CN117597421A - Amine enhanced detergents - Google Patents
Amine enhanced detergents Download PDFInfo
- Publication number
- CN117597421A CN117597421A CN202280047480.XA CN202280047480A CN117597421A CN 117597421 A CN117597421 A CN 117597421A CN 202280047480 A CN202280047480 A CN 202280047480A CN 117597421 A CN117597421 A CN 117597421A
- Authority
- CN
- China
- Prior art keywords
- amine
- phthalimide
- grams
- charged
- sulfonate
- 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.)
- Pending
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- 239000003599 detergent Substances 0.000 title claims abstract description 78
- 150000001412 amines Chemical class 0.000 title claims description 100
- 239000000203 mixture Substances 0.000 claims abstract description 132
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 29
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims abstract description 28
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 25
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 55
- 239000010687 lubricating oil Substances 0.000 claims description 53
- 125000000217 alkyl group Chemical group 0.000 claims description 43
- 229910052751 metal Inorganic materials 0.000 claims description 41
- 239000002184 metal Substances 0.000 claims description 41
- 125000003118 aryl group Chemical group 0.000 claims description 30
- 125000003342 alkenyl group Chemical group 0.000 claims description 28
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 27
- 239000003921 oil Substances 0.000 claims description 25
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 21
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 14
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 12
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 11
- IMLAIXAZMVDRGA-UHFFFAOYSA-N 2-phenoxyethanamine Chemical compound NCCOC1=CC=CC=C1 IMLAIXAZMVDRGA-UHFFFAOYSA-N 0.000 claims description 11
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 11
- 150000003839 salts Chemical group 0.000 claims description 11
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims description 10
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 8
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 8
- OTTCLTLOYAZCAZ-UHFFFAOYSA-N 2-[2-(methylamino)ethyl]isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCNC)C(=O)C2=C1 OTTCLTLOYAZCAZ-UHFFFAOYSA-N 0.000 claims description 7
- NFCPRRWCTNLGSN-UHFFFAOYSA-N 2-n-phenylbenzene-1,2-diamine Chemical compound NC1=CC=CC=C1NC1=CC=CC=C1 NFCPRRWCTNLGSN-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 239000004471 Glycine Substances 0.000 claims description 6
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 5
- WJVAPEMLIPHCJB-UHFFFAOYSA-N 1-n-methylpropane-1,2-diamine Chemical compound CNCC(C)N WJVAPEMLIPHCJB-UHFFFAOYSA-N 0.000 claims description 5
- ASUDFOJKTJLAIK-UHFFFAOYSA-N 2-methoxyethanamine Chemical compound COCCN ASUDFOJKTJLAIK-UHFFFAOYSA-N 0.000 claims description 5
- NGOMYFUIWZJUET-UHFFFAOYSA-N 2-naphthalen-2-yloxyethanamine Chemical compound C1=CC=CC2=CC(OCCN)=CC=C21 NGOMYFUIWZJUET-UHFFFAOYSA-N 0.000 claims description 5
- LYUQWQRTDLVQGA-UHFFFAOYSA-N 3-phenylpropylamine Chemical compound NCCCC1=CC=CC=C1 LYUQWQRTDLVQGA-UHFFFAOYSA-N 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- DTSDBGVDESRKKD-UHFFFAOYSA-N n'-(2-aminoethyl)propane-1,3-diamine Chemical compound NCCCNCCN DTSDBGVDESRKKD-UHFFFAOYSA-N 0.000 claims description 5
- UKXSMVIDPJCDAQ-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]benzamide Chemical compound CN(C)CCCNC(=O)C1=CC=CC=C1 UKXSMVIDPJCDAQ-UHFFFAOYSA-N 0.000 claims description 5
- WSTNFGAKGUERTC-UHFFFAOYSA-N n-ethylhexan-1-amine Chemical compound CCCCCCNCC WSTNFGAKGUERTC-UHFFFAOYSA-N 0.000 claims description 5
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 5
- 239000003760 tallow Substances 0.000 claims description 5
- FISUQCYYLJGIIU-UHFFFAOYSA-N 2-(2-aminoethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCN)C(=O)C2=C1 FISUQCYYLJGIIU-UHFFFAOYSA-N 0.000 claims description 4
- MWFLUYFYHANMCM-UHFFFAOYSA-N 2-(2-hydroxyethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCO)C(=O)C2=C1 MWFLUYFYHANMCM-UHFFFAOYSA-N 0.000 claims description 4
- AAYUGMOUMAINTE-UHFFFAOYSA-N 2-[3-(methylamino)propyl]isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCCNC)C(=O)C2=C1 AAYUGMOUMAINTE-UHFFFAOYSA-N 0.000 claims description 4
- BSMILTTURCQDGJ-UHFFFAOYSA-N N-(3-Hydroxypropyl)phthalimide Chemical compound C1=CC=C2C(=O)N(CCCO)C(=O)C2=C1 BSMILTTURCQDGJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001413 amino acids Chemical class 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- UOKZUTXLHRTLFH-UHFFFAOYSA-N o-phenylhydroxylamine Chemical compound NOC1=CC=CC=C1 UOKZUTXLHRTLFH-UHFFFAOYSA-N 0.000 claims description 4
- SRMYNTUZHJDDER-UHFFFAOYSA-N 2-(3-aminopropyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCCN)C(=O)C2=C1 SRMYNTUZHJDDER-UHFFFAOYSA-N 0.000 claims description 3
- 230000001050 lubricating effect Effects 0.000 claims description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims 6
- 150000004982 aromatic amines Chemical class 0.000 claims 3
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 210
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 127
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- 239000004571 lime Substances 0.000 description 127
- 239000000047 product Substances 0.000 description 99
