US3210279A - Thiophosphonate ester dispersants for lubricating oils - Google Patents
Thiophosphonate ester dispersants for lubricating oils Download PDFInfo
- Publication number
- US3210279A US3210279A US189971A US18997162A US3210279A US 3210279 A US3210279 A US 3210279A US 189971 A US189971 A US 189971A US 18997162 A US18997162 A US 18997162A US 3210279 A US3210279 A US 3210279A
- Authority
- US
- United States
- Prior art keywords
- lubricating oil
- phosphosulfurized
- ester
- range
- reaction
- 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
- 239000010687 lubricating oil Substances 0.000 title claims description 27
- 150000002148 esters Chemical class 0.000 title description 20
- 239000002270 dispersing agent Substances 0.000 title description 12
- 239000000203 mixture Substances 0.000 claims description 40
- -1 HYDROXYL GROUP Chemical group 0.000 claims description 26
- 229920000098 polyolefin Polymers 0.000 claims description 18
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 17
- 239000007795 chemical reaction product Substances 0.000 claims description 13
- 239000004327 boric acid Substances 0.000 claims description 12
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 10
- 239000000194 fatty acid Substances 0.000 claims description 10
- 229930195729 fatty acid Natural products 0.000 claims description 10
- 150000004665 fatty acids Chemical class 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 239000003599 detergent Substances 0.000 description 22
- 239000003921 oil Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- 150000005846 sugar alcohols Chemical class 0.000 description 17
- 239000000654 additive Substances 0.000 description 16
- 229960002645 boric acid Drugs 0.000 description 16
- 235000010338 boric acid Nutrition 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 229930195733 hydrocarbon Natural products 0.000 description 13
- 150000002430 hydrocarbons Chemical class 0.000 description 13
- 239000010802 sludge Substances 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 229920002367 Polyisobutene Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000001593 sorbitan monooleate Substances 0.000 description 6
- 235000011069 sorbitan monooleate Nutrition 0.000 description 6
- 229940035049 sorbitan monooleate Drugs 0.000 description 6
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 5
- 239000004147 Sorbitan trioleate Substances 0.000 description 5
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 235000019337 sorbitan trioleate Nutrition 0.000 description 5
- 229960000391 sorbitan trioleate Drugs 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229930195725 Mannitol Natural products 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000594 mannitol Substances 0.000 description 4
- 235000010355 mannitol Nutrition 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 235000008504 concentrate Nutrition 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical class [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 description 3
- 239000010688 mineral lubricating oil Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 150000003871 sulfonates Chemical class 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 2
- LJKQIQSBHFNMDV-UHFFFAOYSA-N 7-thiabicyclo[4.1.0]hepta-2,4-dien-6-ol Chemical class C1=CC=CC2(O)C1S2 LJKQIQSBHFNMDV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 229940077388 benzenesulfonate Drugs 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- GOHYJHLGLUVFQB-UHFFFAOYSA-N 1-nonyl-7-thiabicyclo[4.1.0]hepta-2,4-dien-6-ol Chemical compound C1=CC=CC2(CCCCCCCCC)C1(O)S2 GOHYJHLGLUVFQB-UHFFFAOYSA-N 0.000 description 1
- URRHKOYTHDCSDA-UHFFFAOYSA-N 2,5,8,11-tetramethyldodec-2-ene Chemical group CC(C)CCC(C)CCC(C)CC=C(C)C URRHKOYTHDCSDA-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- SPBWHPXCWJLQRU-FITJORAGSA-N 4-amino-8-[(2r,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]-5-oxopyrido[2,3-d]pyrimidine-6-carboxamide Chemical compound C12=NC=NC(N)=C2C(=O)C(C(=O)N)=CN1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1O SPBWHPXCWJLQRU-FITJORAGSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- VKCLPVFDVVKEKU-UHFFFAOYSA-N S=[P] Chemical compound S=[P] VKCLPVFDVVKEKU-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 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
- 239000006185 dispersion Substances 0.000 description 1
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- FBPFZTCFMRRESA-GUCUJZIJSA-N galactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-GUCUJZIJSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229940059904 light mineral oil Drugs 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 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
- 230000003389 potentiating effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- 239000010723 turbine oil Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/04—Reaction products of phosphorus sulfur compounds with hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
-
- 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
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/123—Reaction products obtained by phosphorus or phosphorus-containing compounds, e.g. P x S x with organic compounds
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
-
- 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/024—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings having at least two phenol groups but no condensed ring
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/027—Neutral salts thereof
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/32—Esters of carbonic acid
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/086—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/11—Complex polyesters
- C10M2209/111—Complex polyesters having dicarboxylic acid centres
-
- 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
- C10M2215/065—Phenyl-Naphthyl amines
-
- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/028—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
-
- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
-
- 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
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
-
- 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
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
-
- 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
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
-
- 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
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
- C10M2219/088—Neutral salts
-
- 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
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
- C10M2219/089—Overbased salts
-
- 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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
- C10M2223/065—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds containing sulfur
-
- 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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/12—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of organic compounds, e.g. with PxSy, PxSyHal or PxOy
-
- 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
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2225/04—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
- C10M2225/041—Hydrocarbon polymers
-
- 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
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/061—Esters derived from boron
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/06—Groups 3 or 13
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/08—Groups 4 or 14
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/14—Group 7
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/135—Steam engines or turbines
Definitions
- This invention concerns novel ashless detergents and detergents of low ash content and improved lubricating oil compositions containing them. These compositions are especially effective as crankcase lubricants for automotive gasoline engines.
- the ashless detergent additives of the invention are prepared by esterifying sugar alcohols with fatty acids and then reacting the esters with phosphosulfurized hydrocarbons.
- the detergents of low ash content are prepared by further reacting the additives with boric acid.
- particularly effective ashless dispersing agents or detergents for crankcase lubricants can be prepared by esterifying sugar alcohols with aliphatic acids and then reacting the esters with phosphosulfurized hydrocarbons. These additives can be further modified by reaction with boric acid to prepare additives of very low ash content.
