US3718589A - Preparation of neutral and highly basic alkylphenates and sulfurized alkylphenates - Google Patents
Preparation of neutral and highly basic alkylphenates and sulfurized alkylphenates Download PDFInfo
- Publication number
- US3718589A US3718589A US00176676A US3718589DA US3718589A US 3718589 A US3718589 A US 3718589A US 00176676 A US00176676 A US 00176676A US 3718589D A US3718589D A US 3718589DA US 3718589 A US3718589 A US 3718589A
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- US
- United States
- Prior art keywords
- alkylphenol
- process defined
- parts
- sulfurized
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 230000007935 neutral effect Effects 0.000 title abstract description 30
- 238000002360 preparation method Methods 0.000 title description 12
- 238000000034 method Methods 0.000 claims abstract description 116
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 108
- 239000011777 magnesium Substances 0.000 claims abstract description 108
- 230000008569 process Effects 0.000 claims abstract description 106
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 105
- 239000000203 mixture Substances 0.000 claims abstract description 81
- 239000000463 material Substances 0.000 claims abstract description 45
- 239000003085 diluting agent Substances 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 238000010992 reflux Methods 0.000 claims abstract description 18
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 11
- 239000003921 oil Substances 0.000 claims description 66
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 53
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 37
- 239000011541 reaction mixture Substances 0.000 claims description 22
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 19
- 239000010688 mineral lubricating oil Substances 0.000 claims description 9
- 239000010689 synthetic lubricating oil Substances 0.000 claims description 8
- JKTAIYGNOFSMCE-UHFFFAOYSA-N 2,3-di(nonyl)phenol Chemical compound CCCCCCCCCC1=CC=CC(O)=C1CCCCCCCCC JKTAIYGNOFSMCE-UHFFFAOYSA-N 0.000 claims description 6
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 abstract description 27
- 238000010438 heat treatment Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 235000019198 oils Nutrition 0.000 description 54
- 239000000047 product Substances 0.000 description 29
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 19
- 239000001569 carbon dioxide Substances 0.000 description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 description 12
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 11
- -1 magnesium alkoxy alkoxides Chemical class 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000010687 lubricating oil Substances 0.000 description 7
- 239000007858 starting material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BIHAYMZIGOJYKX-UHFFFAOYSA-M C([O-])(O)=O.C(C)OC([O-])C.[Mg+2] Chemical compound C([O-])(O)=O.C(C)OC([O-])C.[Mg+2] BIHAYMZIGOJYKX-UHFFFAOYSA-M 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- YXOSSQSXCRVLJY-UHFFFAOYSA-N magnesium;2-methoxyethanolate Chemical compound COCCO[Mg]OCCOC YXOSSQSXCRVLJY-UHFFFAOYSA-N 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 241001647090 Ponca Species 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([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])[H] 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- JRLTTZUODKEYDH-UHFFFAOYSA-N 8-methylquinoline Chemical group C1=CN=C2C(C)=CC=CC2=C1 JRLTTZUODKEYDH-UHFFFAOYSA-N 0.000 description 1
- DWKXSNPRMXPRKO-UHFFFAOYSA-M C([O-])(O)=O.COC([O-])C.[Mg+2] Chemical compound C([O-])(O)=O.COC([O-])C.[Mg+2] DWKXSNPRMXPRKO-UHFFFAOYSA-M 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 125000003901 ceryl group Chemical group [H]C([*])([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])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])C([H])([H])[H] 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 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
- 230000000694 effects Effects 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- FYAQQULBLMNGAH-UHFFFAOYSA-N hexane-1-sulfonic acid Chemical compound CCCCCCS(O)(=O)=O FYAQQULBLMNGAH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000010699 lard oil Substances 0.000 description 1
- PGBDMBUYZOQDOH-UHFFFAOYSA-N magnesium;1-ethoxyethanolate Chemical compound [Mg+2].CCOC(C)[O-].CCOC(C)[O-] PGBDMBUYZOQDOH-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001802 myricyl group Chemical group [H]C([*])([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])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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000346 nonvolatile oil Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
- C07C37/66—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring by conversion of hydroxy groups to O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/06—Well-defined aromatic compounds
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/024—Propene
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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/028—Overbased salts thereof
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
- C10M2207/404—Fatty vegetable or animal oils obtained from genetically modified species
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- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/084—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/042—Metal salts thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
- C10N2070/02—Concentrating of additives
Definitions
- ABSTRACT A process for preparing neutral and highly basic magnesium alkylphenates or sulfurized alkylphenates wherein the process comprises:
- alkaline earth metal alkylphenates and sulfurized alkylphenates as lubricating oil additives has long been known.
- the presence of these materials in the lubricating oils improves the detergency characteristics, reduces engine wear, minimizes the formation of harmful deposits on engine parts, and improves the resistance of the oil to oxidation.
- the described phenate salts can be advantageously overbased by the dispersion in the neutral phenate compositions of basic alkaline earth metal compounds.
- the highly basic compositions as thus formulated function effectively in neutralizing harmful acidic compounds formed during the combustion of fuels used in association with the lubricating oils to which the compositions are added.
- US. Pat. No. 2,788,325 discloses the preparation of neutral magnesium phenates by the reaction under substantially anhydrous conditions of magnesium alkoxy alkoxides with an alkylphenol, with the alkoxides being used in substantially less than the stoichiometric amount required for neutralization of the alkylphenol.
- the water employed in admixture with the alkylphenol to be neutralized is from about 1 to about 2.5 moles of water per mole of dispersed basic alkaline earth metal compound which is to be incorporated in the product.
- an additional amount of magnesium alcoholate which is stoichiometrically required for neutralization of the phenol is added to the reaction mixture. This addition is carried out at a relatively higher temperature than that employed during the initial addition of magnesium alcoholate.
- the volatile materials are removed from the reaction mixture by heating.
- the present invention concerns a process for preparing highly basic magnesium alkylphenates or sulfurized alkylphenates, wherein the process comprises the steps of:
- step (c) The process of the present invention also contemplates the overbasing of the described neutral phenate compositions by following the neutralization step [step (c) described above] with the gradual concurrent addition to the neutral phenate compositions of an overbasing amount of carbonated magnesium alcoholate and water in a ratio of from about 1.1 to about 4 moles of water per mole of the carbonated magnesium alcoholate. This addition is carried out at a temperature of from about 55C to about 90C. After this addition is completed, volatile solvents are removed as described in step (d) above.
- An object of the present invention is to provide an improved process by which neutral and overbased magnesium phenate compositions useful as lubricating oil additives may be prepared.
- Another object of the invention is to provide a process for producing neutral and overbased magnesium phenate compositions having low viscosity facilitating ease of blending in lubricating oil formulations.
- R is a straight chain or branched chain, saturated or unsaturated, aliphatic hydrocarbon radical having from four to 30 carbon atoms, preferably from nine to 15 carbon atoms, and n is an integer having a value of l or 2.
- the total number of carbon atoms for the alkyl groups has a minimum value of eight and a maximum value of 40. Thus, when n is l, the minimum number of carbon atoms in R is eight.
- hydrocarbon radicals examples include alkyl radicals such as butyl, hexyl, octyl, nonyl, decyl, dodecyl, hexadecyl, eicosyl, hexacosyl and triacontyl; radicals derived from petroleum hydrocarbons such as white oil, wax and olefin polymers (e.g., polypropylene and polybutylene).
- Suitable sulfurized alkylphenols include those materials prepared by sulfurizing alkylphenols using any of the known methods. For example, it is known that sulfur monochloride can be used to prepare sulfurized alkylphenols. Such a method is described in US. Pat. No. 2,409,687.
- the sulfurized alkylphenols which are suitable in our process can be illustrated by materials represented by the following formula:
- the sulfurized alkylphenols which are useful in our process suitably contain from about 2 to about 14 percent by weight sulfur. Preferably, the amount of sulfur is from about 4 to about 12 percent by weight. It may be here pointed out that in the preparation of overbased dispersions (as contrasted with neutral dispersions), the utilization of the sulfurized alkylphenols is preferred to use of the unsulfurized alkylphenols.
- nonvolatile diluent oils are suitable in the process of our invention since the principle requisites for these materials are that they function as a solvent for the alkylphenate or sulfurized alkylphenate, and serve to reduce the viscosity of the final product mixture. Often a small amount of the nonvolatile diluent oil is present in conjunction with the alkylphenol or sulfurized alkylphenol used in the process.
- the nonvolatile diluent oils have a boiling point in excess of about 160C.
- nonvolatile diluent oils examples include mineral lubricating oils obtained by conventional refining procedures, synthetic lubricating oils such as polymers of propylene, polyoxyalkalenes, polyoxypropylene; dicarboxylic acid esters, and esters of acids of phosphorus, synthetic hydrocarbon lubricating oils, such as di-n-alkylbenzenes and oligomers of C C a-olefins; vegetable oils, such as corn oil, cottonseed oil, and castor oil; animal oils, such as lard oil and sperm oil. Mixtures of these materials can also be employed as the nonvolatile diluent.
