EP0201197B1 - Sulfurized olefins - Google Patents
Sulfurized olefins Download PDFInfo
- Publication number
- EP0201197B1 EP0201197B1 EP86302488A EP86302488A EP0201197B1 EP 0201197 B1 EP0201197 B1 EP 0201197B1 EP 86302488 A EP86302488 A EP 86302488A EP 86302488 A EP86302488 A EP 86302488A EP 0201197 B1 EP0201197 B1 EP 0201197B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- accordance
- kpa
- psi
- sulfur
- olefin
- 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 - Lifetime
Links
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000314 lubricant Substances 0.000 claims abstract description 15
- -1 hydrocarbyl olefin Chemical class 0.000 claims abstract description 12
- 239000000446 fuel Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 24
- 229910052717 sulfur Inorganic materials 0.000 claims description 24
- 239000011593 sulfur Substances 0.000 claims description 24
- 239000000654 additive Substances 0.000 claims description 20
- 239000003921 oil Substances 0.000 claims description 14
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 13
- 230000001050 lubricating effect Effects 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 9
- 239000004519 grease Substances 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- KXPHJGWRCICEDH-UHFFFAOYSA-N 1-sulfanylidene-3h-dithiole Chemical class S=S1SCC=C1 KXPHJGWRCICEDH-UHFFFAOYSA-N 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 5
- 239000002480 mineral oil Substances 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 4
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 239000005077 polysulfide Substances 0.000 claims description 3
- 229920001021 polysulfide Polymers 0.000 claims description 3
- 150000008117 polysulfides Polymers 0.000 claims description 3
- FAMJUFMHYAFYNU-JTQLQIEISA-N (4r)-1-methyl-4-propan-2-ylcyclohexene Chemical compound CC(C)[C@@H]1CCC(C)=CC1 FAMJUFMHYAFYNU-JTQLQIEISA-N 0.000 claims description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- DRHABPMHZRIRAH-UHFFFAOYSA-N 2,4,4,6,6-pentamethylhept-2-ene Chemical group CC(C)=CC(C)(C)CC(C)(C)C DRHABPMHZRIRAH-UHFFFAOYSA-N 0.000 claims description 2
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 claims description 2
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229940087305 limonene Drugs 0.000 claims description 2
- 235000001510 limonene Nutrition 0.000 claims description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 2
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 claims description 2
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims 3
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims 2
- 229940043279 diisopropylamine Drugs 0.000 claims 1
- 239000005069 Extreme pressure additive Substances 0.000 abstract description 2
- 239000007866 anti-wear additive Substances 0.000 abstract description 2
- 230000009972 noncorrosive effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 11
- 239000012530 fluid Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 241001061127 Thione Species 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- GQGTXJRZSBTHOB-UHFFFAOYSA-N 1-phenoxy-4-(4-phenoxyphenoxy)benzene Chemical class C=1C=C(OC=2C=CC(OC=3C=CC=CC=3)=CC=2)C=CC=1OC1=CC=CC=C1 GQGTXJRZSBTHOB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical class CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 150000001669 calcium Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 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
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical class [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012208 gear oil Substances 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
- 239000003879 lubricant additive Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- VWSUVZVPDQDVRT-UHFFFAOYSA-N phenylperoxybenzene Chemical class C=1C=CC=CC=1OOC1=CC=CC=C1 VWSUVZVPDQDVRT-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- This invention is directed to sulfurized products which are useful as additives to lubricant compositions, various greases and liquid hydrocarbyl fuels. This invention is particularly directed to a process of preparing these sulfurized products, the products so prepared and lubricating and fuel compositions containing them.
- Sulfurized olefins have been extensively used in many lubricant applications requiring extreme pressure/antiwear activity. It is well known that many methods have been used for producing organic sulfides by treating olefins. It is also well known that many sulfurized organic compositions are useful as lubricant additives.
- the prior art processes provide sulfurized products having undesirably high levels of thiones, such as dithiol-thiones, and high levels of thiones in combination with various complex sulfurized mixtures.
- these processes which are expensive and difficult to control, provide products having a highly disagreeable odor.
- This invention relates to a process of preparing sulfurized organic additive products. These products consist essentially of mixtures of polysulfides, oligomers and dithiol-thione type compounds.
- the additive products are prepared under pressure by the reaction of olefinic compounds with elemental sulfur within a relatively narrow range of temperatures, pressures and ratio of reactants to form products containing sulfur.
