CA2126388C - Olefin oligomerization process - Google Patents
Olefin oligomerization process Download PDFInfo
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- CA2126388C CA2126388C CA002126388A CA2126388A CA2126388C CA 2126388 C CA2126388 C CA 2126388C CA 002126388 A CA002126388 A CA 002126388A CA 2126388 A CA2126388 A CA 2126388A CA 2126388 C CA2126388 C CA 2126388C
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- polyether
- olefin
- mole ratio
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- protic
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 150000001336 alkenes Chemical class 0.000 title description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title description 9
- 238000006384 oligomerization reaction Methods 0.000 title description 8
- 229920000570 polyether Polymers 0.000 claims abstract description 24
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 23
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 239000000539 dimer Substances 0.000 claims description 16
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical group COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 10
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000013638 trimer Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 5
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical group CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000004292 cyclic ethers Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- -1 glycol ethers Chemical class 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 1
- MQTLTQMOALIWRO-UHFFFAOYSA-N 1,3-dimethoxycyclohexane Chemical compound COC1CCCC(OC)C1 MQTLTQMOALIWRO-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- KIAMPLQEZAMORJ-UHFFFAOYSA-N 1-ethoxy-2-[2-(2-ethoxyethoxy)ethoxy]ethane Chemical compound CCOCCOCCOCCOCC KIAMPLQEZAMORJ-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- RLPGNHILYGVQDE-UHFFFAOYSA-N 2,3-dimethoxybutane Chemical compound COC(C)C(C)OC RLPGNHILYGVQDE-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- OKAMTPRCXVGTND-UHFFFAOYSA-N 2-methoxyoxolane Chemical compound COC1CCCO1 OKAMTPRCXVGTND-UHFFFAOYSA-N 0.000 description 1
- AWCKLOPZHLHTAD-UHFFFAOYSA-N 4-[4-(4-carbamimidoyl-2-methoxyphenoxy)butoxy]-3-methoxybenzenecarboximidamide Chemical compound COC1=CC(C(N)=N)=CC=C1OCCCCOC1=CC=C(C(N)=N)C=C1OC AWCKLOPZHLHTAD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/08—Halides
- C07C2527/12—Fluorides
- C07C2527/1213—Boron fluoride
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
Abstract
A process for making an .alpha.-olefin oligomer comprises contacting a C6 to C20 .alpha.-olefin monomer with a catalyst which includes boron trifluoride, a protic promotor and a polyether.
Description
OLEFIN OLIGOMERIZATION PROCESS
This invention relates generally to the preparation of alpha-olefin oligomers which are useful as synthetic lubricants and functional fluids and more particularly to a BF3-promoter catalyst system which uses a polyether modifier to control the oligomer product distribution and provide higher percentages of lower oligomers.
Alpha-olefin oligomers and their use as synthetic lubricants ("synlubes") are well-known. The oligomers are usually hydrogenated in order to improve their stability. Early reports of such synlubes are in Seger et al. U.S. Pat. No.
This invention relates generally to the preparation of alpha-olefin oligomers which are useful as synthetic lubricants and functional fluids and more particularly to a BF3-promoter catalyst system which uses a polyether modifier to control the oligomer product distribution and provide higher percentages of lower oligomers.
Alpha-olefin oligomers and their use as synthetic lubricants ("synlubes") are well-known. The oligomers are usually hydrogenated in order to improve their stability. Early reports of such synlubes are in Seger et al. U.S. Pat. No.
2,500,161 1o and Garwood U.S. Pat. No. 2,500,163. U.S. Pat. No. 2,766,312 describes the oligomerization of a-olefins in a Group IV metal oxide bed using a BF3-protic promoter catalyst. Promoters include water, carboxylic acid, alkyl halides, alcohols and ethers. U.S. Pat. No. 2,806,072 discloses the dimerization of C6-C,2 poly-propylenes using a preformed BF3-dialkylether catalyst. U.S. Pat. No.
3,382,291 describes the oligomerization of olefins using BF3-promoter catalyst complexes which include acid anhydrides, esters, ketones and aldehydes. U.S. Pat. No.
4,172,855 describes BF3-promoter catalysts for grafting a second a-olefin onto C6-C,2 a-olefin dimer to form a low volatility lubricating oil. The promoters include glycol ethers such as ethylene glycol monomethyl ether, propylene glycol monoethyl ether, and di-e o isobutyl ether.