- nonvolatile diluent oils the mineral lubricating oils and the synthetic lubricating oils are considered more suitable, with the mineral lubricating oils being preferred.
- the process solvents which are useful in the process of the present invention have a boiling point below about l50C.
- suitable volatile process solvents include aromatic hydrocarbons, such as benzene, toluene and xylene; aliphatic hydrocarbons, such as hexane and heptane; petroleum naphtha, glycol ethers, as hereinafter defined, and primary aliphatic C -C alcohols.
- the carbonated magnesium alcoholates used in the process of the invention are derived from monoethers of ethylene glycol and diethylene glycol containing up to 8 carbon atoms.
- the monoethers of ethylene glycol are also known as alkoxy alkanols, and the carbonated magnesium alcoholate complexes thereof are sometimes referred to as magnesium alkoxide-carbonate complexes.
- the carbonated magnesium alcoholates derived from the monoethers of ethylene glycol have the generic formula:
- Mtg- O OHQCHzOR where R is either a C to C alkyl group or an organic radical of the formula If H where R is a C to C alkyl group, and x is from 0.5 to 1.5, preferably 0.75 to 1.0.
- the carbonated magnesium alcoholates are derived from the monoethyl and monomethyl ethers of ethylene glycol. These latter materials are available commercially under the trademarks Cellosolve and methyl Cellosolve, respectively.
- the complexes employed contain from about 0.5 mole to about 2.0 mole of CO per mole of metal alcoholate, and preferably from about 0.8 mole to about 1.2 mole per mole of the alcoholate.
- the magnesium content of the preferred complexes ranges from 3 weight percent to about 10 weight percent.
- the carbonated magnesium alcoholates are added to the mixture containing the phenol compounds to be neutralized in the form of a solution of the alcoholate in glycol ether. Solutions containing from about 30 weight percent to about weight percent of the alcoholate are preferably utilized.
- the water required during the hydrolysis of the overbasing step of the process can be water per se or an azeotrope mixture of water and glycol ether.
- the product is improved by the addition of small amounts of oil-soluble sulfonic acid to the starting material.
- the amount of sulfonic acid employed in such cases is from about 0.1 to about 50 parts per parts of the alkylphenol or sulfurized alkylphenol starting material.
- the acid is preferably used in a hexane solution.
- Particularly suitable oil-soluble sulfonic acids are those prepared from various synthetic hydrocarbon sulfonation feedstocks. These materials are usually monoor di-alkylbenzenes and generally have molecular weights of from about 300 to about 1,000. The nature and derivation of the suitable sulfonic acids are further detailed in Nield U.S. Pat. No. 3,525,599 which is incorporated herein by reference.
- NEUTRAL PHENATE COMPOSITIONS Suitable Preferred Alkylphenol or Sulfurized Alkylphenol 5-l00 10-70 Volatile Process Solvent 5-l20 l-l00 Nonvolatile Diluent Oil 2-100 10-90 Water 0.00-1.13 0.00-0.05 Magnesium Alkoxide- Carbonate Complex 2-160 4-100 OVERBASED PHENATE COMPOSITIONS Alkylphenol (or sulfurized) 5-100 -60 Volatile Process Solvent 5-120 10-100 Nonvolatile Diluent Oil 2-100 -90 Water 0.l-l0 0.2-7.5
- an admixture is initially fonned which contains the alkylphenol or sulfurized alkylphenol to be neutralized, nonvolatile diluent oil and a volatile process solvent. Moreover, the admixture may contain a small amount of water which is less than 1 mole of water per mole of the magnesium alkoxide-carbonate complex utilized.
- alkylphenols which may be used in the process of the present invention as hereinbefore described, we prefer to utilize mixtures of monoalkyl and dialkylphenols, either sulfurized or unsulfurized, since we have observed that the neutral phenates yielded therefrom exhibit lower viscosity and improved oil solubility with respect to the phenates derived from the monoalkylphenol starting material.
- the mixture contains at least 20 weight percent dialkylphenol.
- the admixture is stirred and heated to a temperature of from about C to about 60C.
- the temperature of the admixture is brought within the range of 50C to 60C. While the admixture is at this temperature, the stoichiometric amount of magnesium alkoxide-carbonate complex is added thereto in a gradual manner.
- the time period over which the complex is added is not critical, it is desirable that the addition be carried out in a time period of from about 5 minutes to about 120 minutes. Preferably, the addition is carried out in a period of between about 20 minutes and about 60 minutes.
- the addition of the complex is made in such a way that the complex is introduced to the admixture beneath the surface thereof, since generally better results are obtained.
- the amount of the complex added is, as has been previously explained, an amount which is stoichiometrically sufficient to neutralize the alkylphenol or sulfurized alkylphenol present in the admixture.
- the use of a stoichiometric quantity of the complex is to be contrasted with the procedure described in U. S. Pat. No. 2,788,325, and is believed to be made possible in the process of the present invention as a result of the enhanced reactivity of the carbonated alcoholate as contrasted with the noncarbonated alcoholate.
- reaction mixture Upon completion of the addition of the complex, the reaction mixture is heated to reflux temperature, which is generally between about C to about C, and is maintained at this temperature for a period of from about 20 minutes to about 1% hours with concurrent stirring. This step is important to the procurement of complete reactivity of the stoichiometric amount of the magnesium alkoxide-carbonate complex with the alkylphenol.
- an overbasing amount of magnesium alkoxide-carbonate complex is introduced at this point in the process, along with water or a wateralcohol azeotrope.
- the amount of the magnesium alkoxide-carbonate complex used for the purpose is varied according to the specific complex used and to the extent of overbasing desired, but in general is from about 15 weight percent to about 40 weight percent based on the total weight of the admixture to which it .is added.
- An amount of water is added concurrently with the complex in an amount which is a stoichiometric excess of that required to hydrolyze the complex to the alkoxy alcohol and magnesium carbonate.
- the volatile components of the mixture are removed by distillation.
- the distillation is continued until a bottoms temperature reaches about C to about 160C, and preferably about C. It should be here pointed out that nonvolatile diluent oil may be added to the reaction mixture at any time prior to this point in the process, provided the total amount present does not exceed the 100 weight parts previously referred to.
- this temperature is maintained and the reaction mixture is then subjected to stripping of residual volatile materials therefrom by bubbling an inert gas, and preferably, carbon dioxide, through the mixture for a period of from about 30 minutes to 1% hours.
- an inert gas and preferably, carbon dioxide
- an additional amount of a nonvolatile diluent oil can be added to the product at this time.
- EXAMPLE 1 This example illustrates the preparation of a neutral magnesium alkylphenate solution using the process of the present invention.
- This alkylphenol contained about 97 weight percent mono-p-nonylphenol having a molecular weight of 220.3 and containing 3 weight percent free oil.
- the nonyl side chain was branched.
- This oil was a commercially available, nonvolatile naphthenic oil. ""This material contained 7.9 weight percent magnesium and 14.3 weight percent carbon dioxide.
- EXAMPLE 2 This example illustrates the preparation of a neutral magnesium alkylphenate composition utilizing an uncarbonated magnesium alcoholate for neutralization.
- Example 2 the same alkylphenol was employed as that which was used in Example 1, and this material was mixed with the same nonvolatile naphthenic oil used in Example 1 in amounts equivalent to those there used.
- the admixture also contained 100 grams of nhexane.
- To the admixture as thus constituted were added 68.5 grams of magnesium ethoxy ethoxide (magnesium methyl Cellosolve) which contained 9.2 weight percent magnesium and 0.4 weight percent carbon dioxide.
- the addition was carried out as described in Example 1, and was followed by heating the mixture to reflux temperature and retaining it at this temperature for a period of 1 hour with concurrent stirring. After this, the volatile materials were removed from the mixture by elevating the temperature to 150C. The mixture was then stripped with nitrogen gas for a period of 1 hour at about 150C.
- EXAMPLE 3 This example describes two runs carried out for comparative purposes, utilizing in each case, a commercially available alkylphenol composition which contained 7 weight percent free oil, with the balance being active alkylphenols.
- the alkylphenols in the composition comprised 65 weight percent mono-p-nonylphenol and 35 weight percent dinonylphenol.
- the average molecular weight of the phenol materials in the composition was 250.
- 123.5 grams of the alkylphenol composition was employed in admixture with 171.4 grams of nonvolatile naphthenic oil and 100 grams of n-hexane.
- One of the runs was carried out using a magnesium alkoxide-carbonate complex which contained 7.9 weight percent magnesium and 14.3 weight percent carbon dioxide.
- EXAMPLE4 A commercially available alkylphenol composition which contained weight percent mono-pdodecylphenol having a molecular weight of 262.4 and 5 weight percent of free oil was subjected to two neutralization runs in one of which, the carbonated magnesium methoxy ethoxide complexv described in Example 1 was used for neutralization, and in the other of which an uncarbonated magnesium methoxy ethoxide of the type described in Example 2 was utilized for neutralization. 121.2 grams of the alkylphenol composition was employed in admixture of 173.9 grams of nonvolatile naphthenic oil and 100 grams of hexane in each of the runs.