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- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 70
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- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 42
- 239000000920 calcium hydroxide Substances 0.000 description 42
- 235000011116 calcium hydroxide Nutrition 0.000 description 42
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- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 6
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- 150000003949 imides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000010699 lard oil Substances 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
-
- 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
- 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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
-
- 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
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
-
- 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
- C10M2203/003—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/26—Amines
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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
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
- C10M2223/061—Metal salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/04—Detergent property or dispersant property
-
- 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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/36—Seal compatibility, e.g. with rubber
-
- 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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/45—Ash-less or low ash content
-
- 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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/52—Base number [TBN]
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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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
Abstract
A process for preparing a low ash detergent is described. The process involves mixing a surfactant composition comprising a hydroxybenzoate, sulfonate or phosphonate detergent with an ashless nitrogen-containing compound to enhance the base number of the hydroxybenzoate, sulfonate or phosphonate detergent.
Description
Technical Field
The present disclosure relates to detergent additive compositions. More specifically, the present disclosure describes amine enhanced detergent compositions and lubricating oil compositions containing the same.
Background
Metallic detergent additives are commonly used in automotive lubricants to provide important benefits such as preventing deposit formation and improving fuel economy.
In particular, overbasing the detergent can provide a metal base reservoir that neutralizes corrosive acids generated in the engine environment. For calcium detergents, the degree to which the detergent has been highly alkalized depends on the presence of calcium carbonate (CaCO) 3 ) Is a level of (c).
Highly alkalized calcium metal detergents are oil soluble particles having a surfactant shell and a calcium carbonate core. The high degree of basification is indicated by Total Base Number (TBN). Generally, higher TBNs extend the operational period before lubricant replacement is required under severe conditions.
One disadvantage of these types of detergents is that the presence of metal results in sulfated ash that can contaminate the exhaust gas treatment catalyst. While calcium carbonate contributes to TBN, it can also lead to the production of sulfated ash. One way to solve this problem is to limit the metal content of the additive package.
Disclosure of Invention
In one aspect, a process for preparing a low ash detergent is provided, the process comprising: a surfactant composition comprising a hydroxybenzoate, sulfonate or phosphonate detergent is mixed with an ashless nitrogen-containing compound to enhance the base number of the hydroxybenzoate, sulfonate or phosphonate detergent.
In another aspect, a process for preparing a low ash detergent is provided, the process comprising: mixing a hydroxybenzoate, sulfonate or phosphonate detergent with an amine or amine derivative, wherein the amine or amine derivative is added to overbase the hydroxybenzoate, sulfonate or phosphonate detergent or to enhance the base number of the hydroxybenzoate, sulfonate or phosphonate detergent.
In yet another aspect, a lubricating oil composition is provided, comprising: a major amount of an oil of lubricating viscosity; and a minor amount of a low ash detergent made by a process comprising: mixing a hydroxybenzoate, sulfonate or phosphonate detergent with an amine or amine derivative, wherein the amine or amine derivative is added to overbase the hydroxybenzoate, sulfonate or phosphonate detergent or to enhance the base number of the hydroxybenzoate, sulfonate or phosphonate detergent.
Detailed Description
In this specification, the following words and expressions (if and when used) have the meanings given below.
The term "alkyl" or related terms refer to a saturated hydrocarbon group that may be straight-chain, branched, cyclic, or a combination of cyclic, straight-chain, and/or branched. The term "alkenyl" or related terms refer to an unsaturated hydrocarbon group that may be linear, branched, cyclic, or a combination of cyclic, linear, and/or branched.