The particular application for which the oligomer oils are used depends upon their viscosity, with viscosities of about 2-10 cSt at 100°C being preferred for general lubricating oil applications. These materials are mixtures of different percentages of dimer, trimer, tetramer, pentamer and higher oligomers, which olig-2 5 omers are produced in different proportions in the oligomerization process. In order to increase the viscosity, processes are used which either produce more of the higher oligomers or some of the lower oligomers are removed such as by distillation.
Most CASE PA-6788 ~ 12 ~ 3 8 8 lower viscosity dimer products are obtained as by-products of the production of higher viscosity synthetic oils. Due to the increasing use of dimers in applications such as low temperature lubricants and drilling fluids, methods for their preferential produc-tion are of interest. It is known that higher temperatures favor dimer production, but such higher temperatures can cause corrosion of production equipment. U.S.
Pat. No.
The particular application for which the oligomer oils are used depends upon their viscosity, with viscosities of about 2-10 cSt at 100°C being preferred for general lubricating oil applications. These materials are mixtures of different percentages of dimer, trimer, tetramer, pentamer and higher oligomers, which olig-2 5 omers are produced in different proportions in the oligomerization process. In order to increase the viscosity, processes are used which either produce more of the higher oligomers or some of the lower oligomers are removed such as by distillation.
Most CASE PA-6788 ~ 12 ~ 3 8 8 lower viscosity dimer products are obtained as by-products of the production of higher viscosity synthetic oils. Due to the increasing use of dimers in applications such as low temperature lubricants and drilling fluids, methods for their preferential produc-tion are of interest. It is known that higher temperatures favor dimer production, but such higher temperatures can cause corrosion of production equipment. U.S.
Pat. No.
5,068,487 discloses a process for making predominantly dimers and trimers of a-olefins using an alcohol alkoxylate promoted BF3 catalyst. U.S. Pat. No.
5,191,140 discloses a process for making a-olefin oligomers which uses BF3 promoted by at least two of water, alcohols and anhydrides to peak the reaction at lower molecular 1 o weight product.
The discovery has now been made that polyethers will moderate BF3 catalyzed oligomerizations to provide either predominantly dimer or trimer containing oligomers.
In accordance with this invention there is provided a process for making an a-olefin oligomer which comprises contacting an a-olefin monomer which contains from about 6 to 20 carbon atoms with a catalyst comprising boron trifluoride, a protic promotor and a polyether.
The olefins used in making the oligomers are predominantly (at least SO
mole percent) C6 to CZO straight chain monoolefinically unsaturated hydrocarbons in 2 0 which the olefinic unsaturation occurs at the 1- or alpha-position of the straight carbon chain. Such alpha-olefins are commercially available and can be made by the thermal cracking of paraffinic hydrocarbons or by the well-known Ziegler ethylene chain growth process. Individual olefins may be used as well as mixtures of such olefins.
Examples of such olefins are 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-hexadecene and 1-tetradecene. The more preferred normal-alpha-olefin monomers are those containing about 8-14 carbon atoms. The most preferred olefin monomer is 1-decene.
CASE PA-6788 ~ 12 6 3 ~ 8 The olefin monomers can also contain minor amounts of up to about 50, and usually less than 25 mole percent, of internal olefins and vinylidene olefins.
The olefin is contacted as known in the art with a catalytic amount of boron trifluoride which should be at least about 0.002 moles per mole of olefin.
Preferably, the reaction mixture is saturated with BF3. To be effective, the boron trifluoride is used in combination with a protic promoter such as water, carboxylic acids, mineral acids, alcohols, phenols, carboxylic acid esters and anhydrides, ketones and aldehydes. Preferred are water and C, to C24 alcohols and, more preferably, C, to C,2 alcohols (e.g. methanol, ethanol, n-propanol, isopropanol, n-butanol, to isobutanol, n-hexanol, 2-ethylhexanol, n-decanol, n-dodecanol, and the like). The amount of promotor should be an amount which is effective to cause the BF3 to act as an oligomerization catalyst, for example, from about 0.001 to 0.040 moles per mole of a-olefin monomers. In general, the BF3 is used in molar excess to the amount of promotor. This can be accomplished by using a closed reactor and a small BF3 pressure over the reaction mixture. The promoter can be mixed with the olefin feed and the reaction can be carried out in a batch or continuous process at temperatures of about 0° to 200°C. and pressures ranging from atmospheric up to, for example, 1,000 psig. The reaction temperature will change the oligomer distribution with temperatures of about 45°C and above favoring the production of lower oligomers, 2o namely dimer. Preferred reaction temperatures and pressures are about 20° to 65°C.
and 5 to 100 psig.
