EP0228489B1 - Sulfurized olefin process and products thereof, and compositions containing such olefins and their production - Google Patents
Sulfurized olefin process and products thereof, and compositions containing such olefins and their production Download PDFInfo
- Publication number
- EP0228489B1 EP0228489B1 EP85309479A EP85309479A EP0228489B1 EP 0228489 B1 EP0228489 B1 EP 0228489B1 EP 85309479 A EP85309479 A EP 85309479A EP 85309479 A EP85309479 A EP 85309479A EP 0228489 B1 EP0228489 B1 EP 0228489B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- sulfur
- sulfurized olefin
- olefin
- adduct
- lubricating oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 46
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000000203 mixture Substances 0.000 title claims description 26
- 238000000034 method Methods 0.000 title claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 41
- 239000011593 sulfur Substances 0.000 claims abstract description 41
- -1 alkyl mercaptan Chemical compound 0.000 claims abstract description 40
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 23
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 23
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010687 lubricating oil Substances 0.000 claims abstract description 11
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000005673 monoalkenes Chemical class 0.000 claims abstract 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 5
- 239000002199 base oil Substances 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 230000001050 lubricating effect Effects 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 2
- 229920013631 Sulfar Polymers 0.000 claims 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 239000005069 Extreme pressure additive Substances 0.000 claims 1
- 239000012141 concentrate Substances 0.000 claims 1
- 238000010790 dilution Methods 0.000 claims 1
- 239000012895 dilution Substances 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 abstract description 22
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 abstract description 8
- 239000012429 reaction media Substances 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 5
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 4
- JMMZCWZIJXAGKW-UHFFFAOYSA-N 2-methylpent-2-ene Chemical compound CCC=C(C)C JMMZCWZIJXAGKW-UHFFFAOYSA-N 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012208 gear oil Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methyl-1-pentene Chemical compound CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 description 2
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 2
- BDFAOUQQXJIZDG-UHFFFAOYSA-N 2-methylpropane-1-thiol Chemical compound CC(C)CS BDFAOUQQXJIZDG-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- LOCHFZBWPCLPAN-UHFFFAOYSA-N butane-2-thiol Chemical compound CCC(C)S LOCHFZBWPCLPAN-UHFFFAOYSA-N 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- BEQGRRJLJLVQAQ-GQCTYLIASA-N (e)-3-methylpent-2-ene Chemical compound CC\C(C)=C\C BEQGRRJLJLVQAQ-GQCTYLIASA-N 0.000 description 1
- WJECKFZULSWXPN-UHFFFAOYSA-N 1,2-didodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1CCCCCCCCCCCC WJECKFZULSWXPN-UHFFFAOYSA-N 0.000 description 1
- ZRKMQKLGEQPLNS-UHFFFAOYSA-N 1-Pentanethiol Chemical compound CCCCCS ZRKMQKLGEQPLNS-UHFFFAOYSA-N 0.000 description 1
- GGQRKYMKYMRZTF-UHFFFAOYSA-N 2,2,3,3-tetrakis(prop-1-enyl)butanedioic acid Chemical compound CC=CC(C=CC)(C(O)=O)C(C=CC)(C=CC)C(O)=O GGQRKYMKYMRZTF-UHFFFAOYSA-N 0.000 description 1
- UCJMHYXRQZYNNL-UHFFFAOYSA-N 2-Ethyl-1-hexanethiol Chemical compound CCCCC(CC)CS UCJMHYXRQZYNNL-UHFFFAOYSA-N 0.000 description 1
- IQIBYAHJXQVQGB-UHFFFAOYSA-N 2-methylbutane-2-thiol Chemical compound CCC(C)(C)S IQIBYAHJXQVQGB-UHFFFAOYSA-N 0.000 description 1
- ZQXSFZAMFNRZOQ-UHFFFAOYSA-N 2-methylpropan-2-ol;hydrate Chemical compound O.CC(C)(C)O ZQXSFZAMFNRZOQ-UHFFFAOYSA-N 0.000 description 1
- ZPRPOWRPPXIVBL-UHFFFAOYSA-N 2-methylpropan-2-ol;propan-2-ol Chemical compound CC(C)O.CC(C)(C)O ZPRPOWRPPXIVBL-UHFFFAOYSA-N 0.000 description 1
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical compound CCC=CCC ZQDPJFUHLCOCRG-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GIJGXNFNUUFEGH-UHFFFAOYSA-N Isopentyl mercaptan Chemical compound CC(C)CCS GIJGXNFNUUFEGH-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- KJRCEJOSASVSRA-UHFFFAOYSA-N Propane-2-thiol Natural products CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007866 anti-wear additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010730 cutting oil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- YWNGAZCSSDIRSK-UHFFFAOYSA-N dodecane-3-thiol Chemical compound CCCCCCCCCC(S)CC YWNGAZCSSDIRSK-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- BZXFEMZFRLXGCY-UHFFFAOYSA-N octane-2-thiol Chemical compound CCCCCCC(C)S BZXFEMZFRLXGCY-UHFFFAOYSA-N 0.000 description 1
- 230000003606 oligomerizing effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/02—Sulfurised compounds
- C10M135/04—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
- C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
Definitions
- No 3 471 404 describes a product in which sulfur monochloride is reacted with olefin to obtain an intermediate which is reacted with sulfur and alkali metal sulfide at a critical ratio of 1.8-2.2 gram moles of metal sulfide per gram mole of sulfur. This material is then refluxed for 1-24 hours with aqueous alkali metal hydroxide.
