US2007208206A1PendingUtilityA1
Novel catalyst systems and a process for reacting chemical compounds in the presence of said catalyst systems
Est. expiryFeb 22, 2026(expired)· nominal 20-yr term from priority
C08C 19/00C08C 19/08B01J 23/00B01J 31/22B01J 31/02B01J 31/2208C08G 61/08B01J 31/2265B01J 31/0239B01J 31/26C08C 19/02B01J 31/2273B01J 31/30B01J 31/2278B01J 31/0268
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Claims
Abstract
New catalyst systems for metathesis reactions, in particular for the metathesis of nitrile rubber, are provided.
Claims
exact text as granted — not AI-modified1 . A Catalyst system comprising a metathesis catalyst and one or more salts of the general formula (I)
K n+ A z− (I)
where
K is a cation with the exception of copper and
A is an anion,
where
n is 1, 2 or 3 and
z is 1, 2 or 3.
2 . The Catalyst system according to claim 1 , wherein the cation or cations K in the general formula (I) is/are lithium, sodium, potassium rubidium, caesium, francium, beryllium, magnesium, calcium, strontium, barium, aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth, scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, silver, gold, zinc, cadmium, mercury and also all elements of the group of the rare earths, in particular cerium, praseodynium and neodymium, or the elements of the actinides.
3 . The Catalyst system according to claim 1 , wherein the cation or cations K in the general formula (I) is/are complex cations based on nitrogen, phosphorus or sulphur, preferably tetralkylammonium, tetraarylammonium, hydroxylammonium, tetraalkylphosphonium, tetraarylphosphonium, sulphonium, anilinium, pyridinium, imidazolium, guanidinium and hydrazinium cations and cationic ethylenediamine derivatives.
4 . The Catalyst system according to claim 3 , wherein the cation or cations K in the general formula (I) is/are benzyldodecyldimethylammonium, didecyldimethylammonium, dimethylanilinium, N-alkyl-N,N-bis-(2-hydroxyalkyl)-N-benzylammonium, N,N,N-triethylbenzolmethanaminium, O-methyluronium, S-methylthiuronium, pyridinium, tetrabutylaammonium, tetramethyluronium, tetracetylammonium, tetrabutylphosphonium, tetraphenylphosphonium, diphenylguanidinium, di-o-tolylguanidinium, butyldiphenylsulphonium or tributylsulphonium.
5 . The Catalyst system according to claim 1 or 2 , wherein the anion or anions in the general formula (I) is/are selected from the group consisting of halides, pseudohalides, complex anions, anions of organic acids, aliphatic or aromatic sulphonates, aliphatic or aromatic sulphates, phosphonates, phosphates, thiophosphates, xanthogenates, dithiocarbamates and noncoordinating anions.
6 . The Catalyst system according to claim 5 , wherein the anion or anions in the general formula (I) is/are fluoride, chloride, bromide, iodide, triiodide, azide, cyamide, thiocyamide, thiocyanate, interhalides, sulphite, sulphate, dithionite, thiosulphate, carbonate, hydrogencarbonate, perthiocarbonate, nitrite, nitrate, perchlorate, tetrafluoroborate, tetrafluoroaluminate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, hexachloroantimonate, anions or organic carboxylic acids having from 1 to 20 carbon atoms which are saturated or monounsaturated or polyunsaturated, in particular formate, acetate, propionate, butyrate, oleate, palmitate, stearate, versatate, acrylate, methacrylate, crotonate, benzoate, naphthalenecarbonate, oxalate, salicylate, terephthalate, fumarate, maleate, itaconate and abietate, anthraquinone-2-sulphonate, benzenesulphonate, benzene-1,3-disulphonate, decane-1-sulphonate, hexadecane-1-sulphonate, hydroquinonemonosulphonate, methyl-4-toluenesulphonate, naphthalene-1-sulphonate, naphthalene-1,5-disulphonate, tosylate, mesylate, dodecylsulphate, alkylbenzenesulphates, vinylphosphonate, ethylphosphonate, butylphosphonate, cetylphosphonate, dibutylphosphate, dioctylphosphate, dibutyldithiophosphate, dioctylthiophosphate, ethylxanthogenate, butylxanthogenate, phenylxanthogenate, benzylxanthogenate, dimethyldithiocarbamate, diethyldithiocarbamate, dibutyldithiocarbamate, dibenzyldithiocarbamate, tetrakis[pentafluorophenyl]borate, pentakis[pentafluorophenyl]phosphate, tetrakis[3,5-trifluoromethylphenyl]borate, pentakis[3,5-trifluoromethylphenyl]phosphate or pentakis[pentafluorophenyl]cyclo-hexadienyl anion.