- EXAMPLE 5 Two runs were carried out utilizing the procedure described in the preceding examples and each employing 143.7 grams of a commercially available alkylphenol composition which contained 3 weight percent free oil, 27 weight percent di-nonylphenol and 70 weight percent mono-p-nonylphenol. In one of the described runs, the alkylphenol composition described was mixed with 100 grams of hexane and 143.8 grams of 150 SSU naphthenic oil. In the other run, the alkylphenol composition was admixed with 100 grams of hexane and 147.6 grams of 150 SSU naphthenic oil.
- EXAMPLE 6 This example illustrates the preparation of magnesium alkylphenate compositions derived from sulfurized phenols. Two comparative runs were carried out utilizing, in each case, a commercially available, sulfurized alkylphenol composition which contained about 48.5
- EXAMPLE 7 This example illustrates the employment of the present invention in the production of an overbased magnesium alkylphenate dispersion, using a small amount of an oil-soluble sulfonic acid in the starting material.
- the hexane solution contained 29 weight percent of a sulfonic acid composition derived from alkylbenzenes and having a combining weight of 488.
- the sulfonic acid acidity of the solution was 0.587 meqjgli, and the acid contained 10.5 weight percent nonvolatile miner 01.
- EXAMPLE 8 an overbased composition was prepared by the process of the present invention, using a sulfurized alkylphenol starting material admixed with a minor amount of an oil soluble sulfonic acid.
- the hexane solution contained 26.3 weight percent of a sulfonic acid composition derived from alkylbenzenes and having a combining weight of 440.
- the sulfonic acid acidity of the solution was 0.59 meq./ g., and the acid contained 17.5 weight percent nonvolatile mineral oil.
- the volatile solvents were then removed by distillation to a bottoms temperature of 150C.
- the product was stripped by bubbling CO, therethrough for a period of 1 hour while maintaining the temperature between 140C and 160C.
- the final product had a base number of 248, and a viscosity at 210F of 248 centistokes.
- a process for preparing a magnesium phenatecontaining composition comprising:
- alkylphenol i. about 5 to about parts by weight of alkylphenol or sulfurized alkylphenol, wherein the alkylphenol is represented by the formula wherein R is a straight or branched chain, saturated or unsaturated, aliphatic hydrocarbon radical having from four to 30 carbon atoms, and n is an integer having a value of 1 or 2, said alkylphenol being characterized further in that the total number of alkyl group carbon atoms is from eight to 40;
- magnesium alcoholate contains from about 0.5 mole to about 2.0 moles of CO, per mole of metal alcoholate;
- alkylphenol employed is a mixture containing at least 20 weight percent dialkylphenol with the balance being a monoalkylphenol.
- nonvolatile diluent oil is selected from the group consisting of mineral lubricating oils and synthetic lubricating oils.
- step (a) contains additionally from about 0.1 to about 50 parts of oil soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.
- step (a) 6. The process defined in claim 1 wherein the amounts of materials admixed in step (a) are:
- magnesium alcoholate is derived from the monomethyl ether of ethylene glycol or the monoethyl ether of ethylene glycol, and contains from about 0.8 mole to about 1.2 mole of C0 per mole of magnesium alcoholate.
- alkylphenol employed is a mixture containing at least 20 weight percent dialkylphenol with the balance being a monoalkylphenol.
- nonvolatile diluent oil is selected from the group consisting of mineral lubricating oils and synthetic lubricating oils.
- step (a) The process defined in claim 12 wherein the amounts of materials admixed in step (a) are:
- step (a) 19. The process defined in claim 14 wherein the amounts of materials admixed in step (a) are:
- step (a) contains additionally from about 0.1 to about 50 parts of oil soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.
- nonvolatile diluent oil is selected from the group consisting of mineral lubricating oils and synthetic lubricating oils.
- step (a) contains additionally from about 0.1 to about 50 parts of an oil-soluble sulfonic acid per l00 parts of alkylphenol or sulfurized alkylphenol.
- step (a) contains additionally from about 0.1 to about 50 parts of an oil soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.
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Abstract
A process for preparing neutral and highly basic magnesium alkylphenates or sulfurized alkylphenates wherein the process comprises: A. FORMING AN ADMIXTURE OF ALKYLPHENOL OR SULFURIZED ALKYLPHENOL, NONVOLATILE DILUENT OIL, AND A VOLATILE PROCESS SOLVENT; B. ADDING A STOICHIOMETRIC NEUTRALIZING AMOUNT OF A CARBONATED MAGNESIUM ALCOHOLATE AT A TEMPERATURE OF FROM ABOUT 30*C to about 60*C; c. heating the mixture to a reflux temperature of from about 65*C to about 90*C, and maintaining the mixture at this reflux temperature for a period of from about 20 minutes to about 1 1/2 hours; then D. REMOVING THE VOLATILE MATERIALS BY HEATING. If a highly basic (overbased) product is to be prepared, the same steps are followed as in the production of the neutral phenate, except that after neutralization, and prior to removing the volatile materials from the mixture, carbonated magnesium alcoholate and water are added concurrently to the mixture.
Description
United f'States Patent [191 Rogers et air 51 Feb. 27, 1973 PREPARATION OF NEUTRAL AND HIGHLY BASIC ALKYLPHENATES AND SULFURIZED ALKYLPHENATES [75] Inventors: Lynn C. Rogers; Mack W. Hunt,
both of Ponca City, Okla.
[73] Assignee: .Continental Oil Company, Ponca City, Okla.
[22] Filed: Aug. 31, 1971 21 Appl. No.: 176,676
Primary Examiner-Daniel E. Wyman Assistant ExaminerW. Cannon Attorney-Joseph C. Kotarski et al.
[ 5 7 ABSTRACT A process for preparing neutral and highly basic magnesium alkylphenates or sulfurized alkylphenates wherein the process comprises:
a. forming an admixture of alkylphenol or sulfurized alkylphenol, nonvolatile diluent oil, and a volatile process solvent;
b. adding a stoichiometric neutralizing amount of a carbonated magnesium alcoholate at a temperature of from about C to about C;
c. heating the mixture to a reflux temperature of from about C to about C, and maintaining the mixture at this reflux temperature for a period of from about 20 minutes to about 1% hours; then d. removing the volatile materials by heating.
If a highly basic (overbased) product is to be prepared, the same steps are followed as in the production of the neutral phenate, except that after neutralization, and prior to removing the volatile materials from the mixture, carbonated magnesium alcoholate and water are added concurrently to the mixture.
29 Claims, No Drawings PREPARATION OF NEUTRAL AND HIGHLY BASIC ALKYLPIIENATES AND SULFURIZED ALKYLPIIENATES BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to the preparation of neutral and overbased alkaline earth metal alkylphenates and sulfurized alkylphenates, and more particularly, to the preparation of low viscosity magnesium alkylphenate compositions which may be neutral, or may be overbased with dispersed magnesium carbonate.
2. Brief Description of the Prior Art The utility of alkaline earth metal alkylphenates and sulfurized alkylphenates as lubricating oil additives has long been known. The presence of these materials in the lubricating oils improves the detergency characteristics, reduces engine wear, minimizes the formation of harmful deposits on engine parts, and improves the resistance of the oil to oxidation. It is further known that the described phenate salts can be advantageously overbased by the dispersion in the neutral phenate compositions of basic alkaline earth metal compounds. The highly basic compositions as thus formulated function effectively in neutralizing harmful acidic compounds formed during the combustion of fuels used in association with the lubricating oils to which the compositions are added.
US. Pat. No. 2,788,325 discloses the preparation of neutral magnesium phenates by the reaction under substantially anhydrous conditions of magnesium alkoxy alkoxides with an alkylphenol, with the alkoxides being used in substantially less than the stoichiometric amount required for neutralization of the alkylphenol.
In our co-pending US. application Ser. No. 148,262 filed May 17, 1971, we disclose a process for preparing highly basic alkaline earth metal phenates and sulfurized alkaline earth metal phenates by first adding, at a relatively low temperature, a carbonated magnesium alcoholate derived from a glycol ether containing from one to eight carbon atoms, to a mixture which comprises water and an alkylphenol or sulfurized alkylphenol. In this first step, the amount of the magnesiurn alcoholate used is that which is to be employed in excess of the amount required for neutralization of the phenol, and which is thus the amount to be used in overbasing the product. The water employed in admixture with the alkylphenol to be neutralized is from about 1 to about 2.5 moles of water per mole of dispersed basic alkaline earth metal compound which is to be incorporated in the product. Following the addition of the overbasing amount of magnesium alcoholate to the admixture of water and alkylphenol or sulfurized alkylphenol, an additional amount of magnesium alcoholate which is stoichiometrically required for neutralization of the phenol is added to the reaction mixture. This addition is carried out at a relatively higher temperature than that employed during the initial addition of magnesium alcoholate. Finally, the volatile materials are removed from the reaction mixture by heating.