- an effective sulfurized olefin is made by reacting sulfur monochloride with an olefin in the presence of a lower alkanol promoter to obtain an adduct which is reacted with sodium sulfide and sulfur in aqueous alkanol.
- U.S. 4 188 297 discloses a method for making a lubricating additive in which an olefinically unsaturated hydrocarbon is reacted with elemental sulfur and a mercaptan.
- a sulfurized olefin having improved solubility especially in alpha-olefin oligomer lubricating oil is made by a process comprising:
- the olefins used are the monoethylenically unsaturated aliphatic hydrocarbons referred to as aliphatic monoolefins containing 3 to 6 carbon atoms.
- Useful olefins are the monoethylenically unsaturated aliphatic hydrocarbons referred to as aliphatic monoolefins containing 3 to 6 carbon atoms. These include 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 1-hexene, 2-hexene, 3-hexene, 2-methyl-1-pentene, 2-methyl-2-pentene, 2-ethyl-2-butene and the like including mixtures thereof.
- the olefins are branched-chain olefin such as isobutene, 2-methyl-1-butene, 2-methyl-2-butene, 2-methyl-2-pentene and the like. More preferably the ethylenic double bond adjoins a tertiary carbon atom such as isobutylene, the most preferred olefin.
- the first stage reaction is preferably conducted by adding the olefin to sulfur monochloride.
- the olefin can be added as a gas or liquid. Preferably it is added beneath the surface of the sulfur monochloride as a liquid.
- olefin is added until the reaction with the sulfur monochloride stops as indicated by loss of exotherm.
- An amount of 0.75-3.0 gram moles of olefin for each 0.3-0.75 gram mole of sulfur monochloride usually suffices.
- a preferred amount is 1.5-2.0 gram moles of olefin per gram mole of sulfur monochloride.
- the reaction between sulfur monochloride and olefin will proceed without adding an alcohol promoter, and since alcohol will tend to cause corrosion of metal equipment, it is not a highly preferred method of conducting the first stage.
- the use of an alcohol promoter is included in one embodiment of the invention.
- Lower alcohol promoters which can be used in the first stage contains from 1 to 4 carbon atoms. Typical examples are methanol, ethanol, n-propanol, isopropanol, isobutanol, tert-butanol and the like.
- a preferred promoter is methanol.
- the amount of alcohol promoter is preferably 0.001 to 0.3 gram moles for each 0.3-0.75 gram mole of sulfur monochloride.
- the first stage reaction can be conducted at any temperature high enough to cause the reaction to proceed, but not so high as to cause decomposition of the reactants or products.
- a useful range is 30 ° -100 ° C.
- a more preferred range is 40 ° -75 ° C and a most preferred range is 50 ° -60 ° C.
- the first stage reaction should be conducted for a time sufficient to complete the reaction between the sulfur chloride and olefin. This time is controlled by the rate at which heat can be removed. Olefin feed rate is preferably controlled to hold the temperature within the desired range. When the sulfur chloride has been consumed the temperature will drop. External heat may be added to continue the reaction for a further time, but this does not appear to be necessary.
- the overall time required to complete the reaction depends upon the scale of the process and can vary from a few minutes up to 12 or more hours. The time is not critical.
- HCI gas is evolved so means should be provided to scrub the vent gas from the reactor to remove HCI prior to releasing it to the atmosphere.
- adduct from the first stage is reacted with sodium sulfide, sulfur, alkyl mercaptan and optionally sodium hydrosulfide in an aqueous alcohol reaction medium.
- the second stage is preferably carried out by charging aqueous sodium hydrosulfide, sodium hydroxide, water, alcohol and elemental sulfur flowers or powdered sulfur to a reactor and then adding the adduct and alkyl mercaptan to this at reaction temperature.
- the NaSH and NaOH react to form sodium sulfide. Excess NaSH remains.