7 . The Catalyst system according to claim 1 , 2 or 5 , wherein compounds of the general formula (A),
where
M is osmium or ruthenium,
the radicals R are identical or different and are each an alkyl, preferably C 1 -C 30 -alkyl, cycloalkyl, preferably C 3 -C 20 -cycloalkyl, alkenyl, preferably C 2 -C 20 -alkenyl, alkynyl, preferably C 2 -C 20 -alkynyl, aryl, preferably C 6 -C 24 -aryl, carboxylate, preferably C 1 -C 20 -carboxylate, alkoxy, preferably C 1 -C 20 -alkoxy, alkenyloxy, preferably C 2 -C 20 -alkenyloxy, alkynyloxy, preferably C 2 -C 20 -alkynyloxy, aryloxy, preferably C 6 -C 24 -aryloxy, alkoxycarbonyl, preferably C 2 -C 20 -alkoxycarbonyl, alkylamino, preferably C 1 -C 30 -alkylamino, alkylthio, preferably C 1 -C 30 -alkylthio, arylthio, preferably C 6 -C 24 -arylthio, alkylsulphonyl, preferably C 1 -C 20 -alkylsulphonyl, or alkylsulphinyl, preferably C 1 -C 20 -alkylsulphinyl radical, each of which may optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals,
X 1 and X 2 are identical or different and are two ligands, preferably anionic ligands, and
L represents identical or different ligands, preferably uncharged electron donors,
are used as catalyst.
8 . The Catalyst system according to claim 7 , wherein X 1 and X 2 are identical or different and are each hydrogen, halogen, pseudohalogen, straight-chain or branched C 1 -C 30 -alkyl, C 6 -C 24 -aryl, C 1 -C 20 -alkoxy, C 6 -C 24 -aryloxy, C 3 -C 20 -alkyldiketonate, C 6 -C 24 -aryldiketonate, C 1 -C 20 -carboxylate, C 1 -C 20 -alkylsulphonate, C 6 -C 24 -arylsulphonate, C 1 -C 20 -alkylthiol, C 6 -C 24 -arylthiol, C 1 -C 20 -alkylsulphonyl or C 1 -C 20 -alkylsulphinyl radicals.
9 . The Catalyst system according to claim 8 , wherein X 1 and X 2 are identical or different and are each halogen, in particular fluorine, chlorine, bromine or iodine, benzoate, C 1 -C 5 -carboxylate, C 1 -C 5 -alkyl, phenoxy, C 1 -C 5 -alkoxy, C 1 -C 8 -alkylthiol, C 6 -C 24 -arylthiol, C 6 -C 24 -aryl or C 1 -C 5 -alkylsulphonate.
10 . The Catalyst system according to claim 8 or 9 , wherein X 1 and X 2 are identical and are each halogen, in particular chlorine, CF 3 COO, CH 3 COO, CFH 2 COO, (CH 3 ) 3 CO, (CF 3 ) 2 (CH 3 )CO, (CF 3 )(CH 3 ) 2 CO, PhO (phenoxy), MeO (methoxy), EtO (ethoxy), tosylate (p-CH 3 —C 6 H 4 —SO 3 ), mesylate (2,4,6-trimethylphenyl) or CF 3 SO 3 (trifluoromethanesulphonate).
11 . The Catalyst system according to claims 7 , 8 . 9 or 10 , wherein the two ligands L are each, independently of one another, a phosphine, sulphonated phosphine, phosphate, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulphoxide, carboxyl, nitrosyl, pyridine, thioether or imidazolidine (“Im”) ligand.
12 . The Catalyst system according to claim 11 , wherein the imidazolidine radical (Im) has a structure of the general formula (IIa) or (IIb),
where
R 8 , R 9 , R 10 , R 11 are identical or different and are each hydrogen, straight-chain or branched C 1 -C 30 -alkyl, C 3 -C 20 -cycloalkyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, C 1 -C 20 -carboxylate, C 1 -C 20 -alkoxy, C 2 -C 20 -alkenyloxy, C 2 -C 20 -alkynyloxy, C 6 -C 20 -aryloxy, C 2 -C 20 -alkoxycarbonyl, C 1 -C 20 -alkylthio, C 6 -C 20 -arylthio, C 1 -C 20 -alkylsulphonyl, C 1 -C 20 -alkylsulphonate, C 6 -C 20 -arylsulphonate or C 1 -C 20 -alkylsulphinyl.