Preferred polyether modifiers can be defined by the formula:
RO f C-Co-C-O ~mR
2 5 R' R' where each R is individually a hydrocarbyl group and, preferably, a C, to C3o alkyl or cycloalkyl group or a C6 to C3o aryl group; each R' is individually hydrogen or a hydrocarbyl group or, taken together, form a hydrocarbyl ring;
also, R and R' taken together can form a cyclic ether, when R' is a hydrocarbyl group, it is preferably a C, to C~ alkyl or cycloalkyl group or a C6 to C~
aryl group; n = 0, l, 2, or 3 and m = 1 to 8. Non-limiting examples of such poly-ethers include 1,2-dimethoxyethane, diethylene glycol diethyl ether, 1,2-diethoxy-ethane, triethylene glycol diethyl ether, 1,2-dimethoxypropane, 1,2-dirt~ethoxybenzene, 1,3-dimethoxycyclohexane, methyl tetrahydrofuryl ether, 1,3-io dimethoxybutane, 2,3-dimethoxybutane, and the like.
The polyether modifters are used in mole ratios of promotor to modifier which are selected to peak the oligomers at either dimer or trimer.
The ratios will vary somewhat depending upon the particular combination of promotor and polyether which are used. In general, there is a range of ratios of promotor to polyether which will peak dimer. Above and below such ratios, the product will peak at trimer. For example, when using a combination of n-butanol and 1,2-dimethoxyethane, mole ratios of alcohol to polyether of up to about 1 peaked trimer whereas ratios of about 1.3 to 6.5 peaked dimer. At ratios of above 6.5, trimer again became the predominant product. When diethylene glycol diethyl 2 o ether was used, a ratio of about 1 produced predominantly dimer. The ratio which will peak the process at dimer for each catalyst combination can be readily determined by running a few oligomerizations according to the procedures described in the following examples which are intended to illustrate, but not limit, the process of the invention.
In a preferred embodiment, the invention comprises a process for making an a-olefin comprising contacting an a-olefin monomer containing from about 6 to 20 carbon atoms with a catalyst comprising boron trifluoride, a protic promoter and a polyether wherein the polyether is 1,2-dimethoxyethane and the mole ratio of the protic promotor to the polyether is in the range of about 1 to 1 to about 6.5 to 1. In another preferred embodiment, the invention comprises a process for making an a-olefin comprising contacting an a-olefin monomer containing from about 6 to 20 carbon atoms with a catalyst comprising boron trifluoride, a protic promoter and a polyether wherein the polyether is diethylene glycol diethyl ether and the mole ratio of the protic promotor to the glycol diethylene ether is in the range of about 0.5 to 1 to about 4.0 to 1.
Examples 1 to 10 1-Decene, 1-butanol ( 1.0 mol % based on decene), and the appropriate amount of polyether (see Table I), were charged into the reactor which -4a-CASE PA-6788 2 i 2 fi 3 8 8 was then assembled and purged with Nz. The reactor contents were brought up to the appropriate reaction temperature by a heating coil circulating system. The stirred reactor was then pressurized with BF3 ( 10 psig) via a sparge tube located below the surface of the liquid. The reaction was stopped after 2 hours by venting the BF3 through a caustic scrubber and quenching the reactor contents with 5 aqueous NaOH. The oligomer content of the final product was then determined by GC.
Comparative examples were run with no ether modifier at temperatures of 45 and 25°C (Comparisons 1 and 2). A comparative example was 1o run using a monoether (Comparison 3). Without an ether modifier, the dimer content was only 17 % even at a reaction temperature of 45 ° C. Using a mono-ether (dibutyl ether) had little effect on the reaction. This illustrates the importance of using a polyether as the moderator.
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5,191,140 discloses a process for making a-olefin oligomers which uses BF3 promoted by at least two of water, alcohols and anhydrides to peak the reaction at lower molecular 1 o weight product.
The discovery has now been made that polyethers will moderate BF3 catalyzed oligomerizations to provide either predominantly dimer or trimer containing oligomers.
