CN87105448A - Overbased sulfurized alkylphenates of group II metals having high total base number and low viscosity - Google Patents
Overbased sulfurized alkylphenates of group II metals having high total base number and low viscosity Download PDFInfo
- Publication number
- CN87105448A CN87105448A CN87105448.5A CN87105448A CN87105448A CN 87105448 A CN87105448 A CN 87105448A CN 87105448 A CN87105448 A CN 87105448A CN 87105448 A CN87105448 A CN 87105448A
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- China
- Prior art keywords
- oil
- family metal
- weight
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- 229910052784 alkaline earth metal Inorganic materials 0.000 title abstract 3
- 239000004480 active ingredient Substances 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims description 134
- 239000002184 metal Substances 0.000 claims description 134
- 239000003921 oil Substances 0.000 claims description 96
- 239000000203 mixture Substances 0.000 claims description 92
- 125000000217 alkyl group Chemical group 0.000 claims description 73
- 239000010687 lubricating oil Substances 0.000 claims description 63
- 239000011575 calcium Substances 0.000 claims description 56
- -1 hydrocarbyl sulfonate Chemical compound 0.000 claims description 53
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 52
- 229910052791 calcium Inorganic materials 0.000 claims description 52
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 37
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 239000000314 lubricant Substances 0.000 claims description 12
- 239000012141 concentrate Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 description 110
- 239000000047 product Substances 0.000 description 76
- 238000000034 method Methods 0.000 description 75
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 50
- 150000001336 alkenes Chemical class 0.000 description 44
- 229910052799 carbon Inorganic materials 0.000 description 42
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 37
- 239000005864 Sulphur Substances 0.000 description 35
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 34
- 238000002360 preparation method Methods 0.000 description 28
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical group C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 27
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 24
- 235000011089 carbon dioxide Nutrition 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 239000003054 catalyst Substances 0.000 description 19
- 238000001914 filtration Methods 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 18
- 125000001183 hydrocarbyl group Chemical group 0.000 description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 18
- 239000000126 substance Substances 0.000 description 18
- 239000002585 base Substances 0.000 description 16
- 229960003742 phenol Drugs 0.000 description 16
- 229960002317 succinimide Drugs 0.000 description 15
- 244000089742 Citrus aurantifolia Species 0.000 description 14
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 14
- 235000011941 Tilia x europaea Nutrition 0.000 description 14
- 229910052500 inorganic mineral Inorganic materials 0.000 description 14
- 239000004571 lime Substances 0.000 description 14
- 235000010755 mineral Nutrition 0.000 description 14
- 239000011707 mineral Substances 0.000 description 14
- IHKVRWIVEOFRKE-UHFFFAOYSA-N C1(=CC=CC=C1)O.C1=CC=CC=C1.C=CC.C=CC.C=CC.C=CC Chemical compound C1(=CC=CC=C1)O.C1=CC=CC=C1.C=CC.C=CC.C=CC.C=CC IHKVRWIVEOFRKE-UHFFFAOYSA-N 0.000 description 13
- 239000005909 Kieselgur Substances 0.000 description 13
- 125000003118 aryl group Chemical group 0.000 description 13
- RYSNDQDGZQEOAL-UHFFFAOYSA-N calcium;phenol Chemical compound [Ca].OC1=CC=CC=C1 RYSNDQDGZQEOAL-UHFFFAOYSA-N 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 150000001335 aliphatic alkanes Chemical class 0.000 description 12
- 150000001721 carbon Chemical group 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical group O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 11
- 241000255964 Pieridae Species 0.000 description 10
- 239000000654 additive Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 10
- 235000011116 calcium hydroxide Nutrition 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 229940031826 phenolate Drugs 0.000 description 10
- 230000000630 rising effect Effects 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229920002367 Polyisobutene Polymers 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 125000001118 alkylidene group Chemical group 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 7
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 229920001281 polyalkylene Chemical group 0.000 description 7
- 229920000768 polyamine Polymers 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 description 6
- 238000000247 postprecipitation Methods 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- JNVCSEDACVAATK-UHFFFAOYSA-L [Ca+2].[S-]SSS[S-] Chemical compound [Ca+2].[S-]SSS[S-] JNVCSEDACVAATK-UHFFFAOYSA-L 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 159000000007 calcium salts Chemical class 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 description 4
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000000502 dialysis Methods 0.000 description 4
- 229930195357 gramphenol Natural products 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000005077 polysulfide Substances 0.000 description 4
- 229920001021 polysulfide Polymers 0.000 description 4
- 150000008117 polysulfides Polymers 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OFQCQIGMURIECL-UHFFFAOYSA-N 2-[2-(diethylamino)ethyl]-2',6'-dimethylspiro[isoquinoline-4,4'-oxane]-1,3-dione;phosphoric acid Chemical compound OP(O)(O)=O.O=C1N(CCN(CC)CC)C(=O)C2=CC=CC=C2C21CC(C)OC(C)C2 OFQCQIGMURIECL-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- SRTXXUBDPVIROV-UHFFFAOYSA-N S=C1C(C=CC=C1)[O-].[Ca+2].S=C1C(C=CC=C1)[O-] Chemical compound S=C1C(C=CC=C1)[O-].[Ca+2].S=C1C(C=CC=C1)[O-] SRTXXUBDPVIROV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 230000003190 augmentative effect Effects 0.000 description 3
- 239000002199 base oil Substances 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 239000003729 cation exchange resin Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- RFPMGSKVEAUNMZ-UHFFFAOYSA-N pentylidene Chemical group [CH2+]CCC[CH-] RFPMGSKVEAUNMZ-UHFFFAOYSA-N 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- QRYFCNPYGUORTK-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-yldisulfanyl)morpholine Chemical compound C1COCCN1SSC1=NC2=CC=CC=C2S1 QRYFCNPYGUORTK-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- JAEZSIYNWDWMMN-UHFFFAOYSA-N 1,1,3-trimethylthiourea Chemical compound CNC(=S)N(C)C JAEZSIYNWDWMMN-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- KFFQABQEJATQAT-UHFFFAOYSA-N N,N'-dibutylthiourea Chemical compound CCCCNC(=S)NCCCC KFFQABQEJATQAT-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- SYBWLZWESMCEPG-UHFFFAOYSA-N OP(O)(S)=S.CCCC[Zn]CCCC Chemical compound OP(O)(S)=S.CCCC[Zn]CCCC SYBWLZWESMCEPG-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 244000171726 Scotch broom Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 239000000385 dialysis solution Substances 0.000 description 1
- HIKZOIYUQFYFBB-UHFFFAOYSA-N didodecyl decanedioate Chemical compound CCCCCCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCCCCCC HIKZOIYUQFYFBB-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 239000005414 inactive ingredient Substances 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- YZKRIHZCXGPZGB-UHFFFAOYSA-L zinc;oxido-propan-2-yloxy-propan-2-ylsulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CC(C)OP([O-])(=S)SC(C)C.CC(C)OP([O-])(=S)SC(C)C YZKRIHZCXGPZGB-UHFFFAOYSA-L 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
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
-
- 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
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A group II metal sulfurized alkylphenate of extremely high basicity having a viscosity of less than 800 centistokes at 100 ℃ and having less than about 10% of unsulfurized group II metal alkylphenate in the active ingredient is disclosed.
Description
The present invention relates to the very high alkyl monosulfide phenates of the alkalescence of II family metal, contain the lubricating oil composition of overbased sulfurized alkylphenols as active phenates of these II family metals and the lubricant oil concentrate that contains the overbased sulfurized alkylphenols as active phenates of these II family metals.
Specifically, the present invention relates to the overbased sulfurized alkylphenols as active phenates of oil-soluble II family metal, it is characterized in that its total basicnumber (TBN) is very high, more than about 300 TBN, be about 800 centistokes or lower usually 100 ℃ viscosity.Product of the present invention is further characterized in that the content of the alkyl phenate of unvulcanized II family metal in the active ingredient is lower than about 10%.
The overbased sulfurized alkylphenols as active phenates of II family metal is as lubricating oil additive, and this additive is given lubricating oil composition with quietness and dispersed and the deposit of the basicity in the oil is provided.For in and the acid that produces during the running of an engine, need the basicity deposit.Do not have this basicity deposit, consequent acid can produce deleterious corrosion to engine.
United States Patent (USP) 3,178 has been described a kind of method of the overbased sulfurized alkylphenols as active phenates of preparation II family metal for No. 368, in the method, alkylphenol, sulfonate, high molecular weight alcohol, lubricating oil and sulphur are under agitation mixed and heats; Add white lime then, the reacting by heating system also adds 1; Remove the water that reaction generates, cooling mixture, and add carbonic acid gas; Remove uncombined carbonic acid gas, and the reacting by heating container, to remove 1, water and high molecular ethanol.Because add white lime and carbonic acid gas therein, so this product is overbasic.
The TBN of the overbased sulfurized alkylphenols as active phenates of the II family metal that these prior art methods provide is approximately 250.Overbased sulfurized alkylphenols as active phenates greater than the II family metal of 275 TBN in the prior art is too sticking, and operation for convenience needs a large amount of thinners, and efficient is low.High this problem of viscosity that relates to for the overbased sulfurized alkylphenols as active phenates that solves the high II family metal of TBN, United States Patent (USP) 3,367, disclose the mixture that the alkyl that uses is straight chain and branched-chain alkyl for No. 867 on alkylphenol, thereby produced product with suitable viscosity and anti-bubble property.United States Patent (USP) 3,367, the TBN that the merchant who provides for No. 867 sells product is about 250 usually.
When attempting to enlarge United States Patent (USP) 3,367, be used to prepare the method for 250 TBN products in No. 867 with acceptable viscosity, during with the overbased sulfurized alkylphenols as active phenates of II family metal of preparation TBN high (about 300 TBN and Geng Gao), the result is the hydrolytic instability that the viscosity of product increases and increased product.Therefore, the overbased sulfurized alkylphenols as active phenates that needs the II family metal that exploitation viscosity is suitable, TBN is high.If the overbased sulfurized alkylphenols as active phenates of viscosity II family metal suitable, high TBN also has stability to hydrolysis, this will be more favourable.
I have found the overbased sulfurized alkylphenols as active phenates of new II family metal, and its total basicnumber (TBN) is about 300 and Geng Gao, and the viscosity in the time of 100 ℃ is about 800 centistokes and lower.New product of the present invention also has surprising stability to hydrolysis.
The overbased sulfurized alkylphenols as active phenates of II of the present invention family metal is usually by using the method for suitable alkylphenol and " sulphurized catalyst " to prepare in the preparation of these additives.A kind of particularly preferred catalyzer is 2-mercaptobenzothiazole (MBT) and its derivative.
As far as I know, do not point out in the prior art in the preparation of the overbased sulfurized alkylphenols as active phenates of II family metal, to use sulphurized catalyst.The prior art bibliography comprises United States Patent (USP) 4,100, and No. 085, this patent has been described in overbased sulfurized alkylphenols as active phenol synthetic, uses ammonia or ammonium hydroxide as promotor.Similarly, United States Patent (USP) 4,212 has been described for No. 752 and used some amino accelerator, for example primary and secondary alkyl amine, polyalkylene amine, amino acid etc. in synthetic overbased sulfurized alkylphenols as active phenates.
The present invention relates to the overbased sulfurized alkylphenols as active phenates of the II family metal that viscosity is low, TBN is high.Specifically, in its Composition Aspects, the present invention relates to be dissolved in the overbased sulfurized alkylphenols as active phenates of oily II family metal, it is characterized in that its total basicnumber is about 300 and Geng Gao, be about 800 centistokes or lower 100 ℃ viscosity, and the content of the alkyl phenate of unvulcanized II family metal is lower than about 10% in active ingredient.
Alkyl in the alkylphenol contains the carbon atom of enough numbers, makes the overbased sulfurized alkylphenols as active phenates of II family metal be dissolved in oil.In a preferred specific embodiments, the alkyl in the described alkylphenol contains 25 to 100%(moles) be mainly the straight chained alkyl of 15 to 35 carbon atoms, 75 to 0%(moles) alkyl be the polypropylene-base of 9 to 18 carbon atoms.Alkyl in the more preferably described alkylphenol contains 35 to 100%(moles) be mainly the straight chained alkyl of 15 to 35 carbon atoms, 65 to 0%(moles) alkyl be the polypropylene-base of 9 to 18 carbon atoms.In another preferred specific embodiments, the alkyl in the described alkylphenol contains 40 to 70%(moles) be mainly the straight chained alkyl of 15 to 35 carbon atoms, 60 to 30%(moles) alkyl be the polypropylene-base of 9 to 18 carbon atoms.Alkyl in the most preferably described alkylphenol contains about 50%(mole) be mainly the straight chained alkyl of 15 to 35 carbon atoms, approximately 50%(mole) alkyl be the polypropylene-base of 9 to 18 carbon atoms.