In the context of hydrocarbon-based formulations (particularly lubricants), the term "ash" or related terms refer to the metal compounds remaining after the hydrocarbon is calcined. This ash is mainly derived from chemicals used in certain additives as well as solids. The term "sulfated ash" refers to the combustion products of metals commonly found in detergents. As a lubricant property, the sulphated ash content is a measure of the metal content (typically Zn, ca and Mg).
The term "ashless" or related terms refer to a formulation or additive that does not produce ash or limits the production of ash. Ashless additives are generally free of metals (including boron), silicon, halogens, or contain concentrations of these elements below the detection limit of typical instruments.
"minor amount" or related terms means less than 50wt% of the composition, expressed with respect to the stated additives and with respect to the total weight of the composition, as active ingredient of the additive.
"major amount" or related terms means an amount of greater than 50wt% based on the total weight of the composition.
The term "lime" refers to calcium hydroxide, also known as slaked lime or hydrated lime.
The term "total base number" or "TBN" refers to the level of alkalinity in an oil sample indicative of the ability of the composition to continue to neutralize corrosive acids according to ASTM standard number D2896 or equivalent procedure. The test measures the change in conductivity and the results are expressed as mg KOH/g (milliequivalents of KOH required to neutralize 1 gram of product). Thus, a high TBN reflects a strongly highly alkalized product and is therefore a higher base reserve for neutralizing acids.
A low ash detergent is described which, when used as an additive in a lubricating oil under engine operating conditions, results in lower sulfated ash yield per Base Number (BN) than conventional high alkalized detergents. The low ash detergent of the present invention comprises: 1) A surfactant and 2) a nitrogen-containing compound. Nitrogen-containing compounds (such as amines or amine derivatives) are used to overbase the detergent and enhance TBN. In one aspect, the present invention relates to an amine enhanced detergent wherein the nitrogen-containing compound is an amine or an amine derivative. In another aspect, the nitrogen-containing compound is ashless.
And the severe dependence on metal salts (e.g. CaCO) during engine operation 3 ) The low ash detergents of the present invention generally contain less metal salts than conventional detergents to neutralize acids. Thus, the detergents of the present invention produce less sulfated ash. The nitrogen-containing compounds contribute to the total base number but do not contribute to the production of sulphated ash.
Particularly useful surfactants compatible with the present invention include metal detergents such as hydroxybenzoates, sulfonates and phosphonates. Some non-limiting examples of compatible metal detergents include sulfurized or unsulfided metal salts of alkyl or alkenyl aromatic sulfonates, borated sulfonates, polyhydroxy alkyl or alkenyl aromatic compounds, metal salts of alkyl or alkenyl hydroxybenzoic acids, alkyl or alkenyl hydroxy aromatic sulfonates, sulfurized or unsulfided alkyl or alkenyl naphthenates, metal salts of alkanoic acids, metal salts of alkyl or alkenyl polyacids, and chemical and physical mixtures thereof. Other non-limiting examples of suitable metal detergents include salicylates, thiophosphonates, and the like. Non-limiting examples of suitable metals include alkali metals, alkaline metals, and transition metals. In some embodiments, the metal is Ca, mg, ba, K, na, li, or the like.
Particularly useful nitrogen-containing compounds compatible with the present invention include amines and amine derivatives such as carbamates, ureas, amides and imides. The nitrogen-containing compound may contain heteroatoms (e.g., alcohols), saturated groups, aromatic groups, and the like.
Examples of amines or amine derivatives include alkylated amines (e.g., 2-ethylhexyl (tallow) methylamine, ethylhexyl amine, octylamine), hydrocarbylamine, ethylenediamine, N-methylethanolamine, 1, -dimethylethylenediamine, 2-methoxyethylamine, ethanolamine (e.g., diethanolamine), N-methylpropylenediamine, piperazine (e.g., dodecylpiperazine), urea, tetramethylurea, diphenylamine, alkylated diphenylamines, benzylamine, N-phenylphenylenediamine, triethylenetetramine, triethanolamine, 1, 4-diazabicyclo [2.2.2] octane, N' -bis (3-aminopropyl) ethylenediamine ("N4 amine"), phenoxyamine (e.g., 2-phenoxyethylamine, C20-C24 alkyl-2-phenoxyethylamine), 2- (2-aminoethoxy) naphthalene, N- (3- (dimethylamino) propyl) benzamide, anilines (e.g., 3-phenylpropylamine), benzamide, amino acids, and phthalimide.
