# US 4,400,565 A · Co-catalyst for use with boron trifluoride in olefin oligomerization > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,400,565 A - Document ID: US4400565A - Status: Granted - Kind: A - Application number: 06/372,494 - Filed: 1982-04-28 - Granted: 1983-08-23 - Earliest claimed: 1982-04-28 - Assignees: Texaco Inc. - Inventors: Jerome W. Darden; Edward T. Marquis; Lewis W. Watts, Jr. - Web page: https://patentgrep.com/patent/US4400565A ## CPC - C10M 107/10: containing aliphatic monomer having more than 4 carbon atoms - C07C 2/28: with ion-exchange resins - C07C 5/03: of non-aromatic carbon-to-carbon double bonds - C07C 9/22: with more than fifteen carbon atoms - C07C 2523/72: Copper - C07C 2523/75: Cobalt - C07C 2523/755: Nickel - C07C 2523/86: Chromium - C07C 2527/1213: Boron fluoride - C07C 2531/10: sulfonated - C10M 2205/00: Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions - C10M: LUBRICATING COMPOSITIONS (well drilling compositions C09K8/02); USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION (mould release, i.e. separating, agents for metals B22C3/00, for plastics or substances in a plastic state, in general B29C33/56, for glass C03B40/02; textile lubricating compositions D06M11/00, D06M13/00, D06M15/00; immersion oils for microscopy G02B21/33) - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS ## Abstract A method for oligomerizing olefins in the presence of boron trifluoride and a co-catalyst comprising a heterogeneous cationic ion exchange resin catalyst is described. While the resin catalyst cannot oligomerize olefins by itself at temperatures around 75.degree.-85.degree. C., when used together with boron trifluoride an oligomer mixture may be created which has improved properties over oligomers made over only boron trifluoride. If a resin catalyst is used, a protonic promoter is not required. ## Claims ### Claim 1 A method for the production of olefin oligomers comprising reacting a mixture of alpha olefins and internal olefins in the presence of boron trifluoride and a cationic ion exchange resin under oligomerization conditions, the mixture of olefins being comprised of greater than 50 weight percent internal olefins. ### Claim 2 (depends on 1) The method of claim 1 in which both the alpha and internal olefins each have between 9 and 24 carbon atoms, inclusive. ### Claim 3 (depends on 1) The method of claim 1 in which both the alpha and internal olefins each have between 13 and 15 carbon atoms, inclusive. ### Claim 4 (depends on 1) The method of claim 1 in which the alpha and internal olefin mixture contains alpha and internal olefins that have carbon numbers identical to or within one carbon of each other and in which the internal olefins have the double bond randomly distributed. ### Claim 5 (depends on 1) The method of claim 1 in which the ion exchange resin is a perfluorosulfonic acid resin. ### Claim 6 (depends on 1) The method of claim 1 in which the oligomerization reaction is conducted at a temperature in the range of 25.degree. to 100.degree. C. and at a pressure in the range of ten to 2,000 psig. ### Claim 7 (depends on 1) The method of claim 1 in which the oligomerization reaction is conducted at a temperature in the range of about 75.degree. to 85.degree. C. ### Claim 8 (depends on 1) The method of claim 1 in which the amount of ion exchange resin is between about 0.1 and 10 weight percent of the total olefin charge. ### Claim 9 (depends on 1) The method of claim 1 in which the amount of ion exchange resin is about 2 weight percent of the total olefin mixture. ### Claim 10 (depends on 1) The method of claim 1 in which the oligomerized olefins are hydrogenated. ### Claim 11 (depends on 10) The method of claim 10 in which the hydrogenation takes place over a catalyst selected from the group of catalysts consisting of nickel-copper-chromia and cobalt-copper-chromia. ### Claim 12 (depends on 1) A synthetic lubricant component prepared according to the method of claim 1. ### Claim 13 A method for the production of olefin oligomers comprising (a) reacting a mixture of alpha olefins and internal olefins, both the alpha and internal olefins having between 9 and 24 carbon atoms, inclusive, in the presence of boron trifluoride and a cationic ion exchange resin in an amount of 0.1 to 10 weight percent of the total olefin mixture at a temperature in the range of 25.degree. to 100.degree. C., the mixture of olefins being comprised of greater than 50 weight percent internal olefins, (b) hydrogenating the resulting oligomers in the presence of hydrogen and a hydrogenation catalyst, and (c) separating out any unreacted monomer as the only separation step. ### Claim 14 (depends on 13) The method of claim 13 in which both the alpha and internal olefins each have between 13 and 15 carbon atoms, inclusive. ### Claim 15 (depends on 13) The method of claim 13 in which the alpha and internal olefin mixture contains alpha and internal olefins that have carbon numbers identical to or within one carbon of each other and in which the internal olefins have the double bond randomly distributed. ### Claim 16 (depends on 13) The method of claim 13 in which the ion exchange resin is a perfluorosulfonic acid resin. ### Claim 17 (depends on 13) The method of claim 13 in which the oligomerization reaction is conducted at a temperature in the range of about 75.degree. to 85.degree. C. ### Claim 18 (depends on 13) The method of claim 13 in which the amount of ion exchange resin is about 2 weight percent of the total olefin mixture. ### Claim 19 (depends on 13) The method of claim 13 in which the hydrogenation takes place over a catalyst selected from the group of catalysts consisting of nickel-copper-chromia and cobalt-copper-hromia. ### Claim 20 (depends on 13) A synthetic lubricant component prepared according to the method of claim 13. ### Claim 21 A method for the production of olefin oligomers comprising (a) reacting a mixture of alpha olefins and