It is about 300 to 400,315 to 400 better that the total basicnumber that the overbased sulfurized alkylphenols as active phenates of II of the present invention family metal has is preferably, and 315 to 360 is better, is preferably 325 to 360.
II family metal should be selected from calcium, magnesium, barium and its mixture.II family metal is calcium preferably.
The overbased sulfurized alkylphenols as active phenates that is dissolved in the II family metal of oil of the present invention can be used as lubricating oil additive, and it is to keep basicity in the oil also with quietness and dispersiveness that this additive is given lubricating oil.When the overbased sulfurized alkylphenols as active phenates of II family metal that is dissolved in oil used in this mode, its amount ranges was about 0.5 to 40%(weight of all lubricating oil compositions), but preferably be about 1 to 25%(weight of all lubricating oil compositions).Therefore, another aspect of the present invention is lubricating oil and about 0.5 to the 40%(weight that contains certain viscosity) lubricating oil composition that is dissolved in the overbased sulfurized alkylphenols as active phenates of oily II family metal of the present invention.Lubricating oil composition of the present invention is used for diesel engine, petrol motor and ship engine.When being used for ship engine, the overbased sulfurized alkylphenols as active phenates that is dissolved in the II family metal of oil usually share with the natural or synthetic hydrocarbyl sulfonate of high alkalinity that is dissolved in oily II family metal.Therefore, of the present invention on the one hand is to contain the lubricating oil of certain viscosity and (a) about 0.5 to 40%(weight again) the overbased sulfurized alkylphenols as active phenates of the II family metal that is dissolved in oil of the present invention and (b) about 0.5 to 40%(weight) be dissolved in the composition of the natural or synthetic hydrocarbyl sulfonate of the high alkalinity of II family metal of oil.
" total basicnumber " used herein or " TBN " speech are meant the alkali number that is equivalent to potassium hydroxide milligram number in the 1 gram sample.Therefore, the TBN number is high more, and the alkalescence of corresponding product is strong more, thereby the basicity that keeps is big more.
" stability to hydrolysis " speech that is used for the overbased sulfurized alkylphenols as active phenates of II family metal is meant that containing these product combination things will lose in improved ASTM D 2619 tests and be less than about 25% their total basicnumber.Improved test is to be exposed to the alkali that it lost in the moisture by mensuration, the stability to hydrolysis of measure product.The stability to hydrolysis of the overbased sulfurized alkylphenols as active phenates of II family metal is extremely important character to the use that is exposed to crank axle for vessel case waterborne usually especially.See Van der Horst, lubrication engineering, " Development of Modern Lubricants for Mdeium-Speed Marine Diesel Engines " (1977); People's such as Thomas " Modern Marine Diesel Engines Lubricant and their Development ", second international lubricating oil discussion, Cairo, Egyptian (1979).
In the process of preparation overbased sulfurized alkylphenols as active phenates, only the overbased sulfurized alkylphenols as active phenates of II family metal can be overbasic.Therefore, in reaction process, wish that the amount of the sulfenyl phenolate of II family metal increases to maximum.On the other hand, sulfenyl phenolate does not generate II family metal-salt after adding calcium hydroxide (with corresponding raw material) and carbonic acid gas, but this salt can not be overbasic.Therefore, in reaction process, wish that the amount of the not alkyl monosulfide phenates of II family metal reduces to minimum.
" active ingredient " speech that is used for the present composition is meant the alkyl phenate of II family metal and the alkyl monosulfide phenates of II family metal, and " inactive ingredients " speech is meant unreacted alkylphenol and all contained thinning oils of composition.
The alkyl monosulfide phenates of II family metal and the II family amount of metal alkyl phenates in active ingredient can be measured by standard analytical techniques.A kind of technology used herein be utilize with
1The dialysis that the H-NMR lotus root is closed.
" being mainly straight chained alkyl " used herein speech is meant and is mainly linear alkyl, also can contain some side chain in molecular structure.
Except also using the sulphurized catalyst, the overbased sulfurized alkylphenols as active phenolate of II of the present invention family metal prepares by being similar to processing method described above.It is 300 or higher product that the prior art method of the overbased sulfurized alkylphenols as active phenates of preparation II family metal can provide total basicnumber, and some product has acceptable viscosity, but wherein some is a hydrolytically unstable.The prior art method can not be produced the reason of the high overbased sulfurized alkylphenols as active phenols of the TBN of hydrolysis-stable consistently and also do not made clear rapidly.
According to the restriction that anatomizing of this problem is not subjected to this theory, it seems that the hydrolytic instability of the product that TBN is high partly is owing to contain a large amount of high alkyl phenates that does not vulcanize II family metal in active ingredient.When using the white lime of high mole to feed intake (promptly greater than 2) to alkylphenol, it is very general mixing part sulphur.That is to say, in the method for preparing the overbased sulfurized alkylphenols as active phenates, often add white lime, sulphur and alkylphenol in the reaction system.Use enough sulphur, so that all alkylphenols change into sulfenyl phenolate.When the molar feed ratio of white lime and alkylphenol is 2 or lower the time, alkylphenol changes into calcium sulfenyl phenolate usually, and when molar feed ratio greater than 2 the time, product contains a large amount of unvulcanized alkylphenol calcium.On the other hand, the molar feed ratio that requires white lime and alkylphenol usually is greater than 2, and with the product of acquisition greater than 300 TBN, thereby problem is apparent in view.When all other factorses such as sulphur feeds intake, carbonic acid gas feeds intake etc. remain unchanged, obtain product greater than 300 TBN, require the molar feed ratio of white lime and alkylphenol to surpass 2, but this must produce a large amount of unvulcanized alkylphenol calcium, because it can not be overbasic, thereby the TBN when having reduced fusion, and increased the viscosity of product.Molar feed ratio at white lime and alkylphenol is higher, and promptly greater than 2 o'clock, the incomplete vulcanization of alkylphenol is not recognized so far as yet, and the reason of this effect can not be explained rapidly.
We have now found that, under any circumstance, in the method for using greater than 2 normal white limes or other II family metal oxide or oxyhydroxide, use sulphurized catalyst, increase the amount of the alkyl monosulfide phenates of II family metal in the active ingredient greatly, and greatly reduced the amount of the alkyl phenate of unvulcanized II family metal in the active ingredient.The product that TBN of the present invention is high is characterised in that and contains the mole at least about 90%(in the active ingredient), preferably at least about the 95%(mole) II family sulfurized metal phenate salt.Product of the present invention conversely speaking, must contain about at the most 10%(mole in active ingredient), preferably about at the most 5%(mole) do not vulcanize the alkyl phenate of II family metal.Because the amount of the alkyl phenate of unvulcanized II family metal reduces in active ingredient, the product that TBN is higher is possible.In addition, these products have improved stability to hydrolysis and have reduced viscosity.
According to the present invention, have found that the overbased sulfurized alkylphenols as active phenates that is dissolved in the II family metal of oil of the present invention can pass through in lubricating oil an amount of sulphurized catalyst, sulphur, alkylphenol, II family metal oxide, oxyhydroxide or C
1-C
6The alcohol reactant salt, then the method with the carbonic acid gas carboxylation prepares.Reaction system also will contain C
2-C
4Aklylene glycol (as 1, ammediol, 1,4-butyleneglycol, 1 etc., but preferred C
2-C
4Aklylene glycol is a 1), the high alkalinity of II family the metal natural or synthetic hydrocarbyl sulfonate of sulfuration and high-molecular weight alcohol.The overbased sulfurized alkylphenols as active phenates that is called II family metal on the product technology that this reaction obtains.The overbased sulfurized alkylphenols as active phenates of II of the present invention family metal is characterised in that its total basicnumber is about 300 or higher, is about 800 centistokes or lower 100 ℃ viscosity, and the content of unvulcanized II family metal alkyl phenates is about the 10%(mole) or still less.
Sulphurized catalyst makes sulphur obtain catalysis, enters in the alkylphenol.Suitable sulphurized catalyst comprise 2-mercaptobenzothiazole (MBT) and its derivative as two (2,2 '-benzothiazolyl) disulphide; 2(3H)-benzothiazole thioketones zinc salt; 2-[4-morpholinodithio base-N, N '-diethyl thiocarbamyl sulfide; 4-morpholinyl-2-[4-morpholinodithio disulphide etc.Another kind of suitable sulphurized catalyst comprises dithiophosphates such as zinc diisopropyl dithiophosphate; Di-n-butyl zinc dithiophosphate etc.Suitable sulphurized catalyst comprises thiocarbamide, thiuram, calcium polysulfide etc. to also have a class.The specific examples of these catalyzer comprises N, N '-dibutyl thiourea, ethylene thiourea; Trimethyl thiourea, curing two pentylidene thiurams, four sulfurations, two pentylidene thiocarbamides; Six sulfurations, two pentylidene thiocarbamides etc.
The consumption of sulphurized catalyst is about 0.5 to 10%(weight of alkylphenol in the reaction system usually), preferably be about 1 to 2%(weight).In a preferred specific embodiments, sulphurized catalyst joins in the reaction mixture with liquid state, and this can be by being dissolved in sulphurized catalyst fused sulphur or finishing as the method that the pre-composition before the reaction is dissolved in the alkylphenol.
The usual amounts of sulphur is about 2 to 4 moles an of alkylphenol in every molar reactive system, is preferably about 2 to 3 moles of every mole of alkylphenol.Can use all allotropic substances of sulphur.Perhaps available sulfur monochloride replaces sulphur.For purposes of the invention, think that sulfur monochloride and sulphur are equivalent.The sulphur that uses both can be fused sulphur, also can be solid-state sulphur.
Be used to prepare II family metal oxide, oxyhydroxide or the C of II family metal alkyl phenates
1-C
6Alkoxide comprises oxide compound, oxyhydroxide and the alkoxide of calcium, strontium, barium or magnesium.But calcium, barium and magnesium are preferred, and calcium is most preferred.Used II family metal oxide, oxyhydroxide or C
1-C
6The molar feed ratio of alkoxide and alkylphenol is greater than 2 to 4, but is greater than 2 to 3 preferably.
With carbonic acid gas and II family metal oxide, oxyhydroxide or C
1-C
6Alkoxide adds in the reaction system together, and generating the high alkalinity product, and consumption is about 1 to 3 mole of every mole of alkylphenol usually, but about 2 to 3 moles of every mole of alkylphenol that adds reaction system preferably.
The used alkylphenol of the present invention is represented with following formula:
R contains the alkyl of carbon atom of enough numbers so that the overbased sulfurized alkylphenols as active phenates of the II family metal that generates is dissolved in oil in the formula.
R should be following alkyl, wherein, about 25 to 100%(moles) alkyl mainly be the straight chained alkyl of 15 to 35 carbon atoms, about 75 to 0%(moles) alkyl be the polypropylene-base of 9 to 18 carbon atoms.But the preferably following alkyl of R, wherein, about 35 to 100%(moles) alkyl mainly is the straight chained alkyl of 15 to 35 carbon atoms, about 65 to 0%(moles) alkyl be the polypropylene-base of 9 to 18 carbon atoms.Using increases the amount that is mainly straight chained alkyl, causes the common viscosity of the high product of TBN lower.On the other hand, polypropylene-base phenol is more a little than the alkylphenol economy that is mainly straight chain usually, and when the high alkalinity alkyl phenate of preparation II family metal, the polypropylene-base phenol of use is greater than the 75%(mole), cause the viscosity height of product must be difficult to accept usually.But use the 75%(mole) or the polypropylene-base phenol and the 25%(mole of lower 9 to 18 carbon atoms) or more be mainly the mixture of the straight chained alkyl phenol of 15 to 35 carbon atoms, can obtain the product of the suitable and less expensive of viscosity.
The induced by alkyl hydroxybenzene of following formula I can by will suitable alkene or alkene mixture and phenol in the presence of alkylation catalyst, at about 60 ℃ to 200 ℃, preferably under 125 ℃ to 180 ℃ the temperature, purified or be to react in the inert solvent and under the normal atmosphere to make basically.Preferred alkylation catalyst is a sulfonic acid catalyst, as Amberlyst 15
(can be from Rohm and Haas, Philadelphia, Pennsylvania has bought).Can use reactant molar ratio, the perhaps phenol of super molar weight is promptly when unreacted phenol recycles, whenever amount alkene 2 to 2.5 equivalent phenol.The aftermentioned method can make the amount of monoalkyl phenol increase to maximum.The example of inert solvent comprises benzene, toluene, chlorobenzene and 250 thinners, and this thinner is aromatic substance, alkane and naphthenic mixture.