- the sugar alcohols are hexahydric alcohols which are well known in the art. They can be prepared by reducing mono saccharides or di saccharides. The sugar alcohols also occur in nature. The most common sugar alcohols are sorbitol, mannitol and dulcitol. Also contemplated for use in this invention are the partially dehydrated sugar alcohols such as sorbitan and other hexitans.
- sugar alcohol can first be dehydrated to a hexitan by conventional methods, and the latter then used to esterify the fatty acid.
- the conversion of the sugar alcohol to an ester of a fatty acid is conducted by the usual esterification techniques.
- a mono, di, or tri ester may be formed, as for example mannitol trilaurate, sorbitol distearate, sorbitan mono oleate, etc.
- Fatty acids in the range of from 6 to 20 carbon atoms may be used. Suitable acids include caproic, caprylic, undecylic, lauric, myristic, oleic, stearic, and linoleic.
- the sugar alcohol ester is then further reacted with a dialkenyl thiophosphonic acid.
- the latter acids are prepared by treating polyolefins with P 8 Polymers of ethylene, propylene or butylene may be used.
- the olefin polymers have Staudinger molecular weights in the range of from about 500 to about 200,000 and contain from 2 to 6 carbon atoms per olefin monomer.
- the phosphosulfurized polyolefin is prepared by reacting the polyolefin with from 5 to 30 Weight percent of a sulfide of phosphorus, and preferably with 10 to 20 weight percent of phosphorus pentasulfide.
- the phosphosulfurization reaction is conducted under anhydrous conditions at temperatures in the range of to about 600 F. for from about /2 to 15 hours. It is advisable to treat or blow the phosphosulfurized product with an inert gas such as nitrogen for a period of from 10 minutes to 2 hours to aid in reducing hydrogen sulfide evolution and its corresponding odor.
- an inert gas such as nitrogen
- the reaction of the sugar alcohol ester and the phos phosulfurized polyolefin is preferably conducted at temperatures in the range of about 200 to 240 F. using reaction times of about 9 to 15 hours.
- Mole ratios of phosphosulfurized polyolefin to sugar alcohol ester may range from about 1:2 to about 3:1. The preferred ratio is about 1:1.
- the products of the reaction of the sugar alcohol esters with the phosphosulfurized polyolefins may be employed in weight concentrations of from about 0.2 to 5 percent in lubricating oils to impart detergency sludge dispersancy and antioxidant properties. Greater dispersant potency and potency life may be obtained by further converting these materials to the borate esters. This may be done by heating the products with equivalent weights of boric acid (preferably orthoboric acid) in the presence of a refluxing Water-entraining agent such as hexane, xylene, benzene, or toluene until about one equivalent or mole of water produced by esterification is removed.
- a refluxing Water-entraining agent such as hexane, xylene, benzene, or toluene until about one equivalent or mole of water produced by esterification is removed.
- orthoboric acid is used there will actually be 2 moles of water formed, one resulting from dehydration of the acid to metaboric acid, and the second resulting from the esterification reaction.
- the final products obtained may be added in weight concentrations of from 0.5 to 5 percent to lubricating oil compositions to impart antioxidant and sludge dispersing properties.
- Reaction temperatures in the boric acid esterification step are preferably in the range of about 150 to 275 F. Reaction times may vary in the range of about 2 to 20 hours, lower temperatures requiring relatively longer reaction times than higher temperatures.
- the additives of this invention may be used not only as the sole detergents in a lubricating oil composition, wherein they function as low-temperature-sludge dispersants and as antioxidants, but they may also be employed as boosters for conventional detergents, wherein the latter are used in concentrations in the range of about 0.5 to 5 weight percent.
- the conventional detergents are metals-containing materials it is possible, by utilizing the additives of the present invention in combination therewith, to obtain added detergency without materially increasing the total ash-forming properties of the composition.
- Such metals-containing detergents or combination detergent-inhibitors include the alkaline earth metal salts of alkylated phenols or of alkylated phenol sulfides, as for example nonyl phenol sulfide, the so-called basic alkaline earth metal sulfonates, and dispersions of barium carbonate or calcium carbonate in mineral oils containing various surfactants such as phosphosulfurized polyoleiin, for example.
- the sulfonates are well known in the art and are the oil-soluble alkaline earth metal salts of high molecular weight sulfonic acids obtained by sulfonating either natural or synthetic hydrocarbons.
- Suitable sulfonates include calcium petroleum sulfonate, barium petroleum sulfonate, calcium di-C alkyl benzene sulfonate (C group from tripropylene), and barium C alkyl benzene sulfonate (C group from tetraisobutylene).
- the sulfonates may be of either the neutral type or of the over-based or high alkalinity type, containing metal base in excess of that required for simple neutralization, wherein the excess metal base has been neutralized with carbon dioxide.
- Metal salts of alkyl phenols and of alkyl phenol sulfides are also Well known in the art. Metal salts of alkyl phenols having alkyl groups of from 5 to 20 carbon atoms are usually preferred, and the metal used to form the phenate is preferably an alkaline earth metal, e.g., calcium or barium although the salts such as those of aluminum, cobalt, lead or tin are sometimes used. A specific example is the barium salt of the alkylation prodnot of phenol with tripropylene. Metal salts of the corresponding alkyl phenol sulfides may also be used. The latter are the thioethers and polysulfides of alkyl phenols, i.e.
- alkyl phenols can be converted to phenol sulfides by reaction with sulfur dichloride. If sulfur monochloride is used, the resulting products are primarily alkyl phenol disulfides.
- detergent additives include the reaction products of phosphosulfurized hydrocarbons with alkaline earth metal oxides or hydroxides can be prepared by first treating a hydrocarbon with the phosphorus sulfide and then reacting the product with an alkaline earth hydroxide or oxide, for example barium hydroxide, preferably in the presence of an alkyl phenol or an alkyl phenol sulfide and also preferably in the presence of carbon dioxide.