In accordance with this invention there is provided a process for making an a-olefin oligomer which comprises contacting an a-olefin monomer which contains from about 6 to 20 carbon atoms with a catalyst comprising boron trifluoride, a protic promotor and a polyether.
The olefins used in making the oligomers are predominantly (at least SO
mole percent) C6 to CZO straight chain monoolefinically unsaturated hydrocarbons in 2 0 which the olefinic unsaturation occurs at the 1- or alpha-position of the straight carbon chain. Such alpha-olefins are commercially available and can be made by the thermal cracking of paraffinic hydrocarbons or by the well-known Ziegler ethylene chain growth process. Individual olefins may be used as well as mixtures of such olefins.
Examples of such olefins are 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-hexadecene and 1-tetradecene. The more preferred normal-alpha-olefin monomers are those containing about 8-14 carbon atoms. The most preferred olefin monomer is 1-decene.
CASE PA-6788 ~ 12 6 3 ~ 8 The olefin monomers can also contain minor amounts of up to about 50, and usually less than 25 mole percent, of internal olefins and vinylidene olefins.
The olefin is contacted as known in the art with a catalytic amount of boron trifluoride which should be at least about 0.002 moles per mole of olefin.
Preferably, the reaction mixture is saturated with BF3. To be effective, the boron trifluoride is used in combination with a protic promoter such as water, carboxylic acids, mineral acids, alcohols, phenols, carboxylic acid esters and anhydrides, ketones and aldehydes. Preferred are water and C, to C24 alcohols and, more preferably, C, to C,2 alcohols (e.g. methanol, ethanol, n-propanol, isopropanol, n-butanol, to isobutanol, n-hexanol, 2-ethylhexanol, n-decanol, n-dodecanol, and the like). The amount of promotor should be an amount which is effective to cause the BF3 to act as an oligomerization catalyst, for example, from about 0.001 to 0.040 moles per mole of a-olefin monomers. In general, the BF3 is used in molar excess to the amount of promotor. This can be accomplished by using a closed reactor and a small BF3 pressure over the reaction mixture. The promoter can be mixed with the olefin feed and the reaction can be carried out in a batch or continuous process at temperatures of about 0° to 200°C. and pressures ranging from atmospheric up to, for example, 1,000 psig. The reaction temperature will change the oligomer distribution with temperatures of about 45°C and above favoring the production of lower oligomers, 2o namely dimer. Preferred reaction temperatures and pressures are about 20° to 65°C.
and 5 to 100 psig.
Preferred polyether modifiers can be defined by the formula:
RO f C-Co-C-O ~mR
2 5 R' R' where each R is individually a hydrocarbyl group and, preferably, a C, to C3o alkyl or cycloalkyl group or a C6 to C3o aryl group; each R' is individually hydrogen or a hydrocarbyl group or, taken together, form a hydrocarbyl ring;
also, R and R' taken together can form a cyclic ether, when R' is a hydrocarbyl group, it is preferably a C, to C~ alkyl or cycloalkyl group or a C6 to C~
aryl group; n = 0, l, 2, or 3 and m = 1 to 8. Non-limiting examples of such poly-ethers include 1,2-dimethoxyethane, diethylene glycol diethyl ether, 1,2-diethoxy-ethane, triethylene glycol diethyl ether, 1,2-dimethoxypropane, 1,2-dirt~ethoxybenzene, 1,3-dimethoxycyclohexane, methyl tetrahydrofuryl ether, 1,3-io dimethoxybutane, 2,3-dimethoxybutane, and the like.
The polyether modifters are used in mole ratios of promotor to modifier which are selected to peak the oligomers at either dimer or trimer.
The ratios will vary somewhat depending upon the particular combination of promotor and polyether which are used. In general, there is a range of ratios of promotor to polyether which will peak dimer. Above and below such ratios, the product will peak at trimer. For example, when using a combination of n-butanol and 1,2-dimethoxyethane, mole ratios of alcohol to polyether of up to about 1 peaked trimer whereas ratios of about 1.3 to 6.5 peaked dimer. At ratios of above 6.5, trimer again became the predominant product. When diethylene glycol diethyl 2 o ether was used, a ratio of about 1 produced predominantly dimer. The ratio which will peak the process at dimer for each catalyst combination can be readily determined by running a few oligomerizations according to the procedures described in the following examples which are intended to illustrate, but not limit, the process of the invention.