- the additive product is suitable for use in an oil of lubricating viscosity or grease thereof or a liquid hydrocarbyl fuel and is prepared in a process comprising reacting in a suitable reaction zone an olefinic hydrocarbyl compound having at least one olefinic double bond with elemental sulfur in a molar ratio of sulfur to olefin of from 1.9:1 to 2.1:1 under pressures of from 2070 kPa (300 psi) to 6200 kPa (900 psi) at temperatures ranging from 140 to 180°C for a time sufficient and until the reaction pressure drops to 340 kPa (50 psi) to 690 kPa (100 psi) thereby producing a sulfurized additive product containing at least 45 weight percent of sulfur, preferably 45 to 55 weight percent sulfur, and consisting essentially of a major- amount of polysulfides and a minor amount of dithiol-thione type compounds.
- Sulfurized additive products of enhanced extreme pressure/antiwear activity and improved corrosivity are obtained.
- This invention is also directed to the additive products themselves and to compositions comprising oils of lubricating viscosity or greases prepared therefrom or liquid hydrocarbyl fuels containing the same.
- the specific and significantly improved discrete compositions produced by the narrowly defined processing conditions disclosed herein provide thermally and oxidatively stable, noncorrosive, low-odor, extreme pressure/antiwear additives for lubricating oils, greases and fuels.
- the invention in a particular aspect is directed to lubricant oil additives prepared in a one step-one pot process comprising reacting in a suitable reaction zone an olefinic hydrocarbyl compound having at least one olefinic double bond with elemental sulfur.
- olefinic substances may be utilized in the process in accordance with the invention. This includes olefins with terminal or internal double bonds and containing from about 2 to 8 or more carbon atoms per molecule in either straight, branched chain or cyclic compounds and these may be exemplified by ethylene, propylene, 1-butene, cis and trans-2-butene, isobutylene, diisobutylene, triisobutylene, pentene, cyclopentene, hexene, cyclohexene, octene, 1-decene, etc.
- diolefins for example butadiene, isoprene, divinyl benzene, pinene, p-menthene and limonene.
- C 3 to C 6 olefins or mixtures thereof are preferred and more preferably butylenes are desirable for preparing the sulfurized products embodied herein because the combined sulfur content of the product decreases with increasing carbon content and the miscibility of the product with oil is lower in the case of propylene and ethylene derivatives.
- isobutylene is particularly preferred as the predominant olefinic reactant, but it may be employed, desirably in major proportions, in mixtures containing one or more other olefins.
- substantial proportions of saturated aliphatic hydrocarbons as exemplified by methane, ethane, propane, butane, pentane, etc. may be contained in the olefinic feed.
- alkanes are preferably present in minor proportions in most instances to avoid unnecessary dilution of the reaction since they neither react nor remain in the product, but are expelled in the off-gases or by subsequent distillation.
- such mixed feed can substantially improve the economics of the process since such streams are of lower value than a stream of, for example, relatively pure isobutylene.
- Volatile olefins are often readily available in liquid form, and it is usually desirable to utilize olefinic liquids which are vaporized by the heat of reaction, as such evaporation provides a substantial cooling effect that permits the flowing of water for cooling the reactor to be reduced considerably for greater economy. Also, there are indications that the use of a volatile liquid olefin reactant has the unexpected and desirable effect of lowering the viscosity of the final product.
- the specifically narrow molar ratio of sulfur to olefin may range from 1.9:1 to 2.1:1. In the case of butylene, the optimum ratio preferably is from 1.95:1 to 2.05:1.
- the reaction temperature may range from 140 to 180°C, preferably from 158 to 165°C and most preferably from 159 to 161°C. The preferred temperature is 160°C.
- the reaction pressure is allowed to seek its own optimum level and may range from 2070 kPa (300 psi) to 6200 kPa (900 psi). The preferred pressures are from 5170 kPa (750 psi) to 5860 kPa (850 psi).
- a critical aspect of the pressure parameter is the pressure at which the reaction is stopped.
- the reaction begins to seek its own pressure level and is held at a specific temperature most preferably 160°C until the pressure begins to drop.
- the pressure at the reaction temperature must not be allowed to drop out of the range of from 340 kPa (50 psi) to 690 kPa (100 psi). Any conventional means known in the art for accomplishing this may be used.
- the final pressure is indicative of the cited stoichiometry in accordance with the invention whereby the optimum product containing 45 to 61.5 weight % sulfur, preferably 45 to 55 weight % sulfur with no more than 10 to 20 weight % dithiol-thione type compounds based upon total weight of the additive product, is obtained.
- the weight percent of sulfur to unsaturated olefin is preferably 59 to 61.5 weight percent for a C 3 olefin (propylene), 52 to 54.5 weight percent for a C 4 olefin (butylene) and 46.5 to 49 weight percent for a C s olefin (pentane).
- the reaction may be catalyzed with a rate accelerating catalyst.