- an alkaline earth hydroxide or oxide for example barium hydroxide
- the dispersants of this invention may also be used in conjunction with ashless detergents such as high molecular weight polymeric dispersants made with one or more polar monomers, such as vinyl acetate, vinyl pyrrolidone, methacrylates, fumarates and maleates. These dispersants have molecular weights in the range of about 500 to 50,000.
- One example is a copolymer of 65 to 85 weight percent of mixed C C fumarates, to 20 weight percent of vinyl acetate, and 5 to 15 percent of N-vinyl pyrrolidone.
- Another example is the copolymer derived by reaction of mixed tallow fumarates and C serve to illustrate this EXAMPLE 1
- a phosphosulfurized hydrocarbon was prepared by reacting parts by weight of a polyisobutene having an average Staudinger molecular weight of about 830 with 15 parts by weight of P 8 for about 10 hours at about 450 F. The product was then diluted with 30 weight percent of light mineral oil for ease of handling. The 70 weight percent concentrate analyzed 2.45 weight percent phosphorus and 4.24 weight per cent sulfur.
- the hydrogen sulfide that was evolved during the react1on was trapped in an ammoniacal solution of cadmium chloride. From the weight of cadmium sulfide that was precipitated it was determined that the reaction product was largely the oxygen ester, or thionophosphate, of sorbitan trioleate.
- the reaction may be envisaged by the following equation:
- the incremental addition of orthoboric acid was necessary to avoid excessive foaming.
- the mixture was refluxed for a total of about 3 hours, the stopping point being determined by the lack of additional water being riven off. In this instance the total amount of water collected was 31.5 ml.
- the mixture was filtered hot, after which the solvent was removed from the filtrate under vacuum, giving approximately 1600 grams of product in the form of a thick viscous brown syrupy liquid.
- the borate had the following analysis:
- Example 5 In the manner of Example 3, the product of Example 4 is further reacted with orthoboric acid on an equimolar basis in the presence of xylene as the refluxing waterentraining agent.
- Example 6 The materal of Example 2 was compared with a commercially available detergent inhibitor in a soluble sludge dispersancy test. The test was conducted as follows. A mixture is prepared consisting of ml. of a neutral mineral lubricating oil of 150 SSU viscosity at 100 F. (in which the additive to be tested is incorporated), 10 ml. of a petroleum naphtha (boiling range 3t)0400 E), and ml. of a solution of crankcase sludge in chloroform (prepared in the ratio of 87 grams of sludge to 1275 grams of CHCl The mixture is placed in a crystallizing dish and evaporated on the steam bath for one hour.
- the mixture is centrifuged and 5 ml. of the supernatant liquid is dissolved in 35 ml. of the petroleum naphtha and filtered through a regular grade of laboratory filter paper.
- the light transmission of the filtrate is then measured and compared With a standard consisting of 10 ml. of the neutral mineral oil and 10 ml. of the petroleum naphtha. Light transmission may be meaured by a standard instrument such as the Lumetron photoelectric colorimeter.
- EXAMPLE 7 The product of Example 2 was employed as a booster detergent in a low temperature engine test, in which conditions were intended to simulate stop-and-go driving. A six-cylinder Ford engine was used, charged with 4 quarts of the oil under test, and run for atotal of 242 hours, under the conditions given in Table II, the cycles being repeated until the end of the test.
- the engine was inspected by removing the oil pan, the rocker arm cover, and the push rod chamber cover, and various parts including the oil screen, the oil pan, the crankshaft, the push rod chamber, the push rod chamber cover, the rocker arm cover, and the rocker arm assembly, were rated for sludge deposition, using a merit system in which 10 represents a clean part and zero a part covered with the maximum amount of sludge possible.
- test oil was an SAE- lubricating oil containing 3.5 weight percent of a commercial detergent inhibitor and 0.5 weight percent of the sorbitan trioleate-phosphosulfurized hydrocarbon product of Example 2.
- the test results obtained are shown in Table III.
- EXAMPLE 10 In the prior art it was known to react phosphosulfurizcd polyisobutene with other reagents, e.g. amines. For a direct comparison with the compositions of the present invention, a sample of the phosphosulfurized polyisobutene of Example 1 was reacted with an equimolar proportion of a high-molecular-weight amine known as Primene 8lR, and the product was added in 0.5% concentration, in place of the product of Example 2, to the same SAE-20 lubricating oil containing 3.5 wt. percent commercial detergent inhibitor as was tested with results shown in Table III. The results of the engine test on the oil containing 0.5% of the above-described amine-treated phosphosulfurized polyisobutene are given in Table VI.
- Primene 8lR a high-molecular-weight amine known as Primene 8lR
- the lubricating oil base stocks to which the dispersant additives of this invention may be added include not only mineral lubricating oils but various synthetic oils.
- the mineral lubricating oils may be of any preferred type including those derived from the ordinary parafiinic, naph thenic, asphaltic or mixed base mineral crude oils by suitable refining methods. Synthetic hydrocarbon lubricating oils may also be employed.
- Other synthetic oils include dibasic acid esters such as di-2-ethyl hexyl sebacate, carbonate esters, glycol esters such as C oxo acid diesters of tetraethylene glycol, and complex esters as for example the complex ester formed by the reaction of 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethyl hexanoic acid.
- additives of this invention are primarily intended for use in lubricating oils designed for automotive crankcases, they may also be employed in other hydrocarbon oil compositions including turbine oils, various industrial oils, hydraulic fluids, transmission fluids and the like.
- the oil compositions of the invention may also contain, in addition to the detergent, such additives as viscosity index improvers, e.g. polymethacrylates, olefin polymers, etc., antioxidants such as phenyl-alpha-amine, bis phenols, etc., pour point depressants, dyes, and other additives for improving the properties of the compositions.
- viscosity index improvers e.g. polymethacrylates, olefin polymers, etc.
- antioxidants such as phenyl-alpha-amine, bis phenols, etc.
- pour point depressants e.g., phenyl-alpha-amine, bis phenols, etc.