More specifically, suitable phthalimides include N- (2-hydroxyethyl) phthalimide, N- (2-aminoethyl) phthalimide, N- (3-hydroxypropyl) phthalimide, N- (3-aminopropyl) phthalimide, N- (2- (methylamino) ethyl) phthalimide, N- (3- (methylamino) propyl) phthalimide, N- (2- (dimethylamino) ethyl) phthalimide, and N- (3- (dimethylamino) propyl phthalimide.
In some embodiments, the low ash detergents of the present invention may comprise a mixture of a nitrogen-containing compound (such as an amine) and a carbamate.
Detergent synthesis
The low ash detergents of the present invention may be synthesized by any compatible method. However, one advantage is that the manufacture of the low ash detergents of the present invention is generally compatible with conventional detergent manufacturing processes such as the following. For example, the manufacture of conventional overbased calcium alkyl hydroxybenzoate detergents typically begins by reacting an alkylphenol with a metal base. The product is then carboxylated (i.e. with CO 2 Treatment) and acidification. The resulting acid product may be neutralized with lime and highly alkalized. Some of these steps (e.g., secondary neutralization and overbasing) can be performed simultaneously. A more detailed description of this process can be found in US 8,030,258, which is hereby incorporated by reference.
The detergents of the present invention may be synthesized using any compatible method. In one aspect, the synthesis of the detergents of the invention differs from that of conventional detergents in that the low ash detergents of the invention are enhanced with nitrogen-containing compounds (e.g., amines or amine derivatives) in place of metal bases (e.g., calcium carbonate).
As an illustrative example, a process for preparing a highly alkalized amine enhanced alkaline earth metal alkylaryl sulfonate comprises: (a) Neutralizing an alkaline earth metal alkyl toluene/benzene sulfonate base (e.g., mgO) to form an alkaline earth metal alkyl toluene/benzene sulfonate; (b) Contacting the alkaline earth metal alkyl toluene/benzene sulfonate and alkaline earth metal base from step (a) with at least one carboxylic acid having from about 1 to 4 carbon atoms to form a mixture of alkaline earth metal alkyl aryl sulfonate and at least one alkaline earth metal carboxylate; and (c) overbasing the alkaline earth metal alkylaryl sulfonate from step (b) with an amine or amine derivative and at least one acidic overbasing material in the presence of at least one alkaline earth metal carboxylate from step (b). A more detailed description of the preparation of alkaline earth metal alkylaryl sulfonates can be found in US 6,479,440, which is hereby incorporated by reference.
As an illustrative example, a process for preparing a highly alkalized amine enhanced alkaline earth metal alkylaryl sulfonate comprises: (a) Neutralization of alkaline earth metal alkyl toluene/benzenesulfonate bases (e.g., caO or Ca (OH) 2 ) To form an alkaline earth metal alkyl toluene/benzene sulfonate; to be used forAnd (b) overbasing the alkaline earth metal alkylaryl sulfonates from step (a) with an amine or amine derivative. A more detailed description of the preparation of alkaline earth metal alkylaryl sulfonates can be found in U.S. patent No. 8,076,272, which is hereby incorporated by reference.
As an illustrative example, a process for preparing a highly alkalized amine enhanced alkaline earth metal alkyl hydroxybenzoate comprises: (a) Reacting an alkylphenol with an alkali metal base to produce an alkali metal alkylphenol salt; (b) Carboxylating the alkali metal alkyl phenate obtained in step (a) with carbon dioxide such that at least 50 mole% of the starting alkylphenol is converted to alkali metal alkyl hydroxybenzoate; (c) Acidifying the alkali metal alkylhydroxybenzoate obtained in step (b) with an aqueous solution of a strong acid to produce alkylhydroxybenzoic acid; (d) Neutralizing the alkylhydroxybenzoic acid from step (c) with a molar excess of alkaline earth metal base and at least one solvent from the following to form an alkaline earth metal alkylhydroxybenzoate: aromatic hydrocarbons, aliphatic hydrocarbons, monohydric alcohols, and mixtures thereof; (e) Contacting the alkaline earth metal alkylhydroxybenzoate from step d) and an alkaline earth metal base with at least one carboxylic acid having from about 1 to 4 carbon atoms in the presence of a solvent (i.e., an aromatic hydrocarbon, an aliphatic hydrocarbon, a monohydric alcohol, or mixtures thereof) to form a mixture of the alkaline earth metal alkylhydroxybenzoate and at least one alkaline earth metal carboxylate; and (f) overbasing the alkaline earth metal alkylhydroxybenzoate from step e) with an amine or amine derivative and at least one acidic overbasing species in the presence of at least one alkaline earth metal carboxylate from step (e) and a solvent (i.e., an aromatic hydrocarbon, aliphatic hydrocarbon, monohydric alcohol, or mixtures thereof).