- Alkylamine catalysts such as n-butylamine, di-n-butylamine, n-octylamine, triethylamine, di-cyclohexylamine and the like are suitable.
- any suitable rate acceleration catalyst known in the art may be used, as for example quiholine and attapulgite acid clay.
- the reaction between the sulfur and the olefinic compound may be conducted in any suitable reaction vessel.
- the sulfur may be heated to a predetermined temperature in the reaction vessel prior to contacting it with the olefinic reactant, which may be chilled in order to liquify it and get it into the reactor.
- the olefin is charged to the reaction zone substantially about as rapidly as it is consumed.
- compositions hereof may comprise any oleaginous materials that require lubricativ6;-peoperties under extreme pressure conditions and require protection against excessive wear under operating conditions, but normally exhibit insufficient anti-corrosion properties.
- liquid hydrocarbon oils of lubricating viscosity are suitable for use with the additives of this invention.
- Lubricant oils improved in accordance with the present invention, may be of any suitable lubricating viscosity.
- the lubricant compositions may comprise any mineral or synthetic oil of lubricating viscosity or mixtures thereof.
- the additives of this invention are especially useful in greases and in automotive fluids such as brake fluids and power brake fluids, transmission fluids, power steering fluids, various hydraulic fluids and gear oils and in liquid hydrocarbyl fuels.
- synthetic oils are desired in preference to refined petroleum or mineral oil they may be employed alone or in combination with a mineral oil. They may also be used as the vehicle or base of grease compositions.
- Typical synthetic lubricants include polyisobutylene, polybutenes, hydrogenated polydecenes, polypropylene glycol, polyethylene glycol, trimethylol propane esters, neopentyl and pentaerythritol esters of carboxylic acids, di(2-ethylhexyl) sebacate, di(2-ethylhexyl) adipate, dibutyl phthalate, fluorocarbons, silicate esters, silanes, esters of phosphorus-containing acids, liquid ureas, ferrocene derivatives, hydrogenated mineral oils, chain-type polyphenols, siloxanes and silicones (polysifoxanes), alkyl-substituted diphenyl ethers typified by a butyl-substitute
- the aforementioned additives can be incorporated as additives in grease compositions.
- mineral oils having a viscosity of at least 40 SSU at 65.6°C (150°F) are useful. Otherwise, those falling within the range of from about 60 SSU to about 6,000 SSU at 37.8°C (100°F) may be employed.
- the lubricating compositions of the improved greases of the present invention are combined with a grease forming quantity of a thickening agent.
- a thickening agent for this purpose, a wide variety of materials can be dispersed in the lubricating oil in grease-forming quantities in such degree as to impart to the resulting grease composition the desired consistency.
- the thickening agents that may be employed in the gease formulation are metal soaps as well as non-soap thickeners, such as surface-modified clays and silicas, aryl ureas, calcium complexes and similar materials.
- grease thickeners are employed which do not melt or dissolve when used at the required temperature within a particular environment; however, in all other respects, any material which is normally employed for thickening or gelling oleaginous fluids or forming greases may be used in the present invention.
- the lubricants and fuels of the present invention contain an amount of the sulfurized product effective to improve extreme pressure properties and antiwear and oxidation characteristics. Normally this amount will be 0.01 to 20% and preferably 0.01 to 10% of the total weight of the lubricant.
- the invention also contemplates the use of other additives in combination with the sulfurized olefin product.
- additives include, for example, detergents and dispersants of the ash-producing or ashless type, corrosion-inhibiting agents, auxiliary oxidation-inhibiting agents, pour point depression agents, auxiliary extreme pressure agents, color stabilizers and anti-foam agents.
- This Example was prepared in accordance with the invention using a molar ratio of sulfur to isobutylene of 2.0:1.
- a 1-gallon stirred autoclave (reactor) was charged with 1,344 g sulfur and 1.2 g n-butylamine (0.05% of the total charge). The reactor was sealed and purged three times with nitrogen to remove oxygen. The reactor was then charged with 1,176 g isobutylene under pressure. The reactor agitator was activated and heated to 160°C and held at that temperaturee until the pressure dropped from its maximum of 4830 kPa (700 psi) to below 520 kPa (75 psi). The reactor was cooled to 100°C and vented to a caustic scrubber. The product was then sparged with nitrogen for three hours at 100°C to remove gaseous contaminates, cooled to less than 30°C and then filtered through diatomaceous earth. The product yield was about 99% of the total reactants charged.
- This Example is outside the scope of the invention and was prepared using a molar ratio of sulfur to isobutylene of 1.8:1.