BRIEF SUMMARY OF THE PRESENT INVENTION Broadly stated, the present invention concerns a process for preparing highly basic magnesium alkylphenates or sulfurized alkylphenates, wherein the process comprises the steps of:
a. forming an admixture of alkylphenol or sulfurized alkylphenol, nonvolatile diluent oil, and volatile process solvent;
b. adding to the admixture, at a temperature of from about 30C to about 60C, an amount of a carbonated magnesium alcoholate which is stoichiometrically sufficient to neutralize said alkylphenol;
c. heating the mixture to a temperature of from about 65C to about C, and maintaining this temperature for a period of from 20 minutes to 1% hour with stirring; then d. removing the volatile materials by heating and stripping with an inert gas.
The foregoing procedure is used in the preparation of oil soluble neutral magnesium alkylphenates useful as lubricating oil additives. The process of the present invention also contemplates the overbasing of the described neutral phenate compositions by following the neutralization step [step (c) described above] with the gradual concurrent addition to the neutral phenate compositions of an overbasing amount of carbonated magnesium alcoholate and water in a ratio of from about 1.1 to about 4 moles of water per mole of the carbonated magnesium alcoholate. This addition is carried out at a temperature of from about 55C to about 90C. After this addition is completed, volatile solvents are removed as described in step (d) above.
a We have determined that by using carbonated magnesium alcoholate, a significant improvement in the viscosity of both the neutral and overbased products is realized as compared to the viscosity of products prepared using uncarbonated magnesium alcoholate. Moreover, the carbonated magnesium alcoholates react more rapidly with phenols than uncarbonated magnesium alcoholates, and thus process time requirements are reduced.
An object of the present invention is to provide an improved process by which neutral and overbased magnesium phenate compositions useful as lubricating oil additives may be prepared.
Another object of the invention is to provide a process for producing neutral and overbased magnesium phenate compositions having low viscosity facilitating ease of blending in lubricating oil formulations.
Additional objects and advantages of the invention will become apparent as the following detailed description of preferred embodiments of the invention is considered.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION Suitable alkylphenols for use in the process of the present invention may be represented by the structural formula:
Wherein R is a straight chain or branched chain, saturated or unsaturated, aliphatic hydrocarbon radical having from four to 30 carbon atoms, preferably from nine to 15 carbon atoms, and n is an integer having a value of l or 2. The total number of carbon atoms for the alkyl groups has a minimum value of eight and a maximum value of 40. Thus, when n is l, the minimum number of carbon atoms in R is eight.
Examples of suitable hydrocarbon radicals include alkyl radicals such as butyl, hexyl, octyl, nonyl, decyl, dodecyl, hexadecyl, eicosyl, hexacosyl and triacontyl; radicals derived from petroleum hydrocarbons such as white oil, wax and olefin polymers (e.g., polypropylene and polybutylene).
Suitable sulfurized alkylphenols include those materials prepared by sulfurizing alkylphenols using any of the known methods. For example, it is known that sulfur monochloride can be used to prepare sulfurized alkylphenols. Such a method is described in US. Pat. No. 2,409,687. The sulfurized alkylphenols which are suitable in our process can be illustrated by materials represented by the following formula:
O H OH wherein m is a number in range of from 1 to 3, more usually in the range of l to 2, and R and n are as described in the preceding description of the alkylphenols. It is to be understood that the preceding description is typical of the sulfurized alkylphenols which can be used, and that our process is not limited to materials having the formula shown in the foregoing.
Regardless of the manner in which they are prepared, the sulfurized alkylphenols which are useful in our process suitably contain from about 2 to about 14 percent by weight sulfur. Preferably, the amount of sulfur is from about 4 to about 12 percent by weight. It may be here pointed out that in the preparation of overbased dispersions (as contrasted with neutral dispersions), the utilization of the sulfurized alkylphenols is preferred to use of the unsulfurized alkylphenols.
A number of nonvolatile diluent oils are suitable in the process of our invention since the principle requisites for these materials are that they function as a solvent for the alkylphenate or sulfurized alkylphenate, and serve to reduce the viscosity of the final product mixture. Often a small amount of the nonvolatile diluent oil is present in conjunction with the alkylphenol or sulfurized alkylphenol used in the process. The nonvolatile diluent oils have a boiling point in excess of about 160C.
Examples of suitable nonvolatile diluent oils which can be used include mineral lubricating oils obtained by conventional refining procedures, synthetic lubricating oils such as polymers of propylene, polyoxyalkalenes, polyoxypropylene; dicarboxylic acid esters, and esters of acids of phosphorus, synthetic hydrocarbon lubricating oils, such as di-n-alkylbenzenes and oligomers of C C a-olefins; vegetable oils, such as corn oil, cottonseed oil, and castor oil; animal oils, such as lard oil and sperm oil. Mixtures of these materials can also be employed as the nonvolatile diluent.
Of the preceding examples of nonvolatile diluent oils, the mineral lubricating oils and the synthetic lubricating oils are considered more suitable, with the mineral lubricating oils being preferred.
The process solvents which are useful in the process of the present invention have a boiling point below about l50C. Examples of suitable volatile process solvents include aromatic hydrocarbons, such as benzene, toluene and xylene; aliphatic hydrocarbons, such as hexane and heptane; petroleum naphtha, glycol ethers, as hereinafter defined, and primary aliphatic C -C alcohols.
The carbonated magnesium alcoholates used in the process of the invention are derived from monoethers of ethylene glycol and diethylene glycol containing up to 8 carbon atoms. The monoethers of ethylene glycol are also known as alkoxy alkanols, and the carbonated magnesium alcoholate complexes thereof are sometimes referred to as magnesium alkoxide-carbonate complexes. The carbonated magnesium alcoholates derived from the monoethers of ethylene glycol have the generic formula:
Mtg- O OHQCHzOR where R is either a C to C alkyl group or an organic radical of the formula If H where R is a C to C alkyl group, and x is from 0.5 to 1.5, preferably 0.75 to 1.0. The preparation of these complexes is described in detail in US. Pat. No. 3,150,089. Preferably, the carbonated magnesium alcoholates are derived from the monoethyl and monomethyl ethers of ethylene glycol. These latter materials are available commercially under the trademarks Cellosolve and methyl Cellosolve, respectively. The complexes employed contain from about 0.5 mole to about 2.0 mole of CO per mole of metal alcoholate, and preferably from about 0.8 mole to about 1.2 mole per mole of the alcoholate. The magnesium content of the preferred complexes ranges from 3 weight percent to about 10 weight percent. In the practice of the invention, the carbonated magnesium alcoholates are added to the mixture containing the phenol compounds to be neutralized in the form of a solution of the alcoholate in glycol ether. Solutions containing from about 30 weight percent to about weight percent of the alcoholate are preferably utilized.
The water required during the hydrolysis of the overbasing step of the process can be water per se or an azeotrope mixture of water and glycol ether.
Although it is not essential to the practice of the present invention, we have determined that for some usages in which low sedimentation upon dilution of overbased products of the invention is desired, the product is improved by the addition of small amounts of oil-soluble sulfonic acid to the starting material. The amount of sulfonic acid employed in such cases is from about 0.1 to about 50 parts per parts of the alkylphenol or sulfurized alkylphenol starting material. The acid is preferably used in a hexane solution.
Particularly suitable oil-soluble sulfonic acids are those prepared from various synthetic hydrocarbon sulfonation feedstocks. These materials are usually monoor di-alkylbenzenes and generally have molecular weights of from about 300 to about 1,000. The nature and derivation of the suitable sulfonic acids are further detailed in Nield U.S. Pat. No. 3,525,599 which is incorporated herein by reference.
The amounts of the various materials used in our process, both suitable and preferred ranges, are shown below in parts by weight. Since the invention contemplates the production of both the neutral and overbased phenate compositions, the amounts of materials used in each procedure are set forth. In general, the weight ratio of carbonated magnesium alcoholate used for overbasing to that used for neutralization ranges from 0.5 to 3.0.
NEUTRAL PHENATE COMPOSITIONS Suitable Preferred Alkylphenol or Sulfurized Alkylphenol 5-l00 10-70 Volatile Process Solvent 5-l20 l-l00 Nonvolatile Diluent Oil 2-100 10-90 Water 0.00-1.13 0.00-0.05 Magnesium Alkoxide- Carbonate Complex 2-160 4-100 OVERBASED PHENATE COMPOSITIONS Alkylphenol (or sulfurized) 5-100 -60 Volatile Process Solvent 5-120 10-100 Nonvolatile Diluent Oil 2-100 -90 Water 0.l-l0 0.2-7.5
Magnesium Alkoxide- Carbonate Complex 10-300 20-200 PROCESS CONDITIONS In carrying out the process of the invention, an admixture is initially fonned which contains the alkylphenol or sulfurized alkylphenol to be neutralized, nonvolatile diluent oil and a volatile process solvent. Moreover, the admixture may contain a small amount of water which is less than 1 mole of water per mole of the magnesium alkoxide-carbonate complex utilized. Within the broad description of the types of alkylphenols which may be used in the process of the present invention as hereinbefore described, we prefer to utilize mixtures of monoalkyl and dialkylphenols, either sulfurized or unsulfurized, since we have observed that the neutral phenates yielded therefrom exhibit lower viscosity and improved oil solubility with respect to the phenates derived from the monoalkylphenol starting material. Preferably the mixture contains at least 20 weight percent dialkylphenol.