- the sodium sulfide may be obtained from any of a number of sources. For example, it can be made by mixing approximately equal mole amounts of sodium hydrosulfide and sodium hydroxide. If hydrogen sulfide is available, it can be adsorbed in aqueous NaOH to form a solution of sodium sulfide and/or sodium hydrosulfide depending upon the amount of hydrogen sulfide absorbed. Whatever the source, the resulting solution should be adjusted with either NaOH, NaSH or H 2 S so that the resulting solution consists mainly of sodium sulfide and optionally sodium hydrosulfide with little or no free sodium hydroxide.
- the amount of sodium sulfide can vary from 0.5-2.0 gram mole for each gram mole of sulfur chloride used in the first reaction stage.
- the amount of sodium sulfide is 0.5-1.0 gram mole per mole of sulfur chloride and most preferably 0.6-1.0 gram mole per gram mole sulfur chloride.
- Presence of NaSH is optional. Use of up to 0.5 gram moles of NaSH per mole of S 2 CI 2 has given satisfactory results. A preferred amount is 0.1-0.3 gram moles and most preferably 0.25 moles per mole of S 2 CI 2 .
- Alcohol is required in the second stage reaction.
- these are lower alcohols containing 1-4 carbon atoms such as methanol, ethanol, n-propanol, n-butanol, isobutanol, tert-butanol and the like, including mixtures thereof.
- the preferred alcohol is isopropanol either alone or mixed with other alkanols such as tert-butanol.
- the amount of alcohol can likewise vary over a wide range.
- a useful range is 0.25-0.75 parts by weight per each part by weight of water.
- a more preferred range is 0.4-0.6 parts by weight alcohol per each part by weight water.
- the alkyl mercaptan can be added separately to the aqueous alcohol reaction medium or it can be mixed with the first stage adduct and the mixture added to the aqueous alcohol containing the sodium sulfide and sulfur. When added separately it is preferred that it be added concurrently with the first stage adduct to the aqueous alcohol containing the sodium sulfide and sulfur. Sequential addition can be used but it is not preferred.
- the alkyl mercaptans used are those in which the alkyl group contains 1 to 12 carbon atoms. Representative example of these are methyl mercaptan, ethyl mercaptan, n-propyl mercaptan, i-propyl mercaptan, n-butyl mercaptan, isobutyl mercaptan, sec-butyl mercaptan, tert-butyl mercaptan, n-pentyl mercaptan, isopentyl mercaptan, tert-pentyl mercaptan, 2-ethyl hexyl mercaptan, n-octyl mercaptan, 1-methyl-heptyl mercaptan, 1-ethyl-decyl mercaptan and the like including mixtures thereof.
- mercaptans are the tert-alkyl mercaptans. Of these the more preferred are the tert-alkyl mercaptans containing 4-8 carbon atoms. The most preferred alkyl mercaptan is tert-butyl mercaptan.
- the amount of alkyl mercaptan can vary over a wide range.
- a useful range in which to test is 0.05 to 0.8 moles for each mole of sulfur monochloride used in the first stage.
- a preferred range is 0.08 to 0.5 moles of alkyl mercaptan per mole of sulfur monochloride and a more preferred range is 0.1 to 0.4 moles per mole of sulfur monochloride.
- the most preferred amount of alkyl mercaptan is 0.25 to 0.35 moles per mole of sulfur monochloride.
- the preferred amount of sulfur added is 0-0.3 gram atom for each gram mole of S 2 CI 2 . More preferably, 0.05-0.15 gram atom of sulfur and most preferably 0.0-0.15 gram atom are used per gram mole of S P OI 2 .
- the mixture of sodium sulfide, sulfur and aqueous alkanol is stirred and heated to reaction temperature and then the adduct and alkyl mercaptan are added to it.
- the reaction can be carried out in other ways such as by adding the sodium sulfide, sulfur, alkyl mercaptan and aqueous alkanol mixture to the adduct or by mixing everything together and heating the mixture.
- Preferred second stage reaction temperature is 50 ° C up to reflux temperature.
- a more preferred 10 reaction temperature is 75-85°C.
- the mixture is preferably heated to reflux just below for 2-8 hours to assure completion of the reaction.
- a very convenient way in which to make an effective sulfurized isobutylene is to base the amount of Na 2 S and NaSH (or NaOH plus NaSH or NaOH plus H 2 S), sulfur and tert-butyl mercaptan on the weight of S 2 CI 2 - isobutylene adduct.
- the Kg of Na 2 S, NaSH, sulfur and tert-butyl mercaptan per each 100 Kg of sulfurized isobutylene is preferably 15-45:0-12:0-7.5:3-20:100, more preferably 20-35:2-10:1-6:4-18:100 and most preferably 25-30:4-8:2-5:5-15:100.
- a sulfurized isobutylene adduct was made by adding isobutylene to sulfur monochloride at 50-65°C until reaction stopped.