- Example 1 The procedure for Example 1 was used, but a lower sulfur:isobutylene mole ratio was charged. The charge consisted of: 1,300 sulfur, 1.2 g n-butylamine and 1,264 g isobutylene. Maximum pressure achieved was 5790 kPa (840 psi) with a pressure drop to less than 520 kPa (50 psi). Total reaction time was about eleven hours.
- This Example was prepared using a molar ratio of sulfur to isobutylene of 1.0:1. It accordingly is outside the scope of the invention.
- Example 2 The procedure for Example 2 was used, but a lower sulfur:isobutylene mole ratio was charged. The charge consisted of: 739 g sulfur, 1.2 g n-butylamine, and 1,249 g isobutylene. The product yield was only 86.5% of reactants charged and minimum pressure did not drop below about 1380 kPa (200 psi), indicating an excess of unreacted olefin which was removed during the venting and sparging steps.
- Example 1 The products of Example 1, Comparative Example A, and Comparative B were blended into a fully formulated gear lubricant with a standard detergent/antirust/antioxidant package.
- the EP/antiwear activity was determined by evaluations using CRC (Coordination Research Counsel) L-42 gear testing as well as Four Ball testing.
- CRC L-42 Test is referred to in U.S. Patent 4,431,552, and is further identified as ASTM D-2782 modified January 1983. Test data is summarized in Table 1.
- U.S. Patent 3,423,316 A prior art sulfurized olefin prepared in accordance with U.S. Patent 3,703,504, Comparative Example C, was used for comparison with Example 1 of the invention and was evaluated at 3.79% in the identical package and oil blend.
- U.S. Patent 3,703,504 is directed to a process for producing sulfurized olefins comprising sulfohalogenating an olefin with a sulfur halide to form a sulfohalogenated organic intermediate and thereafter sulfurizing and dehalogenating with aaueous alkali metal monosulfide.
- Example 1 in accordance with the invention, significantly outperforms the very similar Comparative Example A and even outperforms the product of Example B, even though Comparative Example B was tested at a much higher concentration.
- Example 1 in accordance with the invention significantly outperforms the very similar Example at 4% concentration. In fact, 2% of Example 1 is almost as good as twice the concentration of Comparative Example C. Also, as can be seen from Table 2, % of Example 1 significantly outperforms Comparative Example A.
- the products of this invention provide exceptional and highly improved extreme pressure/ antiwear activity coupled with improved copper corrosion performance.
- the use of the novel sulfurized additives in premium quality automotive and industrial lubricants provide an unexpected significant combination of improved extreme pressure/antiwear activity and anticorrosion characteristics as well as reduced costs.
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- Organic Chemistry (AREA)
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Abstract
Description
- This invention is directed to sulfurized products which are useful as additives to lubricant compositions, various greases and liquid hydrocarbyl fuels. This invention is particularly directed to a process of preparing these sulfurized products, the products so prepared and lubricating and fuel compositions containing them.
- Sulfurized olefins have been extensively used in many lubricant applications requiring extreme pressure/antiwear activity. It is well known that many methods have been used for producing organic sulfides by treating olefins. It is also well known that many sulfurized organic compositions are useful as lubricant additives. Typically, the prior art processes provide sulfurized products having undesirably high levels of thiones, such as dithiol-thiones, and high levels of thiones in combination with various complex sulfurized mixtures. Typically also these processes, which are expensive and difficult to control, provide products having a highly disagreeable odor.
- This invention relates to a process of preparing sulfurized organic additive products. These products consist essentially of mixtures of polysulfides, oligomers and dithiol-thione type compounds. The additive products are prepared under pressure by the reaction of olefinic compounds with elemental sulfur within a relatively narrow range of temperatures, pressures and ratio of reactants to form products containing sulfur. The additive product is suitable for use in an oil of lubricating viscosity or grease thereof or a liquid hydrocarbyl fuel and is prepared in a process comprising reacting in a suitable reaction zone an olefinic hydrocarbyl compound having at least one olefinic double bond with elemental sulfur in a molar ratio of sulfur to olefin of from 1.9:1 to 2.1:1 under pressures of from 2070 kPa (300 psi) to 6200 kPa (900 psi) at temperatures ranging from 140 to 180°C for a time sufficient and until the reaction pressure drops to 340 kPa (50 psi) to 690 kPa (100 psi) thereby producing a sulfurized additive product containing at least 45 weight percent of sulfur, preferably 45 to 55 weight percent sulfur, and consisting essentially of a major- amount of polysulfides and a minor amount of dithiol-thione type compounds.
- Sulfurized additive products of enhanced extreme pressure/antiwear activity and improved corrosivity are obtained. This invention is also directed to the additive products themselves and to compositions comprising oils of lubricating viscosity or greases prepared therefrom or liquid hydrocarbyl fuels containing the same. The specific and significantly improved discrete compositions produced by the narrowly defined processing conditions disclosed herein provide thermally and oxidatively stable, noncorrosive, low-odor, extreme pressure/antiwear additives for lubricating oils, greases and fuels.