The used induced by alkyl hydroxybenzene of the present invention is the adjacent alkylphenol of formula II:
Or the formula III to alkylphenol:
R mainly is in contraposition, no more than about 50%(mole) the R alkyl comparatively suitable at the ortho position, no more than about 35%(mole) alkyl then better at the ortho position.It is believed that the preparation that alkyl phenate (III) is helped the very high II family sulfurized metal phenate salt of alkalescence.What therefore, the alkene that wish to adopt can make generation increases to maximum to alkylphenol content in alkylphenol.In this respect, when polypropylene is added in contraposition usually, the alkene that does not contain side chain will be added in ortho position or contraposition.It mainly is the linear olefin cut that a kind of method of the contraposition content in the alkylphenol that increase is made by normal olefine is to use, and some wherein contained side chain is arranged on two keys of molecular structure, as structure IV and V,
(vinylidene) (trisubstituted vinyl)
R in the formula
1, R
2And R
3Form the nubbin of alkene.When mainly being straight chain, in alkylation process, the chain portion in the molecular structure can be for forming the tertiary carbon ion.Be not bound by any theory, it is believed that the sterically hindered ortho-alkylating that suppressed that interrelates with uncle's ion, thereby strengthened para-orientation.Suitable mainly is that linear olefin is following alkene, wherein about 75 to 100%, and each carbon atom of the alkene of preferably about 85 to 100% numbers is the primary (CH
3-) or secondary (CH
2-).Being included in has an alpha-olefines (CH=CH in term " primary " or " second month in a season "
2) and the internal olefin class (CH=CH-).This conversely speaking, mainly is that linear olefin can contain 0 to 25%, preferably 0 carbon atom to about 15% number.Be included in the term " uncle " have trisubstituted vinyl (
C=CH-) and vinylidene (
C=CH
2).
Mainly be that the linear olefin cut is that the merchant sells product, as C
18-C
30Alkene can (Baton Rouge Louisiana) have bought from Ethyl company.These alkene mainly are straight chains, and the carbon atom of 80 to 100% numbers is uncle or secondary carbon(atom) in the alkene.On the other hand, alkene about 40%(mole in olefin fraction) is branched-chain alkene.That is to say, when other except that the main straight chain, the 40%(mole of all alkene) be the trisubstituted vinyl or the vinylidene structure formation of side chain.Similarly, C
24-C
28Olefin fraction (from Chevron Chemical company, San Francisco, CA has bought) mainly be straight chain also, but contain about 40%(mole) or more branched-chain alkene (mainly being vinylidene alkene).(branched-chain alkene content is lower than about 5% mole) can (Houton Texas) have bought normal olefine from Shell Chemical company.
Be now difference " what contain the uncle of 80 to 100% numbers or secondary carbon(atom) in alkene mainly is linear olefin " and " contain about 40%(mole) alkene be side chain mainly be the linear olefin cut " suitable the time.Under first kind of situation, alkene is conceived to molecular structure, and the carbon atom that requires at least 80% number is uncle or secondary carbon(atom).In this case, if the residual carbon atom of enough numbers is uncle or secondary carbon(atom), so that the carbon atom of at least 80% number is uncle or secondary carbon(atom) in this alkene, then branched-chain alkene still is mainly straight chain as three substituted ethylene bases or vinylidene.
On the other hand, contain about 40%(mole) alkene be side chain mainly be that the linear olefin cut is conceived to form.Being mainly the linear olefin cut in other words can contain such as alkene such as alpha-olefin, internal olefin, three substituted ethylene bases and vinylidenes.From the whole linear olefin cut that is mainly, 40%(mole) alkene be side chain, i.e. three substituted ethylene base or vinylidenes, and residual part is alpha-olefin or internal olefin.
Aklylene glycol is also used in the reaction for preparing the overbased sulfurized alkylphenols as active phenates of II of the present invention family metal, i.e. 1, the natural or synthetic hydrocarbyl sulfonate of high alkalinity of high molecular weight alcohol (being generally decyl alcohol) and II family metal.
Usually the 1 that adopts and the molar feed ratio of alkylphenol are about 1 to 4, preferably are about 2 to 3.Perhaps, also 2-Ethylhexyl Alcohol can be used with 1, for example, its weight ratio is a 80%(weight) 2-Ethylhexyl Alcohol and 20%(weight) 1.
Preferred high molecular weight alcohol is a decyl alcohol, and the used decyl alcohol and the molar feed ratio of alkylphenol are about 0.5 to 4, preferably are about 1 to 2.
Natural or the synthetic hydrocarbyl sulfonate of the high alkalinity of II family metal can be sulfonated petro-leum, synthetic alkanisation aromatic sulphonate or aliphatic sulfonate, and Tathagata is from the derivative of polyisobutene.Alkyl must have the carbon atom of enough numbers so that sulfonate molecules is dissolved in oil.Hydrocarbyl portion preferably has 20 carbon atoms at least, and can be aromatics or aliphatic series, but alkane aromatics normally.Preferably use the aromatic sulphonate of calcium, magnesium or barium.
The typical method for making of some sulfonate is the petroleum fractions that sulfonation has aryl (normally single-or dialkyl phenyl organic), generates the metal-salt of sulfonic acid then.Other raw material that is used to prepare these sulfonate comprises synthetic alkanisation benzene and the aliphatic hydrocrbon that makes by polymerization list or diolefinic (for example polymerization iso-butylene make polyisobutenyl).Use well-known step, directly or by double decomposition generate metal-salt.
Undertaken high alkalinityization by adding carbonic acid gas and II family metal oxide or oxyhydroxide p-sulfonic acid salt then, to obtain total basicnumber up to about 400 or higher product.Calcium hydroxide and calcium oxide are to produce the most frequently used raw material of overbased sulfonate.These raw materials are well-known technically.
The high alkalinity of II family metal consumption natural or synthetic hydrocarbyl sulfonate is about 1 to 20%(weight of alkylphenol), be preferably about 1 to 10%(weight).Natural or the synthetic hydrocarbyl sulfonate of high alkalinity of above-mentioned II family metal also can be used from lubricant formula with the overbased sulfurized alkylphenols as active phenates one of II family metal, especially crank axle for vessel case prescription.
Perhaps, available alkenyl succinimide replaces the natural or synthetic hydrocarbyl sulfonate of high alkalinity of II family metal.Alkenyl succinimide is well-known technically.Alkenyl succinimide is succinyl oxide and the amine that polyolefin polymer replaces, the preferably reaction product of polyalkylene polyamine.The succinyl oxide that polyolefin polymer replaces is that the polyolefin polymer or derivatives thereof reacts with maleic anhydride and obtains.With thus obtained succinyl oxide and amine compound reaction.The preparation of alkenyl succinimide was described repeatedly technically.For example, see United States Patent (USP) 3,390,082; 3,219,666; With 3,172, No. 892, these open source literatures as a reference and incorporate the present invention into.Succinyl oxide reduction with alkenyl substituted obtains corresponding alkyl derivative.Regulation is included in the alkyl succinimide in the scope of term " alkenyl succinimide ".Mainly contain single-or the product of two-succinimide can be by the mole preparation recently of control reagent.Therefore, if 1 mole amine and 1 mole the thiazolinyl or the succinyl oxide reaction of alkyl replacement mainly are the products of single succinimide with making.If 2 moles of succinyl oxides and every mole of polyamine reaction will make two-succinimide.
The used polymerization iso-butylene of succinyl oxide resulting by the polymerization iso-butylene, that can produce the polyisobutene replacement can effectively wide variation in its composition.The scope of carbon atom mean number is 30 or still less to 250 or more, and the number-average molecular weight of corresponding gained is about 400 or more be low to moderate 3000 or higher.The average carbon atom number of each polyisobutene molecule should be about 50 to about 100 scope, and the number-average molecular weight of corresponding polyisobutene is preferably about 600 to about 1500.Best, the average carbon atom number of each polyisobutene molecule is in 60 to 90 scope, and the number-average molecular weight of corresponding polyisobutene is about 800 to 1300.According to well-known step,, obtain the succinyl oxide that polyisobutene replaces with polyisobutene and maleic anhydride reaction.
When the preparation alkenyl succinimide, succinyl oxide and polyalkylene polyamine reaction with replacing obtain corresponding succinimide.Each alkylidene group of polyalkylene polyamine has about at the most 8 carbon atoms usually.The number range of alkylidene group can reach about 8 at the most.The example of alkylidene group has ethylene, propylene, tetramethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene etc.Amino number (but and nonessential) is usually Duoed one than the alkylidene group number that is present in the amine, that is, if polyalkylene polyamine contains 3 alkylidene groups, then it will contain 4 amino usually.The scope of amino number is reducible up to 9.Alkylidene group preferably contains 2 to 4 carbon atoms approximately, and all amino preferably uncle or secondary amine.In this case, An Ji number Duos 1 than the alkylidene group number.Polyalkylene polyamine preferably contains 3 to 5 amino.The object lesson of polyalkylene polyamine comprises ethylene diamine, diethylenetriamine, Triethylenetetramine (TETA), trimethylene diamine, tri propylidene tetramine, tetren, 1,3-trimethylene diamine, five ethylidene, six ammoniums, two-(1, the 3-propylidene) triamine, three (hexamethylene) tetramine etc.
During use, the consumption of alkenyl succinimide is about 1 to 20%(weight of alkylphenol), be preferably about 1 to 10%(weight).
The reaction for preparing the overbased sulfurized alkylphenols as active phenates of II of the present invention family metal is used by the alkylphenol that adds suitable proportion, the natural or synthetic hydrocarbyl sulfonate of high alkalinity of II family metal, the method for the pure and mild sulphurized catalyst of high molecular and is undertaken.Reaction is carried out in inert diluent such as lubricating oil usually.The lubricating oil dilution agent that is fit to comprises the 100N solvent (RLOP100N) of purified 100N solvent (Cit Con 100N) and hydrotreatment.After the said components mixing, stir down and reaction system is heated between 90 ℃ to 155 ℃ oxide compound, oxyhydroxide or the C of adding sulphur and II family metal
1-C
6Alkoxide then adds 1.Remove the water of reaction, heated mixt is to about 175 ℃, and the adding carbonic acid gas.Remove any uncombined carbonic acid gas then, and the reacting by heating system is to remove 1, water and high molecular weight alcohol, to obtain being referred to as the composition of the overbased sulfurized alkylphenols as active phenates of II family metal.
In a preferred specific embodiments, have found that to add the stability to hydrolysis that emulsion splitter such as Triton x-45 and Triton x-100 can be worked in coordination with the overbased sulfurized alkylphenols as active phenates that increases II family metal.Triton x-45 and Triton x-100 as emulsion splitter are the quiet agent of non-ionic type, can PA.) buy from Rohm and Haas(Philadelphia.These emulsion splitters are paraoctyl phenol classes of ethoxylation.Other suitable emulsion splitter comprises Igpal(CO-610, can (New York NY) has bought from GAF company.In a preferred specific embodiments, be that emulsion splitter and sulphurized catalyst are share.The aqueous solution that contains calcium polysulfide and Triton x-100 is exactly this situation.This product is by ((San Francisco, CA is with trade name ORTHORIX in Chevron Chemical company
Sell.The add-on of emulsion splitter is generally 0.1 to 0%(weight of alkylphenol), 0.1 to 0.5%(weight preferably).
Lubricating oil composition of the present invention uses finished lube, and it can be independent or multiviscosisty.Multigrade oil can make by adding viscosity index (VI) improving agent.Typical viscosity index improver is a polyalkyl methacrylate, ethene, propylene copolymer, vinylbenzene-diene copolymers or the like.Have viscosity index and dispersing property be referred to as viscosity index (VI) improving agent also be applicable to prescription of the present invention.
The lubricating oil that is used for composition of the present invention can be mineral oil or synthetic oil, and its viscosity is applicable to the crankcase of oil engine, and the example of described oil engine has petrol motor and comprises the diesel engine of marine diesel.The viscosity of crankcase oil is about 1300 centistokes (0) to 24 centistokes (210 °F).Lubricating oil can obtain from synthetic or natural origin.Comprise that as the mineral oil of base oil paraffin oil, naphthenic oil and other generally are used for the oil of lubricating oil composition in the present invention.Synthetic oil comprises synthetic hydrocarbon oil and synthetic ester.Useful synthetic hydrocarbon oil comprises the alpha-olefinic polymer class with appropriate viscosity.C especially effectively
6To C
12 α-hydrogenation of olefin liquid oligomer such as 1-decene trimer.Similarly, also can use the suitable alkyl benzene of viscosity, as dodecylbenzene.Useful synthetic ester comprises the ester of monocarboxylic acid and polycarboxylic acid and monohydroxy alkanol and polyvalent alcohol.Typical example have the two dodecyl esters of hexanodioic acid, tetramethylolmethane four capronates, hexanodioic acid two-2-(ethyl hexyl) ester, sebacic acid dilauryl ester etc.The complex ester that also can use the mixture by monobasic and di-carboxylic acid and single and two hydroxyl alkanols to make.
The blend of hydrocarbon ils and synthetic oil also is useful.10 to 25%(weight for example) hydrogenant 1-decene trimer 75 to 90%(weight) blend of general second (SUS) (100) mineral oil of 150 Saybolt viscositys obtains fabulous lubricating base oil.