- aqueous alcohol (64.7 wt% isopropanol, 13.8 wt% tert-butanol, 20.3 wt% water), 23.4g water, 240.4g 29.09% aqueous NaSH solution (0.9 moles), 76.2g 81.6g 50% aqueous NaOH solution (0.95 moles) and 12.3g (0.38 moles) sulfur.
- aqueous alcohol (same as in Example 1), 23.3g water 246.0g 29.09 wt% aqueous NaSH (1.27 moles), 78.0g 50% aqueous NaOH (0.98 moles) and 6.1g sulfur (0.44 moles).
- This mixture was stirred and heated to 75 ° C and then 270.0g of the sulfurized isobutylene adduct described in Example 1 was fed to the reaction mixture together with 33.9g tert-butyl mercaptan over a two hour period at 75 ° to reflux. Reflux was continued for three hours and then solvent was distilled out up to liquid temperature of 90 ° C. Vacuum was applied and heating stopped.
- Example 3 Another product was made following the same procedure as Example 3 except using 98.27g 34.3 wt% aqueous NaSH, 36.48g 50wt% aqueous NaOH, 2.95g sulfur, 42.70g water, 84.66g of same aqueous isopropanol tert-butanol solution 16.33g tert-butyl mercaptan and 130.64g S 2 CI 2 - isobutylene adduct. The product analyzed 46.4 weight percent sulfur.
- Example 3 followed the same procedure as Example 3 except using 94.85g 35.04 wt% aqueous NaSH, 35.96g 50 wt% aqueous NaOH, 6.22g sulfur, 29.77g water, 99.83g 56.39 wt% isopropanol - 13.85 wt% tert-butanol - water solution, 16.21g tert-butyl mercaptan and 129.70g S 2 CI 2 - isobutylene adduct. The product analyzed 48 weight percent sulfur.
- the sulfurized olefins are especially useful in lubricating oil formulations used in gear applications.
- the base oil may be a mineral oil or a synthetic oil.
- Useful synthetic oils include olefin oligomers such as decene trimer, tetramer and pentamer made by oligomerizing 1-decene using a BFa catalyst.
- Useful olefin oligomers can be made using other catalysts such as the aluminum alkyl Ziegler catalyst.
- other olefins can be used such as Cs- 14 1-olefins.
- Synthetic alkylbenzenes can also be used such as di-dodecylbenzene and the like.
- Synthetic ester lubricating oil can also be employed such as the alkyl esters of dicarboxylic acid (e.g. di-2-ethylhexylsebacate), fatty acid esters of polyols (e.g. trimethylolpropane, tripelargonate) or complex esters of alkanols, alkane, polyols and carboxylic or polycarboxylic acid.
- dicarboxylic acid e.g. di-2-ethylhexylsebacate
- fatty acid esters of polyols e.g. trimethylolpropane, tripelargonate
- complex esters of alkanols, alkane, polyols and carboxylic or polycarboxylic acid e.g. di-2-ethylhexylsebacate
- the sulfurized olefin is added in an amount sufficient to improve the EP property of the lubricant.
- An amount of 0.1 to 10.0 wt % is usually sufficient.
- Fully formulated gear lubricants include other conventional additives which perform various functions.
- other additives are corrosion inhibitors for ferrous and non-ferrous metals such as tetrapropenyl succinic acid and bis-(2,5-alkyldithia)-1,3,4-thiadiazoles.
- Antiwear additives such as alkyl or aryl phosphonates, phosphite, thiophosphates, dithiophosphates, and phosphoric acids. Also zinc dialkyl or diaryl dithiophosphate, chlorinated hydrocarbons, sulfurized fatty esters and amines.
- the tests were conducted in SAE 90 mineral oil. The first was a 4-ball weld test (ASTM D2783) in which a steel ball is rotated in loaded contact with three fixed balls. The maximum load without weld is recorded as the pass load.
- test additive was blended in the base oil at a concentration which imparted 1.0 weight percent sulfur to the oil. Results obtained were as follows:
- the present additive was used as a component in a formulated gear oil.
- the test was an L-42 High Speed Axle Test. Using the additives of Example 1 or 2 gave a gear oil which passed the test.
- the mercaptan-capped sulfurized olefins of this invention have been found to be much more soluble in hydrogen-treated mineral oil and alpha-olefin oligomer synthetic lubricating oil compared to the same sulfurized olefin made without mercaptans.
- first comparison blends are made at 4.0 weight percent sulfurized olefin in a hydrotreated base oil, a hydrocracked base oil an alpha-decene oligomer.