The admixture is stirred and heated to a temperature of from about C to about 60C. Preferably, the temperature of the admixture is brought within the range of 50C to 60C. While the admixture is at this temperature, the stoichiometric amount of magnesium alkoxide-carbonate complex is added thereto in a gradual manner. Although the time period over which the complex is added is not critical, it is desirable that the addition be carried out in a time period of from about 5 minutes to about 120 minutes. Preferably, the addition is carried out in a period of between about 20 minutes and about 60 minutes. The addition of the complex is made in such a way that the complex is introduced to the admixture beneath the surface thereof, since generally better results are obtained.
The amount of the complex added is, as has been previously explained, an amount which is stoichiometrically sufficient to neutralize the alkylphenol or sulfurized alkylphenol present in the admixture. The use of a stoichiometric quantity of the complex is to be contrasted with the procedure described in U. S. Pat. No. 2,788,325, and is believed to be made possible in the process of the present invention as a result of the enhanced reactivity of the carbonated alcoholate as contrasted with the noncarbonated alcoholate.
Upon completion of the addition of the complex, the reaction mixture is heated to reflux temperature, which is generally between about C to about C, and is maintained at this temperature for a period of from about 20 minutes to about 1% hours with concurrent stirring. This step is important to the procurement of complete reactivity of the stoichiometric amount of the magnesium alkoxide-carbonate complex with the alkylphenol.
If an overbased product is to be produced, rather than a neutral composition, an overbasing amount of magnesium alkoxide-carbonate complex is introduced at this point in the process, along with water or a wateralcohol azeotrope. The amount of the magnesium alkoxide-carbonate complex used for the purpose is varied according to the specific complex used and to the extent of overbasing desired, but in general is from about 15 weight percent to about 40 weight percent based on the total weight of the admixture to which it .is added. An amount of water is added concurrently with the complex in an amount which is a stoichiometric excess of that required to hydrolyze the complex to the alkoxy alcohol and magnesium carbonate. In general, from about 1.1 moles to about 4 moles of water is utilized per mole of the alkoxide complex. The concurrent addition is carried out slowly with the water preferably being added in the form of an azeotrope with the alkoxy alcohol from which the complex is derived.
Either after completion of the overbasing step by concurrent addition of complex and water, or, where a neutral product is the objective, after completion of period of heating at reflux, the volatile components of the mixture are removed by distillation. In general, the distillation is continued until a bottoms temperature reaches about C to about 160C, and preferably about C. It should be here pointed out that nonvolatile diluent oil may be added to the reaction mixture at any time prior to this point in the process, provided the total amount present does not exceed the 100 weight parts previously referred to.
Upon the attainment of the described bottoms temperature, this temperature is maintained and the reaction mixture is then subjected to stripping of residual volatile materials therefrom by bubbling an inert gas, and preferably, carbon dioxide, through the mixture for a period of from about 30 minutes to 1% hours.
If it should be desired to adjust the activity (i.e., concentration of alkylphenate and dispersoid material) in the final product, an additional amount of a nonvolatile diluent oil can be added to the product at this time.
For the purpose of disclosing more completely the manner in which the present invention is practiced, the following examples are given. The specific conditions and details set forth in these examples are not considered to be limiting relative to the scope of the invention, except insofar as such limitations and details are specified in the appended claims.
EXAMPLE 1 This example illustrates the preparation of a neutral magnesium alkylphenate solution using the process of the present invention.
Materials Used Parts by Weight Alkylphenol' 1 17.8
n-l-lexane 100.0 Nonvolatile Diluent Oil 176.5
Methoxy Ethanol Solution of Magnesium Ethoxy Ethoxide- Carbonate Complex" 79.8
This alkylphenol contained about 97 weight percent mono-p-nonylphenol having a molecular weight of 220.3 and containing 3 weight percent free oil. The nonyl side chain was branched.
This oil was a commercially available, nonvolatile naphthenic oil. ""This material contained 7.9 weight percent magnesium and 14.3 weight percent carbon dioxide.
PROCESS The alkylphenol, oil and hexane were charged to a 1- liter, 3-neck flask equipped with mechanical stirrer, thermometer and condenser. The mixture was stirred and heated to 50C. The magnesium ethoxy ethoxidecarbonate complex was then added slowly over a period of 30 minutes by means of a tube immersed in the reaction mixture. Upon completion of the addition of the complex, the admixture was then heated to reflux temperature of about 72C, and was refluxed and stirred for 1 hour. The volatile solvents, including water of neutralization, methoxy ethanol and hexane were then removed by distilling the mixture to a bottoms temperature of 150C. The mixture was stripped with CO for a period of 1 hour at about 150C.
300 grams of neutral magnesium alkylphenate composition was produced which was calculated to contain 40 weight percent of magnesium mono-p-nonylphenate. The product had a B.S.&W. value of 0.015 volume percent, an acetic base number of 89 and a viscosity in centistokes at 210F of 93.4.
EXAMPLE 2 This example illustrates the preparation of a neutral magnesium alkylphenate composition utilizing an uncarbonated magnesium alcoholate for neutralization.
In this example, the same alkylphenol was employed as that which was used in Example 1, and this material was mixed with the same nonvolatile naphthenic oil used in Example 1 in amounts equivalent to those there used. The admixture also contained 100 grams of nhexane. To the admixture as thus constituted were added 68.5 grams of magnesium ethoxy ethoxide (magnesium methyl Cellosolve) which contained 9.2 weight percent magnesium and 0.4 weight percent carbon dioxide. The addition was carried out as described in Example 1, and was followed by heating the mixture to reflux temperature and retaining it at this temperature for a period of 1 hour with concurrent stirring. After this, the volatile materials were removed from the mixture by elevating the temperature to 150C. The mixture was then stripped with nitrogen gas for a period of 1 hour at about 150C.
310.1 grams of neutral magnesium alkylphenate composition were produced, and were calculated to contain 40 weight percent magnesium mono-p-nonylphenate. The product had a B.S.&W. value of 0.002 volume percent, an acetic base number of and a viscosity in centistokes at 210F of 3513.2. It may thus be readily perceived that when the uncarbonated magnesium alcoholate is employed for neutralization, the product obtained has a viscosity which is dramatically higher than the viscosity o. the product obtained by the practice of the present invention, using the carbonated magnesium alcoholate material for neutralization.
EXAMPLE 3 This example describes two runs carried out for comparative purposes, utilizing in each case, a commercially available alkylphenol composition which contained 7 weight percent free oil, with the balance being active alkylphenols. The alkylphenols in the composition comprised 65 weight percent mono-p-nonylphenol and 35 weight percent dinonylphenol. The average molecular weight of the phenol materials in the composition was 250. In each of the comparative runs, 123.5 grams of the alkylphenol composition was employed in admixture with 171.4 grams of nonvolatile naphthenic oil and 100 grams of n-hexane. One of the runs was carried out using a magnesium alkoxide-carbonate complex which contained 7.9 weight percent magnesium and 14.3 weight percent carbon dioxide. 1n the other run, 60.7 grams of uncarbonated magnesium alcoholate was utilized. 1n the two runs, the procedures described in Examples 1 and 2 were utilized, employing carbon dioxide for stripping residual volatile materials from the run carried out using the carbonated complex, and using nitrogen gas for stripping volatile materials from the run carried out using uncarbonated magnesium alcoholate for neutralization.
1n the run in which the carbonated complex was used for neutralization, 307 grams of product were yielded having a B.S.&W. value of 0.03 volume percent, an acetic base number of 82 and a viscosity at 210F of 82 centistokes. 1n the run carried out using the uncarbonated neutralizing material, 313.2 grams of product were produced, having a B.S.&W. value of 0.04 volume percent, an acetic base number of 83 and a viscosity at 210F of 398 centistokes. The much lower viscosity of the product produced using the carbonated magnesium alkoxy alkoxide complex for neutralization will be readily apparent. Moreover, comparison of the results obtained in the two runs described in this example, in which a mixture of the mono-and di-nonylphenols were used as a starting material, with the results obtained in Examples 1 and 2 will reveal the improvement in viscosity obtained as a result of the use of the mixed alkylphenol starting material.