13 . The Catalyst system according to one or more of claims 1 , 2 and 5 , wherein the catalyst has the structure (III) or (IV), where Cy is in each case cyclohexyl.
14 . The Catalyst system according to according to one or more of claims 1 , 2 and 5 , wherein catalysts of the general formula (B),
where
M is ruthenium or osmium,
Y is oxygen (O), sulphur (S), an N—R 1 radical or a P—R 1 radical,
X 1 and X 2 are identical or different ligands,
R 1 is an alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphynyl radical, each of which may optionally be substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals,
R 2 , R 3 , R 4 and R 5 are identical or different and are each hydrogen, organic or inorganic radicals,
R 6 is hydrogen or an alkyl, alkenyl, alkynyl or aryl radical and
L is a ligand which has the same meanings as the ligand L in the formula (A) mentioned in claim 7 ,
are used.
15 . The Catalyst according to claim 14 , wherein L is a P(R 7 ) 3 radical, where the radicals R 7 are each, independently of one another, C 1 -C 6 -alkyl, C 3 -C 8 -cycloalkyl or aryl or else a substituted or unsubstituted imidazolidine radical (“Im”) which preferably has the structure of the general formula (IIa) or (IIb) mentioned in claim 12 and particularly preferably has one of the structures (Va-f), where Mes is in each case a 2,4,6-trimethylphenyl radical.
16 . The Catalyst system according to claim 14 or 15 , wherein X 1 and X 2 in the general formula (B) assumes the meanings of X 1 and X 2 in any of claims 8 - 10 .
17 . The Catalyst system according to one or more of claims 14 , 15 and 16 , wherein catalysts of the general formula (B1),
where
M, L, X 1 , X 2 , R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given for the general formula (B) in claim 14 ,
are used.
18 . The Catalyst system according to claim 17 , wherein catalysts of the general formula (B1) in which
M is ruthenium, X 1 and X 2 are both halogen, in particular chlorine, R 1 is a straight-chain or branched C 1 -C 12 -alkyl radical, R 2 , R 3 , R 4 , R 5 have the meanings given for the general formula (B) in claim 14 and L has the meanings given for the general formula (B) in claim 14 , are used.
19 . The Catalyst system according to claim 17 , wherein catalysts of the general formula (B1) in which
M is ruthenium, X 1 and X 2 are both chlorine, R 1 is an isopropyl radical, R 2 , R 3 , R 4 , R 5 are all hydrogen and L is a substituted or unsubstituted imidazolidine radical of the formula (IIa) or (IIb), where R 8 , R 9 , R 10 , R 11 are identical or different and are each hydrogen, straight-chain or branched C 1 -C 30 -alkyl, C 3 -C 20 -cycloalkyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, C 1 -C 20 -carboxylate, C 1 -C 20 -alkoxy, C 2 -C 20 -alkenyloxy, C 2 -C 20 -alkynyloxy, C 6 -C 24 -aryloxy, C 2 -C 20 -alkoxycarbonyl, C 1 -C 20 -alkylthio, C 6 -C 24 -arylthio, C 1 -C 20 -alkylsulphonyl, C 1 -C 20 -alkylsulphonate, C 6 -C 24 -arylsulphonate or C 1 -C 20 -alkylsulphinyl, are used.
20 . The Catalyst system according to claim 17 , wherein a catalyst of the following structures (VI), (VII), (VIII), (IX), (X), (XI), (XII), (XIII) or (XVII), where Mes is in each case a 2,4,6-trimethylphenyl radical, is used as catalyst of the general structural formula (B1).
21 . The Catalyst system according to claim 14 , wherein a catalyst of the general formula (B2),
where,
M, L, X, X 2 , R 1 and R 6 have the meanings given for the general formula (B) in claim 14 ,
the radicals R 12 are identical or different and have the meanings given for the radicals R 2 , R 3 , R 4 and R 5 in the general formula (B) in claim 14 , with the exception of hydrogen, and
n is 0, 1, 2 or 3.
is used.
22 . The Catalyst system according to claim 21 , wherein the catalyst of the structures (XIV) or (XV), where Mes is in each case a 2,4,6-trimethylphenyl radical, is used.
23 . The Catalyst system according to claim 14 , wherein a catalyst of the general formula (B3),
where D 1 , D 2 , D 3 and D 4 each have a structure of the general formula (XVI) below which is bound via the methylene group to the silicon of the formula (B3),
where
M, L, X 1 , X 2 , R 1 , R 2 , R 3 , R 5 and R 6 have the meanings given for the general formula (B) in claim 14 ,
is used.