- the blends were rated as clear or cloudy. The results were as follows:
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Abstract
Description
- Sulfurized olefins are well-known additives in lubricating oil, cutting oil and the like. Kimball, U.S. Pat. No 2 249 312, describes such a product. Eby, U.S. Pat. No 2 708 199, describes a similar product in which a sulfur halide is reacted with an olefin using a lower alkanol promoter to obtain an intermediate which is reacted with an alkali or alkaline earth metal polysulfide. Myers, U.S. Pat. No 3 471 404, describes a product in which sulfur monochloride is reacted with olefin to obtain an intermediate which is reacted with sulfur and alkali metal sulfide at a critical ratio of 1.8-2.2 gram moles of metal sulfide per gram mole of sulfur. This material is then refluxed for 1-24 hours with aqueous alkali metal hydroxide. In U.S. 4 204 969, an effective sulfurized olefin is made by reacting sulfur monochloride with an olefin in the presence of a lower alkanol promoter to obtain an adduct which is reacted with sodium sulfide and sulfur in aqueous alkanol.
- U.S. 4 188 297 discloses a method for making a lubricating additive in which an olefinically unsaturated hydrocarbon is reacted with elemental sulfur and a mercaptan.
- According to the present invention, a sulfurized olefin having improved solubility especially in alpha-olefin oligomer lubricating oil is made by a process comprising:
- (a) reacting a sulfur halide selected from SCI2, S2CI2 and mixtures thereof with an aliphatic monoolefin containing 3-6 carbon atoms to produce an adduct;
- (b) reacting said adduct with sulfur, Na2S in an amount of from 0.5 to 2.0 gram mole per gram mole of sulfur chloride, an alkyl mercaptan containing 1-12 carbon atoms and from 0 to 0.5 gram mole NaSH per mole of sulfur halide in an aqueous alcohol medium at a temperature of from 50°C up to reflux to form said sulfurized olefin;
- (c) recovering said sulfurized olefin from the aqueous alcohol medium.
- Although a useful product can be obtained using either SC12 or S2Ct2, superior results were obtained with S2C[2 so this sulfur halide is most preferred.
- The olefins used are the monoethylenically unsaturated aliphatic hydrocarbons referred to as aliphatic monoolefins containing 3 to 6 carbon atoms.
- Although a useful product can be obtained using either S012 or S2Ct2, superior results were obtained with S2CI2 so this sulfur halide is most preferred.
- Useful olefins are the monoethylenically unsaturated aliphatic hydrocarbons referred to as aliphatic monoolefins containing 3 to 6 carbon atoms. These include 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 1-hexene, 2-hexene, 3-hexene, 2-methyl-1-pentene, 2-methyl-2-pentene, 2-ethyl-2-butene and the like including mixtures thereof.
- Preferably the olefins are branched-chain olefin such as isobutene, 2-methyl-1-butene, 2-methyl-2-butene, 2-methyl-2-pentene and the like. More preferably the ethylenic double bond adjoins a tertiary carbon atom such as isobutylene, the most preferred olefin.
- The first stage reaction is preferably conducted by adding the olefin to sulfur monochloride. The olefin can be added as a gas or liquid. Preferably it is added beneath the surface of the sulfur monochloride as a liquid.
- In practice the olefin is added until the reaction with the sulfur monochloride stops as indicated by loss of exotherm. An amount of 0.75-3.0 gram moles of olefin for each 0.3-0.75 gram mole of sulfur monochloride usually suffices. A preferred amount is 1.5-2.0 gram moles of olefin per gram mole of sulfur monochloride.
- The reaction between sulfur monochloride and olefin will proceed without adding an alcohol promoter, and since alcohol will tend to cause corrosion of metal equipment, it is not a highly preferred method of conducting the first stage. The use of an alcohol promoter, however, is included in one embodiment of the invention. Lower alcohol promoters which can be used in the first stage contains from 1 to 4 carbon atoms. Typical examples are methanol, ethanol, n-propanol, isopropanol, isobutanol, tert-butanol and the like. A preferred promoter is methanol. The amount of alcohol promoter is preferably 0.001 to 0.3 gram moles for each 0.3-0.75 gram mole of sulfur monochloride.
- The first stage reaction can be conducted at any temperature high enough to cause the reaction to proceed, but not so high as to cause decomposition of the reactants or products. A useful range is 30°-100°C. A more preferred range is 40°-75°C and a most preferred range is 50°-60°C.
- The first stage reaction should be conducted for a time sufficient to complete the reaction between the sulfur chloride and olefin. This time is controlled by the rate at which heat can be removed. Olefin feed rate is preferably controlled to hold the temperature within the desired range. When the sulfur chloride has been consumed the temperature will drop. External heat may be added to continue the reaction for a further time, but this does not appear to be necessary. The overall time required to complete the reaction depends upon the scale of the process and can vary from a few minutes up to 12 or more hours. The time is not critical.