Lubricating oil additive concentrate is also included within the scope of the present invention.The form of enriched material comprises about 60 to 20%(weight) the lubricating oil and about 40 to 80% of certain viscosity of the present inventionly be dissolved in overbased sulfurized alkylphenols as active phenates oil, the II family metal of hydrolysis-stable.
Other additive that can be present in the prescription comprises rust-preventive agent, defoamer, inhibiter, metal passivator, pour point depressant, antioxidant and various other known additives.
The following example will specify the present invention, and these embodiment and explanation do not limit the scope of the invention going up all in all senses.
Note, use two kinds of TBN among titrimeters measurement this paper embodiment.The TBN that this paper announced is obtained by arbitrary titrimeter.The mutual error of TBN that obtains from these two titrimeters is in the 3-5% scope.Think that the tolerance range of the TBN value that this paper announces is ± 5%.Some embodiment has reported the TBN that is obtained by these two titrimeters.
Embodiment 1
C
18-C
30The preparation of alkylphenol
Adding 857 grams in 2 liters of flasks that agitator, Dean-Stark trap, condenser and nitrogen inlet tube and outlet pipe are housed mainly is C
18To C
30) alkene mixture (olefin(e) centent: C
16-0.5%; C
18-6.6%; C
20-26.2%; C
22-27.7%; C
24-18.2%; C
26-9.0%; C
28-4.5%; C
30-28%; Greater than C
30-4.5%), in whole olefin fractions, at least 30%(mole) described alkene contains trisubstituted vinyl (from Ethyh company, Baton, Rouge.LA has bought), 720 gram phenol, (Amberlyst 15 for catalyzer for 55 gram sulfonic acid cation exchange resin (with the polystyrene of divinyl benzene crosslinked)
, from Pohm and Haas, Philadelphia, Pennsylvania has bought).In nitrogen atmosphere,, last about 6 hours with being heated to about 145 ℃ under the reaction mixture stirring.By heating means stripping reaction mixture in a vacuum, and with the product that obtains by the diatomite heat filtering, obtain 947 grams to have hydroxyl value be 118 and be 56% C to alkylphenol content
18To C
30Alkylphenol.
Embodiment 2
C
20To C
28The preparation of alkylphenol
Adding 674 grams in 2 liters of flasks that agitator, Dean-Stark trap, condenser and nitrogen inlet tube and outlet pipe are housed mainly is C
20To C
28Alkene mixture (olefin(e) centent C
18-2%; C
20-28%; C
22-19%; C
24-13%; C
26-21%; C
28-11%; Greater than C
30-6%) in all olefin fractions, 20%(mole at least) described alkene contains vinylidene (C
20-C
24Alkene and C
24-C
28Alkene can be from Chevron Chemical company, San Francisco, and CA has bought, and then they is carried out mechanically mixing so that C to be provided with equimolar amount
20To C
28Alkene mixture), 211.5 gram phenol, (Amberlyst 15 for catalyzer for 43 gram sulfonic acid cation exchange resin (with the polystyrene of divinyl benzene crosslinked)
And, can be from Rohm and Haas, Philadelphia, PA has bought).In nitrogen atmosphere, reaction mixture under agitation is heated to about 140 ℃, last about 8 hours.By the method stripping reaction mixture of heating in a vacuum, and with product by the diatomite heat filtering, obtain 574 grams to have hydroxyl value be 110 and be 56% C to alkylphenol content
20To C
28Alkylphenol.
Embodiment 3
The preparation of tetrapropylene base phenol
In 2 liters of flasks that agitator, Dean-Stark trap, condenser and nitrogen inlet tube and outlet pipe are housed, add 567 gram tetrapropylenes, 540 gram phenol, (Amberlyst 15 for catalyzer for 72 gram sulfonic acid cation exchange resin (with the polystyrene of divinyl benzene crosslinked)
, can be from Rohm and Haas, Philadelphia, PA has bought).In nitrogen atmosphere, reaction mixture under agitation is heated to about 110 ℃, last about 3 hours.By the method stripping reaction mixture of heating in a vacuum, and with the product of gained by the diatomite heat filtering, obtain 626 grams to have hydroxyl value be 205 and be 96% tetrapropylene base phenol to alkylphenol content.
Embodiment 4
In 0.5 liter of 3 neck flask that agitator, Dean-Stark trap, condenser and nitrogen inlet tube and outlet pipe are housed, add 100 gram phenol.Reaction system is heated to 55 ℃, adds 55 gram C then
24-C
28Alkene (can be from Chevron Chemical company, San Francisco, CA has bought) and 12.5 gram Filtrol-13(acid activation clay, can be from the Los Anqeles of Filtrol company, CA has bought).When heating systems at 135 ℃ between 145 ℃ the time, in 1 hour, add 130.5 gram C
18-C
30Alkene (can be from Ethyl company, Baton Rouqe, LA has bought.Stopped reaction also filters.Filtering product is transferred in the flask of cleaning, be placed on (～50 mmhg) in the vacuum, and under small amount of nitrogen purges, be heated to 215 ℃.Close nitrogen, and kept vacuum (～50 mmhg) 30 minutes down at 215 ℃, the acquisition hydroxyl value is 106 alkylphenol.
Embodiment 5
The preparation of high alkalinity hydroxy acid calcium
A. the preparation of hydroxyl sulfoacid sodium
646 gram raw materials (refined 500N lubricating oil solvent is the mixture of Alkylaromatics, cycloalkanes and alkane) are added in the reactor.At 75 °F, in 10 minutes, restrain oleum (～27.6%SO with 150.8
3) add in the reactor.Temperature of reaction is raise, rise to 100 °F usually approximately.With in 12.3 ml waters and 540 milliliters of Chevron 265 thinners (mixture of aromatic substance, cycloalkanes and alkane) the adding system, system was kept 1 hour at 150 °F then.At this moment, add 125 milliliters in the reaction system and contain 25%(weight) aqueous solution of sodium hydroxide.System was kept 1 hour at 150 °F.After the sedimentation, remove water layer, then organic solution was left standstill 1 hour at least.After this, also to remove the water layer that any deposition is again come out.At 350 °F, under the normal atmosphere, this system of method stripping with air purge obtains hydrocarbyl sulfonic sodium.Its purification step is as follows: hydrocarbyl sulfonic sodium is dissolved in 330 milliliters of moisture sec-butyl alcohols.Contain 4%(weight with 160 milliliters) in the aqueous solution adding system of sodium-chlor.System is heated to 150 °F, and kept 2 hours at 150 °F.Post precipitation is removed salt solution.Add other 80 milliliters in this system and contain 4%(weight) aqueous solution of sodium-chlor.System is heated to 150 °F, and kept 1 hour at 150 °F.Post precipitation is removed salt solution.In system, add 220 ml waters, and system is heated to 150 °F.System was kept 1 hour at 150 °F.Remove then and anhydrate and the unsulfonated oil reservoir, obtain containing the sec-butyl alcohol aqueous solution of alkyl sodium sulfonate.
B. the preparation of hydrocarbyl sulfonic calcium
Toward as above-mentioned A in add 550 milliliters of moisture, sec-butyl alcohols and calcium chloride (～10% Ca Cl in the sec-butyl alcohol aqueous solution that contains the alkyl sodium sulfonate that makes
2) solution, system is heated to 150 °F and kept 1 hour at 150 °F.Post precipitation is removed salt solution.Add 340 ml waters and 170 milliliters in the system and contain 40%(weight) aqueous solution of calcium chloride.System is heated to 150 °F, and kept at least 1 hour at 150 °F.After the deposition, remove salt solution.340 ml waters and 170 milliliters are contained 40%(weight) in the aqueous solution adding system of calcium chloride.System is heated to 150 °F and kept at least 1 hour at 150 °F.Post precipitation is removed salt solution.340 ml waters are added system.System is heated to 150 °F, and kept 1 hour at 150 °F, post precipitation is removed water layer.In system, add 340 other ml waters then.System is heated to 150 °F, and kept 1 hour at 150 °F.Post precipitation is removed water layer.The stripping sec-butyl alcohol aqueous solution under intensification and pressure-lowering condition obtains hydrocarbyl sulfonic calcium then.
C. the preparation of high alkalinity hydrocarbyl sulfonic calcium
In 500 milliliter of 3 neck round-bottomed flask of mechanical stirrer is housed, enough thinning oils are joined in the hydrocarbyl sulfonic calcium that makes above, obtains 270 grams and contain 1.65%(weight) composition of calcium.In system, add 42.4 gram water and 10.8 gram calcium hydroxides.Reflux condensing tube is connected in the eck of a side, and thermometer is contained in the opposite side of 3 neck round-bottomed flasks.System is heated to backflow (～210), and refluxed at least 1 hour, then, under atmospheric pressure by temperature at the bottom of the bottle being heated to 330 °F, the distillation reaction system.Then under vacuum (～20 mmhg), be warming up to 400 °F.Make system be cooled to 300 °F then, and stop to vacuumize.Add 20 gram diatomite in product, and product is filtered by being lined with 1/4 inch diatomaceous Buchner funnel, above-mentioned Buchner funnel is wanted preheating before filtration, obtain total basicnumber and be about 16 title compound usually.
Embodiment 6
The preparation of 340 TBN overbased sulfurized alkylphenols as active phenol calcium
Add 196 grams in 2 liter of four neck flask and be similar to the tetrapropylene benzene phenol that the method for embodiment 3 makes, 354 gram C
18-C
30Alkylphenol (making), 410 gram decyl alcohol, 20 gram 2-mercaptobenzothiazoles, 40 gram high alkalinity hydrocarbyl sulfonic calcium (making) and 200 gram Cit Con, 100 N oil by the method that is similar to embodiment 5 with the method that is similar to embodiment 1.Stir down system is heated to 90 ℃, at this moment, in reaction system, add 296 gram Ca(OH)
2With 108 gram sulphur.Then, reaction system was kept under 90 ℃ 45 minutes.After this in 15 minutes, make temperature of reaction rise to 150 ℃,, in 60 minutes, add 206 gram 1 then by another funnel.After adding 1, in 15 minutes, make temperature rise to 160 ℃, and under this temperature constant temperature 1 hour.At this moment, the stir speed (S.S.) of augmenting response mixture is moderate to speed.Increase temperature of reaction with per 20 minutes 5 ℃ speed then, reach 175 ℃, then in reaction system, add 144 gram carbonic acid gas, last 3 hours by under meter up to temperature of reaction.Make temperature of reaction rise to 195 ℃ then, and under vacuum (～10 mmhg) stripping system 30 minutes, obtain 1269 gram products.The purification process of this product is as follows: add 3%(weight) (merchant sells diatomaceous earth products for the diatomite be made up of 50% Hi FLO and 50% 512 Celite, can be from Manville, Flitration and Minerals Division, Denver, CO has bought) then filter with the Buchner funnel that is lined with 1/4 inch Celite.The total basicnumber of products obtained therefrom is that second titrimeter of 340(is measured as 324), be 720 centistokes 100 ℃ viscosity, sulphur content is a 4.4%(weight), calcium contents is a 12.3%(weight).
Embodiment 7
The preparation of 343 TBN overbased sulfurized alkylphenols as active phenol calcium
In 10 gallons of stainless steel reactors, add 3.53 kilograms of tetrapropylene benzene phenol (making), 6.73 kilograms of C by the method that is similar to embodiment 3
18-C
30Alkylphenol (making) by the method that is similar to embodiment 1,7.6 kilogram decyl alcohol, 380 gram 2-mercaptobenzothiazoles, 760 gram high alkalinity hydrocarbyl sulfonic calcium (making) and 3.8 kilograms of Cit-Con100 N oil by the method that is similar to embodiment 5, stir down system is heated to 90 ℃, at this moment, in reaction system, add 5.62 kg of hydrogen calcium oxide and 2.05 kilograms of sulphur.Then, make reaction system 90 ℃ of constant temperature 45 minutes.Then in 15 minutes, make temperature of reaction rise to 150 ℃, subsequently,, in 60 minutes, add 3.91 gram 1 by means of another flask.After adding 1, make temperature of reaction rise to 160 ℃, and under this temperature constant temperature 1 hour.At this moment, the stir speed (S.S.) of augmenting response mixture, and, reach 175 ℃ until temperature of reaction with per 20 minutes speed rising temperature of reaction of 5 ℃, in reaction system, add 2.74 kilograms of CO subsequently
2, last 3 hours.Make temperature of reaction rise to 195 ℃ then, and descended the stripping system 30 minutes in vacuum (～10 mmhg).With the system cool overnight, heat then and stir.The purification process of products therefrom is as follows: add 3%(weight) (merchant sells diatomite for the diatomite be made up of 50% Hi-FLO and 50% 512 Celite, can be from Manville, Filtration and Minerals Dirision, Denver, CO has bought), then filter, can obtain total basicnumber is that second titrimeter of 343(is measured as 324), be that 463 centistokes, sulphur content are 4.4%(weight 100 ℃ viscosity), calcium contents is 12.4%, rough deposit is 1.6% product.