- An improved lubricating oil composition comprising a lubricating oil to which has been added from 0.2 to 5.0 weight percent of the reaction product of (a) a phosphosulfurized polyolefin and (b) an ester of a fatty acid of from 6 to 20 carbon atoms and a sugar alcohol selected from the group consisting of hexitols, hexitans, and hexides; wherein said polyolefin has a molecular weight in the range of from about 500 to about 200,000 and is derived from an olefin monomer having from 2 to 6 carbon atoms; said (a) and (b) being reacted in a mole ratio of (a):(b) in the range of from about 1:2 to about 3:1.
- composition of matter as defined by claim 6 wherein said ester comprises sorbitan mono-oleate.
- a process for the preparation of a new composition of matter which comprises reacting about equal molar proportions of (a) a phosphosulfurized polyolefin and (b) an ester of a fatty acid of from 6 to 20 carbon atoms and a sugar alcohol selected from the group consisting of hexitols, hexitans, and hexides; wherein said polyolefin has a molecular weight in the range of about 500 to about 200,000 and is derived from an olefin monomer having from 2 to 6 carbon atoms; the reaction being carried out at a temperature of about 200 to 240 F. for a time of about 9 to 15 hours.
- An improved lubricating oil composition comprising a lubricating oil to which has been added from 0.2 to 5.0 weight percent of the composition of claim ll.
- a process for the preparation of a new composition of matter which comprises (1) reacting (a) a phosphosulfurized polyolefin and (b) an ester of a fatty acid of from 6 to 20 carbonatoms and a sugar alcohol selected from the group consisting of hexitols, hexitans, and hexides; wherein said polyolefin has a molecular weight in the range of about 500 to about 200,000 and is derived from an olefin monomer having from 2 to 6 carbon atoms; the reaction being carried out at a temperature of about 200 to 240 F.
- reaction product has at least one free hydroxyl group; (2) reacting about equal molar proportions of said reaction product and boric acid; the reaction being carried out at a temperature about 150 to 275 F. for a time of about 2 to 20 hours.
- An improved lubricating oil composition comprising a lubricating oil to which has been added from 0.2 to 5.0 weight percent of the composition of claim 14.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
Description
United States Patent 3,210,279 THIOPHOSPHONATE ESTER DISPERSANTS FOR LUBRICA'IING OILS Joel R. Siegel, Elizabeth, N.J., assignor to Esso Research and Engineering Company, a corporation of Delaware No Drawing. Filed Apr. 25, 1962, Ser. No. 189,971 16 Claims. (Cl. 252-463) This invention concerns novel ashless detergents and detergents of low ash content and improved lubricating oil compositions containing them. These compositions are especially effective as crankcase lubricants for automotive gasoline engines. The ashless detergent additives of the invention are prepared by esterifying sugar alcohols with fatty acids and then reacting the esters with phosphosulfurized hydrocarbons. The detergents of low ash content are prepared by further reacting the additives with boric acid.
In the development of compounded lubricants to meet the demands of modern internal combustion engines, there has been a recognized need for crankcase lubricants that will have high detergency and that will at the same time possess satisfactory resistance to oxidation. Lubricating oils having high detergency and good oxidation resistance serve to keep the engine free of varnish, sludge and cokelike deposits and thereby promote longer engine life through reduced wear. In order that heavy duty detergent-type lubricating oils will have the ability to maintain a high degree of engine cleanliness, they must be able to disperse insoluble material that is formed during the operation of the engine either by combustion of the fuel or by oxidation of the lubricating oil or that is derived from both of these sources. Most of the detergents, dispersants and antioxidants that are in use in lubricants for heavy duty service in internal combustion engines are metallic derivatives such as alkaline earth metal sulfonates, alkaline earth metal alkyl phenol sulfides, colloidal dispersions of metallic carbonates and the like. Although such additives function quite well as sludge dispersants and detergents, they have one disadvantage in that the ash residue from the lubricant tends to accumulate in the combustion chamber of the engine where it causes pre-ignition, spark plug fouling, valve burning and similar undesirable conditions. For this reason there is a need for effective sludge dispersants and detergents that will either be ash-free or will at least be relatively low in ash-forming tendencies.
In accordance with the present invention it has been found that particularly effective ashless dispersing agents or detergents for crankcase lubricants can be prepared by esterifying sugar alcohols with aliphatic acids and then reacting the esters with phosphosulfurized hydrocarbons. These additives can be further modified by reaction with boric acid to prepare additives of very low ash content.
The sugar alcohols are hexahydric alcohols which are well known in the art. They can be prepared by reducing mono saccharides or di saccharides. The sugar alcohols also occur in nature. The most common sugar alcohols are sorbitol, mannitol and dulcitol. Also contemplated for use in this invention are the partially dehydrated sugar alcohols such as sorbitan and other hexitans. Even if one starts with sugar alcohols that have not been partially dehydrated, some dehydration can and possibly does occur during ester-ification, so that at least a portion of the product of the sugar alcohol esterification would be a hexitan ester (through the loss of one mole of water) or even a hexide ester (through the loss of two moles of water). Alternatively, the sugar alcohol can first be dehydrated to a hexitan by conventional methods, and the latter then used to esterify the fatty acid.
The conversion of the sugar alcohol to an ester of a fatty acid is conducted by the usual esterification techniques. Depending on the molar proportions of the sugar alcohol or partially dehydrated sugar alcohol and the fatty acid, a mono, di, or tri ester may be formed, as for example mannitol trilaurate, sorbitol distearate, sorbitan mono oleate, etc. Fatty acids in the range of from 6 to 20 carbon atoms may be used. Suitable acids include caproic, caprylic, undecylic, lauric, myristic, oleic, stearic, and linoleic.