In a preferred embodiment, the invention comprises a process for making an a-olefin comprising contacting an a-olefin monomer containing from about 6 to 20 carbon atoms with a catalyst comprising boron trifluoride, a protic promoter and a polyether wherein the polyether is 1,2-dimethoxyethane and the mole ratio of the protic promotor to the polyether is in the range of about 1 to 1 to about 6.5 to 1. In another preferred embodiment, the invention comprises a process for making an a-olefin comprising contacting an a-olefin monomer containing from about 6 to 20 carbon atoms with a catalyst comprising boron trifluoride, a protic promoter and a polyether wherein the polyether is diethylene glycol diethyl ether and the mole ratio of the protic promotor to the glycol diethylene ether is in the range of about 0.5 to 1 to about 4.0 to 1.
Examples 1 to 10 1-Decene, 1-butanol ( 1.0 mol % based on decene), and the appropriate amount of polyether (see Table I), were charged into the reactor which -4a-CASE PA-6788 2 i 2 fi 3 8 8 was then assembled and purged with Nz. The reactor contents were brought up to the appropriate reaction temperature by a heating coil circulating system. The stirred reactor was then pressurized with BF3 ( 10 psig) via a sparge tube located below the surface of the liquid. The reaction was stopped after 2 hours by venting the BF3 through a caustic scrubber and quenching the reactor contents with 5 aqueous NaOH. The oligomer content of the final product was then determined by GC.
Comparative examples were run with no ether modifier at temperatures of 45 and 25°C (Comparisons 1 and 2). A comparative example was 1o run using a monoether (Comparison 3). Without an ether modifier, the dimer content was only 17 % even at a reaction temperature of 45 ° C. Using a mono-ether (dibutyl ether) had little effect on the reaction. This illustrates the importance of using a polyether as the moderator.
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Claims (8)
1. A process for making an .alpha.-olefin oligomer comprising reacting an .alpha.-olefin monomer containing from about 6 to 20 carbon atoms in the presence of a catalyst comprising, at least about 0.002 moles of boron trifluoride per mole of said monomer, from about 0.001 to 0.04 mole of a protic promoter per mole of said monomer, and a polyether in a mole ratio of promoter to polyether of from about 0.5 to 10, the mole ratio being selected so as to form predominantly the dimer or trimer oligomerizaton product.
2. The process of claim 1 wherein the mole ratio of protic promoter to polyether is selected such that the oligomer is predominantly dimer.
3. The process of claim 2 wherein the polyether is 1,2-dimethoxyethane and the mole ratio of protic promoter to polyether is from about 1 to about 6.5.
4. The process of claim 3 wherein the mole ratio of protic promoter to 1,2-dimethoxyethane is from about 1.3 to 4Ø
5. The process of claim 2 wherein the polyether is diethylene glycol diethyl ether and the mole ratio of protic promoter to diethylene glycol diethyl ether is from about 0.5 to 4Ø
6. The process of claim 1 wherein the mole ratio of protic promoter to polyether is selected such that the oligomer is predominantly trimer.
7. The process of claim 1 wherein the .alpha.-olefin is 1-decene.
8. The process of claim 1 wherein the polyether has the formula:
0 where each R is individually a C1 to C30 alkyl or cycloalkyl group or a C6 to C30 aryl group or taken with an R' forms a cyclic ether; each R' is individually hydrogen or a C1 to C30 alkyl or cycloalkyl group or a C6 to C30 aryl group or, taken together, form a hydrocarbyl ring; n = 0, 1, 2, or 3 and m = 1 to 8.