- The invention in a particular aspect is directed to lubricant oil additives prepared in a one step-one pot process comprising reacting in a suitable reaction zone an olefinic hydrocarbyl compound having at least one olefinic double bond with elemental sulfur.
- A wide variety of olefinic substances may be utilized in the process in accordance with the invention. This includes olefins with terminal or internal double bonds and containing from about 2 to 8 or more carbon atoms per molecule in either straight, branched chain or cyclic compounds and these may be exemplified by ethylene, propylene, 1-butene, cis and trans-2-butene, isobutylene, diisobutylene, triisobutylene, pentene, cyclopentene, hexene, cyclohexene, octene, 1-decene, etc. Also useful are diolefins, for example butadiene, isoprene, divinyl benzene, pinene, p-menthene and limonene. In general, C3 to C6 olefins or mixtures thereof are preferred and more preferably butylenes are desirable for preparing the sulfurized products embodied herein because the combined sulfur content of the product decreases with increasing carbon content and the miscibility of the product with oil is lower in the case of propylene and ethylene derivatives.
- In some embodiments of the invention, therefore, isobutylene is particularly preferred as the predominant olefinic reactant, but it may be employed, desirably in major proportions, in mixtures containing one or more other olefins. Moreover, substantial proportions of saturated aliphatic hydrocarbons, as exemplified by methane, ethane, propane, butane, pentane, etc. may be contained in the olefinic feed. Such alkanes are preferably present in minor proportions in most instances to avoid unnecessary dilution of the reaction since they neither react nor remain in the product, but are expelled in the off-gases or by subsequent distillation. However, such mixed feed can substantially improve the economics of the process since such streams are of lower value than a stream of, for example, relatively pure isobutylene.
- Volatile olefins are often readily available in liquid form, and it is usually desirable to utilize olefinic liquids which are vaporized by the heat of reaction, as such evaporation provides a substantial cooling effect that permits the flowing of water for cooling the reactor to be reduced considerably for greater economy. Also, there are indications that the use of a volatile liquid olefin reactant has the unexpected and desirable effect of lowering the viscosity of the final product.
- The specifically narrow molar ratio of sulfur to olefin may range from 1.9:1 to 2.1:1. In the case of butylene, the optimum ratio preferably is from 1.95:1 to 2.05:1. The reaction temperature may range from 140 to 180°C, preferably from 158 to 165°C and most preferably from 159 to 161°C. The preferred temperature is 160°C. The reaction pressure is allowed to seek its own optimum level and may range from 2070 kPa (300 psi) to 6200 kPa (900 psi). The preferred pressures are from 5170 kPa (750 psi) to 5860 kPa (850 psi). A critical aspect of the pressure parameter is the pressure at which the reaction is stopped. Once the reaction begins to seek its own pressure level and is held at a specific temperature most preferably 160°C until the pressure begins to drop. When this occurs the pressure at the reaction temperature must not be allowed to drop out of the range of from 340 kPa (50 psi) to 690 kPa (100 psi). Any conventional means known in the art for accomplishing this may be used.
- The final pressure is indicative of the cited stoichiometry in accordance with the invention whereby the optimum product containing 45 to 61.5 weight % sulfur, preferably 45 to 55 weight % sulfur with no more than 10 to 20 weight % dithiol-thione type compounds based upon total weight of the additive product, is obtained. The weight percent of sulfur to unsaturated olefin is preferably 59 to 61.5 weight percent for a C3 olefin (propylene), 52 to 54.5 weight percent for a C4 olefin (butylene) and 46.5 to 49 weight percent for a Cs olefin (pentane). If the process is higher than about 690 kPa (100 psi), not enough olefin has reacted and if the pressure is lower than about 340 kPa (50 psi), too much olefin has reacted to satisfy the desired stoichiometric relationship of the reactants.
- It has been discovered that only within this narrow range of pressure and stoichiometry (mole ratio) will the resultant product or composition exhibit the improved extreme pressure/antiwear characteristics. Typical reaction time for the novel reactions in accordance with this invention range from 5 to 10 hours. As noted hereinabove, the narrow range of temperatures, pressures and molar ratios of the reactants are critical if products with enhanced antiwear activity and improved corrosivity are to be obtained. Any deviation outside of the above stated ranges produces vastly inferior products. The reaction is carried out in the absence of added H2S.
- The reaction may be catalyzed with a rate accelerating catalyst. Alkylamine catalysts such as n-butylamine, di-n-butylamine, n-octylamine, triethylamine, di-cyclohexylamine and the like are suitable. However, any suitable rate acceleration catalyst known in the art may be used, as for example quiholine and attapulgite acid clay.