The sugar alcohol ester is then further reacted with a dialkenyl thiophosphonic acid. The latter acids are prepared by treating polyolefins with P 8 Polymers of ethylene, propylene or butylene may be used. The olefin polymers have Staudinger molecular weights in the range of from about 500 to about 200,000 and contain from 2 to 6 carbon atoms per olefin monomer. Preferably, the phosphosulfurized polyolefin is prepared by reacting the polyolefin with from 5 to 30 Weight percent of a sulfide of phosphorus, and preferably with 10 to 20 weight percent of phosphorus pentasulfide. The phosphosulfurization reaction is conducted under anhydrous conditions at temperatures in the range of to about 600 F. for from about /2 to 15 hours. It is advisable to treat or blow the phosphosulfurized product with an inert gas such as nitrogen for a period of from 10 minutes to 2 hours to aid in reducing hydrogen sulfide evolution and its corresponding odor. The preparation of phosphosulfurized hydrocarbons and the use of catalysts in the phosphosulfurization reaction are more fully described in U.S. Patent 2,875,188.
The reaction of the sugar alcohol ester and the phos phosulfurized polyolefin is preferably conducted at temperatures in the range of about 200 to 240 F. using reaction times of about 9 to 15 hours. Mole ratios of phosphosulfurized polyolefin to sugar alcohol ester may range from about 1:2 to about 3:1. The preferred ratio is about 1:1.
The products of the reaction of the sugar alcohol esters with the phosphosulfurized polyolefins may be employed in weight concentrations of from about 0.2 to 5 percent in lubricating oils to impart detergency sludge dispersancy and antioxidant properties. Greater dispersant potency and potency life may be obtained by further converting these materials to the borate esters. This may be done by heating the products with equivalent weights of boric acid (preferably orthoboric acid) in the presence of a refluxing Water-entraining agent such as hexane, xylene, benzene, or toluene until about one equivalent or mole of water produced by esterification is removed. If orthoboric acid is used there will actually be 2 moles of water formed, one resulting from dehydration of the acid to metaboric acid, and the second resulting from the esterification reaction. The final products obtained may be added in weight concentrations of from 0.5 to 5 percent to lubricating oil compositions to impart antioxidant and sludge dispersing properties.
While, as indicated, it is preferred that the further reaction of the reaction products of phosphosulfurized hydrocarbons and sugar alcohol esters with boric acid be conducted on a mole-per-mole basis, other ratios Within the range of 1:3 to 3.1, ester product to boric acid, are within the contemplation of the invention. In any case there must be available at least one free hydroxyl group in the ester-phosphosulfurized-hydrocarbon product to react with the boric acid. Thus when further reaction with boric acid is contemplated it may be preferable to start with a mono or diester of a sugar alcohol, such as sorbitan mono-oleate or manitol distearate, for
example. Reaction temperatures in the boric acid esterification step are preferably in the range of about 150 to 275 F. Reaction times may vary in the range of about 2 to 20 hours, lower temperatures requiring relatively longer reaction times than higher temperatures.
The additives of this invention may be used not only as the sole detergents in a lubricating oil composition, wherein they function as low-temperature-sludge dispersants and as antioxidants, but they may also be employed as boosters for conventional detergents, wherein the latter are used in concentrations in the range of about 0.5 to 5 weight percent. When the conventional detergents are metals-containing materials it is possible, by utilizing the additives of the present invention in combination therewith, to obtain added detergency without materially increasing the total ash-forming properties of the composition. Such metals-containing detergents or combination detergent-inhibitors include the alkaline earth metal salts of alkylated phenols or of alkylated phenol sulfides, as for example nonyl phenol sulfide, the so-called basic alkaline earth metal sulfonates, and dispersions of barium carbonate or calcium carbonate in mineral oils containing various surfactants such as phosphosulfurized polyoleiin, for example.
The sulfonates are well known in the art and are the oil-soluble alkaline earth metal salts of high molecular weight sulfonic acids obtained by sulfonating either natural or synthetic hydrocarbons.
Specific examples of suitable sulfonates include calcium petroleum sulfonate, barium petroleum sulfonate, calcium di-C alkyl benzene sulfonate (C group from tripropylene), and barium C alkyl benzene sulfonate (C group from tetraisobutylene). The sulfonates may be of either the neutral type or of the over-based or high alkalinity type, containing metal base in excess of that required for simple neutralization, wherein the excess metal base has been neutralized with carbon dioxide.
Metal salts of alkyl phenols and of alkyl phenol sulfides are also Well known in the art. Metal salts of alkyl phenols having alkyl groups of from 5 to 20 carbon atoms are usually preferred, and the metal used to form the phenate is preferably an alkaline earth metal, e.g., calcium or barium although the salts such as those of aluminum, cobalt, lead or tin are sometimes used. A specific example is the barium salt of the alkylation prodnot of phenol with tripropylene. Metal salts of the corresponding alkyl phenol sulfides may also be used. The latter are the thioethers and polysulfides of alkyl phenols, i.e. compounds in which the alkyl groups are joined by one or more divalent sulfur atoms. The alkyl phenols can be converted to phenol sulfides by reaction with sulfur dichloride. If sulfur monochloride is used, the resulting products are primarily alkyl phenol disulfides.
Other detergent additives include the reaction products of phosphosulfurized hydrocarbons with alkaline earth metal oxides or hydroxides can be prepared by first treating a hydrocarbon with the phosphorus sulfide and then reacting the product with an alkaline earth hydroxide or oxide, for example barium hydroxide, preferably in the presence of an alkyl phenol or an alkyl phenol sulfide and also preferably in the presence of carbon dioxide. The preparation of phosphosulfurized hydrocarbons has been described above.
The dispersants of this invention may also be used in conjunction with ashless detergents such as high molecular weight polymeric dispersants made with one or more polar monomers, such as vinyl acetate, vinyl pyrrolidone, methacrylates, fumarates and maleates. These dispersants have molecular weights in the range of about 500 to 50,000. One example is a copolymer of 65 to 85 weight percent of mixed C C fumarates, to 20 weight percent of vinyl acetate, and 5 to 15 percent of N-vinyl pyrrolidone. Another example is the copolymer derived by reaction of mixed tallow fumarates and C serve to illustrate this EXAMPLE 1 A phosphosulfurized hydrocarbon was prepared by reacting parts by weight of a polyisobutene having an average Staudinger molecular weight of about 830 with 15 parts by weight of P 8 for about 10 hours at about 450 F. The product was then diluted with 30 weight percent of light mineral oil for ease of handling. The 70 weight percent concentrate analyzed 2.45 weight percent phosphorus and 4.24 weight per cent sulfur.