Embodiment 8
In 1 liter of 4 neck flask, add 99 gram tetrapropylene benzene phenol (making), 167 gram C by the method that is similar to embodiment 3
20-C
28Alkylphenol (making), 210 gram decyl alcohol, 10 gram 2-mercaptobenzothiazoles, 20 gram high alkalinity hydrocarbyl sulfonic calcium (making) and 100 gram Cit-Con 100N oil by the method that is similar to embodiment 5 by the method that is similar to embodiment 2.Stir down system is heated to 90 ℃, at this moment, in reaction system, add 148 gram calcium hydroxides and 56 milli sublimed sulphurs.Make then and be reflected at 90 ℃ of constant temperature 45 minutes.In 15 minutes, make temperature of reaction rise to 150 ℃ then, in 60 minutes, add 103 gram 1 subsequently.After adding 1, make temperature of reaction rise to 160 ℃, and under this temperature constant temperature 1 hour.At this moment,, reach 175 ℃, in reaction system, add 72 gram carbonic acid gas subsequently, last 3 hours until temperature of reaction with per 20 minutes speed rising temperature of reaction of 5 ℃.And then make temperature of reaction rise to 195 ℃, and descended the stripping system 30 minutes in vacuum (～10 mmhg).Remove settling, adding 800 milliliter of 250 thinner (aromatic substance, alkane and naphthenic mixture) and 3%(weight in the reaction system) (merchant sells diatomaceous earth products for the diatomite be made up of 50% Hi-FLO and 50% 512 Celite, can be from Manville, Filtration and Minerals Division, Denver.CO has bought).System is filtered by the Buchner funnel that is lined with 1/4 inch Celite.Remove thinner by stripping under heating up and reducing pressure then, to obtain 581 gram overbased sulfurized alkylphenols as active phenol calcium, other total basicnumber is that 328(is obtained by second titrimeter), be 365 centistokes 100 ℃ viscosity, sulphur content is a 3.96%(weight), calcium contents is a 12.3%(weight).
Embodiment 9
In 1 liter of 4 neck flask, add 99 gram tetrapropylene benzene phenol (making), 167 gram C by the method that is similar to embodiment 3
20-C
28Alkylphenol (making) by the method that is similar to embodiment 2,210 gram decyl alcohol, 10 gram ORTHORIX
(by Chevron Chemical company, San Francisco, the merchant that CA sells sells the calcium polysulfide product), 20 gram high alkalinity hydrocarbyl sulfonic calcium (making) and 100 gram Cit-Con 100N oil by the method that is similar to embodiment 5.Stir down system is heated to 90 ℃, at this moment, in reaction system, add 148 gram calcium hydroxides and 56 gram sublimed sulphurs.Make then and be reflected at 90 ℃ of constant temperature 45 minutes.In 15 minutes, make temperature of reaction rise to 150 ℃ then, in 60 minutes, add 103 gram 1 subsequently.After adding 1, make temperature of reaction rise to 160 ℃, and under this temperature constant temperature 1 hour.At this moment,, reach 175 ℃, in reaction system, add 72 gram carbonic acid gas subsequently, last 3 hours until temperature of reaction with per 20 minutes speed rising temperature of reaction of 5 ℃.And then make temperature of reaction rise to 195 ℃, and descended the stripping system 30 minutes in vacuum (～10 mmhg).Remove settling, in reaction system, add 800 milliliter of 250 thinner (aromatic substance, alkane and naphthenic mixture) and 3%(weight) sell diatomaceous earth products by 50% Hi-FLO(merchant, can be from Manville, Filtration and Minerals Division, Denver.CO has bought) and 50% 512 Clite(merchants sell diatomaceous earth products, can be from Manville, Filtration and Minerals Division, Denver CO. has bought) diatomite formed.System is filtered by the Buchner funnel that is lined with 1/4 inch Celite.Remove thinner by steam stripped method under intensification and reduced pressure then, obtain 500 gram overbased sulfurized alkylphenols as active phenol calcium, its total basicnumber is that 344(is obtained by second titrimeter), be 632 centistokes 100 ℃ viscosity, sulphur content is a 3.31%(weight), calcium contents is a 12.8%(weight).
Embodiment 10
In 2 liter of 4 neck flask, add 99 gram tetrapropylene benzene phenol (making), 167 gram C by the method that is similar to embodiment 3
20-C
28Alkylphenol (making), 210 gram decyl alcohol, 10 gram 2-mercaptobenzothiazoles, 20 gram high alkalinity hydrocarbyl sulfonic calcium (making) and 100 gram Cit-Con, 100 N oil by the method that is similar to embodiment 5 by the method that is similar to embodiment 2.Stir down system is heated to 90 ℃, at this moment, in reaction system, add 138 gram incinerating Do Lomite[Ca(OH)
2.Mg(OH
2)] and 56 gram sublimed sulphurs.Make then and be reflected at 90 ℃ of constant temperature 45 minutes.Then, in 15 minutes, make temperature of reaction rise to 150 ℃, in 60 minutes, add 103 gram 1 subsequently.After adding 1, make temperature of reaction rise to 160 ℃, and under this temperature constant temperature 1 hour.At this moment,, reach 175 ℃, in 3 hours, add 74 gram carbonic acid gas subsequently until temperature of reaction with per 20 minutes speed rising temperature of reaction of 5 ℃.Then, make temperature of reaction rise to 195 ℃, and descended the stripping system 30 minutes in vacuum (～10 mmhg).Remove settling, and with 800 milliliters of Chevron 250 thinners (aromatic substance, alkane and naphthenic mixture) and 3%(weight) (merchant sells diatomaceous earth products for the diatomite be made up of 50% Hi-FLO and 50% 512 Celite, can be from Manville, Filtration and Minerals Division, Denver.CO has bought) in the adding system.System is filtered by the Buchner funnel that is lined with 1/4 inch Celite.Then remove thinner, obtain 280 gram calcium-magnesium overbased sulfurized alkylphenols as active phenates by steam stripped method under intensification and reduced pressure.Its total basicnumber is that 294(is obtained by second titrimeter), be 154 centistokes 100 ℃ viscosity, sulphur content is a 3.65%(weight), calcium contents is a 7.62%(weight), Mg content is a 2.14%(weight).
Embodiment 11
In 1 liter of 3 neck flask, add 104 gram tetrapropylene benzene phenol (making), 187 gram C by the method that is similar to embodiment 3
18-C
30And C
24-C
28The mixture of alkylphenol (making), 105 gram decyl alcohol, 10 gram 2-mercaptobenzothiazoles, 20 gram high alkalinity hydrocarbyl sulfonic calcium (making) and 100 gram Cit-Con, 100 N oil by the method that is similar to embodiment 5 by the method that is similar to embodiment 4.Stir down system is heated to 90 ℃, at this moment, 148 gram calcium hydroxides and 56 gram sublimed sulphurs are added in the reaction system.。Make then and be reflected at 90 gram constant temperature 45 minutes.Then, in 15 minutes, make temperature of reaction rise to 150 ℃, in 60 minutes, add 103 gram 1 subsequently.After adding 1, make temperature of reaction rise to 160 ℃, and under this temperature constant temperature 1 hour.At this moment,, reach 175 ℃, subsequently, in 3 hours, 72 gram carbonic acid gas are added in the reaction system until temperature of reaction with per 20 minutes speed rising temperature of reaction of 5 ℃.Make temperature of reaction rise to 195 ℃ then, and descended the stripping system 30 minutes in vacuum (～10 mmhg).Remove settling, and with 800 milliliters of Chevron 250 thinners (aromatic substance, alkane and naphthenic mixture) and 3%(weight) (merchant sells diatomaceous earth products for the diatomite be made up of 50% Hi-FLO and 50% 512 Celite, can be from Manville, Filtration and Minerals Division, Denver.CO has bought) in the adding system.System is filtered by the Buchner funnel that is lined with 1/4 inch Cellte.Then remove thinner by steam stripped method under intensification and reduced pressure, obtain 601 gram overbased sulfurized alkylphenols as active phenol calcium, its total basicnumber is that second titrimeter of 349(is measured as 324), 100 ℃ viscosity is 441 centistokes, sulphur content is a 4.27%(weight), calcium contents is 12.4% (weight).
Embodiment 12
In 1 liter of 3 neck flask, add 102 gram tetrapropylene benzene phenol (making), 187 gram C by the method that is similar to embodiment 3
18-C
30And C
24-C
28Alkylphenol (making) by the method that is similar to embodiment 4,105 gram decyl alcohol, 20 gram 2-mercaptobenzothiazoles, 20 gram polyisobutenyl succinyl oxides (wherein the number-average molecular weight of polyisobutenyl is about 950) and 0.87 mole of tetren reaction use thinning oil to be diluted to (containing 2.1% nitrogen) the method preparation of about 50% active ingredient then) and 100 gram Cit-Con, 100 N oil.Stir down system is heated to 90 ℃, at this moment, 148 gram calcium hydroxides and 56 gram sublimed sulphurs are added in the reaction system.Then, make and be reflected at 90 ℃ of constant temperature 45 minutes.Then, in 15 minutes, make temperature of reaction rise to 150 ℃, in 60 minutes, add 103 gram 1 subsequently.After adding 1, make temperature of reaction rise to 160 ℃, and under this temperature constant temperature 1 hour.At this moment,, reach 175 ℃, subsequently, in 3 hours, add 72 gram carbonic acid gas and add in the reaction system until temperature of reaction with per 20 minutes speed rising temperature of reaction of 5 ℃.Make temperature of reaction rise to 195 ℃ then, and descended the stripping system 30 minutes in vacuum (～10 mmhg).Remove settling, and with 800 milliliters of Chevron 250 thinners (aromatic substance, alkane and naphthenic mixture) and 3%(weight) (merchant sells diatomaceous earth products for the diatomite be made up of 50% Hi-FLO and 50% 512 Celite, can be from Manville, Filtration and Minerals Division, Denver.CO has bought) in the adding system.System is filtered by the Buchner funnel that is lined with 1/4 inch Cellte.Then remove thinner by steam stripped method under intensification and reduced pressure, obtain overbased sulfurized alkylphenols as active phenol calcium, its total basicnumber is that 352(is obtained by first titrimeter), be 893 centistokes 100 ℃ viscosity, sulphur content is a 4.02%(weight), calcium contents is a 11.3%(weight).
Embodiment 13
Use is provided with gate, vent line, the top system that links to each other with vacuum pipeline (nozzle) and the mixing tank of hot well pipeline, at first the mixing tank top exit is led in the hot well.The steam off line valve is used trace nitrogen entraining air stream purge mixing tank then.Close thermal source, add 357 gallons of tetrapropylene benzene phenol (with the method preparation that is similar to the foregoing description 3) that have been heated to 180, and add 318 gallons of Cit-Con 100N oil that have been heated to 70.Add 630 gallons and be heated to 150 C
20-C
28Alkylphenol (with the method preparation that is similar to the foregoing description 2), 70 gallons of high alkalinity hydrocarbyl sulfonic calcium (with the method preparation that is similar to the foregoing description 5) and 866 gallons of decyl alcohol that have been heated to 70 that have been heated to 200.
Begin to stir, regulate the temperature to 150 ℃ of mixing tank then.After closing nitrogen, open the sluices and add 275 pounds of 2-mercaptobenzothiazoles in this system, closed shutter, with system 200 heating 4 hours.
Guarantee mixing tank by mixing tank to the pipeline emptying of hot well, make system be cooled to 175 °F.When the system of stirring, add 4010 pounds of white limes.Open vapour line, enter spray jet by condenser, water susceptor.Close the pipeline of mixing tank, and be adjusted to the vacuum of 10 inches of mercury to hot well.Heat 260 °F.Be added in 1327 pounds of sulphur of 250 heating.At 1 hour internal heating to 300.At this moment, at 274 gallons of 1,2 gallon of 1 of 60 minutes internal heating, during beginning, the speed of adding 1 is very slow, after adding, in 1 hour internal heating system to 335.In 2 hours 48 minutes, add 1680 pounds of carbonic acid gas.When adding carbonic acid gas, allow temperature of reaction to rise to 350 °F.
After adding carbonic acid gas, adopt vacuum (at least 28 inch of mercury).Be heated to 400 °F.In case reach 395 °F, beginning kept 30 minutes under these conditions.Be cooled to 350 °F subsequently, and break vacuum with nitrogen, be adjusted to 5 pounds/square inch (gauge pressures), obtain overbased sulfurized alkylphenols as active phenol calcium, its total basicnumber is 327, and the viscosity 100 is 1375 centistokes, calcic 12.3%, and sulfur-bearing 3.70% contains rough deposit 0.8%.By diatomite filtration and use 5%(weight) after 130N oil dilutes, obtain overbased sulfurized alkylphenols as active phenol calcium, its total basicnumber is 312, is 660 lis 100 ℃ viscosity, calcium contents is 11.6%, sulphur content is 3.32%, settling content is 0.02%.