- In accordance with the invention, the reaction between the sulfur and the olefinic compound may be conducted in any suitable reaction vessel. The sulfur may be heated to a predetermined temperature in the reaction vessel prior to contacting it with the olefinic reactant, which may be chilled in order to liquify it and get it into the reactor. Once the reaction begins, the olefin is charged to the reaction zone substantially about as rapidly as it is consumed.
- The compositions hereof may comprise any oleaginous materials that require lubricativ6;-peoperties under extreme pressure conditions and require protection against excessive wear under operating conditions, but normally exhibit insufficient anti-corrosion properties. Especially suitable for use with the additives of this invention are liquid hydrocarbon oils of lubricating viscosity. Lubricant oils, improved in accordance with the present invention, may be of any suitable lubricating viscosity. In general, the lubricant compositions may comprise any mineral or synthetic oil of lubricating viscosity or mixtures thereof. The additives of this invention are especially useful in greases and in automotive fluids such as brake fluids and power brake fluids, transmission fluids, power steering fluids, various hydraulic fluids and gear oils and in liquid hydrocarbyl fuels.
- In instances where synthetic oils are desired in preference to refined petroleum or mineral oil they may be employed alone or in combination with a mineral oil. They may also be used as the vehicle or base of grease compositions. Typical synthetic lubricants include polyisobutylene, polybutenes, hydrogenated polydecenes, polypropylene glycol, polyethylene glycol, trimethylol propane esters, neopentyl and pentaerythritol esters of carboxylic acids, di(2-ethylhexyl) sebacate, di(2-ethylhexyl) adipate, dibutyl phthalate, fluorocarbons, silicate esters, silanes, esters of phosphorus-containing acids, liquid ureas, ferrocene derivatives, hydrogenated mineral oils, chain-type polyphenols, siloxanes and silicones (polysifoxanes), alkyl-substituted diphenyl ethers typified by a butyl-substituted bis(p-phenoxy phenyl) ether, phenoxy phenylethers, dialkylbenzenes, etc.
- As hereinbefore indicated, the aforementioned additives can be incorporated as additives in grease compositions. When high temperature stability is not a requirement of the finished grease, mineral oils having a viscosity of at least 40 SSU at 65.6°C (150°F) are useful. Otherwise, those falling within the range of from about 60 SSU to about 6,000 SSU at 37.8°C (100°F) may be employed.
- The lubricating compositions of the improved greases of the present invention, containing the above- described additives, are combined with a grease forming quantity of a thickening agent. For this purpose, a wide variety of materials can be dispersed in the lubricating oil in grease-forming quantities in such degree as to impart to the resulting grease composition the desired consistency. Exemplary of the thickening agents that may be employed in the gease formulation are metal soaps as well as non-soap thickeners, such as surface-modified clays and silicas, aryl ureas, calcium complexes and similar materials. In general, grease thickeners are employed which do not melt or dissolve when used at the required temperature within a particular environment; however, in all other respects, any material which is normally employed for thickening or gelling oleaginous fluids or forming greases may be used in the present invention.
- Generally, the lubricants and fuels of the present invention contain an amount of the sulfurized product effective to improve extreme pressure properties and antiwear and oxidation characteristics. Normally this amount will be 0.01 to 20% and preferably 0.01 to 10% of the total weight of the lubricant.
- The invention also contemplates the use of other additives in combination with the sulfurized olefin product. Such additives include, for example, detergents and dispersants of the ash-producing or ashless type, corrosion-inhibiting agents, auxiliary oxidation-inhibiting agents, pour point depression agents, auxiliary extreme pressure agents, color stabilizers and anti-foam agents.
- The following examples serve to illustrate the present invention, but are not intended as limitations thereon unless otherwise stated.
- This Example was prepared in accordance with the invention using a molar ratio of sulfur to isobutylene of 2.0:1.
- A 1-gallon stirred autoclave (reactor) was charged with 1,344 g sulfur and 1.2 g n-butylamine (0.05% of the total charge). The reactor was sealed and purged three times with nitrogen to remove oxygen. The reactor was then charged with 1,176 g isobutylene under pressure. The reactor agitator was activated and heated to 160°C and held at that temperaturee until the pressure dropped from its maximum of 4830 kPa (700 psi) to below 520 kPa (75 psi). The reactor was cooled to 100°C and vented to a caustic scrubber. The product was then sparged with nitrogen for three hours at 100°C to remove gaseous contaminates, cooled to less than 30°C and then filtered through diatomaceous earth. The product yield was about 99% of the total reactants charged.