EXAMPLE 2 A mixture of 1320 grams of the 70 weight percent con centrate of phosphosulfurized polybutene of Example 1 and 979 grams of sorbitan trioleate, which was obtained as a commercial product, was stirred and heated at about 240 F. for 12 hours using a purge stream of nitrogen. The syrup-like product had the following inspections:
Gravity, API -1 19.1 Viscosity at 210 F., centistokes 57.1 Viscosity at 100 F., centistokes 978 Phosphorus, wt. percent 1.47 Sulfur, wt. percent 2.48
The hydrogen sulfide that was evolved during the react1on was trapped in an ammoniacal solution of cadmium chloride. From the weight of cadmium sulfide that was precipitated it was determined that the reaction product was largely the oxygen ester, or thionophosphate, of sorbitan trioleate. The reaction may be envisaged by the following equation:
R=polyisobutene component R'=sorbitan trioleate component EXAMPLE 3 In the manner of Example 2, a mixture of 1321 grams of the 70 weight percent concentrate of phosphosulfurized hydrocarbon of Example 1 and 429 grams of sorbitan mono-oleate, purchased commercially, was reacted for 12 hours at 240 F. To an appropriately sized, roundbottom, four-necked flask equipped with a thermometer, stirrer, condenser and water trap, 1749 grams of the above product, containing 400 grams of oil, was added, followed by 250 ml. of toluene. Then, over a period of about one hour, 61.8 grams of orthoboric acid was added in increments to the stirred refluxing mixture. The incremental addition of orthoboric acid was necessary to avoid excessive foaming. The mixture was refluxed for a total of about 3 hours, the stopping point being determined by the lack of additional water being riven off. In this instance the total amount of water collected was 31.5 ml. The mixture was filtered hot, after which the solvent was removed from the filtrate under vacuum, giving approximately 1600 grams of product in the form of a thick viscous brown syrupy liquid. The borate had the following analysis:
Wt. percent Phosphorus 1.80 Boron 0.53 Sulfur 2.75 Active ingredient 79.5
EXAMPLE 4 In the manner of Example 2, phosphosulfurized polybutene is reacted with mannitol distearate on an equimolar basis at 230 F. for 14 hours.
EXAMPLE 5 In the manner of Example 3, the product of Example 4 is further reacted with orthoboric acid on an equimolar basis in the presence of xylene as the refluxing waterentraining agent.
EXAMPLE 6 The materal of Example 2 was compared with a commercially available detergent inhibitor in a soluble sludge dispersancy test. The test was conducted as follows. A mixture is prepared consisting of ml. of a neutral mineral lubricating oil of 150 SSU viscosity at 100 F. (in which the additive to be tested is incorporated), 10 ml. of a petroleum naphtha (boiling range 3t)0400 E), and ml. of a solution of crankcase sludge in chloroform (prepared in the ratio of 87 grams of sludge to 1275 grams of CHCl The mixture is placed in a crystallizing dish and evaporated on the steam bath for one hour. Then the mixture is centrifuged and 5 ml. of the supernatant liquid is dissolved in 35 ml. of the petroleum naphtha and filtered through a regular grade of laboratory filter paper. The light transmission of the filtrate is then measured and compared With a standard consisting of 10 ml. of the neutral mineral oil and 10 ml. of the petroleum naphtha. Light transmission may be meaured by a standard instrument such as the Lumetron photoelectric colorimeter.
The results of the tests are shown in Table I as percent of light transmission. The lower the value in the table, the more sludge is dispersed and hence the more potent the additive is.
Table I .Results of sludge dispersancy test Wt. Percent Percent Detergent-Inhibitor Used Cone. Light Transmission 3. 5 10 Product of Example 2 0. 5 5
Percent Phosphosulfurized polyisobutene 27.0 Alkyl phenol (248 average molecular weight) 11.7 Barium oxide 10.6 Carbon dioxide 2.5 Mineral Oil 48.2
EXAMPLE 7 The product of Example 2 was employed as a booster detergent in a low temperature engine test, in which conditions were intended to simulate stop-and-go driving. A six-cylinder Ford engine was used, charged with 4 quarts of the oil under test, and run for atotal of 242 hours, under the conditions given in Table II, the cycles being repeated until the end of the test.
At the end of the first 66 hours, and every 44 hours thereafter, the engine was inspected by removing the oil pan, the rocker arm cover, and the push rod chamber cover, and various parts including the oil screen, the oil pan, the crankshaft, the push rod chamber, the push rod chamber cover, the rocker arm cover, and the rocker arm assembly, were rated for sludge deposition, using a merit system in which 10 represents a clean part and zero a part covered with the maximum amount of sludge possible.
The test oil was an SAE- lubricating oil containing 3.5 weight percent of a commercial detergent inhibitor and 0.5 weight percent of the sorbitan trioleate-phosphosulfurized hydrocarbon product of Example 2. The test results obtained are shown in Table III.
Table 111 Hours on Test Percent Oil Screen Merit Rating Plugging EXAMPLE 8 in Table IV. It will be seen that the latter additive was more effective than the additive of Example 2.
Table IV Hours on Test Percent Oil Screen Merit Rating Plugging EXAMPLE 9 Table v.
Table V Hours on Test Percent Oil Screen Merit Rating Plugging The lubricating oil containing 0.5% of the booster detergent of Example 2 gave 17% higher merit rating than the commercial, premium grade motor oil after 198 hours of test.