EXAMPLE4 A commercially available alkylphenol composition which contained weight percent mono-pdodecylphenol having a molecular weight of 262.4 and 5 weight percent of free oil was subjected to two neutralization runs in one of which, the carbonated magnesium methoxy ethoxide complexv described in Example 1 was used for neutralization, and in the other of which an uncarbonated magnesium methoxy ethoxide of the type described in Example 2 was utilized for neutralization. 121.2 grams of the alkylphenol composition was employed in admixture of 173.9 grams of nonvolatile naphthenic oil and 100 grams of hexane in each of the runs. In the run utilizing the magnesium methoxy ethoxide-carbonate complex, 67.5 grams of the complex was used for neutralization. In the run utilizing the uncarbonated magnesium alcoholate for neutralization, 58.0 grams of the alcoholate were used for neutralization. The process conditions were those described in the preceding examples, with nitrogen being used for the stripping of the neutral phenate prepared using the uncarbonated neutralizing material, and carbon dioxide being utilized to strip the neutral phenate prepared by the use of the carbonated complex.
In the run carried out using the carbonated complex, 307 grams of product were yielded having an acetic base number of 75 and a viscosity at 210F of 1795.0 centistokes. 306.3 grams of product were prepared in the run utilizing the uncarbonated magnesium alcoholate for neutralization, and this product had an acetic base number of 77 and a viscosity at 210F exceeding 5,000 centistokes.
EXAMPLE 5 Two runs were carried out utilizing the procedure described in the preceding examples and each employing 143.7 grams of a commercially available alkylphenol composition which contained 3 weight percent free oil, 27 weight percent di-nonylphenol and 70 weight percent mono-p-nonylphenol. In one of the described runs, the alkylphenol composition described was mixed with 100 grams of hexane and 143.8 grams of 150 SSU naphthenic oil. In the other run, the alkylphenol composition was admixed with 100 grams of hexane and 147.6 grams of 150 SSU naphthenic oil.
In the first run, 93.3 grams of magnesium alkoxidecarbonate complex were added to the mixture for neutralization purposes. This complex contained 7.49 weight percent magnesium and 14.0 weight percent carbon dioxide. Upon completion of stripping with carbon dioxide, 300 grams of neutral phenate product were yielded which contained 50 weight percent of the magnesium alkylphenate per se. The product composition had a viscosity at 210F of 17.5 centistokes.
In the other run (in which the starting composition contained 147.6 grams of nonvolatile naphthenic oil), 76 grams of an uncarbonated magnesium alcoholate containing 9.20 percent magnesium and 0.30 weight percent carbon dioxide were utilized for neutralization. The 300 grams of product composition yielded following nitrogen stripping contained 50 weight percent magnesium alkylphenate, and had a viscosity exceeding 500 centistokes.
EXAMPLE 6 This example illustrates the preparation of magnesium alkylphenate compositions derived from sulfurized phenols. Two comparative runs were carried out utilizing, in each case, a commercially available, sulfurized alkylphenol composition which contained about 48.5
weight percent sulfur bridged mono-p-nonylphenol, 18.5 weight percent sulfur bridged dinonylphenol and 33 weight percent free nonvolatile oil. In each of the two runs carried out for comparison purposes, 221.6 grams of the described sulfurized phenol composition were mixed with grams of hexane. In the run in which a carbonated magnesium alcoholate was used for neutralization, the starting mixture further contained 85 grams of SSU naphthenic oil. In the run subjected to neutralization with an uncarbonated magnesium alcoholate of the type described in Example 5 (containing 9.20 weight percent magnesium), the starting mixture contained 75.8 grams of 150 SSU naphthenic oil. For neutralization, in the case of the first run, 88.3 grams of magnesium alkoxide-carbonate complex containing 7.49 weight percent magnesium and 14.0 weight percent carbon dioxide were employed for neutralization. In the second run, 71.8 grams of uncarbonated magnesium methoxy ethoxide containing 9.20 weight percent magnesium were utilized.
In each of the runs, 300 grams of product were yielded. In the run in which the magnesium alkoxidecarbonate complex was employed, the product had a viscosity at 210F of 36 centistokes. In the second run using the uncarbonated magnesium alcoholate, the product had a viscosity at 210F of l 1 1.1 centistokes.
EXAMPLE 7 This example illustrates the employment of the present invention in the production of an overbased magnesium alkylphenate dispersion, using a small amount of an oil-soluble sulfonic acid in the starting material.
Materials Used Parts Alkylphenol 145.3 Nonvolatile Naphthenic 127.0 Diluent Oil n-I-Iexane 147.1 Water 8.4
' Hexane Solution of Sulfonic Acid 15.4 Methoxy Ethanol Solution of Magnesium Ethoxy- Ethoxide Carbonate Complefl" 175.5
Same as alkylphenol used in Example 3 "Added as an azeotrope with an equal amount of methoxy ethanol (methyl Cellosolve) "*The hexane solution contained 29 weight percent of a sulfonic acid composition derived from alkylbenzenes and having a combining weight of 488. The sulfonic acid acidity of the solution was 0.587 meqjgli, and the acid contained 10.5 weight percent nonvolatile miner 01.
""This material contained 7.49 weight percent magnesium and 13.6 weight percent carbon dioxide.
PROCESS To a l-liter, 3-neck flask were added the alkylphenol, n-hexane, and hexane solution of sulfonic acid. The mixture was heated to a temperature of 35C, and while the temperature was maintained between about 30C and about 40C, 95.5 parts by weight (54.4 percent) of the methoxy ethanol solution of the complex was added over a period of 15 minutes. The mixture was then heated to a reflux temperature of 73C and refluxing at this temperature was continued for a period of 1 hour.
There were then concurrently added to the reaction mixture, the remainder of the complex solution and the water azeotrope. The addition of complex was completed in 90 minutes and the azeotrope addition was completed in 75 minutes. 50 parts by weight of the nonvolatile naphthenic diluent oil and 25 weight parts of toluene (added for processing purposes) were then added, and removal of volatile solvents by distillation was begun. At a pot temperature of 131C, the remainder of the nonvolatile diluent oil was added. Distillation was then continued to a bottoms temperature of 150C. The resulting product was blow with CO for a period of 30 minutes at a temperature of between 140C and 160C, after which it was filtered through diatomaceous earth and cooled. The acetic base number of the finished product was 162.
EXAMPLE 8 In this example, an overbased composition was prepared by the process of the present invention, using a sulfurized alkylphenol starting material admixed with a minor amount of an oil soluble sulfonic acid.
Materials Used Parts Sulfurized Alkylphenol" 1680.0 Nonvolatile 80 Pale Oil Diluent 127.0 n-Hexane 1200.0 Hexane Solution of Sulfonic Acid 194.7 Water 119.8 Methyl Cellosolve 400.0 Methoxy Ethanol Solution of Magnesium Ethoxyethoxide Carbonate Complex" 1144.0
Same as sulfurized alkylphenols used in Example 6 The hexane solution contained 26.3 weight percent of a sulfonic acid composition derived from alkylbenzenes and having a combining weight of 440. The sulfonic acid acidity of the solution was 0.59 meq./ g., and the acid contained 17.5 weight percent nonvolatile mineral oil.
'"This material contained 7.86 weight percent magnesium and 16.0 weight percent carbon dioxide.
PROCESS The sulfurized alkylphenol, n-hexane, 80 pale oil, hexane sulfonic acid solution, and methyl Cellosolve were charged to a 12 liter, 3 necked creased flask equipped with stirrer, heater, thermometer and reflux condenser. Over a 1 hour period, one half of the total methoxy ethanol-complex solution was added to the reaction mixture while gradually increasing the temperature to 55C. Upon completion of the addition of this neutralizing amount of the complex, the mixture was heated to reflux, and refluxing was then continued for 20 minutes.
There was then added concurrently to the mixture while it was maintained at reflux temperature, the balance of the methoxy ethanol solution of complex and the water. The addition of the complex was accomplished in 60 minutes, and the water was added over a period of 45 minutes.
The volatile solvents were then removed by distillation to a bottoms temperature of 150C. The product was stripped by bubbling CO, therethrough for a period of 1 hour while maintaining the temperature between 140C and 160C. The final product had a base number of 248, and a viscosity at 210F of 248 centistokes.
Although certain preferred embodiments of the invention have been herein described for illustrative purposes, it will be understood that various modifications in the process conditions and reactants used can be effected without departure from the basic principles of the invention. Such changes which continue to be based upon such principles are therefore deemed to be within the spirit and scope of the invention except as the same may be necessarily limited by the appended claims or reasonable equivalents thereof.
