hours (5 extractions). At that time, 175 kg of products per gram of Ni had been produced. Analysis of the different fractions showed that they were composed of 77% of dimers. The composition of the dimers, which was practically identical in all of the fractions, was 67% of 2,3-dimethylbutenes, and 29% of methyl pentenes, the remainder being n-hexenes.
EXAMPLE 5: Propylene dimerisation
The procedure of Example 4 was carried out, with the exception that the molten salt prepared for this purpose was used, and that 0.05 mmole of nickel (2-ethylhexanoate) octoate and 0.5 mmole of 2-dicyclopentylphosphinoethyl-4-pyridine were introduced. The reaction period was 7 hours 15 minutes, at the end of which 5 fractions had been extracted and 220 kg of products per gram of Ni had been produced. The dimer selectivity was 78%. The selectivity for 2,3-dimethylbutenes was 66% in the first fraction and 63% in the final fraction.
EXAMPLE 6: Propylene dimerisation
The procedure of Example 4 was followed, with the exception that the molten salt for this purpose was used, and that 45 mg of the complex prepared in Example 3 was introduced. The reaction period was 7 hours 15 minutes, at the end of which 5 fractions had been extracted and 117 kg of products per gram of Ni had been produced. The dimer selectivity was 74-79%. The selectivity for 2,3-dimethylbutenes was 65% and was constant for the various fractions.

EXAMPLE 7 (comparative): Propylene dimerisation
The procedure of Example 4 was followed, with the exception that the molten salt used was that prepared in Example 1, introducing 0.05 mmole of the complex NiCl2, 2P(cyclohexyl)3. The reaction was left for 8 hours 30 minutes, at the end of which 10 fractions had been extracted. 137 kg of products per gram of Ni were produced, with a dimer selectivity of 83%. The selectivity for 2,3-dimethylbutenes was 70% in the first fraction; it dropped to 35% in the third and to 10% in the sixth fraction. It was 6% in the tenth fraction.
EXAMPLE 8: Butene dimerisation
The molten salt prepared in Example 1 was used. The procedure of Example 4 was used with the exception that butene-1 was used instead of propylene. 0.115 mmole (0.23 mmoles of Ni = 13.5 mg of Ni) of the complex prepared in Example 2 was introduced into the lower stage of the glass reactor then the temperature was reduced to 10°C and 5 ml of the salt and 20 ml of heptane were injected under a butene atmosphere. Agitation was commenced and butene absorption was observed. When the non agitated upper stage was full of fluid, the major portion of the hydrocarbon phase had been extracted. The reaction was stopped after 21 hours (28 extractions). At that moment, 1708 g of butene had been consumed. 76 kg of products per gram of Ni had been produced. Analysis of the different fractions showed that they were composed of 80% of dimers. The ensemble of the organic fractions was treated with 10% nitric acid. 2.25 ml of Ni was found in the nitric acid (X-ray fluorescence determination). A proportion of 19% by weight of nickel (calculated with respect to the nickel introduced) had thus been extracted with the products after 21 hours of reaction.
EXAMPLE 9: Preparation of ligand with formula (9a)
26.1 g (65.58 mmole) of tetrabutylammonium 4-hydroxy benzene sulphonate and 100 ml of toluene were introduced into a three-necked flask. It was heated to 140°C and over 1 hour, 6.82 g (21.8 mmole) of triphenylphosphite and 0.385 g of trioctylamine were added. It was left for another

1 hour at 140°C then placed under vacuum (10"^ mm Hg) for 6 hours at 110°C. The product obtained was analysed by ^"P NMR. It was constituted by a mixture of 3 phosphites corresponding to X = 0, 1 and 2.

EXAMPLE 10: Butene dimerisation
The molten salt prepared in Example 1 was used. The procedure of Example 8 was followed, with the exception that the complex NiCl2,2-pyridine (0.2 mmole; 11.8 mg Ni) was used as the catalyst precursor to which 5 equivalents (670 mg) with respect to the nickel of the phosphite with formula (9a) had been added, prepared as described in Example 9. The reaction was stopped after 43.5 hours (22 extractions). At that time, 1428 g of butene had been consumed. 73 kg of products per gram of Ni was produced. Analysis of the different fractions showed that they were composed of 97-99% of dimers. The ensemble of the organic fractions was treated with 10% nitric acid. 1 mg of Ni was found in the nitric acid (X-ray fluorescence determination). A proportion of 8.5% by weight of nickel (calculated with respect to the nickel introduced) had thus been extracted with the products after 43.5 hours of reaction.
EXAMPLE 11: Butene dimerisation
The procedure of Example 10 was followed, with the exception that 1 equivalent (134 mg) of the phosphite with formula (9a) was added with respect to the complex NiCl2,2-pyridine. The reaction was stopped after 35 hours (12 extractions). At that time, 2102 g of butene had been consumed. 107 kg of products per gram of Ni was produced. Analysis of the different fractions showed that they were composed of 95-97% of dimers. The ensemble of the organic fractions was treated with 10% nitric acid. 1.4 mg of Ni was found in the nitric acid (X-ray fluorescence