EXAMPLE 10 In the prior art it was known to react phosphosulfurizcd polyisobutene with other reagents, e.g. amines. For a direct comparison with the compositions of the present invention, a sample of the phosphosulfurized polyisobutene of Example 1 was reacted with an equimolar proportion of a high-molecular-weight amine known as Primene 8lR, and the product was added in 0.5% concentration, in place of the product of Example 2, to the same SAE-20 lubricating oil containing 3.5 wt. percent commercial detergent inhibitor as was tested with results shown in Table III. The results of the engine test on the oil containing 0.5% of the above-described amine-treated phosphosulfurized polyisobutene are given in Table VI.
At the end of the test the merit rating with this oil was 14% lower than was shown with the oil containing the composition of the present invention. The significance of the difference of 14% is remarkable because only 0.5% of the booster detergent was used in each oil and the only difference between the two booster detergents was in the finishing treatment of the phosphosulfurized polyisobutene.
The lubricating oil base stocks to which the dispersant additives of this invention may be added include not only mineral lubricating oils but various synthetic oils. The mineral lubricating oils may be of any preferred type including those derived from the ordinary parafiinic, naph thenic, asphaltic or mixed base mineral crude oils by suitable refining methods. Synthetic hydrocarbon lubricating oils may also be employed. Other synthetic oils include dibasic acid esters such as di-2-ethyl hexyl sebacate, carbonate esters, glycol esters such as C oxo acid diesters of tetraethylene glycol, and complex esters as for example the complex ester formed by the reaction of 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethyl hexanoic acid.
Also, although the additives of this invention are primarily intended for use in lubricating oils designed for automotive crankcases, they may also be employed in other hydrocarbon oil compositions including turbine oils, various industrial oils, hydraulic fluids, transmission fluids and the like.
The oil compositions of the invention may also contain, in addition to the detergent, such additives as viscosity index improvers, e.g. polymethacrylates, olefin polymers, etc., antioxidants such as phenyl-alpha-amine, bis phenols, etc., pour point depressants, dyes, and other additives for improving the properties of the compositions.
It is to be understood that the examples presented herein are intended to be merely illustrative of the invention and not as limiting it in any manner; nor is the invention to be limited by any theory regarding its operability. The scope of the invention is to 'be determined by the appended claims,- v
What is claimed is:
1. An improved lubricating oil composition comprising a lubricating oil to which has been added from 0.2 to 5.0 weight percent of the reaction product of (a) a phosphosulfurized polyolefin and (b) an ester of a fatty acid of from 6 to 20 carbon atoms and a sugar alcohol selected from the group consisting of hexitols, hexitans, and hexides; wherein said polyolefin has a molecular weight in the range of from about 500 to about 200,000 and is derived from an olefin monomer having from 2 to 6 carbon atoms; said (a) and (b) being reacted in a mole ratio of (a):(b) in the range of from about 1:2 to about 3:1.
2. An improved lubricating oil composition as defined in claim 1 wherein said reaction product has at least one free hydroxyl group and said reaction product has been further reacted with boric acid in a mole ratio in the range of from about 1:3 to about 3:1.
3. Lubricating oil composition as defined by claim 1 wherein said ester is sorbitan mono-oleate.
4. Lubricating oil composition as defined by claim 1 wherein said ester is sorbitan trioleate.
5. Lubricating oil composition as defined by claim 1 wherein said ester is mannitol distearate.
6. As a new composition of matter the reaction product of (a) a phosphosulfurized polyolefin and (b) an ester of a fatty acid of from 6 to 20 carbon atoms and a sugar alcohol selected from the group consisting of hexitols, hexitans and hexides; wherein said polyolefin has a molecular weight in the range of from about 500 to about 200,000 and is derived from an olefin monomer having from 2 to 6 carbon atoms; said (a) and (b) being reacted in a mole ratio of (a): (b) in the range of from about 1:2 to about 3:1.
'7. Composition of matter as defined by claim 6 Wherein said ester comprises sorbitan mono-oleate.
8. Composition of matter as defined 'by claim 6 wherein said ester comprises sorbitan trioleate.
9. As a new composition of matter the reaction product of (a) the composition of claim 6 and (b) boric acid; wherein the mole ratios of (a) (b) are from about 1:3 to about 3:1 and wherein the composition of claim 6 has at least one free hydroxyl group.
10. Composition of matter as defined by claim 9 wherein said ester comprises sorbitan mono-oleate.
11. A process for the preparation of a new composition of matter which comprises reacting about equal molar proportions of (a) a phosphosulfurized polyolefin and (b) an ester of a fatty acid of from 6 to 20 carbon atoms and a sugar alcohol selected from the group consisting of hexitols, hexitans, and hexides; wherein said polyolefin has a molecular weight in the range of about 500 to about 200,000 and is derived from an olefin monomer having from 2 to 6 carbon atoms; the reaction being carried out at a temperature of about 200 to 240 F. for a time of about 9 to 15 hours.
12. The composition prepared by the process of claim 11.
13. An improved lubricating oil composition comprising a lubricating oil to which has been added from 0.2 to 5.0 weight percent of the composition of claim ll.
14. A process for the preparation of a new composition of matter which comprises (1) reacting (a) a phosphosulfurized polyolefin and (b) an ester of a fatty acid of from 6 to 20 carbonatoms and a sugar alcohol selected from the group consisting of hexitols, hexitans, and hexides; wherein said polyolefin has a molecular weight in the range of about 500 to about 200,000 and is derived from an olefin monomer having from 2 to 6 carbon atoms; the reaction being carried out at a temperature of about 200 to 240 F. for a time of about 9 to 15 hours; said (a) and (b) being reacted in a mole ratio of (a) (b) such that the reaction product has at least one free hydroxyl group; (2) reacting about equal molar proportions of said reaction product and boric acid; the reaction being carried out at a temperature about 150 to 275 F. for a time of about 2 to 20 hours.
15. The composition prepared by the process of claim 14.
16. An improved lubricating oil composition comprising a lubricating oil to which has been added from 0.2 to 5.0 weight percent of the composition of claim 14.