Comparative Examples A (comparing) with embodiment 8 and 9
In 1 liter of 3 neck flask, add 99 gram tetrapropylene benzene phenol (making), 167 gram C by the method that is similar to embodiment 3
20-C
28Alkylphenol (making) by the method that is similar to embodiment 2,210 gram decyl alcohol, 20 gram high alkalinity hydrocarbyl sulfonic calcium (by the method preparation that is similar to embodiment 5) and 100 gram Cit-Con 100N oil.Stir down system is heated to 90 ℃, at this moment, 148 gram calcium hydroxides and 56 gram sublimed sulphurs are added in the reaction system.Then, make and be reflected at 90 ℃ of constant temperature 45 minutes.Then, in 15 minutes, make temperature of reaction rise to 150 ℃, in 60 minutes, add 103 gram 1 subsequently.After adding 1, make temperature of reaction rise to 160 ℃, and under this temperature constant temperature 1 hour.At this moment,, reach 175 ℃, subsequently, in 3 hours, add 72 gram carbonic acid gas until temperature of reaction with per 20 minutes speed rising temperature of reaction of 5 ℃.Make temperature of reaction rise to 195 ℃ then, and descended the stripping system 30 minutes in vacuum (～10 mmhg).Remove settling, and in reaction system, add 800 milliliter of 250 thinner (aromatic substance, alkane and naphthenic mixture) and 3%(weight) sell diatomaceous earth products by 50% Hi-FLO(merchant, can be from Manville, Filtration and Minerals Division, Denver.CO has bought) and 50% 512 Celite(merchants sell diatomite, can be from Manville, Filtration and Minerals Division, Denver, CO has bought) diatomite formed.System is filtered by the Buchner funnel that is lined with 1/4 inch Celite.Then remove thinner by steam stripped method under intensification and reduced pressure, obtain 377 gram overbased sulfurized alkylphenols as active phenol calcium, its total basicnumber is 296; 100 ℃ viscosity is 667 centistokes; Sulphur content is a 3.28%(weight) (twice test mean value); Calcium contents is a 11.6%(weight).
Comparative example B(compares with embodiment 11)
In 1 liter of 3 neck flask, add 102 gram tetrapropylene benzene phenol (making), 187 gram C by the method that is similar to embodiment 3
18-C
30And C
24-C
28The mixture of alkylphenol (making) by the method that is similar to embodiment 4,105 gram decyl alcohol, 20 gram high alkalinity hydrocarbyl sulfonic calcium (by the method preparation that is similar to embodiment 5) and 100 gram Cit-Con 100N oil.Stir down system is heated to 90 ℃, at this moment, in reaction system, add 148 gram white limes (Ca(OH)
2) and 56 gram sublimed sulphurs.Make then and be reflected at 90 ℃ of constant temperature 45 minutes.Then in 15 minutes, make temperature of reaction rise to 150 ℃, in 60 minutes, add 103 gram 1 subsequently.After adding 1, make temperature of reaction rise to 160 ℃, and under this temperature constant temperature 1 hour.At this moment,, reach 175 ℃, subsequently, in 3 hours, 72 gram carbonic acid gas are added in the reaction system until temperature of reaction with per 20 minutes speed rising temperature of reaction of 5 ℃.Then, make temperature of reaction rise to 195 ℃, and descended the stripping system 30 minutes in vacuum (～10 mmhg).Remove settling, adding 800 milliliters of Cherron 250 thinners (aromatic substance, alkane and naphthenic mixture) and 3%(weight in the system) (merchant sells diatomaceous earth products for the diatomite be made up of 50% Hi-FLO and 50% 512 Celite, can be from Manville, Filtration and Minerals Division, Denver, CO has bought).System is filtered by the Buchner funnel that is lined with 1/4 inch Cellte.Then remove thinner by steam stripped method under intensification and reduced pressure, obtain 525 gram overbased sulfurized alkylphenols as active phenol calcium, its total basicnumber is that 329(is measured as 327 with second titrimeter), 100 ℃ viscosity is 1190 centistokes, sulphur content is a 3.75%(weight), calcium contents is a 12.2%(weight), rough deposit is a 5.2%(weight).
Comparative example C(compares with embodiment 12)
In 1 liter of 3 neck flask, add 102 gram tetrapropylene base phenol (making), 187 gram C by the method that is similar to embodiment 3
18-C
30And C
24-C
28The mixture of alkylphenol [make by the method that is similar to embodiment 4), 105 gram decyl alcohol, 20 gram polyisobutenyl succinimide (number-average molecular weight of polyisobutenyl is about 950) and 0.87 mole of tetren reaction are then with the method preparation of the thinning oil dilution that contains 2.1% nitrogen into about 50% actives] and 100 gram Cit-Con 100N oil.Stir down system is heated to 90 ℃, at this moment, with 148 gram white limes (Ca(OH)
2) and 56 gram sublimed sulphurs add in the reaction systems.Make then and be reflected at 90 ℃ of constant temperature 45 minutes.Then in 15 minutes, make temperature of reaction rise to 150 ℃, in 60 minutes, add 103 gram 1 subsequently.After adding 1, make temperature of reaction rise to 160 ℃, and under this temperature constant temperature 1 hour.At this moment,, reach 175 ℃, subsequently, in 3 hours, 72 gram carbonic acid gas are added in the reaction system until temperature of reaction with per 20 minutes speed rising temperature of reaction of 5 ℃.Use temperature of reaction to rise to 195 ℃ then, and descended the stripping system 30 minutes in vacuum (～10 mmhg).Remove settling, adding 800 milliliters of Cherron 250 thinners (aromatic substance, alkane and naphthenic mixture) and 3%(weight in the system) (merchant sells diatomaceous earth products for the diatomite be made up of 50% Hi-FLO and 50% 512 Celite, can be from Manville, Filtration and Minerals Division, Denver, CO has bought).System is filtered by the Buchner funnel that is lined with 1/4 inch Celite.Then remove thinner by steam stripped method under intensification and reduced pressure, obtain overbased sulfurized alkylphenols as active phenol calcium, its total basicnumber is that 331(records with first titrimeter), be 907 centistokes 100 ℃ viscosity, sulphur content is a 3.94%(weight), calcium contents is a 10.3%(weight).
Comparative example D(compares with embodiment 6)
In 2 liter of 4 neck flask, add 104 gram tetrapropylene base phenol (making), 178 gram C by the method that is similar to embodiment 3
18-C
30Alkylphenol (making), 105 gram decyl alcohol, 20 gram high alkalinity hydrocarbyl sulfonic calcium (making) and 100 gram Cit-Con 100N oil by the method that is similar to embodiment 5 by the method that is similar to embodiment 1.Stir down system is heated to 90 ℃, at this moment, 148 gram calcium hydroxides and 56 gram sublimed sulphurs are added in the reaction system.Make reaction system 90 ℃ of constant temperature 45 minutes then.Then, in 15 minutes, make temperature of reaction rise to 150 ℃,, in 60 minutes, add 103 gram 1 subsequently by another funnel.After adding 1, in 15 minutes, make temperature of reaction rise to 160 ℃, and under this temperature constant temperature 1 hour.At this moment, the stir speed (S.S.) of augmenting response mixture is moderate to speed, with per 20 minutes speed rising temperature of reaction of 5 ℃, reaches 175 ℃ until temperature of reaction then, in 3 hours 72 gram carbonic acid gas is added reaction system by under meter subsequently.Use temperature of reaction to rise to 195 ℃ then, and descended the stripping system 30 minutes in vacuum (～10 mmhg).Obtain 608 gram products, the purification step of this product is as follows: add 3%(weight) (merchant sells diatomaceous earth products for the diatomite be made up of 50% Hi-Flo and 50% Celite 512, can be from Manville, Filtration and Minerals Division, Denver.CO has bought).Then filter by the Buchner funnel that is lined with 1/4 inch Celite.The total basicnumber of resulting product is that 336(is measured as 335 TBN by second titrimeter), be 1323 centistokes 100 ℃ viscosity, sulphur content is a 3.95%(weight), calcium contents is a 12.5%(weight).
The I of tabulating down illustrates some embodiment and comparative example's comparison arranged side by side.
The table I
Catalyzer TBN viscosity * sulphur calcium rough deposit
Centistoke weight % weight %
Embodiment 8 MBT 328
B365 3.96 12.3 1.2%
Embodiment 9 ORTHORIX
344
B632 3.31 12.8 4%
Contrast implements not have 296
B667 3.28 11.6 7.2%
Example A
Embodiment 11 MBT 349
A441 4.27 12.4 2.8%
Contrast implements not have 329
A1,190 3.75 12.2 5.2%
Example B
Embodiment 12 MBT 352
A893 4.02 11.3 2.8%
Contrast implements not have 331
A907 3.94 10.3 3.2%
Example C
Embodiment 6 MBT 340
B720 4.4 12.3 1.4%
Contrast implements not have 336
B1,323 3.95 12.5 2.4%
Example D
The TBN value that A-is recorded by first titrimeter
The TBN value that B-is recorded by second titrimeter
* under 100 ℃, record
The table I shows that under conditions of similarity, compare with the product that obtains without sulphurized catalyst with the product that sulphurized catalyst obtains, the former TBN is higher, and viscosity is lower, and rough deposit is less.
Under tabulate II and the table III in, TBN height, viscosity that embodiment 14-17 further illustrates product of the present invention are low.These products prepare with the method that is similar to embodiment 6-13.
The table II
Embodiment
*AP lime/sulphur/catalyst agent CO
2' decyl alcohol 1, the 2-glycol/
AP AP AP
AP
Mol ratio mol ratio (gram) mol ratio (gram) mol ratio
14 A 2.7 2.07 MBT 10 2.21 210 2.01
15 A 2.7 2.36 MORFAX
110 2.21 210 2.24
16 A 2.7 2.36 ORTHORIX
210 2.21 210 2.24
17 B 2.7 2.36 MBT 10 2.21 105 2.24
* embodiment 14-17 uses 20 gram high alkalinity hydrocarbyl sulfonic calcium and 100 gram Cit-Con 100N oil
The AP=alkylphenol
The whole alkylphenols of A=0.74 mole (0.37 mole of tetrapropylene benzene phenol and 0.37 mole of (166 gram) C
20-C
28Alkylphenol)
The whole alkylphenols of B=0.74 mole (0.37 mole of tetrapropylene benzene phenol and 0.37 mole of (177 gram) C
18-C
30Alkylphenol)
1.Mor fax=R.T.Vanderbiilt company, Norwalk, the merchant of CT sells prescription, it contains 2-(4-morpholinyl two sulphur) benzothiazole
2.ORTHORIX
=Chevron Chemical company, San Francisco, the merchant of CA sells prescription, it contains 25%(weight) calcium polysulfide, 65%(weight) water, 10%(weight) Triton x-45(merchant sells emulsion splitter, can be from Rohm and Haas, Philadelphia PA has bought) and defoamer
The table III
TBN viscosity sulphur calcium rough deposit
(100 ℃) weight % weight %
Embodiment 14
C338 561 ± 28 4.3 12.2 2.8
Embodiment 15 324 360 3.74 12.4 2.0
Embodiment 16 337 501 3.49 12.7 2.0
Embodiment 17 331 424 4.1 12.7 1.6
C-is diluted to 3% extent of dilution with Cit-Con 100N
The overbased sulfurized alkylphenols as active phenates of II of the present invention family metal is characterised in that in the active ingredient and contains at least 90%, preferably at least 95% II family sulfurized metal phenate salt and in active ingredient, contain no more than about 10%, the best not alkyl monosulfide phenates of no more than about 5% II family metal.TBN contains the not alkyl monosulfide phenates that substantially exceeds 10% II family metal in the prior art in active ingredient greater than the alkyl monosulfide phenates of 300 II family metal.The composition of prior art can prepare with described single stage method of top Comparative Examples A-D or the described two-step approach of following embodiment E.
Comparative example E
Step 1: the preparation of sulfenyl phenolate calcium salt
In 3 liter of 3 neck flask, add 529 gram tetrapropylene benzene phenol (making), 274 gram C by the method that is similar to embodiment 3
18-C
30Alkylphenol (making) and 250 gram Cit-Con 100N by the method that is similar to embodiment 1.System is heated to 90 ℃, and adds 50 gram calcium hydroxides and 112.5 gram sublimed sulphurs.System is heated to 175 ℃, in 30 minutes, adds 32.5 gram 1.System 175 ℃ of constant temperature 1 hour, was vacuumized (～10 mmhg) 4 hours, then with the stripping 1.At 135 ℃, add the C that 127.5 grams are obtained by wax cracking together
15-C
18Alpha-olefin and with 122.5 gram Cit-Con 100N, and system heated in nitrogen atmosphere 8 hours.With the 50-50 mixture (diatomaceous earth products of product by Hi-FLO and Celite 512, can be from Manville, Filtration and Minerals Division, Denver, CO has bought) filter, obtain 1351 gram products, the total basicnumber of this product be 63, contain 1.94%(weight) calcium and 4.47%(weight) sulphur.