determination). A proportion of 12% by weight of nickel (calculated with respect to the nickel introduced) had thus been extracted with the products after 35 hours of reaction.
EXAMPLE 12 (comparative): Butene dimerisation
The molten salt prepared in Example 1 was used. The procedure of Example 7 was followed, with the exception that the complex NiC1, 2P(cyclohexyl)3 (0.2 mmole of Ni; 11.8 mg Ni) was used as the catalyst precursor, and 40 ml of heptane. The reaction was stopped after 14.8 hours (9 extractions). A substantial reduction in butene consumption was observed. At that time, 815 g of butene had been consumed. 84 kg of products per gram of Ni was produced. Analysis of the different fractions showed that they were composed of 90-94% of dimers. The ensemble of the organic fractions was treated with 10% nitric acid. 6.2 mg of Ni was found in the nitric acid (X-ray fluorescence determination). A proportion of 52% by weight of nickel (calculated with respect to the nickel introduced) had thus been extracted with the products after 14.8 hours of reaction.



WE CLAIM:
A catalytic composition comprising at least one nickel compound mixed or complexed with at least one tertiary phosphine carrying a functional group having one of the general formulae:
PR1iR"2R"3 or R1|R"2P-R"-PR"1R"2, where R"j, R"2 and R"3, which may be identical or different, are alkyl, cycloalkyl, aryl or aralkyl radicals containing 1 to 10 carbon atoms at least one of which carries a functional group selected from an amine, a cyclic amine, a nitrogen-containing heterocycle, an ester, an acid, an alcohol, a quaternary ammonium, a quaternary phosphonium, a sulphonium, a sulphonate and a phosphonate group and R" is a divalent aliphatic residue containing 1 to 6 carbon atoms,
at least partly dissolved in a non aqueous medium with an ionic nature resulting from bringing at least one aluminium halide (product B) into contact with at least one quatemafy ammonium halide and/or at least one quaternary phosphonium halide (product
A).
The catalytic composition according to claim 1 wherein the functional tertiary
phosphine is selected from phosphines containing pyridine or imidazole substituents and their quatemisation derivatives with pyridinium or imidazolium substituents. The catalytic composition according to claim 2 wherein the functional tertiary phosphine carrying a pyridine or imidazole substituent is selected from 2-dicyclopentyl-phosphinoethyl-4-pyridine, 2-dicyclopentylphosphinoethyl-2-pyridine, 2-diisobutylphos-phinoethyl-4-pyridine, 2-diisopropylphosphinoethyl-4-pyridine, 2-dicyclopentylphos-phinoetl^yl-N-imidazole, 2-diisopropylphosphinoethyl-N-imidazole and 2-diisobutyl-phosphinoethyl-N-imidazole.

4. The "catalytic composition according to claim 2 wherein the functional tertiary phosphine
carrying a pyridinium or imidazolium substituent is a quatemisation derivative with one of formulae (3) or (6) where R is an alkyl group containing 1 to 10 carbon atoms and X is a weakly co-ordinating anion.
5. The catalytic composition according to claim 4 wherein the weakly co-ordinating anion is
selected from tetrafluoroborate, hexafluorophosphate, tetrachloroaluminate, hexafluoro-antimonate, carboxylate anions, trifluorosulphonate, and the N(CF3S02)2- and C(CF3S02)3" anions.
6. The catalytic composition according to anyone of claims 4 and 5 wherein the functional
tertiary phosphine carrying a pyridinium or imidazolium substituent is selected from 2-dicyclopentylphosphinoethyl-N-ethyl pyridinium tetrafluoroborate, 2-dicyclopentyl-phosphinoethyl-N-ethyl pyridinium chloride and 2-dicyclopentylphosphinoethyl-l-methyl-imideizolium tetrafluoroborate.
7. The catalytic composition according to anyone of claims 1 to 6 wherein the nickel
compound is selected from the chloride, bromide, sulphate, carboxylates, phenates and acetyl acetonate.
8. The catalytic composition according to any one of claims 1 to 7 wherein the nickel
compound mixed or complexed with at least one tertiary phosphine carrying a functional group is selected from the following complexes:
• [NiCl2, 1.5P(2-dicyclopentylethyl-4-pyridine)]2;
• [NiCl2, 2P(2-dicyclopentylethyl-N-ethyl pyridinium tetrafluoroborate)] 2;
• [Ni2Cl4, (2 - dicyclopentylphosphinoethyl - N- ethylpyridinium tetrafIuoroborate)3, I.5CH2CI2];