In another embodiment, the amine may be added during neutralization prior to the overbasing step.
It will be appreciated that the particular sequence of one or more steps in the synthetic pathway of the detergent (e.g., alkylaryl sulfonate, alkyl hydroxybenzoate, etc.) may be reordered, combined, or slightly modified as desired, so long as it is compatible and in accordance with the present invention. For purposes of illustration, the following embodiments are provided relating to detergent synthesis of alkyl hydroxybenzoic acids, alkyl aromatic sulfonic acids and alkenyl aromatic sulfonic acids. These variations are also applicable to other detergent synthetic pathways compatible with the present invention.
For example, in the alkyl hydroxybenzoate detergent synthesis pathway, alkyl hydroxybenzoic acids may be treated with lime slurry (i.e., ca (OH) 2 ) And (5) neutralization. Optionally, an amine may be present in the lime slurry during the neutralization step. Lime slurry and amine or amine derivative may be charged to a reactor, both with CO 2 React together.
According to one embodiment, the amine treatment may be after the alkyl hydroxybenzoic acid has been neutralized with lime slurry and after the excess lime has been reacted with CO 2 The reaction is followed by formation of a metal carbonate (e.g., calcium carbonate).
According to one embodiment, the amine treatment may be after the alkyl hydroxybenzoic acid has been neutralized with the lime slurry and after the lime slurry has been reacted with CO 2 The reaction is carried out before.
According to one embodiment, the amine may be charged to the reactor after neutralization of the alkyl hydroxybenzoic acid with lime slurry. The amine or amine derivative may be dispersed with the neutralized surfactant without further treatment.
According to one embodiment, the alkylhydroxybenzoic acid may be neutralized with an excess of amine relative to the amount required to neutralize the alkylhydroxybenzoic acid. Excess amine can be combined with CO 2 To react to form carbamate.
According to one embodiment, the alkylhydroxybenzoic acid may be neutralized with an excess of amine relative to the amount required to neutralize the alkylhydroxybenzoic acid.
According to one embodiment, the alkyl hydroxybenzoic acid may be neutralized with lime slurry, followed by treatment of the amine with ethylene carbonate. In some embodiments, a metal base may be used in addition to or in addition to lime. Suitable metal bases include alkali metal bases and alkaline earth metal bases. Examples of suitable metal bases include MgO and the like.
According to one embodiment, in the alkyl or alkenyl aromatic sulfonate detergent synthesis pathway, alkyl or alkenyl aromatic sulfonic acid may be treated with lime slurry (i.e., ca (OH) 2 ) And (5) neutralization. Optionally, an amine may be present in the lime slurry during the neutralization step. Lime slurry and amine or amine derivative may be charged to a reactor, both with CO 2 React together.
According to one embodiment, the amine treatment may be after the alkyl or alkenyl aromatic sulfonic acid has been neutralized with lime slurry and after the excess lime has been reacted with CO 2 The reaction is followed by formation of a metal carbonate (e.g., calcium carbonate).
According to one embodiment, the amine treatment may be after the alkyl or alkenyl aromatic sulfonic acid has been neutralized with the lime slurry and after the lime slurry has been reacted with CO 2 The reaction is carried out before.
According to one embodiment, the amine may be charged to the reactor after the alkyl or alkenyl aromatic sulfonic acid is neutralized with lime slurry. The amine or amine derivative may be dispersed with the neutralized surfactant without further treatment.
According to one embodiment, the alkyl or alkenyl aromatic sulfonic acid may be neutralized with an excess of amine relative to the amount required to neutralize the alkyl or alkenyl aromatic sulfonic acid. Excess amine can be combined with CO 2 To react to form carbamate.
According to one embodiment, the alkyl or alkenyl aromatic sulfonic acid may be neutralized with an excess of amine relative to the amount required to neutralize the alkyl or alkenyl aromatic sulfonic acid.
According to one embodiment, the alkyl or alkenyl aromatic sulfonic acid may be neutralized with lime slurry, followed by treatment of the amine with ethylene carbonate. In some embodiments, a metal base may be used in addition to or in addition to lime. Suitable metal bases include alkali metal bases and alkaline earth metal bases. Examples of suitable metal bases include MgO and the like.