Step 2: the preparation of overbased sulfurized alkylphenols as active phenol calcium salt
In 1 liter of 3 neck flask, add the product that 380 gram steps 1 make, 20 gram polyisobutenyl succinimide disperser compositions are (by reacting 1 mole of polyisobutene succinyl oxide (wherein the number-average molecular weight of polyisobutenyl is 950) and 0.87 mole of tetren, be diluted to the method preparation that contains 50% actives approximately with thinning oil then) and 48 restrain decyl alcohol, and system is heated to 150 ℃.Slowly add 74.5 gram 1, and system is heated to 175 ℃.In 4 hours, add 61 gram carbonic acid gas.At 90 ℃, vacuum (～10 mmhg) is stripped product down, and with the 50-50 mixture (diatomaceous earth products of product by Hi-FLO and Celite 512, can be from Manville, Filtration and Minerais Division, Denver, CO. has bought) filter, obtain 485 gram overbased sulfurized alkylphenols as active phenol calcium.Its total basicnumber is 334, is 2405 lis 100 ℃ viscosity, and sulphur content is a 2.7%(weight), calcium contents is a 12.1%(weight).
By following dialysis and
1H-NMR technology (embodiment 18) is analyzed composition of the present invention and prior art composition with the method for the content of the not alkyl monosulfide phenates of the alkyl monosulfide phenates of measuring II family metal and II family metal.
Embodiment 18
With following method composition of the present invention and prior art composition are analyzed.The overbased sulfurized alkylphenols as active phenates additive that claims 50 gram II family metals is in the dialysis bag of crossing with acetone rinsing (Ramses number 18 prevention bags) of packing into.This bag is suspended in 2 liters of beakers that fill the 1.5 liter of 60% volume methylethylketone and the 40% volume trimethyl carbinol.With magnetic stirrer stirred solution at room temperature.Solution of conversion in per 24 hours lasts 7 days.Use rotary evaporator and final stripping blended dialysis solution under 85 ℃, the vacuum of 1 mmhg, obtain product, take by weighing its weight.Measure this product with H-NMR in the hexamethylphosphoramide solvent, the result is that it contains thinning oil (Cit-Con 100N) and sulfenyl phenolate raw material not.Not sulfenyl phenolate in this solvent shows
1The H-NMR peak 10.00 to 10.11ppm(with respect to adding as interior target tetramethylsilane).The alkylphenol of embodiment 1-4 also demonstrates this
1The H-NMR value, therefore, it is the characteristic peak of sulfenyl phenolate not.
Take by weighing the weight of solid residue in the dialysis bag.This residue contains in the overbased sulfurized alkylphenols as active phenates preparation of original II family metal the whole calcium (or other II family metal) more than 95% and is referred to as " active ingredient ".This residue or " active ingredient " Containing Sulfur high alkalinity alkylphenol calcium and any not calcium sulfenyl phenolate.The composition of " active ingredient " is by following assay." active ingredient " is dissolved in the blended hexane, is dissolved in 100% alcoholic acid concentrated hydrochloric acid with 100 milliliters then and handles.After adding hydrochloric acid, at room temperature mixture was stirred 1 hour, make " active ingredient " decalcification fully.Unvulcanized alkylphenol under the sulfenyl phenolate that can obtain to discharge by following step and some situation, these steps comprise and wash hexane solution with water, with 10% sodium bicarbonate aqueous solution washing hexane solution, under 120 mmhg and 80-85 ℃, carry out stripping then, obtain " active ingredient " product of decalcification, this product carries out in the hexamethylphosphoramide (HMPA is as solvent) that contains as interior target TMS
1H-NMR analyzes.The peak that shows of sulfenyl phenolate is not 10.00 to 10.11, and is referred to as S
0The peak.For single sulfide bridge joint alkylphenol, the alkyl monosulfide phenols demonstrates the peak 10.40 to 10.50, and is referred to as S
1The peak.For disulphide bridge joint alkylphenol, the alkyl monosulfide phenols also demonstrates the peak 10.90 to 11.00, and is referred to as S
2The peak.The area at these peaks can obtain by carry out quadrature on Varian T60 or General Electric QE-300MHz NMR spectrometer.By with S
1And S
2Separately integration is asked the method (supposing it is dimeric structure) of peak area, can convert integral area to molar percentage.
Term used herein " active ingredient " is a kind of the measuring of content of the not alkyl monosulfide phenates of the alkyl monosulfide phenates of II family metal in the composition and II family metal, and its available described step and other standard analytical techniques are measured.
The table IV
The analytical results of the active ingredient that embodiment 18 obtains
Molar percentage TBN viscosity in the active ingredient
S
0S
1S
2(centistoke, 100 ℃)
Embodiment 11 0 30 70 349 441
Comparative example B 15 20 65 333 538
Embodiment 12 0 34 66 352 893
Comparative example C 18 29 53 331 901
Comparative example E 16 25 59 334 2405
1.S
0The molar percentage of=calcium (not sulfenyl phenolate)
2.S
1The molar percentage of=calcium (alkyl monosulfide phenol)
3.S
2The molar percentage of=calcium (curing alkylphenol)
Following table V confirms that the content of the not alkyl monosulfide phenates of II family metal is disadvantageous to the overbased sulfurized alkylphenols as active phenates composition of II family metal.Specifically, as the table shows, the calcium salt of the alkylphenol of embodiment 3 is extremely sticking, and therefore, if there is effectively amount, it will obviously increase the viscosity of the overbased sulfurized alkylphenols as active phenates composition of II family metal.Equally, the calcium salt of the alkylphenol of embodiment 4 (viscosity of the calcium salt of the alkylphenol of its viscosity ratio embodiment 3 is much lower) does not have much contributions to the total basicnumber of composition.Therefore, if there is effectively amount, it will reduce the total basicnumber of the overbased sulfurized alkylphenols as active phenates composition of II family metal significantly, on the other hand, the overbased sulfurized alkylphenols as active phenates class of II of the present invention family metal contains the alkyl phenate of unvulcanized II family metal hardly, therefore, has high total basicnumber and suitable viscosity.The result of embodiment 6 comprises illustration purpose.
The table V
TBN viscosity (100 ℃)
The calcium salt of the alkylphenol of embodiment 3
(a)221 is too sticking so that energy measurement not
Be diluted to 50% with Cit-Con 100N
(a)105 112 centistokes
Calcium salt 54 18 centistokes of the alkylphenol of embodiment 4
(representing about 50% conversion)
Embodiment 11 349 441 centistokes
(a) by being reacted in 1 at 175 ℃, alkylphenol and excessive white lime (0.69 equivalent) makes.
Embodiment 19
With continuous V-D test method (according to the test of the candidate of ASTM) the making up oil of overbased sulfurized alkylphenols as active phenates that contains II of the present invention family metal tested.This method is utilized Ford2.3 liter, 4 cylinder Pinto engines.This test method is imitated a class and is just carved occasion testing apparatus (severe field test service), it is characterized in that with low Chuo the city mobility operation and the intermediate road running of low temperature " stop-go " combine.Additive in the oil connects by 0 to 10 grade of scope in the effect on sludge and the lacquer deposits of preventing and measures, and 0 shows it is the settling of black, 10 no paint film of expression or sludgy deposits things.The table VI has been listed its result.
Use is similar to the product that embodiment 6 and 7 described methods make and has carried out continuous V-D test.With these products and TBN is that 250 merchant sells calcium sulfenyl phenolate (being made by embodiment 3 described alkylphenols) and compares.
What make up oil consists of: 5.25% pair-polyisobutenyl succinimide; Every kilogram 20 mmole such as embodiment 5 described high alkalinity hydrocarbyl sulfonates; The product that the method that the hydrocarbyl sulfonate of every kilogram 20 mmole 320 TBN, every kilogram 82 mmole are similar to embodiment 6 and 7 makes, every kilogram 20 mmole curing zinc phosphate; 20% merchant in 150N/600N Exxon base oil (600N of the 150N of 85% weight and 15% weight) sells viscosity index improver.
Replace the high TBN phenates (being made by the method that is similar to embodiment 6 and 7) except selling 250 TBN phenates (being made by embodiment 3 described alkylphenols) with every kilogram 82 mmole merchant, the prescription of comparison is with reference to as above used same recipe.
Continuous V-D result
The prescription settling that contains phenates
AS
（1）AV
（2）PV
（3）
(test of nineteen eighty-three) 8.3 earlier
47.9
47.9
4
(tests in 1984) 8.9 8.0 8.0 are arranged
Skill (tests in 1985) 8.9 7.7 8.0
Art
By being similar to embodiment 6 9.6 9.0 8.8
Make with 7 method
The phenates of high TBN
(5)
(tests in 1985)
(1) average sludge
(2) average paint film
(3) piston paint film
That tests for (4) 6 times is average
That tests for (5) 2 times is average
Claims (32)
1, a kind of overbased sulfurized alkylphenols as active phenates that is dissolved in the II family metal of oil, it is characterized in that: total basicnumber is about 300 and Geng Gao, be about 800 centistokes or lower 100 ℃ viscosity, and the alkyl phenate content of unvulcanized II family metal is lower than about 10% (mole) in active ingredient.
2, the described overbased sulfurized alkylphenols as active phenates that is dissolved in the II family metal of oil of claim 1, wherein the alkyl in the alkylphenol contains 25 to 100%(moles) be mainly the straight chained alkyl of 15 to 35 carbon atoms, 75 at the 0%(mole) alkyl be the polypropylene-base of 9 to 18 carbon atoms.
3, the described overbased sulfurized alkylphenols as active phenates that is dissolved in the II family metal of oil of claim 2, wherein the alkyl in the alkylphenol contains 40 to 70%(moles) be mainly the straight chained alkyl of 15 to 35 carbon atoms, 60 to 30%(moles) alkyl be the polypropylene-base of 9 to 18 carbon atoms.
4, the described overbased sulfurized alkylphenols as active phenates that is dissolved in the II family metal of oil of claim 3, wherein the alkyl in the alkylphenol contains about 50%(mole) be mainly the straight chained alkyl of 15 to 35 carbon atoms, about 50% alkyl is the polypropylene-base of 9 to 18 carbon atoms.
5, the described overbased sulfurized alkylphenols as active phenates of II family metal that is dissolved in oil of claim 1, wherein said II family metal is selected from calcium, magnesium and barium.
6, the described overbased sulfurized alkylphenols as active phenates of II family metal that is dissolved in oil of claim 5, wherein said II family metal is a calcium.
7, the described overbased sulfurized alkylphenols as active phenates of II family metal that is dissolved in oil of claim 4, wherein said II family metal is selected from calcium, magnesium and barium.
8, the described overbased sulfurized alkylphenols as active phenates of II family metal that is dissolved in oil of claim 7, wherein said II family metal is a calcium.
9, a kind of lubricating oil composition, said composition contain a kind of lubricating oil and about 0.5 to 40%(weight with certain viscosity) the described overbased sulfurized alkylphenols as active phenates that is dissolved in the II family metal of oil of claim 1.
10, a kind of lubricating oil composition, said composition contain a kind of lubricating oil and about 0.5 to 40%(weight with certain viscosity) the described overbased sulfurized alkylphenols as active phenates that is dissolved in the II family metal of oil of claim 2.
11, a kind of lubricating oil composition, said composition contain a kind of lubricating oil and about 0.5 to 40%(weight with certain viscosity) the described overbased sulfurized alkylphenols as active phenates that is dissolved in the II family metal of oil of claim 3.
12, a kind of lubricating oil composition, said composition contain a kind of lubricating oil and about 0.5 to 40%(weight with certain viscosity) the described overbased sulfurized alkylphenols as active phenates that is dissolved in the II family metal of oil of claim 4.
13, a kind of lubricating oil composition, said composition contain a kind of lubricating oil and about 0.5 to 40%(weight with certain viscosity) the described overbased sulfurized alkylphenols as active phenates that is dissolved in the II family metal of oil of claim 5.
14, a kind of lubricating oil composition, said composition contain a kind of lubricating oil and about 0.5 to 40%(weight with certain viscosity) the described overbased sulfurized alkylphenols as active phenates that is dissolved in the II family metal of oil of claim 6.
15, a kind of lubricating oil composition, said composition contain a kind of lubricating oil and about 0.5 to 40%(weight with certain viscosity) the described overbased sulfurized alkylphenols as active phenates that is dissolved in the II family metal of oil of claim 7.
16, a kind of lubricating oil composition, said composition contain a kind of lubricating oil and about 0.5 to 40%(weight with certain viscosity) the described overbased sulfurized alkylphenols as active phenates that is dissolved in the II family metal of oil of claim 8.