- This Example is outside the scope of the invention and was prepared using a molar ratio of sulfur to isobutylene of 1.8:1.
- The procedure for Example 1 was used, but a lower sulfur:isobutylene mole ratio was charged. The charge consisted of: 1,300 sulfur, 1.2 g n-butylamine and 1,264 g isobutylene. Maximum pressure achieved was 5790 kPa (840 psi) with a pressure drop to less than 520 kPa (50 psi). Total reaction time was about eleven hours.
- This Example was prepared using a molar ratio of sulfur to isobutylene of 1.0:1. It accordingly is outside the scope of the invention.
- The procedure for Example 2 was used, but a lower sulfur:isobutylene mole ratio was charged. The charge consisted of: 739 g sulfur, 1.2 g n-butylamine, and 1,249 g isobutylene. The product yield was only 86.5% of reactants charged and minimum pressure did not drop below about 1380 kPa (200 psi), indicating an excess of unreacted olefin which was removed during the venting and sparging steps.
- A prior art sulfurized olefin prepared in accordance with U.S. Patent 3,703,504.
- The products of Example 1, Comparative Example A, and Comparative B were blended into a fully formulated gear lubricant with a standard detergent/antirust/antioxidant package. The EP/antiwear activity was determined by evaluations using CRC (Coordination Research Counsel) L-42 gear testing as well as Four Ball testing. The CRC L-42 Test is referred to in U.S. Patent 4,431,552, and is further identified as ASTM D-2782 modified January 1983. Test data is summarized in Table 1.
- The Four Ball Test is described in U.S. Patent 3,423,316. A prior art sulfurized olefin prepared in accordance with U.S. Patent 3,703,504, Comparative Example C, was used for comparison with Example 1 of the invention and was evaluated at 3.79% in the identical package and oil blend. U.S. Patent 3,703,504 is directed to a process for producing sulfurized olefins comprising sulfohalogenating an olefin with a sulfur halide to form a sulfohalogenated organic intermediate and thereafter sulfurizing and dehalogenating with aaueous alkali metal monosulfide.
-
- As can be seen from Table 2, Example 1 in accordance with the invention significantly outperforms the very similar Example at 4% concentration. In fact, 2% of Example 1 is almost as good as twice the concentration of Comparative Example C. Also, as can be seen from Table 2, % of Example 1 significantly outperforms Comparative Example A.
- The lower the rating the better the performance. The data in Table 3 shows that Example 1 in accordance with the invention is clearly superior to the Comparative Example.
- Clearly, the products of this invention provide exceptional and highly improved extreme pressure/ antiwear activity coupled with improved copper corrosion performance. The use of the novel sulfurized additives in premium quality automotive and industrial lubricants provide an unexpected significant combination of improved extreme pressure/antiwear activity and anticorrosion characteristics as well as reduced costs.
Claims (15)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT86302488T ATE54663T1 (en) | 1985-04-08 | 1986-04-04 | SULFURATED OLEFINS. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US72125185A | 1985-04-08 | 1985-04-08 | |
US721251 | 1985-04-08 |
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EP0201197B1 true EP0201197B1 (en) | 1990-07-18 |
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EP86302488A Expired - Lifetime EP0201197B1 (en) | 1985-04-08 | 1986-04-04 | Sulfurized olefins |
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EP (1) | EP0201197B1 (en) |
JP (1) | JPS61233092A (en) |
AT (1) | ATE54663T1 (en) |
AU (1) | AU578353B2 (en) |
CA (1) | CA1306757C (en) |
DE (1) | DE3672675D1 (en) |
ZA (1) | ZA862362B (en) |
Cited By (1)
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---|---|---|---|---|
US7414013B2 (en) | 2003-01-30 | 2008-08-19 | Chevron Oronite Company Llc | Sulfurized polyisobutylene based wear and oxidation inhibitors |
Families Citing this family (13)
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---|---|---|---|---|
CA2021224A1 (en) * | 1989-08-03 | 1991-02-04 | Scott Anthony Culley | Sulfurized olefin polymers soluble in polyalphaolefin lubricant oils |