internal olefins, both the alpha and internal olefins having between 9 and 24 carbon atoms, inclusive, in the presence of boron trifluoride and a perfluorosulfonic acid cationic ion exchange resin in an amount of about 2 weight percent of the total olefin mixture at a temperature in the range of 75.degree. to 85.degree. C., the mixture of olefins being comprised of greater than 50 weight percent internal olefins, (b) hydrogenating the resulting oligomers in the presence of hydrogen and a hydrogenation catalyst, and (c) separating out any unreacted monomer as the only separation step. ### Claim 22 (depends on 21) The method of claim 21 in which both the alpha and internal olefins each have between 13 and 15 carbon atoms, inclusive. ### Claim 23 (depends on 21) The method of claim 21 in which the alpha and internal olefin mixture contains alpha and internal olefins that have carbon numbers identical to or within one carbon of each other and in which the internal olefins have the double bond randomly distributed. ### Claim 24 (depends on 21) The method of claim 21 in which the hydrogenation takes place over a catalyst selected from the group of catalysts consisting of nickel-copper-chromia and cobalt-copper-chromia. ### Claim 25 (depends on 21) A synthetic lubricant component prepared according to the method of claim 21. ### Claim 26 A method for the production of olefin oligomers comprising (a) mixing alpha olefins with internal olefins such that the internal olefins comprise greater than 50 weight percent of the mixture, and such that both the alpha and internal olefins have between 13 and 15 carbon atoms, inclusive, and such that the internal olefins have the double bond randomly distributed, (b) reacting the components of the mixture in the presence of boron trifluoride and a perfluorosulfonic acid cationic ion exchange resin in an amount of 0.1 to 10 weight percent of the total olefin mixture at a temperature in the range of 75.degree. to 85.degree. C., (c) hydrogenating the resulting oligomers in the presence of hydrogen and a hydrogenation catalyst, and (d) separating out any unreacted monomer as the only separation step. ### Claim 27 (depends on 26) The method of claim 26 in which the amount of ion exchange resin is about 2 weight percent of the total olefin mixture. ### Claim 28 (depends on 26) The method of claim 26 in which the hydrogenation takes places over a catalyst selected from the group of catalysts consisting of nickel-copper-chromia and cobalt-copper-chromia. ### Claim 29 (depends on 26) A synthetic lubricant component prepared according to the method of claim 26. ### Claim 30 A method for the production of olefin oligomers suitable for use as synthetic lubricant base oils comprising contacting a mixture of alpha and internal mono olefins where internal olefins comprise greater than 50 weight percent of the mixture with a boron trifluoride catalyst and a cationic ion exchange resin under oligomerization conditions, to form oligomers composed of 2 or more but less than 10 oligomer units. ### Claim 31 (depends on 30) The method of claim 30 in which both the alpha and internal olefins each have between 9 and 24 carbon atoms. ### Claim 32 A method for the production of olefin oligomers suitable for use as synthetic lubricant base oils comprising contacting a mixed mono olefin feedstock comprising (a) a first olefin component comprising one or more alpha olefins having the formula R"CH.dbd.CH.sub.2 where R" is an alkyl radical of 7 to 22 carbon atoms, and (b) greater than 50 weight percent of a second olefin component comprising one or more internal olefins having the formula RCH.dbd.CHR' where R and R' are the same or different alkyl radicals of 1 to 21 carbon atoms, except that the total number of carbon atoms is between 9 and 24, inclusive, with a boron trifluoride catalyst and a cationic ion exchange resin under oligomerization conditions to form synthetic lubricant components having a viscosity at 210.degree. F. of between 3.5 and 5.0 centistokes, a viscosity at 25.degree. C. of between 25.0 and 40.0 centistokes, a viscosity index of greater than 100 and a thermogravimetric analysis value of greater than 80 weight percent. ### Claim 33 (depends on 30, 32) The method of claim 30 or 32 in which both the alpha and internal olefins each have between 13 and 15 carbon atoms, inclusive. ### Claim 34 (depends on 30, 32) The method of claim 30 or 32 in which the alpha and internal olefin mixture contains alpha and internal olefins that have carbon numbers identical to or within one carbon of each other and in which the internal olefins have the double bond randomly distributed. ### Claim 35 (depends on 30, 32) The method of claim 30 or 32 in which the ion exchange resin is a perfluorosulfonic acid resin. ### Claim 36 (depends on 30, 32) The method of claim 30 or 32 in which the oligomerization reaction is conducted at a temperature of the range of 25.degree. to 100.degree. C. and at a pressure in the range of 10 to 2,000 psig. ### Claim 37 (depends on 30, 32) The method of claim 30 or 32 in which the oligomerization reaction is conducted at a temperature in the range of about 75.degree. to 85.degree. C. ### Claim 38 (depends on 30, 32) The method of claim 30 or 32 in which the amount of ion exchange resin is between about 0.1 and 10 weight percent of the total olefin charge. ### Claim 39 (depends on 30, 32) The method of claim 30 or 32 in which the amount of ion exchange resin is about 2 weight percent of the total olefin mixture. ### Claim 40 (depends on 30, 32) The method of claim 30 or 32 in which the oligomerized olefins are hydrogenated. ### Claim 41 (depends on 30, 32) The method of claim 30 or 32 in which the oligomerized olefins are hydrogenated over a catalyst selected from the group of catalysts consisting of nickel-copper-chromia and cobalt-copper-chromia. ### Claim 42 (depends on 30, 32) A synthetic lubricant component prepared according to the method of claim 30 or 32.