Amine treated products include ammonium carbamate and calcium carbonate. The latter is produced in reduced amounts compared to the manufacture or synthesis of conventional detergents.
Any amine or amine derivative reagent compatible with the present invention may be used. These amines include, for example, primary, secondary and tertiary amines and derivatives thereof. The amine may contain heteroatoms (e.g., alcohols), saturated groups, aromatic groups, and the like.
Compatible primary amines or amine derivatives include, for example, glycine, 2-ethylhexyl amine, octyl amine, 2-methoxyethylamine, 2-phenoxyethylamine, 2- (2-aminoethoxy) naphthalene, 3-phenylpropylamine, benzamide, and the like.
Compatible secondary amines or amine derivatives include, for example, ethylenediamine, diphenylamine, alkylated diphenylamines, triethylenetetramine, N-phenylphenylenediamine, N-ethylbutylamine, isopropylmethylamine, N-ethylhexyl amine, N-methylethanolamine, diethanolamine, phthalimides, and the like.
Compatible tertiary amines or amine derivatives include, for example, triethanolamine, 1, 4-diazabicyclo [2.2.2] octane, dialkylpiperazine, 2-ethylhexyl (tallow) methylamine, tetramethylurea, and the like.
Some amines or amine derivatives may have a variety of amines or amine derivatives that are independently primary, secondary or tertiary amines. Examples include 1, -dimethylethylenediamine, N-methylpropylenediamine, 1-dodecylpiperazine, N' -bis (3-aminopropyl) ethylenediamine ("N4 amine"), N- (3- (dimethylamino) propyl) benzamide, and the like.
Amine treatment one or more solvents are used during the amine treatment step. Suitable solvents include xylene, toluene, methanol, and the like.
The alkyl or alkenyl groups of the amine enhanced alkaline earth metal alkyl hydroxybenzoate or alkylaryl sulfonate may be derived from alkyl substituents having C10-40 alkyl groups, preferably C12-C30, C14-C18, C18-30, C20-28, C20-24 or mixtures thereof.
In one embodiment, the alkyl substituent is a residue derived from an alpha-olefin having 14 to 28 carbon atoms per molecule. In one embodiment, the alkyl substituent is a residue derived from an alpha-olefin having 14 to 18 carbon atoms per molecule. In one embodiment, the alkyl substituent is a residue derived from an alpha-olefin having 20 to 28 carbon atoms per molecule. In one embodiment, the alkyl substituent is a residue derived from an alpha-olefin having 20 to 24 carbon atoms per molecule. In one embodiment, the alkyl substituent is a residue derived from an olefin comprising a C12 to C40 oligomer of a monomer selected from propylene, butene, or mixtures thereof. Examples of such olefins include propylene tetramer, butene trimer, isobutene oligomer, and the like.
The olefins employed may be linear, isomerized linear, branched or partially branched linear. The olefin may be a mixture of linear olefins, a mixture of isomerized linear olefins, a mixture of branched olefins, a mixture of partially branched linear olefins, or a mixture of any of the foregoing. The alpha-olefin may be an n-alpha-olefin, an isomerized n-alpha-olefin, or a mixture thereof.
In one embodiment where the alkyl substituent is a residue derived from isomerizing an alpha olefin, the alpha olefin may have an isomerization level (I) of 0.1 to 0.4 (e.g., 0.1 to 0.3 or 0.1 to 0.2). Level of isomerization (I) can be determined by 1 H NMR spectroscopy and indicates the relative amount of methyl (-CH 3) (chemical shift 0.30 to 1.01 ppm) attached to the methylene backbone (-CH 2- (chemical shift 1.01 to 1.38 ppm) group and is defined by the formula:
I＝m/(m+n)
wherein m is methyl with a chemical shift between 0.30.+ -. 0.03 and 1.01.+ -. 0.03ppm 1 H NMR integral, and n is methylene with chemical shift between 1.01.+ -. 0.03 and 1.38.+ -. 0.10ppm 1 H NMR integration.
The amine enhanced alkaline earth metal alkylhydroxybenzoates of the present disclosure have a TBN of 90 to 600mg KOH/g, such as 90 to 500mg KOH/g, 90 to 450mg KOH/g or 90 to 400mg KOH/g, 90 to 350mg KOH/g, 90 to 300mg KOH/g, 150 to 590mg KOH/g, 150 to 500mg KOH/g, 150 to 450mg KOH/g, 150 to 400mg KOH/g, 150 to 350mg KOH/g, 150 to 300mg KOH/g, 200 to 590mg KOH/g, 200 to 500mg KOH/g, 200 to 450mg KOH/g, 200 to 400mg KOH/g or 200 to 350mg KOH/g on an active basis.