0 where each R is individually a C1 to C30 alkyl or cycloalkyl group or a C6 to C30 aryl group or taken with an R' forms a cyclic ether; each R' is individually hydrogen or a C1 to C30 alkyl or cycloalkyl group or a C6 to C30 aryl group or, taken together, form a hydrocarbyl ring; n = 0, 1, 2, or 3 and m = 1 to 8.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US08/090,648 US5396013A (en) | 1993-07-12 | 1993-07-12 | Olefin oligomerization process |
US090,648 | 1993-07-12 |
Publications (2)
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CA2126388A1 CA2126388A1 (en) | 1995-01-13 |
CA2126388C true CA2126388C (en) | 2006-01-24 |
Family
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Application Number | Title | Priority Date | Filing Date |
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CA002126388A Expired - Lifetime CA2126388C (en) | 1993-07-12 | 1994-06-21 | Olefin oligomerization process |
Country Status (6)
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US (1) | US5396013A (en) |
EP (1) | EP0634381B1 (en) |
JP (1) | JP3843140B2 (en) |
CA (1) | CA2126388C (en) |
DE (1) | DE69412937T2 (en) |
ZA (1) | ZA945054B (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
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US5420373A (en) * | 1994-03-24 | 1995-05-30 | Chevron Chemical Company | Controlled formation of olefin oligomers |
DE69509082T2 (en) * | 1995-06-12 | 1999-11-25 | Amoco Corp | Process for the preparation of oligomers of mono-olefins |
US5650548A (en) * | 1995-06-16 | 1997-07-22 | Amoco Corporation | Olefin oligomerization process |
US5633420A (en) * | 1995-09-22 | 1997-05-27 | Amoco Corporation | Olefin oligomerization process |
US5744676A (en) * | 1996-02-26 | 1998-04-28 | Theriot; Kevin J. | Olefin oligomerization process |
US6734329B1 (en) * | 2000-10-02 | 2004-05-11 | Chevron U.S.A. Inc. | Oligomerization of alpha olefins in the presence of carboxylic acids |
DE10236927A1 (en) * | 2002-08-12 | 2004-02-26 | Basf Ag | Production of synthetic hydrocarbons for use in engine oil involves oligomerization of 1-olefins such as decene in presence of boron trifluoride, alkanol and dialkyl ether or chlorinated hydrocarbon |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
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US2500161A (en) * | 1948-08-14 | 1950-03-14 | Socony Vacuum Oil Co Inc | Conversion of 1-olefins in the presence of lead tetraacetate |
US2500163A (en) * | 1948-10-29 | 1950-03-14 | Socony Vacuum Oil Co Inc | Synthetic lubricants |
US2766312A (en) * | 1952-08-19 | 1956-10-09 | Exxon Research Engineering Co | Process for polymerizing olefins |
US2806072A (en) * | 1953-12-31 | 1957-09-10 | Exxon Research Engineering Co | Dimerization process |
US3382291A (en) * | 1965-04-23 | 1968-05-07 | Mobil Oil Corp | Polymerization of olefins with bf3 |
US4172855A (en) * | 1978-04-10 | 1979-10-30 | Ethyl Corporation | Lubricant |
US4436947A (en) * | 1981-09-11 | 1984-03-13 | Gulf Research & Development Company | Olefin oligomerization using boron trifluoride and a three-component cocatalyst |
US5171918A (en) * | 1990-07-19 | 1992-12-15 | Ethyl Corporation | Apparatus and oil compositions containing olefin dimer products |
US5068487A (en) * | 1990-07-19 | 1991-11-26 | Ethyl Corporation | Olefin oligomerization with BF3 alcohol alkoxylate co-catalysts |
JPH0764757B2 (en) * | 1990-09-20 | 1995-07-12 | 出光石油化学株式会社 | Method for producing olefin oligomer |
US5095172A (en) * | 1991-03-20 | 1992-03-10 | Ethyl Corporation | Olefin purification process |
BE1006694A5 (en) * | 1991-06-22 | 1994-11-22 | Basf Ag | PREPARATION PROCESS EXTREMELY REACTIVE polyisobutenes. |
-
1993
- 1993-07-12 US US08/090,648 patent/US5396013A/en not_active Expired - Lifetime
-
1994
- 1994-06-21 CA CA002126388A patent/CA2126388C/en not_active Expired - Lifetime
- 1994-07-08 JP JP17977294A patent/JP3843140B2/en not_active Expired - Lifetime
- 1994-07-12 EP EP94110814A patent/EP0634381B1/en not_active Expired - Lifetime
- 1994-07-12 ZA ZA945054A patent/ZA945054B/en unknown
- 1994-07-12 DE DE69412937T patent/DE69412937T2/en not_active Expired - Lifetime
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DE69412937D1 (en) | 1998-10-08 |
US5396013A (en) | 1995-03-07 |
ZA945054B (en) | 1995-03-01 |
DE69412937T2 (en) | 1999-01-14 |
JPH07173083A (en) | 1995-07-11 |
CA2126388A1 (en) | 1995-01-13 |
JP3843140B2 (en) | 2006-11-08 |
EP0634381A1 (en) | 1995-01-18 |
EP0634381B1 (en) | 1998-09-02 |
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