What is claimed is: l. A process for preparing a magnesium phenatecontaining composition comprising:
a. forming an admixture comprising:
i. about 5 to about parts by weight of alkylphenol or sulfurized alkylphenol, wherein the alkylphenol is represented by the formula wherein R is a straight or branched chain, saturated or unsaturated, aliphatic hydrocarbon radical having from four to 30 carbon atoms, and n is an integer having a value of 1 or 2, said alkylphenol being characterized further in that the total number of alkyl group carbon atoms is from eight to 40;
ii. from 2 to 100 parts by weight of a nonvolatile diluent oil having a boiling point in excess of about 160C; and
iii. from 5 to parts by weight of a volatile process solvent having a boiling point below about 150C;
b. while the temperature is in the range of from about 30C to about 60C, adding to the admixture of alkylphenol, nonvolatile diluent oil and volatile process solvent, a stoichiometric neutralizing amount of carbonated magnesium alcoholate represented by the formula 0 CHzCHzO R) where R is a C to C alkyl group, x is from 0.5 to
1.5, and wherein said magnesium alcoholate contains from about 0.5 mole to about 2.0 moles of CO, per mole of metal alcoholate;
c. heating the mixture to a reflux temperature of from about 65C to about 90C, and maintaining the mixture at this reflux temperature for a period of from about 20 minutes to about 1% hours; then d. removing the volatile materials boiling below about C from the reaction mixture.
2. The process of claim 1 wherein x in said carbonated magnesium alcoholate formula is from about 0.75 to about 1, and wherein said magnesium alcoholate contains from about 0.8 mole to about 1.2 mole of CO, per mole of magnesium alcoholate.
The process of claim 1 wherein the alkylphenol employed is a mixture containing at least 20 weight percent dialkylphenol with the balance being a monoalkylphenol.
4. The process defined in claim 1 wherein the nonvolatile diluent oil is selected from the group consisting of mineral lubricating oils and synthetic lubricating oils.
5. The process defined in claim 1 wherein the admixture of step (a) contains additionally from about 0.1 to about 50 parts of oil soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.
6. The process defined in claim 1 wherein the amounts of materials admixed in step (a) are:
. Parts by Weight i. alkylphenol or sulfurized alkylphenol 10 70 ii. nonvolatile diluent l 90 iii. volatile process solvent 100 7. The process defined in claim 1 wherein said carbonated magnesium alcoholate is derived from the monomethyl ether of ethylene glycol or from the monoethyl ether of ethylene glycol.
8. The process defined in claim 1 wherein said volatile process solvent consists essentially of hexane.
9. The process defined in claim 1 wherein said volatile material removal is accomplished by a. distilling the reaction mixture to a bottoms temperature of at least 140C; then b. stripping the mixture with CO while maintaining the temperature of the mixture between about 140C and 160C.
10. The process defined in claim 9 wherein said magnesium alcoholate is derived from the monomethyl ether of ethylene glycol or the monoethyl ether of ethylene glycol, and contains from about 0.8 mole to about 1.2 mole of C0 per mole of magnesium alcoholate.
11. The method defined in claim 10 wherein the alkylphenol employed is a mixture containing at least 20 weight percent dialkylphenol with the balance being a monoalkylphenol.
12. The process defined in claim 11 wherein said nonvolatile diluent oil is selected from the group consisting of mineral lubricating oils and synthetic lubricating oils.
13. The process defined in claim 12 wherein the amounts of materials admixed in step (a) are:
Parts by Weight i. alkylphenol or sulfurized alkylphenol l0 70 ii. nonvolatile diluent I0 90 iii. volatile process solvent l0 100 14. The process defined in claim 1 and further characterized to include the step of adding to the reaction mixture after refluxing as described in step (c) and prior to removing volatile materials as described in step (d), an overbasing amount of said carbonated magnesium alcoholate, and concurrently with said addition, adding to the reaction mixture an amount of water exceeding the stoichiometric amount required to hydrolyze the overbasing amount of carbonated magnesium alcoholate.
15. The process defined in claim 14 wherein an amount of carbonated magnesium alcoholate is added which is in a weight ratio to the neutralizing amount of alcoholate added in step (b) of claim 1 of from about 0.5 to 3.0.
16. The process defined in claim 14 wherein from about 0.1 part by weight to about 10 parts by weight of water are added to the reaction mixture concurrently with said overbasing amount of magnesium alcoholate.
17. The process defined in claim 14 wherein sulfurized alkylphenol is mixed with nonvolatile diluent oil and volatile process solvent in step (a) of claim 1.
18. The process defined in claim 14 wherein the overbasing amount of carbonated magnesium alcoholate used is from about 10 parts by weight to about 300 parts by weight.
19. The process defined in claim 14 wherein the amounts of materials admixed in step (a) are:
Parts by Weight i. alkylphenol or sulfurized alkylphenol l0 ii. nonvolatile diluent oil 10 iii. volatile process solvent 10 20. The process defined in claim 14 wherein the admixture in step (a) contains additionally from about 0.1 to about 50 parts of oil soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.
21. The process defined in claim 14 wherein the nonvolatile diluent oil is selected from the group consisting of mineral lubricating oils and synthetic lubricating oils.
22. The process defined in claim 15 wherein the admixture of step (a) contains additionally from about 0.1 to about 50 parts of an oil-soluble sulfonic acid per l00 parts of alkylphenol or sulfurized alkylphenol.
23. The process defined in claim 16 wherein from about 1.1 moles to about 4 moles of water are added to the reaction mixture per mole of the overbasing amount of carbonated magnesium alcoholate added thereto.
24. The process defined in claim 17 wherein the sulfurized alkylphenol content of said admixture is a 'mixture of sulfurized monononylphenol and sulfurized dinonylphenol.
25. The process defined in claim 19 wherein an amount of carbonated magnesium alcoholate is added which is in weight ratio to the neutralizing amount of alcoholate added in step (b) of claim 1 of from 0.5 to 3.0.
26. The process defined in claim 25 wherein from about 0.1 part by weight to about 10 parts by weight of water are added to the reaction mixture concurrently with said overbasing amount of magnesium alcoholate.
27. The process defined in claim 26 wherein a mixture of sulfurized monoalkylphenol and sulfurized dial"- kylphenol is mixed with nonvolatile diluent oil and volatile process solvent in step (a) of claim 1.
28. The process defined in claim 27 wherein the admixture of step (a) contains additionally from about 0.1 to about 50 parts of an oil soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.
29. The process defined in claim 14 wherein less than 70 weight parts of nonvolatile diluent oil is present in said admixture formed in step (a), and further charactherefrom in step (e); said additional amount of nonterized as including the step of adding an additional volatile diluent oil together with said amount in said adamount of nonvolatile diluent oil to the reaction mixmixture totaling less than 70 weight parts.
ture prior to the removal of all of said volatile materials I 4* x I: a
Claims (28)
- 2. The process of claim 1 wherein x in said carbonated magnesium alcoholate formula is from about 0.75 to about 1, and wherein said magnesium alcoholate contains from about 0.8 mole to about 1.2 mole of CO2 per mole of magnesium alcoholate.
- 3. The process of claim 1 wherein the alkylphenol employed is a mixture containing at least 20 weight percent dialkylphenol with the balance being a monoalkylphenol.
- 4. The process defined in claim 1 wherein the nonvolatile diluent oil is selected from the group consisting of mineral lubricating oils and synthetic lubricating oils.
- 5. The process defined in claim 1 wherein the admixture of step (a) contains additionally from about 0.1 to about 50 parts of oil soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.
- 6. The process defined in claim 1 wherein the amounts of materials admixed in step (a) are: Parts by Weight i. alkylphenol or sulfur- ized alkylphenol 10 -70 ii. nonvolatile diluent 10 - 90 iii. volatile process solvent 10 - 100
- 7. The process defined in claim 1 wherein said carbonated magnesium alcoholate is derived from the monomethyl ether of ethylene glycol or from the monoethyl ether of ethylene glycol.
- 8. The process defined in claim 1 wherein said volatile process solvent consists essentially of hexane.
- 9. The process defined in claim 1 wherein said volatile material removal is accomplished by a. distilling the reaction mixture to a bottoms temperature of at least 140*C; then b. stripping the mixture with CO2 while maintaining the temperature of the mixture between about 140*C and 160*C.
- 10. The process defined in claim 9 wherein said magnesium alcoholate is derived from the monomethyl ether of ethylene glycol or the monoethyl ether of ethylene glycol, and contains from about 0.8 mole to about 1.2 mole of CO2 per mole of magnesium alcoholate.
- 11. The method defined in claim 10 wherein the alkylphenol employed is a mixture containing at least 20 weight percent dialkylphenol with the balance being a monoalkylphenol.
- 12. The process defined in claim 11 wherein said nonvolatile diluent oil is selected from the group consisting of mineral lubricating oils and synthetic lubricating oils.
- 13. The process defined in claim 12 wherein the amounts of materials admixed in step (a) are: Parts by Weight i. alkylphenol or sul- furized alkylphenol 10 -70 ii. nonvolatile diluent 10 - 90 iii. volatile process solvent 10 - 100
- 14. The process defined in claim 1 and further characterized to include the step of adding to the reaction mixture after refluxing as described in step (c) and prior to removing volatile materials as described in step (d), an overbasing amount of said carbonated magnesium alcoholate, and concurrently with said addition, adding to the reaction mixture an amount of water exceeding the stoichiometric amount required to hydrolyze the overbasing amount of carbonated magnesium alcoholate.