The amine enhanced alkaline earth metal alkylaryl sulfonates of the present disclosure have a TBN of from 20 to 700mg KOH/g, such as from 20 to 650mg KOH/g, from 20 to 600mg KOH/g, from 20 to 550mg KOH/g, from 20 to 500mg KOH/g, from 150 to 700mg KOH/g, from 150 to 650mg KOH/g, from 150 to 600mg KOH/g, from 150 to 550mg KOH/g, from 150 to 500mg KOH/g, from 200 to 700mg KOH/g, from 250 to 700mg KOH/g, from 300 to 700mg KOH/g, from 200 to 600mg KOH/g, from 250 to 550mg KOH/g, from 300 to 500mg KOH/g, or from 350 to 450mg KOH/g on an active basis.
In another embodiment, the amine enhanced alkaline earth metal detergent comprises more than one surfactant, which is commonly referred to in the art as a complex or hybrid detergent. For example, amine enhanced highly alkalized alkaline earth metal detergents comprise alkyl hydroxybenzoates and alkylaryl sulfonates in the surfactant system.
Lubricating oil composition
The detergent compositions of the present disclosure are useful in lubricating oils. When used in this manner, the detergent is typically present in the lubricating oil composition at a concentration in the range of from 0.05 wt.% to 10 wt.% (including, but not limited to, 0.1 to 5 wt.%, 0.2 to 4 wt.%, 0.5 to 3 wt.%, 1 to 2 wt.%, etc.), based on the total weight of the lubricating oil composition. If other detergents are present in the lubricating oil composition, smaller amounts of the detergent of the present invention may be used.
The oil used as the base oil will be selected or blended depending on the desired end use and additives in the finished oil to obtain a desired grade of engine oil, such as an Society of Automotive Engineers (SAE) viscosity grade lubricating oil composition having a viscosity grade of 0W, 0W-8, 0W-16, 0W-20, 0W-30, 0W-40, 0W-50, 0W-60, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W-20, 10W-30, 10W-40, 10W-50, 15W-20, 15W-30 or 15W-40.
An oil of lubricating viscosity (sometimes referred to as a "base stock" or "base oil") is the primary liquid component of the lubricant into which additives and possibly other oils are blended, for example, to produce the final lubricant (or lubricant composition). The base oils useful in preparing the concentrate and in preparing the lubricating oil composition therefrom may be selected from natural (vegetable, animal or mineral) lubricating oils and synthetic lubricating oils and mixtures thereof.
The base stock and base oil definitions in this disclosure are the same as those in annex E ("API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils,", month 12 in 2016) of American Petroleum Institute (API) publication 1509. Using the test methods specified in Table E-1, group I base stocks contain less than 90% saturated hydrocarbons and/or greater than 0.03% sulfur and have a viscosity index of greater than or equal to 80 and less than 120. Using the test methods specified in Table E-1, group II base stocks contain greater than or equal to 90% saturated hydrocarbons and less than or equal to 0.03% sulfur and have a viscosity index greater than or equal to 80 and less than 120. Using the test methods specified in Table E-1, group III basestocks contain greater than or equal to 90% saturated hydrocarbons and less than or equal to 0.03% sulfur, and have a viscosity index greater than or equal to 120. Group IV base stocks are Polyalphaolefins (PAOs). Group V base stocks include all other base stocks not included in group I, group II, group III or group IV.
Natural oils include animal oils, vegetable oils (e.g., castor oil and lard oil), and mineral oils. Animal and vegetable oils having good thermal oxidation stability can be used. Among the natural oils, mineral oils are preferred. Mineral oils vary widely with respect to their crude oil sources (e.g., whether they are paraffinic, naphthenic or mixed paraffinic-naphthenic). Oils derived from coal or shale are also useful. Natural oils also differ in terms of the process used for their production and purification (e.g., their distillation ranges) or whether they are straight run or cracked, hydrofinished or solvent extracted.
Synthetic oils include hydrocarbon oils. Hydrocarbon oils include oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene isobutylene copolymers, ethylene-olefin copolymers, and ethylene-alpha-olefin copolymers). Polyalphaolefin (PAO) oil basestocks are commonly used synthetic hydrocarbon oils. For example, a derivative derived from C may be used 8 To C 14 Olefins, e.g. C 8 、C 10 、C 12 、C 14 PAO of olefins or mixtures thereof.
Other useful fluids for use as base oils include non-conventional or unconventional base oils that have been processed (preferably catalytic processed) or synthesized to provide high performance characteristics.