17, a kind of lubricating oil composition, said composition contain a kind of lubricating oil with certain viscosity and
(a) the described overbased sulfurized alkylphenols as active phenates that is dissolved in II family metal oil, hydrolysis-stable of claim 1 about 0.5 to 40%(weight); With
Natural or the synthetic hydrocarbyl sulfonate of high alkalinity of the II family metal that is dissolved in oil (b) about 0.5 to 40%(weight).
18, a kind of lubricating oil composition, said composition contain a kind of lubricating oil with certain viscosity and
(a) about 0.5 to 40%(weight) the described overbased sulfurized alkylphenols as active phenol that is dissolved in the II family metal of oil of claim 2; With
(b) about 0.5 to 40%(weight) be dissolved in the natural or synthetic hydrocarbyl sulfonate of high alkalinity of II family metal of oil.
19, a kind of lubricating oil composition, said composition contain a kind of lubricating oil with certain viscosity and
(a) about 0.5 to 40%(weight) the described overbased sulfurized alkylphenols as active phenol that is dissolved in the II family metal of oil of claim 3; With
(b) about 0.5 to 40%(weight) be dissolved in the natural or synthetic hydrocarbyl sulfonate of high alkalinity of II family metal of oil.
20, a kind of lubricating oil composition, said composition contain a kind of lubricating oil with certain viscosity and
(a) about 0.5 to 40%(weight) the described overbased sulfurized alkylphenols as active phenol that is dissolved in the II family metal of oil of claim 4; With
(b) about 0.5 to 40%(weight) be dissolved in the natural or synthetic hydrocarbyl sulfonate of high alkalinity of II family metal of oil.
21, a kind of lubricating oil composition, said composition contain a kind of lubricating oil with certain viscosity and
(a) about 0.5 to 40%(weight) the described overbased sulfurized alkylphenols as active phenol that is dissolved in the II family metal of oil of claim 5; With
(b) about 0.5 to 40%(weight) be dissolved in the natural or synthetic hydrocarbyl sulfonate of high alkalinity of II family metal of oil.
22, a kind of lubricating oil composition, said composition contain a kind of lubricating oil with certain viscosity and
(a) about 0.5 to 40%(weight) the described overbased sulfurized alkylphenols as active phenol that is dissolved in the II family metal of oil of claim 6; With
(b) about 0.5 to 40%(weight) be dissolved in the natural or synthetic hydrocarbyl sulfonate of high alkalinity of II family metal of oil.
23, a kind of lubricating oil composition, said composition contain a kind of lubricating oil with certain viscosity and
(a) about 0.5 to 40%(weight) the described overbased sulfurized alkylphenols as active phenol that is dissolved in the II family metal of oil of claim 7; With
(b) about 0.5 to 40%(weight) be dissolved in the natural or synthetic hydrocarbyl sulfonate of high alkalinity of II family metal of oil.
24, a kind of lubricating oil composition, said composition contain a kind of lubricating oil with certain viscosity and
(a) about 0.5 to 40%(weight) the described overbased sulfurized alkylphenols as active phenol that is dissolved in the II family metal of oil of claim 8; With
(b) about 0.5 to 40%(weight) be dissolved in the natural or synthetic hydrocarbyl sulfonate of high alkalinity of II family metal of oil.
25, a kind of lubricant oil concentrate, this enriched material contain about 60 to 20%(weight) lubricating oil and about 40 to 80%(weight of certain viscosity) the described overbased sulfurized alkylphenols as active phenates that is dissolved in the II family metal of oil of claim 1.
26, a kind of lubricant oil concentrate, this enriched material contain about 60 to 20%(weight) lubricating oil and about 40 to 80%(weight of certain viscosity) the described overbased sulfurized alkylphenols as active phenates that is dissolved in the II family metal of oil of claim 2.
27, a kind of lubricant oil concentrate, this enriched material contain about 60 to 20%(weight) lubricating oil and about 40 to 80%(weight of certain viscosity) the described overbased sulfurized alkylphenols as active phenates that is dissolved in the II family metal of oil of claim 3.
28, a kind of lubricant oil concentrate, this enriched material contain about 60 to 20%(weight) lubricating oil and about 40 to 80%(weight of certain viscosity) the described overbased sulfurized alkylphenols as active phenates that is dissolved in the II family metal of oil of claim 4.
29, a kind of lubricant oil concentrate, this enriched material contain about 60 to 20%(weight) lubricating oil and about 40 to 80%(weight of certain viscosity) the described overbased sulfurized alkylphenols as active phenates that is dissolved in the II family metal of oil of claim 5.
30, a kind of lubricant oil concentrate, this enriched material contain about 60 to 20%(weight) lubricating oil and about 40 to 80%(weight of certain viscosity) the described overbased sulfurized alkylphenols as active phenates that is dissolved in the II family metal of oil of claim 6.
31, a kind of lubricant oil concentrate, this enriched material contain about 60 to 20%(weight) lubricating oil and about 40 to 80%(weight of certain viscosity) the described overbased sulfurized alkylphenols as active phenates that is dissolved in the II family metal of oil of claim 7.
32, a kind of lubricant oil concentrate, this enriched material contain about 60 to 20%(weight) lubricating oil and about 40 to 80%(weight of certain viscosity) the described overbased sulfurized alkylphenols as active phenates that is dissolved in the II family metal of oil of claim 8.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US89459986A | 1986-08-08 | 1986-08-08 | |
| US894,599 | 1986-08-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87105448A true CN87105448A (en) | 1988-04-13 |
| CN1021345C CN1021345C (en) | 1993-06-23 |
Family
ID=25403296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87105448A Expired - Fee Related CN1021345C (en) | 1986-08-08 | 1987-08-08 | Lubricant composition using high tbn, low viscosity, group 2 metal overbased sulfurized alkylphenols as active constituent |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP0259974B2 (en) |
| JP (1) | JPS6346297A (en) |
| KR (1) | KR880002818A (en) |
| CN (1) | CN1021345C (en) |
| AU (1) | AU602343B2 (en) |
| BR (1) | BR8704053A (en) |
| CA (1) | CA1341002C (en) |
| DE (1) | DE3785807T3 (en) |
| DK (1) | DK410087A (en) |
| ES (1) | ES2054677T3 (en) |
| IN (1) | IN170575B (en) |
| MX (1) | MX168483B (en) |
| NO (1) | NO167659C (en) |
| NZ (1) | NZ221128A (en) |
| ZA (1) | ZA875686B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045309C (en) * | 1993-11-23 | 1999-09-29 | 辛辛那提米勒克朗公司 | Sulfurized aqueous machining fluid composition |
| CN103987693A (en) * | 2011-11-10 | 2014-08-13 | 雪佛龙奥伦耐有限责任公司 | Lubricating oil compositions |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3454593B2 (en) * | 1994-12-27 | 2003-10-06 | 旭電化工業株式会社 | Lubricating oil composition |
| US7405185B2 (en) | 2003-09-26 | 2008-07-29 | Chevron Oronite Company Llc | Process for making Group II metal overbased sulfurized alkylphenols |
| ES2655116T3 (en) * | 2006-09-19 | 2018-02-16 | Infineum International Limited | A lubricating oil composition |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3178368A (en) * | 1962-05-15 | 1965-04-13 | California Research Corp | Process for basic sulfurized metal phenates |
| NL134001C (en) * | 1965-10-29 | |||
| US3367867A (en) * | 1966-01-04 | 1968-02-06 | Chevron Res | Low-foaming overbased phenates |
| US3424679A (en) * | 1966-08-15 | 1969-01-28 | Chevron Res | Nonvicinal glycols in overbased phenate preparation |
| GB1144084A (en) * | 1966-08-24 | 1969-03-05 | Orobis Ltd | Improvements in or relating to lubricant additives |
| US3464970A (en) * | 1967-03-13 | 1969-09-02 | Maruzen Oil Co Ltd | Process for preparing over-based sulfurized calcium phenates |
| GB1280749A (en) * | 1970-06-18 | 1972-07-05 | Maruzen Oil Company Ltd | Process for preparation of over-based sulphurized phenates |
| US3801507A (en) * | 1972-08-18 | 1974-04-02 | Chevron Res | Sulfurized metal phenates |
| GB1429243A (en) * | 1973-02-22 | 1976-03-24 | Orobis Ltd | Overbased phenates |
| GB1551819A (en) * | 1975-05-23 | 1979-09-05 | Exxon Research Engineering Co | Production of basic magnesium detergent additives |
| US4104180A (en) * | 1975-05-23 | 1978-08-01 | Exxon Research & Engineering Co. | Production of overbased metal phenates |
| BE871932R (en) * | 1977-11-11 | 1979-05-10 | Orobis Ltd | ADDITIVE FOR LUBRICATING OILS FORMED BY NEUTRALIZATION OF AN ALKYLPHENOL SULFIDE AND A MANNICH BASE |
| EP0094814B1 (en) * | 1982-05-14 | 1989-04-19 | Exxon Research And Engineering Company | Lubricating oil additives |
| FR2529226B1 (en) * | 1982-06-24 | 1987-01-16 | Orogil | PROCESS FOR THE PREPARATION OF SULFURIZED ALKYLPHENATES OF ALKALINE EARTH METALS FOR USE AS ADDITIVES FOR LUBRICATING OILS |
| FR2549080B1 (en) * | 1983-07-11 | 1986-04-04 | Orogil | PROCESS FOR THE PREPARATION OF VERY HIGH ALKALINITY DETERGENT-DISPERSANT ADDITIVES BASED ON CALCIUM AND DETERGENT-DISPERSANT ADDITIVES FOR LUBRICATING OILS THUS OBTAINED |
| FR2587353B1 (en) * | 1985-09-17 | 1987-11-20 | Orogil | NOVEL HYDROLYSIS-STABLE SURALKALINIZED DETERGENT-DISPERSANT ADDITIVES FOR LUBRICATING OILS AND PROCESS FOR PREPARING THE SAME |
-
1987
- 1987-07-20 NZ NZ221128A patent/NZ221128A/en unknown
- 1987-07-28 CA CA000543119A patent/CA1341002C/en not_active Expired - Fee Related
- 1987-07-31 AU AU76334/87A patent/AU602343B2/en not_active Ceased
- 1987-07-31 ZA ZA875686A patent/ZA875686B/en unknown
- 1987-08-06 DK DK410087A patent/DK410087A/en not_active Application Discontinuation
- 1987-08-07 NO NO873316A patent/NO167659C/en unknown
- 1987-08-07 BR BR8704053A patent/BR8704053A/en not_active Application Discontinuation
- 1987-08-07 EP EP87307025A patent/EP0259974B2/en not_active Expired - Lifetime
- 1987-08-07 MX MX026955A patent/MX168483B/en unknown
- 1987-08-07 KR KR1019870008668A patent/KR880002818A/en not_active Application Discontinuation
- 1987-08-07 ES ES87307025T patent/ES2054677T3/en not_active Expired - Lifetime
- 1987-08-07 DE DE3785807T patent/DE3785807T3/en not_active Expired - Fee Related
- 1987-08-07 JP JP62197989A patent/JPS6346297A/en active Pending
- 1987-08-08 CN CN87105448A patent/CN1021345C/en not_active Expired - Fee Related
-
1988
- 1988-01-05 IN IN05/MAS/88A patent/IN170575B/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045309C (en) * | 1993-11-23 | 1999-09-29 | 辛辛那提米勒克朗公司 | Sulfurized aqueous machining fluid composition |
| CN103987693A (en) * | 2011-11-10 | 2014-08-13 | 雪佛龙奥伦耐有限责任公司 | Lubricating oil compositions |
| CN103987693B (en) * | 2011-11-10 | 2017-02-22 | 雪佛龙奥伦耐有限责任公司 | Lubricating oil compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0259974A2 (en) | 1988-03-16 |
| DK410087A (en) | 1988-02-09 |
| BR8704053A (en) | 1988-04-05 |
| ES2054677T3 (en) | 1994-08-16 |
| JPS6346297A (en) | 1988-02-27 |
| MX168483B (en) | 1993-05-26 |
| KR880002818A (en) | 1988-05-11 |
| NO873316L (en) | 1988-02-09 |
| IN170575B (en) | 1992-04-11 |
| EP0259974B1 (en) | 1993-05-12 |
| CA1341002C (en) | 2000-05-30 |
| NO873316D0 (en) | 1987-08-07 |
| ZA875686B (en) | 1988-04-27 |
| EP0259974A3 (en) | 1988-08-10 |
| DK410087D0 (en) | 1987-08-06 |
| AU602343B2 (en) | 1990-10-11 |
| DE3785807T2 (en) | 1993-10-07 |
| DE3785807T3 (en) | 1997-06-12 |
| CN1021345C (en) | 1993-06-23 |
| EP0259974B2 (en) | 1997-03-26 |
| NO167659B (en) | 1991-08-19 |
| DE3785807D1 (en) | 1993-06-17 |
| AU7633487A (en) | 1988-02-11 |
| NO167659C (en) | 1991-11-27 |
| NZ221128A (en) | 1989-09-27 |
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