References Cited by the Examiner UNITED STATES PATENTS 2,768,954 10/56 Fields 25246.6 2,795,548 6/57 Thomas et al. 252.-49.6 2,898,299 8/59 Lowe 252-466 3,002,925 10/61 Sabol et al. 25232.7
DANIEL E. WYMAN, Primary Examiner.
Claims (2)
1. AN IMPROVED LUBRICATING OIL COMPOSITION COMPRISING A LUBRICATING OIL TO WHICH HAS BEEN ADDED FROM 0.2 TO 5.0 WEIGHT PERCENT OF THE REACTION PRODUCT OF (A) A PHOSPHOSULFURIZED POLYOLEFIN AND (B) AN ESTER OF A FATTY ACID OF FROM 6 TO 20 CARBON ATOMS AND ASUGAR ALCOHOL SELECTED FROM THE GROUP CONSISTING OF HEXITOLS, HEXITANS, AND HEXIDES; WHEREIN SAID POLYOLEFIN HAS A MOLECULAR WEIGHT IN THE RANGE OF FROM ABOUT 500 TO ABOUT 200,000 AND IS DERIVED FROM AN OLEFIN MONOMER HAVING FROM 2 TO 6 CARBON ATOMS; SAID (A) AND (B) BEING REACTED IN A MOLE RATIO OF (A):(B) IN THE RANGE OF FROM ABOUT 1:2 TO ABOUT 3:1.
2. AN IMPROVED LUBRICATING OIL COMPOSITION AS DEFINED IN CLAIM 1 WHEREIN SAID REACTION PRODUCT HAS AT LEAST ONE FREE HYDROXYL GROUP AND SAID REACTION PRODUCT HAS BEEN FURTHER REACTED WITH BORIC ACID IN A MOLE RATIO IN THE RANGE OF FROM ABOUT 1:3 TO ABOUT 3:1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US189971A US3210279A (en) | 1962-04-25 | 1962-04-25 | Thiophosphonate ester dispersants for lubricating oils |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US189971A US3210279A (en) | 1962-04-25 | 1962-04-25 | Thiophosphonate ester dispersants for lubricating oils |
Publications (1)
Publication Number | Publication Date |
---|---|
US3210279A true US3210279A (en) | 1965-10-05 |
Family
ID=22699527
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US189971A Expired - Lifetime US3210279A (en) | 1962-04-25 | 1962-04-25 | Thiophosphonate ester dispersants for lubricating oils |
Country Status (1)
Country | Link |
---|---|
US (1) | US3210279A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5472637A (en) * | 1990-09-17 | 1995-12-05 | Betz Laboratories, Inc. | Control of foam in hydrocarbon fluids |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US768954A (en) * | 1904-07-29 | 1904-08-30 | Harry R Romberger | Nut-lock. |
US2795548A (en) * | 1954-06-29 | 1957-06-11 | California Research Corp | Lubricant compositions |
US2898299A (en) * | 1957-05-31 | 1959-08-04 | California Research Corp | Ester-containing lubricant compositions |
US3002925A (en) * | 1958-05-26 | 1961-10-03 | Standard Oil Co | Lubricant additive and composition containing same |
-
1962
- 1962-04-25 US US189971A patent/US3210279A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US768954A (en) * | 1904-07-29 | 1904-08-30 | Harry R Romberger | Nut-lock. |
US2795548A (en) * | 1954-06-29 | 1957-06-11 | California Research Corp | Lubricant compositions |
US2898299A (en) * | 1957-05-31 | 1959-08-04 | California Research Corp | Ester-containing lubricant compositions |
US3002925A (en) * | 1958-05-26 | 1961-10-03 | Standard Oil Co | Lubricant additive and composition containing same |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5472637A (en) * | 1990-09-17 | 1995-12-05 | Betz Laboratories, Inc. | Control of foam in hydrocarbon fluids |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3367943A (en) | Process for preparing oil soluble additives which comprises reacting a c2 to c5 alkylene oxide with (a) reaction product of an alkenylsuccinic anhydride and an aliphaticpolyamine (b) reaction product of alkenylsuccinic anhydride, a c1 to c30 aliphatic hydrocarbon carboxylic acid and an aliphatic polyamine | |
US3448049A (en) | Polyolefinic succinates | |
RU2051170C1 (en) | Lubricating oil for internal combustion engines | |
US3311558A (en) | N-alkylmorpholinone esters of alkenylsuccinic anhydrides | |
US3211652A (en) | Phenolic compositions | |
EP0020037B1 (en) | Oil-soluble friction-reducing additive, process for the preparation thereof, and lubricating oil or fuel composition containing the additive | |
US3288714A (en) | Lubricating oil compositions containing alkenyl succinic anhydrides | |
US3451933A (en) | Formamido-containing alkenylsuccinates | |
JP2997057B2 (en) | Low pressure derived hybrid phosphorus- and sulfur-containing reaction products useful in power transmission compositions and methods for their preparation | |
US3388066A (en) | Reaction products of dihydrocarbon dithiophosphoric acid and phosphite | |
US3684713A (en) | Compositions containing oil-soluble azo compounds | |
US3342735A (en) | Alkenyl succinic anhydride-amine-ps reaction product | |
US2658062A (en) | Mineral oil additive | |
US2758971A (en) | Blending agents for mineral oils | |
US2733235A (en) | Table ii | |
US3359203A (en) | Ashless dithiophosphoric acid derivatives | |
US3821302A (en) | Olefinic ketone imines and oil compositions containing them | |
US3377281A (en) | Lubricating composition | |
US2636858A (en) | Mineral oil additive | |
US4356097A (en) | Alkylphosphonate lubricating oil | |
US3459662A (en) | Phospho-sulfurized phosphite esters and hydrocarbon compositions containing the same | |
US3210279A (en) | Thiophosphonate ester dispersants for lubricating oils | |
US2766207A (en) | Hydrocarbon oil products | |
US3306856A (en) | Aryl keto acid pour-point depressants and dispersants for oleaginous compositions | |
US3340191A (en) | Fuel and lubricant compositions |