# US 5,349,115 A · Dimerization of low .alpha.-olefins > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,349,115 A - Document ID: US5349115A - Status: Granted - Kind: A - Application number: 08/057,843 - Filed: 1993-05-07 - Granted: 1994-09-20 - Earliest claimed: 1992-05-08 - Assignees: Sumitomo Chemical Company, Limited - Inventors: Kotohiro Nomura; Masaru Ishino; Michio Yamamoto; Gohfu Suzukamo; Makoto Itagaki - Web page: https://patentgrep.com/patent/US5349115A ## CPC - C07C 2/36: as phosphines, arsines, stilbines or bismuthines - C07C 2531/02: containing organic compounds or metal hydrides - C07C 2531/025: Sulfonic acids - C07C 2531/04: containing carboxylic acids or their salts - C07C 2531/14: of aluminium or boron - C07C 2531/24: Phosphines - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS ## Abstract A process for preparing a dimer of a lower .alpha.-olefin in the presence of Catalyst (A) containing a nickel compound, a trialkylaluminum, a halogenated phenol, a phosphorus compound and a sulfur compound, Catalyst (B) containing a nickel compound, a trialkylaluminum, a fluorinated isopropyl alcohol, a phosphorus compound, a sulfonic acid and water, or Catalyst (C) containing a nickel compound, a trialkylaluminum, a halogenated phenol, a phosphorus compound, a sulfonic acid and water, by which method, the dimer of the lower .alpha.-olefin is prepared in a high yield and high selectivity. ## Claims ### Claim 1 A process for preparing a dimer of a lower .alpha.-olefin comprising dimerizing an .alpha.-olefin in the presence of a catalyst system A which consists essentially of: (1) at least one nickel (II) compound selected from the group consisting of organic acid salts, inorganic acid salts and complex compounds of nickel, (2) a trialkylaluminum, (3) at least one compound selected from the group consisting of halogenated phenols of the general formula: ##STR3## wherein X.sub.1 to X.sub.5 independently represent a halogen atom, a hydrogen atom, or a hydroxyl group, with the proviso that at least one of them is a halogen atom, and a fluorinated isopropyl alcohol, (4) at least one phosphorous compound selected from the group consisting of compounds of the formulae: PR.sup.1 R.sup.2 R.sup.3 (II) P(NR.sup.4.sub.2).sub.3 (III) P(OR.sup.5).sub.3 (IV) and PR.sup.6 R.sup.7 (CH.sub.2).sub.n PR.sup.6 R.sup.7 (V) wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 independently represent an alkyl group, a cycloalkyl group, an aralkyl group or a phenyl group optionally substituted by alkyl groups or alkoxy groups and n is an integer from 1 to 6, and (5) at least one sulfur compound selected from the group consisting of sulfonic acids and dialkylsulfates; a catalyst system B which comprises: (1) at least one nickel (II) compound selected from the group consisting of organic acid salts, inorganic acid salts and complex compounds of nickel, (2) a trialkylaluminum, (3) a fluorinated isopropyl alcohol, (4) at least one phosphorous compound selected from the group consisting of compounds of the formulae: PR.sup.1 R.sup.2 R.sup.3 (II) P(NR.sup.4.sub.2).sub.3 (III) P(OR.sup.5).sub.3 (IV) and PR.sup.6 R.sup.7 (CH.sub.2).sub.n PR.sup.6 R.sup.7 (V) wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 independently represent an alkyl group, a cycloalkyl group, an aralkyl group or a phenyl group optionally substituted by alkyl groups or alkoxy groups and n is an integer from 1 to 6, (5) a sulfonic acid and (6) water; or a catalyst system C which comprises: (1) at least one nickel (II) compound selected from the group consisting of organic acid salts, inorganic acid salts and complex compounds of nickel, (2) a trialkylaluminum, (3) a halogenated phenol represented by the general formula: ##STR4## wherein X.sub.1 to X.sub.5 independently represent a halogen atom, a hydrogen atom, or a hydroxyl group, with the proviso that at least one of them is a halogen atom, (4) at least one phosphorous compound selected from the group consisting of compounds of the formulae: PR.sup.1 R.sup.2 R.sup.3 (II) P(NR.sup.4.sub.2).sub.3 (III) and P(OR.sup.5).sub.3 (IV) wherein R.sup.1,R.sup.2, R.sup.3, R.sup.4 and R.sup.5 independently represent an alkyl group, a cycloalkyl group, an aralkyl group, or a phenyl group optionally substituted by alkyl groups or alkoxy groups, (5) a sulfonic acid and (6) water. ### Claim 2 (depends on 1) The process according to claim 1, wherein the catalyst system is Catalyst A. ### Claim 3 (depends on 1) The process according to claim 1, wherein the catalyst system is Catalyst B. ### Claim 4 (depends on 1) The process according to claim 1, wherein the catalyst system is Catalyst C. ### Claim 5 (depends on 1) The process according to claim 1, wherein the lower .alpha.-olefin is ethylene, propylene, or isobutene. ### Claim 6 (depends on 2) The process according to claim 2 wherein at least one compound selected from the group consisting of the halogenated phenols and the fluorinated isopropyl alcohols is a halogenated phenol. ### Claim 7 (depends on 1) The process according to claim 1, wherein in Catalyst A or B a molar ratio of the halogenated phenol to the trialkylaluminum is from 0.4 to 20. ### Claim 8 (depends on 2) The process according to claim 2, wherein the compound selected from the group consisting of the halogenated phenols and the fluorinated isopropyl alcohols is a fluorinated isopropyl alcohol. ### Claim 9 (depends on 8) The process according to claim 8, wherein the fluorinated iso-propyl alcohol is 1,1,1,3,3,3-hexafluoroisopropyl alcohol. ### Claim 10 (depends on 3) The process according to claim 3, wherein a molar ratio of the fluorinated isopropyl alcohol to the trialkylaluminum is from 0.2 to 10. ### Claim 11 (depends on 1) The process according to claim 1, wherein the trialkylaluminum is triethylaluminum. ### Claim 12 (depends on 1) The process according to claim 1, wherein a molar ratio of the trialkylaluminum to the nickel (II) compound is from 2 to 500. ### Claim 13 (depends on 1) The process according to claim 1, wherein a molar ratio of the phosphorous compound to the nickel (II) compound is from 0.1 to 50. ### Claim 14 (depends on 1) The process according to claim 1, wherein in Catalyst B or C a molar ratio of water to the nickel (II) compound is from 0.1 to 10 and a molar ratio of water to the trialkylaluminum is from 0.1 to 2. ### Claim 15 (depends on 2) The process according to claim 2, wherein the sulfur compound is a sulfonic acid and a dialkyl sulfate. ### Claim 16 (depends on 2) The process according to claim 2, wherein a molar ratio of the sulfur compound to the nickel (II) compound is from 0.1 to 20. ### Claim 17 (depends on 1) The process according to claim 1, wherein in Catalyst B or C a molar ratio of the sulfonic acid to the nickel (II) compound is from 0.1 to 20. ### Claim 18 (depends on 1) The process according to claim 1, wherein a concentration of the catalyst system is from 10.sup.-5 to 10.sup.-1 mol/liter in terms of a concentration of the nickel (II) compound. ### Claim 19 (depends on 1) The process according to claim 1, wherein a reaction temperature is from -70.degree. to 150.degree. C. ### Claim 20 (depends on 1) The process according to claim 1, wherein a reaction pressure is from 0 to 30 Kg/cm.sup.2 G.