- During the first stage reaction HCI gas is evolved so means should be provided to scrub the vent gas from the reactor to remove HCI prior to releasing it to the atmosphere.
- In the second stage reaction, adduct from the first stage is reacted with sodium sulfide, sulfur, alkyl mercaptan and optionally sodium hydrosulfide in an aqueous alcohol reaction medium. The second stage is preferably carried out by charging aqueous sodium hydrosulfide, sodium hydroxide, water, alcohol and elemental sulfur flowers or powdered sulfur to a reactor and then adding the adduct and alkyl mercaptan to this at reaction temperature. The NaSH and NaOH react to form sodium sulfide. Excess NaSH remains.
- The sodium sulfide may be obtained from any of a number of sources. For example, it can be made by mixing approximately equal mole amounts of sodium hydrosulfide and sodium hydroxide. If hydrogen sulfide is available, it can be adsorbed in aqueous NaOH to form a solution of sodium sulfide and/or sodium hydrosulfide depending upon the amount of hydrogen sulfide absorbed. Whatever the source, the resulting solution should be adjusted with either NaOH, NaSH or H2S so that the resulting solution consists mainly of sodium sulfide and optionally sodium hydrosulfide with little or no free sodium hydroxide.
- The amount of sodium sulfide can vary from 0.5-2.0 gram mole for each gram mole of sulfur chloride used in the first reaction stage. Preferably the amount of sodium sulfide is 0.5-1.0 gram mole per mole of sulfur chloride and most preferably 0.6-1.0 gram mole per gram mole sulfur chloride.
- Presence of NaSH is optional. Use of up to 0.5 gram moles of NaSH per mole of S2CI2 has given satisfactory results. A preferred amount is 0.1-0.3 gram moles and most preferably 0.25 moles per mole of S2CI2.
- The amount of water can vary widely without detrimental effect. Good results can be obtained using 10-20 gram moles of water per gram mole of sodium sulfide. This includes water added as such, water in aqueous reactants and water which might be formed by reaction of hydrogen sulfide or sodium hydrosulfide with sodium hydroxide in forming sodium sulfide solution.
- Alcohol is required in the second stage reaction. Preferably, these are lower alcohols containing 1-4 carbon atoms such as methanol, ethanol, n-propanol, n-butanol, isobutanol, tert-butanol and the like, including mixtures thereof. The preferred alcohol is isopropanol either alone or mixed with other alkanols such as tert-butanol.
- The amount of alcohol can likewise vary over a wide range. A useful range is 0.25-0.75 parts by weight per each part by weight of water. A more preferred range is 0.4-0.6 parts by weight alcohol per each part by weight water.
- The alkyl mercaptan can be added separately to the aqueous alcohol reaction medium or it can be mixed with the first stage adduct and the mixture added to the aqueous alcohol containing the sodium sulfide and sulfur. When added separately it is preferred that it be added concurrently with the first stage adduct to the aqueous alcohol containing the sodium sulfide and sulfur. Sequential addition can be used but it is not preferred.
- The alkyl mercaptans used are those in which the alkyl group contains 1 to 12 carbon atoms. Representative example of these are methyl mercaptan, ethyl mercaptan, n-propyl mercaptan, i-propyl mercaptan, n-butyl mercaptan, isobutyl mercaptan, sec-butyl mercaptan, tert-butyl mercaptan, n-pentyl mercaptan, isopentyl mercaptan, tert-pentyl mercaptan, 2-ethyl hexyl mercaptan, n-octyl mercaptan, 1-methyl-heptyl mercaptan, 1-ethyl-decyl mercaptan and the like including mixtures thereof.
- Of the foregoing the more preferred mercaptans are the tert-alkyl mercaptans. Of these the more preferred are the tert-alkyl mercaptans containing 4-8 carbon atoms. The most preferred alkyl mercaptan is tert-butyl mercaptan.
- The amount of alkyl mercaptan can vary over a wide range. A useful range in which to test is 0.05 to 0.8 moles for each mole of sulfur monochloride used in the first stage. A preferred range is 0.08 to 0.5 moles of alkyl mercaptan per mole of sulfur monochloride and a more preferred range is 0.1 to 0.4 moles per mole of sulfur monochloride. The most preferred amount of alkyl mercaptan is 0.25 to 0.35 moles per mole of sulfur monochloride.
- The preferred amount of sulfur added is 0-0.3 gram atom for each gram mole of S2CI2. More preferably, 0.05-0.15 gram atom of sulfur and most preferably 0.0-0.15 gram atom are used per gram mole of SPOI2.
- In a preferred mode of operation the mixture of sodium sulfide, sulfur and aqueous alkanol is stirred and heated to reaction temperature and then the adduct and alkyl mercaptan are added to it. However, the reaction can be carried out in other ways such as by adding the sodium sulfide, sulfur, alkyl mercaptan and aqueous alkanol mixture to the adduct or by mixing everything together and heating the mixture.