- 15. The process defined in claim 14 wherein an amount of carbonated magnesium alcoholate is added which is in a weight ratio to the neutralizing amount of alcoholate added in step (b) of claim 1 of from about 0.5 to 3.0.
- 16. The process defined in claim 14 wherein from about 0.1 part by weight to about 10 parts by weight of water are added to the reaction mixture concurrently with said overbasing amount of magnesium alcoholate.
- 17. The process defined in claim 14 wherein sulfurized alkylphenol is mixed with nonvolatile diluent oil and volatile process solvent in step (a) of claim 1.
- 18. The process defined in claim 14 wherein the overbasing amount of carbonated magnesium alcoholate used is from about 10 parts by weight to about 300 parts by weight.
- 19. The process defined in claim 14 wherein the amounts of materials admixed in step (a) are: Parts by Weight i. alkylphenol or sul- furized alkylphenol 10 -70 ii. nonvolatile diluent oil 10 - 90 iii. volatile process solvent 10 - 100
- 20. The process defined in claim 14 wherein the admixture in step (a) contains additionally from about 0.1 to about 50 parts of oil soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.
- 21. The process defined in claim 14 wherein the nonvolatile diluent oil is selected from the group consisting of mineral lubricating oils and synthetic lubricating oils.
- 22. The process defined in claim 15 wherein the admixture of step (a) contains additionally from about 0.1 to about 50 parts of an oil-soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.
- 23. The process defined in claim 16 wherein from about 1.1 moles to about 4 moles of water are added to the reaction mixture per mole of the overbasing amount of carbonated magnesium alcoholate added thereto.
- 24. The process defined in claim 17 wherein the sulfurized alkylphenol content of said admixture is a mixture of sulfurized monononylphenol and sulfurized dinonylphenol.
- 25. The process defined in claim 19 wherein an amount of carbonated magnesium alcoholate is added which is in weight ratio to the neutralizing amount of alcoholate added in step (b) of claim 1 of from 0.5 to 3.0.
- 26. The process defined in claim 25 wherein from about 0.1 part by weight to about 10 parts by weight of water are added to the reaction mixture concurrently with said overbasing amount of magnesium alcoholate.
- 27. The process defined in claim 26 wherein a mixture of sulfurized monoalkylphenol and sulfurized dialkylphenol is mixed with nonvolatile diluent oil and volatile process solvent in step (a) of claim 1.
- 28. The process defined in claim 27 wherein the admixture of step (a) contains additionally from about 0.1 to about 50 parts of an oil soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.
- 29. The process defined in claim 14 wherein less than 70 weight parts of nonvolatile diluent oil is present in said admixture formed in step (a), and further characterized as including the step of adding an additional amount of nonvolatile diluent oil to the reaction mixture prior to the removal of all of said volatile materials therefrom in step (e), said additional amount of nonvolatile diluent oil together with said amount in said admixture totaling less than 70 weight parts.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US17667671A | 1971-08-31 | 1971-08-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3718589A true US3718589A (en) | 1973-02-27 |
Family
ID=22645374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00176676A Expired - Lifetime US3718589A (en) | 1971-08-31 | 1971-08-31 | Preparation of neutral and highly basic alkylphenates and sulfurized alkylphenates |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US3718589A (en) |
| JP (1) | JPS5938212B2 (en) |
| BE (1) | BE827090Q (en) |
| CA (1) | CA992104A (en) |
| DE (1) | DE2236189C2 (en) |
| FR (1) | FR2150718B1 (en) |
| GB (1) | GB1392255A (en) |
| IT (1) | IT961841B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2429203A1 (en) * | 1978-06-20 | 1980-01-18 | Witco Chemical Corp | PROCESS FOR THE PREPARATION OF SURBASIC MAGNESIUM SULPHIDE PHENATES |
| US4295981A (en) * | 1979-07-27 | 1981-10-20 | Burnop Victor C | Production of overbased magnesium detergent additives |
| WO1987003868A1 (en) * | 1985-12-20 | 1987-07-02 | The Lubrizol Corporation | Basic metal salts having improved color and stability and vinyl halide polymers containing same |
| US5854184A (en) * | 1996-04-25 | 1998-12-29 | Institut Francais Du Petrole | Colloidal products, their preparation and their uses |
| US20190177636A1 (en) * | 2014-05-28 | 2019-06-13 | The Lubrizol Corporation | Alkylphenol detergents |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6337516U (en) * | 1986-08-25 | 1988-03-10 | ||
| GB8730220D0 (en) * | 1987-12-29 | 1988-02-03 | Exxon Chemical Patents Inc | Detergents |
| JPH068201U (en) * | 1992-07-02 | 1994-02-01 | 株式会社四国製作所 | Sorted grain bagging device for grain sorter |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2788325A (en) * | 1953-07-27 | 1957-04-09 | Texas Co | Process for preparing magnesium alkyl phenolates |
| US2895913A (en) * | 1957-05-28 | 1959-07-21 | Continental Oil Co | Magnesium containing organic compositions and method of preparing the same |
| US2916454A (en) * | 1957-02-18 | 1959-12-08 | Socony Mobil Oil Co Inc | Preparation of complex carbonated metal salts of alkyl phenol sulfides and mineral oil fractions containing the same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US26811A (en) * | 1860-01-10 | Seth boyden | ||
| US3036971A (en) * | 1958-12-24 | 1962-05-29 | Socony Mobil Oil Co Inc | Lubricating oils containing carbonated basic sulfurized calcium phenates |
| NL262166A (en) * | 1960-03-16 | |||
| US3336224A (en) * | 1965-04-28 | 1967-08-15 | Chevron Res | High alkalinity overbased phenate |
| USRE26811E (en) * | 1965-08-23 | 1970-03-03 | Basic, sulfurized phenates and salicylates and method for their preparation | |
| NL134001C (en) * | 1965-10-29 | |||
| US3367867A (en) * | 1966-01-04 | 1968-02-06 | Chevron Res | Low-foaming overbased phenates |
| GB1132040A (en) * | 1966-03-31 | 1968-10-30 | Monsanto Co | Complex salts of alkyl phenols and alkyl phenol sulphides |
-
1971
- 1971-08-31 US US00176676A patent/US3718589A/en not_active Expired - Lifetime
-
1972
- 1972-06-01 CA CA143,613A patent/CA992104A/en not_active Expired
- 1972-07-12 GB GB3249972A patent/GB1392255A/en not_active Expired
- 1972-07-24 DE DE2236189A patent/DE2236189C2/en not_active Expired
- 1972-08-01 FR FR7227755A patent/FR2150718B1/fr not_active Expired
- 1972-08-03 IT IT51954/72A patent/IT961841B/en active
- 1972-08-23 JP JP47083816A patent/JPS5938212B2/en not_active Expired
-
1975
- 1975-03-24 BE BE154678A patent/BE827090Q/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2788325A (en) * | 1953-07-27 | 1957-04-09 | Texas Co | Process for preparing magnesium alkyl phenolates |
| US2916454A (en) * | 1957-02-18 | 1959-12-08 | Socony Mobil Oil Co Inc | Preparation of complex carbonated metal salts of alkyl phenol sulfides and mineral oil fractions containing the same |
| US2895913A (en) * | 1957-05-28 | 1959-07-21 | Continental Oil Co | Magnesium containing organic compositions and method of preparing the same |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2429203A1 (en) * | 1978-06-20 | 1980-01-18 | Witco Chemical Corp | PROCESS FOR THE PREPARATION OF SURBASIC MAGNESIUM SULPHIDE PHENATES |
| US4196089A (en) * | 1978-06-20 | 1980-04-01 | Witco Chemical Corporation | Preparation of overbased magnesium sulfurized phenates |
| US4295981A (en) * | 1979-07-27 | 1981-10-20 | Burnop Victor C | Production of overbased magnesium detergent additives |
| WO1987003868A1 (en) * | 1985-12-20 | 1987-07-02 | The Lubrizol Corporation | Basic metal salts having improved color and stability and vinyl halide polymers containing same |
| US5854184A (en) * | 1996-04-25 | 1998-12-29 | Institut Francais Du Petrole | Colloidal products, their preparation and their uses |
| US20190177636A1 (en) * | 2014-05-28 | 2019-06-13 | The Lubrizol Corporation | Alkylphenol detergents |
| US11466226B2 (en) * | 2014-05-28 | 2022-10-11 | The Lubrizol Corporation | Alkylphenol detergents |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5938212B2 (en) | 1984-09-14 |
| IT961841B (en) | 1973-12-10 |
| JPS4834863A (en) | 1973-05-22 |
| FR2150718B1 (en) | 1976-08-13 |
| BE827090Q (en) | 1975-07-16 |
| FR2150718A1 (en) | 1973-04-13 |
| DE2236189C2 (en) | 1983-12-15 |
| CA992104A (en) | 1976-06-29 |
| GB1392255A (en) | 1975-04-30 |
| DE2236189A1 (en) | 1973-03-01 |
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