• NiCl2, 2 pyridine mixed with at least one equivalent of fiinctionalised tertiary phosphine or functionalised phosphite;
• nickel chloride mixed with at least one equivalent of 2-dicyclopentylphosphinoethyl-4-pyridine;
• nickel acetate mixed with at least one equivalent of 2-dicyclopentylphosphinoethyl-4-pyridine;
• nickel (2-ethyl hexanoate) octoate mixed with at least one equivalent of 2-dicyclopentylphosphinoethyl-4-pyridine;and
• 2-dicyclopentylphosphinoethyl-4-pyridine n-allyl nickel chloride.
9. A catalytic composition comprising at least one nickel compound mixed or coraplexed
with at least one tertiary phosphite carrying a functional group having one of the general
formulae:
P(OR",) (OR"2) (0R"3) or (-0-R"5-0-)P(OR"2); where R"i, R"2, R"3 and R"5, which may be identical or different, are aryl or aralkyl radicals wherein at least one carries a functional group such as an amine, a cyclic amine, a nitrogen-containing heterocycle, an ester, an acid, an alcohol, a quaternary ammonium, a quaternary phosphonium, a sulphonium, a sulphonate or a phosphonate, at least partly dissolved in a non aqueous medium with an ionic nature resulting from bringing at least one aluminium halide (product B) into contact with at least one quaternary ammonium halide and/or at least one quaternary phosphonium halide (product A).
10. The catalytic composition according to claim 9 wherein the functional phosphite has general
formula (9) where x=0 to 2, in which cation Y:

• is selected from sodium, lithium or potassium and the quaternary ammonium and quaternary phosphonium cations have general formulae:
N+R1R2R3R4 and P1R2R3R4R"* where R", R^, R^ and R"*, which may be identical or different, each represent hydrogen, a saturated or unsaturated aliphatic or an aromatic hydrocarbon group containing 1 to 12 carbon atoms; or
• is derived from a heterocycle containing 1, 2 or 3 nitrogen and/or phosphorus atoms.
11. The catalytic composition according to claim 9 wherein the phosphite has general formula
(10) where cation Y
• is selected from sodium, lithium or potassium and quaternary ammonium and
quaternary phosphonium cations with general formulae N"+R1R2R3"R4 and P1R2R3R4R"*
where R1, R2, R3 and R"", which may be identical or different, each represent
hydrogen, a saturated or unsaturated aliphatic or an aromatic hydrocarbon group
containing 1 to 12 carbon atoms; or
• is derived from a heterocyclic containing 1, 2 or 3 nitrogen and/or phosphorus atoms.
12. The catalytic composition according to claim 10 or claim 11 wherein the quaternary
ammonium or phosphonium is selected from tetrabutylammonium, tetrabutylphos-phonium, N-butylpyridinium, ethylpyridinium, 3-butyI-l-methyl imidazolium, diethyl-pyrazolium and trimethylphenyl ammonium.
13. The catalytic composition according to claim 9 wherein the phosphite has general formula
(11) where anion X is a weakly co-ordinating anion.
14. The catalytic composition according to claim 13 wherein the weakly co-ordinating anion is
selected from tetrafluoroborate, hexafluorophosphate, tetrachloroaluminate, hexafluoro-

antimonate, carboxylate anions such as acetate, trifluoroacetate, trifluorosulphonate, the N(CF3S02)2- and C(CF3S02)3" anions, the tetraphenylborate anion and tetraphenylborate anions wherein the aromatic rings are substituted.
15. The catalytic composition according to anyone of claims 9 to 14 wherein the tertiary
phosphite carrying a functional group is selected from phosphites described by formulae (9a), (9b), (10a), (10b), and (11a).
16. The catalytic composition according to anyone of claims 9 to 15 wherein the nickel
compound is selected from the chloride, bromide, sulphate, carboxylates, phenates and acetylacetonate.
17. The catalytic composition according to any one of claims 1 to 16 wherein the quaternary
ammonium halide or quaternary phosphonium halide used as product A satisfies:
• one of general formulae: NR1R2R3R4"X with the exception of NH4X, PR1"R2R3R4X,
R1R2N=CR3R4"X or R1R2P=CR3R4X,
where X represents CI or Br and R", R2, R3" and R4", which may be identical or different, each represent hydrogen or a hydrocarbyl residue containing 1 to 12 carbon atoms;
• or one of the following general formulae:


where the nitrogen-containing or phosphorus-containing heterocycles containing 1, 2 or 3 nitrogen and/or phosphorus atoms are constituted by 4 to 10 atoms and X, R1 and R2 are defined as above.
18. The catalytic composition according to claim 17 wherein the quaternary ammonium halide
or quaternary phosphonium halide is tetrabutyl phosphonium chloride, N-butyl pyridinium chloride, ethylpyridinium bromide, 3-butyl-l-methyl imidazolium chloride, diethylpyrazolium chloride, pyridinium hydrochloride, trimethylphenylammonium chloride or 1-ethyl-3-methyl imidazolium chloride.
19. The catalytic composition according to any one of claims 1 to 18 wherein the aluminium
halide used as product B is aluminium chloride or bromide.
20. The catalytic composition according to any one of claims 1 to 19 wherein products A and B
are used in an A:B mole ratio of 1:0.5 to 1:3.
21. The catalytic composition according to any one of claims 1 to 20 wherein the non-aqueous
medium with an ionic nature also comprises a product C, consisting of at least one organometallic aluminium compound.
22. The catalytic composition according to claim 21 wherein the organometallic aluminium
compound used as optional product C of the invention has general formula AlRxX3.x where R is a linear or branched alkyl residue containing 2 to 8 carbon atoms, X is chlorine or bromine and the value of x is 1, 2 or 3.
23. The catalytic composition according to claim 21 or claim 22 wherein product C is
isobutylaluminium sesquichloride, ethylaluminium sesquichloride, dichloroisobutyl-aluminium, dichloroethylaluminium, or chlorodiethylaluminium.
24. The catalytic composition according to any one of claims 1 to 23, wherein product C is used
in a mole ratio of at most 1; 100 with product B.

25. A process for dimerising, co-dimerising or oligomerising at least one olefin comprising
bringing said olefin into contact with a catalytic composition according to anyone of
claims 1 to 24.
26. The process according to claim 25 wherein the dimerisation, co-dimerisation or oligomeri-
sation reaction is carried out in a closed system, in a semi-open system or in a continuous system, with one or more reaction stages, with agitation and at a temperature of -40""C to +70°C.
27. The process according to claim 25 or claim 26 wherein the olefins are ethylene, propylene,
n-butenes and n-pentenes, used alone or as a mixture, pure or diluted by an alkane.
28. The process according to one of anyone of claims 25 to 27 wherein the olefins are contained
in "cuts" from oil refining processes.

Documents:

87-mas-2001 abstract-duplicate.pdf

87-mas-2001 abstract.pdf

87-mas-2001 claims-duplicate.pdf

87-mas-2001 claims.pdf

87-mas-2001 correspondence-others.pdf

87-mas-2001 correspondence-po.pdf

87-mas-2001 description (complete)-duplicate.pdf

87-mas-2001 description (complete).pdf

87-mas-2001 form-1.pdf

87-mas-2001 form-18.pdf

87-mas-2001 form-26.pdf

87-mas-2001 form-3.pdf

87-mas-2001 form-5.pdf

87-mas-2001 others.pdf

87-mas-2001 petition.pdf


Patent Number 215922
Indian Patent Application Number 87/MAS/2001
PG Journal Number 13/2008
Publication Date 31-Mar-2008
Grant Date 05-Mar-2008
Date of Filing 31-Jan-2001
Name of Patentee INSTITUT FRANCAIS DU PETROLE
Applicant Address 1& 4 AVENUE DE BOIS-PREAU, 92852 RUEIL MALMAISON CEDEX,
Inventors:
# Inventor's Name Inventor's Address
1 COMMEREUC DOMINIQUE 32 RUE ABEL VACHER, 92190 MEUDON,
2 LE PENNEC DOMINIQUE 16 RUE DU CLOS DES BOURGOGNES, 78910 ORGERUS,
3 OLIVIER-BOURBIGOU HELENE 9 PLACE DES IMPRESSIONNISTES, 92500 RUEIL MALMAISON,
PCT International Classification Number B01J 1/00
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 00/01.512 2000-02-04 France