- Preferred second stage reaction temperature is 50°C up to reflux temperature. A more preferred 10 reaction temperature is 75-85°C.
- After the adduct and alkyl mercaptan have been added to the sodium sulfide/sulfur/aqueous alkanol mixture, which is usually completed in 1-8 hours, the mixture is preferably heated to reflux just below for 2-8 hours to assure completion of the reaction.
- A very convenient way in which to make an effective sulfurized isobutylene is to base the amount of Na2S and NaSH (or NaOH plus NaSH or NaOH plus H2S), sulfur and tert-butyl mercaptan on the weight of S2CI2 - isobutylene adduct. Following this procedure the Kg of Na2S, NaSH, sulfur and tert-butyl mercaptan per each 100 Kg of sulfurized isobutylene is preferably 15-45:0-12:0-7.5:3-20:100, more preferably 20-35:2-10:1-6:4-18:100 and most preferably 25-30:4-8:2-5:5-15:100. After reaction of the adduct with sodium sulfide, sodium hydrosulfide, alkyl mercaptan and sulfur the product is recovered by conventional methods such as removing alkanol, water washing and filtering.
- The following example illustrates the manner of making the sulfurized olefin.
- A sulfurized isobutylene adduct was made by adding isobutylene to sulfur monochloride at 50-65°C until reaction stopped. In a separate vessel was placed 177.9g aqueous alcohol (64.7 wt% isopropanol, 13.8 wt% tert-butanol, 20.3 wt% water), 23.4g water, 240.4g 29.09% aqueous NaSH solution (0.9 moles), 76.2g 81.6g 50% aqueous NaOH solution (0.95 moles) and 12.3g (0.38 moles) sulfur. This was stirred at 75°C while 255.3g of the above adduct and 32.0g tart-butyl mercaptan (0.36 moles) were concurrently added dropwise over a two hour period. Heat was continued at reflux for three hours and then solvent alcohol was distilled out up to 90°C. Vacuum was applied to remove more solvent. Heat was stopped and when the mixture cooled to 65°C the mixture was washed with water. The aqueous brine layer was removed and the organic layer was stripped of volatiles under vacuum at 100-110°C for one hour and then filtered a second time giving a clear amber product which analyzed 47.7 weight percent sulfur.
- In a reaction vessel was placed 188.4g aqueous alcohol (same as in Example 1), 23.3g water 246.0g 29.09 wt% aqueous NaSH (1.27 moles), 78.0g 50% aqueous NaOH (0.98 moles) and 6.1g sulfur (0.44 moles). This mixture was stirred and heated to 75°C and then 270.0g of the sulfurized isobutylene adduct described in Example 1 was fed to the reaction mixture together with 33.9g tert-butyl mercaptan over a two hour period at 75° to reflux. Reflux was continued for three hours and then solvent was distilled out up to liquid temperature of 90°C. Vacuum was applied and heating stopped. When the temperature dropped to 65°C water was added to wash the organic phase. The lower aqueous brine layer was removed. The organic phase was stripped under vacuum at 100-110°C for one hour and then filtered using a filter aid. Product analyzed 43.6 weight percent sulfur.
- In a reaction vessel was placed 100.41 g of a 34.3 wt% aqueous solution NaSH containing 1.03 wt% Na2S, 37.27g of a 50 wt% aqueous NaOH solution, 4.0g of sulfur, 43.64g water and 86.19g of a mixture of 65.17 wt% isopropanol, 16.89 wt% tertbutanol and the balance water. this was stirred and heated to 75°C at which time 133.47g of S2CI2 - isobutylene adduct made by adding isobutylene to S2Cl2 at 60°C to the point where no further isobutylene would react was added concurrently with 6.66g tert-butyl mercaptan over a two hour period. Stirring was continued at reflux (about 80°C) for three hours at which time alcohol-water was distilled out up to 90°C. Vacuum was applied and distillation continued until 70°C liquid temperature at a vacuum of twenty-four inches Hg. The mixture was then water washed at 70°C. Wash water was drained off and 1% Dicalite filter aid added. The mixture was stirred at 100-105°C at 28" Hg vacuum for one hour and then filtered. Product analyzed 48.8 weight percent sulfur.
- Another product was made following the same procedure as Example 3 except using 98.27g 34.3 wt% aqueous NaSH, 36.48g 50wt% aqueous NaOH, 2.95g sulfur, 42.70g water, 84.66g of same aqueous isopropanol tert-butanol solution 16.33g tert-butyl mercaptan and 130.64g S2CI2 - isobutylene adduct. The product analyzed 46.4 weight percent sulfur.