FR2712824B1 (en) * | 1993-11-26 | 1996-02-02 | Inst Francais Du Petrole | Catalyst regeneration process. |
EP0714970A1 (en) * | 1994-11-28 | 1996-06-05 | Institut Français du Pétrole | Olefinic hydrocarbons sulfurized with elemental sulfur in the presence of alkali on alkaline earth metal hydroxides and glycols, polyglycols or their alkyl ethers and/or water |
FR2727427B1 (en) * | 1994-11-28 | 1997-04-25 | Inst Francais Du Petrole | ETHYLENIC HYDROCARBONS SULFURATED BY ELEMENTARY SULFUR IN THE PRESENCE OF ALKYLENEGLYCOLS OR DERIVATIVES OF ALKYLENEGLYCOLS AND OF ALKALINE OR ALKALINE EARTH METALS, THEIR PREPARATION AND THEIR USE |
FR2727425A1 (en) * | 1994-11-28 | 1996-05-31 | Inst Francais Du Petrole | New sulphurised organic cpds. |
FR2729154A1 (en) * | 1995-01-10 | 1996-07-12 | Inst Francais Du Petrole | ETHYLENIC HYDROCARBONS SULFURATED BY ELEMENTARY SULFUR IN THE PRESENCE OF ALKALINE CARBONATE OR HYDROGENOCARBONATE, THEIR PREPARATION AND THEIR USES |
US5849677A (en) * | 1995-12-27 | 1998-12-15 | Exxon Chemical Patents Inc | Sulfurized olefin composition and its method of preparation |
FR2808272B1 (en) | 2000-04-28 | 2002-06-14 | Atofina | PROCESS FOR THE MANUFACTURE OF SULFURATED OLEFINS |
FR2808273B1 (en) | 2000-04-28 | 2002-06-14 | Atofina | PROCESS FOR THE MANUFACTURE OF SULFURATED OLEFINS |
JP2016505072A (en) * | 2013-01-29 | 2016-02-18 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | Polysulfide polyol, method for producing and using the same |
WO2016064615A1 (en) * | 2014-10-24 | 2016-04-28 | The University Of Tulsa | Sulfur-limonene polysulfide |
CN104844772B (en) * | 2015-04-28 | 2017-11-10 | 中科院广州化学有限公司 | It is a kind of that there is soluble elemental sulfur/alicyclic olefin copolymer and preparation method thereof |
DE202021002910U1 (en) | 2021-09-08 | 2021-11-26 | Metall-Chemie Technologies Gmbh | Limonene sulfide |
Family Cites Families (9)
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US2237625A (en) * | 1938-10-07 | 1941-04-08 | Sharples Solvents Corp | Sulphurization of sulphur-containing organic conpounds |
US3703504A (en) * | 1970-01-12 | 1972-11-21 | Mobil Oil Corp | Process for producing sulfurized olefins |
US3703505A (en) * | 1970-08-31 | 1972-11-21 | Mobil Oil Corp | Preparation of sulfurized olefins |
US3796661A (en) * | 1971-07-19 | 1974-03-12 | Texaco Inc | Sulfurized triisobutylene |
GB1599288A (en) * | 1977-07-22 | 1981-09-30 | Cooper & Co Ltd Edwin | Sulphurized olefins and their use as lubricant additives |
US4153563A (en) * | 1978-05-24 | 1979-05-08 | Mobil Oil Corporation | Lubricant compositions containing benzotriazole-allyl sulfide reaction products |
JPS5538820A (en) * | 1978-09-09 | 1980-03-18 | Lubrizol Corp | Producing lubricant composition* adding agent concentrate material * and sulfide composition |
US4331564A (en) * | 1980-10-15 | 1982-05-25 | Ferro Corporation | Catalyzing the sulfurization of olefins by tertiary phosphines, and an oil based material containing an additive amount of a sulfurized olefin so produced |
CA1208208A (en) * | 1982-05-07 | 1986-07-22 | Kirk E. Davis | Sulfurized olefin-containing compositions |
-
1986
- 1986-03-27 ZA ZA862362A patent/ZA862362B/en unknown
- 1986-04-03 CA CA000505756A patent/CA1306757C/en not_active Expired - Lifetime
- 1986-04-04 DE DE8686302488T patent/DE3672675D1/en not_active Revoked
- 1986-04-04 AT AT86302488T patent/ATE54663T1/en not_active IP Right Cessation
- 1986-04-04 EP EP86302488A patent/EP0201197B1/en not_active Expired - Lifetime
- 1986-04-04 JP JP61078085A patent/JPS61233092A/en active Pending
- 1986-04-08 AU AU55730/86A patent/AU578353B2/en not_active Ceased
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7414013B2 (en) | 2003-01-30 | 2008-08-19 | Chevron Oronite Company Llc | Sulfurized polyisobutylene based wear and oxidation inhibitors |
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AU578353B2 (en) | 1988-10-20 |
DE3672675D1 (en) | 1990-08-23 |
ZA862362B (en) | 1987-11-25 |
JPS61233092A (en) | 1986-10-17 |
EP0201197A1 (en) | 1986-11-12 |
AU5573086A (en) | 1986-10-16 |
ATE54663T1 (en) | 1990-08-15 |
CA1306757C (en) | 1992-08-25 |
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