Process for reacting chemical compounds in the presence of catalyst systems
View Patent ↗New catalyst systems for metathesis reactions, in particular for the metathesis of nitrile rubber, are provided.
1. A process for reacting a nitrile rubber comprising subjecting the nitrile rubber to a metathesis reaction in the presence of the 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,
wherein metathesis 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 represents identical or different ligands are used as the catalyst.
2. The process 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, or the elements of the actinides.
3. The process 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, tetraarylammoni urn, hydroxylammonium, tetraalkylphosphonium, tetraarylphosphonium, sulphonium, anilinium, pyridinium, imidazolium, guanidinium and hydrazinium cations and cationic ethylenediamine derivatives.
4. The process 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-methyl-thiuronium, pyridinium, tetrabutylammonium, tetramethyluronium, tetracetylammonium, tetrabutylphosphonium, tetraphenylphosphonium, diphenylguanidinium, di-o-tolylguanidinium, butyldiphenylsulphonium or tributylsulphonium.
5. The process according to claim 1 , 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 process according to claim 5 , wherein the anion or anions in the general formula (I) is/are fluoride, chloride, bromide, iodide, triiodide, azide, cyanide, thiocyanide, 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.
7. The process according to claim 1 , 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 has one of the structures (Va-f), where Mes is in each case a 2,4,6-trimethylphenyl radical
8. The process according to claim 7 , wherein X 1 and X 2 in the general formula (B)
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 l -C 20 alkylsulphonate, C 6 -C 24 -arylsulphonate, C 1 -C 20 -alkylthiol, C 6 -C 24 -arylthiol, C l -C 20 -alkylsulphonyl or C 1 -C 20 -alkylsulphinyl radicals.
9. The process according to claim 7 , wherein catalysts of the general formula (B1),
where
M is ruthenium or osmium,
X 1 and X 2 are identical or different ligands,
R l 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, and
are used as the catalyst.
10. The process according to claim 9 , 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 are identical or different and are each hydrogen, organic or inorganic radicals and
L represents identical or different ligands,
are used as the catalyst.
11. The process according to claim 9 , wherein catalysts of the general formula (B1) in which
M s 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 l -C 30 -alkyl, C 3 -C 20 -cycloalkyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, C l -C 20 -carboxylate, C l -C 20 -alkoxy, C 2 -C 20 -alkenyloxy, C 2 -C 20 -alkynyloxy, C 6 -C 24 -aryloxy, C 2 -C 20 -alkoxycarbonyl, C l -C 20 -alkylthio, C 6 -C 24 -arylthio, C 1 -C 20 -alkylsulphonyl, C l -C 20 -alkylsulphonate, C 6 -C 24 -arylsulphonate or C 1 -C 20 -alkylsulphinyl,
are used.
12. The process according to claim 9 , 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)
13. The process according to claim 1 wherein a catalyst of the general formula (B2),
where
the radicals R 12 are identical or different and are organic or inorganic radicals, and
M is ruthenium or osmium,
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 6 is hydrogen or an alkyl, alkenyl, alkynyl or aryl radical and
L represents identical or different ligands,
n is 0, 1,2 or 3,
is used.
14. The process according to claim 13 , wherein the catalyst of the structures (XIV) or (XV), where Mes is in each case a 2,4,6-trimethylphenyl radical, is used
15. The process according to claim 1 , 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.
16. The process according to claim 1 , wherein the metatheses reaction is a ring-closing metatheses (RCM), a cross-metatheses (CM) or a ring-opening metatheses (ROMP).
17. The process according to claim 1 , 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.
18. The process according to claim 1 , wherein the amount of the catalyst of the catalyst system is from 1 to 1000 ppm of noble metal.
19. The process according to claim 1 by using a salt of the general formula (I) as constituent of the catalyst system.
20. The process according to claim 10 , where L of the general formula (B1) represents uncharged electron donors.
21. The process according to claim 13 , where L of the general formula (B2) represents uncharged electron donors.