- This example followed the same procedure as Example 3 except using 94.85g 35.04 wt% aqueous NaSH, 35.96g 50 wt% aqueous NaOH, 6.22g sulfur, 29.77g water, 99.83g 56.39 wt% isopropanol - 13.85 wt% tert-butanol - water solution, 16.21g tert-butyl mercaptan and 129.70g S2CI2 - isobutylene adduct. The product analyzed 48 weight percent sulfur.
- The sulfurized olefins are especially useful in lubricating oil formulations used in gear applications. The base oil may be a mineral oil or a synthetic oil. Useful synthetic oils include olefin oligomers such as decene trimer, tetramer and pentamer made by oligomerizing 1-decene using a BFa catalyst. Useful olefin oligomers can be made using other catalysts such as the aluminum alkyl Ziegler catalyst. Likewise, other olefins can be used such as Cs-14 1-olefins.
- Synthetic alkylbenzenes can also be used such as di-dodecylbenzene and the like.
- Synthetic ester lubricating oil can also be employed such as the alkyl esters of dicarboxylic acid (e.g. di-2-ethylhexylsebacate), fatty acid esters of polyols (e.g. trimethylolpropane, tripelargonate) or complex esters of alkanols, alkane, polyols and carboxylic or polycarboxylic acid.
- In this use the sulfurized olefin is added in an amount sufficient to improve the EP property of the lubricant. An amount of 0.1 to 10.0 wt % is usually sufficient.
- Fully formulated gear lubricants include other conventional additives which perform various functions. Examples of such other additives are corrosion inhibitors for ferrous and non-ferrous metals such as tetrapropenyl succinic acid and bis-(2,5-alkyldithia)-1,3,4-thiadiazoles. Antiwear additives such as alkyl or aryl phosphonates, phosphite, thiophosphates, dithiophosphates, and phosphoric acids. Also zinc dialkyl or diaryl dithiophosphate, chlorinated hydrocarbons, sulfurized fatty esters and amines.
- Tests have been conducted which demonstrate the EP effectiveness of the sulfurized olefin.
- The tests were conducted in SAE 90 mineral oil. The first was a 4-ball weld test (ASTM D2783) in which a steel ball is rotated in loaded contact with three fixed balls. The maximum load without weld is recorded as the pass load.
-
- In another standard test the present additive was used as a component in a formulated gear oil. The test was an L-42 High Speed Axle Test. Using the additives of Example 1 or 2 gave a gear oil which passed the test.
- The mercaptan-capped sulfurized olefins of this invention have been found to be much more soluble in hydrogen-treated mineral oil and alpha-olefin oligomer synthetic lubricating oil compared to the same sulfurized olefin made without mercaptans. In the first comparison blends are made at 4.0 weight percent sulfurized olefin in a hydrotreated base oil, a hydrocracked base oil an alpha-decene oligomer. The blends were rated as clear or cloudy. The results were as follows:
-
- These results show the improvement in solubility in a synthetic alpha-olefin oligomer gear oil base stock due to use of the alkyl mercaptan.
Claims (9)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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US06/556,968 US4563302A (en) | 1983-12-01 | 1983-12-01 | Sulfurized olefin process |
EP85309479A EP0228489B1 (en) | 1985-12-24 | 1985-12-24 | Sulfurized olefin process and products thereof, and compositions containing such olefins and their production |
DE8585309479T DE3571048D1 (en) | 1985-12-24 | 1985-12-24 | Sulfurized olefin process and products thereof, and compositions containing such olefins and their production |
AT85309479T ATE44043T1 (en) | 1985-12-24 | 1985-12-24 | PROCESSES FOR THE PREPARATION OF SULFURATED OLEFINS AND PRODUCTS THEREOF AND COMPOSITIONS CONTAINING THESE OLEFINS AND THE PREPARATION THEREOF. |
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EP85309479A EP0228489B1 (en) | 1985-12-24 | 1985-12-24 | Sulfurized olefin process and products thereof, and compositions containing such olefins and their production |
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EP0228489B1 true EP0228489B1 (en) | 1989-06-14 |
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CA2007144A1 (en) * | 1989-01-31 | 1990-07-31 | David J. Degonia | Hydrotreated oil soluble sulfurized olefins and their preparation |
US5428714A (en) * | 1990-11-16 | 1995-06-27 | Seiko Epson Corporation | Status and command function extension for industry standard printer interfaces |
CN108409619A (en) * | 2018-03-16 | 2018-08-17 | 山东豪迈化工技术有限公司 | The synthetic method of sulphur chlorination isobutene |
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US4204969A (en) * | 1978-10-10 | 1980-05-27 | Edwin Cooper, Inc. | Lubricant composition containing sulfurized olefin extreme pressure additive |
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