24 . The Catalyst system according to one or more of claims 1 , 2 and 5 , wherein a catalyst of the general formula (B4),
where the symbol
represents a support,
is used.
25 . The Catalyst systems according to one or more of claims 1 , 2 and 5 , wherein a catalyst of the general formula (C),
where
M is ruthenium or osmium,
X 1 and X 2 are identical or different and are anionic ligands,
the radicals R′ are identical or different and are organic radicals,
Im is a substituted or unsubstituted imidazolidine radical and
An is an anion,
is used.
26 . The Catalyst systems according to one or more of claims 1 , 2 and 5 , wherein a catalyst of the general formula (D),
where
M is ruthenium or osmium,
R 13 and R 14 are each, independently of one another, hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, C 1 -C 20 -carboxylate, C 1 -C 20 -alkoxy, C 2 -C 20 -alkenyloxy, C 2 -C 20 -alkynyloxy, C 6 -C 24 -aryloxy, C 2 -C 20 -alkoxycarbonyl, C 1 -C 20 -alkylthio, C 1 -C 20 -alkylsulphonyl or C 1 -C 20 -alkylsulphinyl,
X 3 is an anionic ligand,
L 2 is an uncharged n-bonded ligand, regardless of whether it is monocyclic or polycyclic,
L 3 is a ligand from the group of phosphines, sulphonated phosphines, fluorinated phosphines, functionalized phosphines having up to three aminoalkyl, ammonioalkyl, alkoxyalkyl, alkoxycarbonylalkyl, hydrocarbonylalkyl, hydroxyalkyl or ketoalkyl groups, phosphites, phosphinites, phosphonites, phosphine amines, arsines, stibines, ethers, amines, amides, imines, sulphoxides, thioethers and pyridines,
Y − is a noncoordinating anion and
n is 0, 1, 2, 3, 4 or 5.
is used.
27 . The Catalyst systems according to one or more of claims 1 , 2 and 5 , wherein a catalyst of the general formula (E),
where
M 2 is molybdenum or tungsten,
R 15 and R 16 are identical or different and are each hydrogen, C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, C 1 -C 20 -carboxylate, C 1 -C 20 -alkoxy, C 2 -C 20 -alkenyloxy, C 2 -C 20 -alkynyloxy, C 6 -C 24 -aryloxy, C 2 -C 20 -alkoxycarbonyl, C 1 -C 20 -alkylthio, C 1 -C 20 -alkylsulphonyl or C 1 -C 20 -alkylsulphinyl,
R 17 and R 18 are identical or different and are each a substituted or halogen-substituted C 1 -C 20 -alkyl, C 6 -C 24 -aryl, C 6 -C 30 -aralkyl radical or a silicone-containing analogue thereof,
is used.
28 . The Catalyst systems according to one or more of claims 1 , 2 and 5 , wherein a catalyst of the general formula (F),
where
M is ruthenium or osmium,
X 1 and X 2 are identical or different and are anionic ligands which can assume all the meanings of X 1 and X 2 in the general formulae (A) and (B),
L are identical or different ligands which can assume all the meanings of L in the general formulae (A) and (B),
R 19 and R 20 are identical or different and are each hydrogen or substituted or unsubstituted alkyl,
is used.
29 . The Catalyst system according to one or more of claims 1 , 2 and 5 , wherein the metathesis catalyst and the salt or salts of the general formula (I) is/are used in a weight ratio of salt(s):metathesis catalyst of from 0.01:1 to 10000:1.
30 . A process for reacting a chemical compound comprising subjecting said chemical compound to a metathesis reaction in the presence of the catalyst system according to one or more of claims 1 , 2 and 5 .
31 . The process according to claim 30 , wherein the metatheses reaction is a ring-closing metatheses (RCM), a cross-metatheses (CM) or a ring-opening metatheses (ROMP).
32 . The process according to claim 30 , wherein the chemical compound is a nitrile rubber.
33 . The process according to claim 30 , wherein the salt or salts of the general formula (I) is/are added in a solvent or without solvent to the catalyst or a solution of the catalyst.
34 . The process according to claim 30 , wherein the amount of the catalyst of the catalyst system is from 1 to 1000 ppm of noble metal.
35 . A process of preparing the catalyst system according to claim 1 by using a salt of the general formula (I) as constituent of the catalyst system.Cited by (0)
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