The non-conventional or extra-conventional base stock/base oil includes one or more of the following: mixtures of base stocks derived from one or more natural gas liquids (GTL) materials, as well as isomerate/isodewaxed (isodewaxed) base stocks derived from natural waxes or waxy feeds, mineral and non-mineral oil waxy feeds such as slack waxes, natural waxes and waxy feeds such as gas oils, waxy fuel hydrocracker bottoms, waxy raffinate, hydrocracker products, thermal cracking products, or other mineral, mineral oil, or even non-petroleum derived waxy materials such as those obtained from coal liquefaction or shale oil, and mixtures of such base stocks.
The base oils used in the lubricating oil compositions of the present disclosure are any type of oils corresponding to API group I, group II, group III, group IV and group V oils and mixtures thereof, preferably API group II, group III, group IV and group V oils and mixtures thereof, more preferably group III to group V base oils, due to their superior volatility, stability, viscosity and cleanliness characteristics.
Typically, the base oil will have a viscosity of from 2.5 to 20mm at 100 ℃ (ASTM D445) 2 S (e.g. 3 to 12mm 2 S, 4 to 10mm 2 S or 4.5 to 8mm 2 Kinematic viscosity in the range of/s).
The lubricating oil composition of the present invention may also contain conventional lubricant additives for imparting auxiliary functions to obtain a finished lubricating oil composition in which these additives are dispersed or dissolved. For example, the lubricating oil composition may be blended with antioxidants, ashless dispersants, antiwear agents, detergents, rust inhibitors, dehazers, demulsifiers, friction modifiers, metal deactivators, pour point depressants, viscosity modifiers, defoamers, co-solvents, package compatibilisers, corrosion inhibitors, dyes, extreme pressure agents and the like, and mixtures thereof. Various additives are known and commercially available. These additives or similar compounds may be employed to prepare the lubricating oil compositions of the present invention by conventional blending procedures.
When used, each of the foregoing additives is used in a functionally effective amount to impart the desired properties to the lubricant. Thus, for example, if the additive is an ashless dispersant, a functionally effective amount of such ashless dispersant will be an amount sufficient to impart the desired dispersion characteristics to the lubricant. Generally, unless otherwise indicated, the concentration of each of these additives, when used, may be in the range of about 0.001 to about 20wt%, such as about 0.01 to about 10 wt%.
The following illustrative examples are intended to be non-limiting.
Examples
The examples provide low ash detergents synthesized from alkyl hydroxybenzoate or sulfonate compositions. The reaction was carried out under nitrogen in a 5 liter four-necked glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 300 to 350rpm, located for the addition of CO 2 An air inlet pipe (2 mm inner diameter) right above the stirrer blade, a distillation column and a condenser.
Example 1
Ethylenediamine
In example 1, ethylenediamine is introduced simultaneously with lime slurry to neutralize alkyl hydroxybenzoic acid and to react the ethylenediamine with CO 2 And (3) reacting.
The beaker was charged with 175.8 grams of methanol, 222.5 grams of xylene solvent, and 175.8 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry and 76.1g ethylenediamine 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. The mixture was stirred for a few minutes. Next, 1820.4g of alkylhydroxybenzoic acid (C14-16-18 alkylhydroxybenzoic acid) was introduced. The resulting mixture was stirred at 40℃for 15min. The reactor was cooled to 30 ℃ over 15min. 56.9g of CO was introduced at 0.95g/min over 60min 2 . 55.5g of CO were then introduced at 0.95g/min over 58min 2 . At the same time with CO 2 During the reaction, the reactor temperature was increased from 30 ℃ to 40 ℃.
The first distillation step was then started at atmospheric pressure by heating the reactor from 40 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, and then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 613.4g of 140N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products. The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 170 ℃ under 30 millimeter Hg vacuum for about 45 minutes and holding the product at 170 ℃ under 30 millimeter Hg vacuum for 60 minutes. The vacuum was broken with air and cooled to ambient temperature.
Example 2
Diphenylamine
In example 2, diphenylamine is introduced simultaneously with lime slurry to neutralize alkyl hydroxybenzoic acid and react the diphenylamine with CO 2 And (3) reacting.
The beaker was charged with 150 grams of methanol, 222.5 grams of xylene solvent, and 150 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry and 200g of diphenylamine 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. The mixture was stirred for a few minutes. Then, 1820.4 g of alkylhydroxybenzoic acid (C14-16-18 alkylhydroxybenzoic acid) was introduced. The mixture was stirred at 40℃for 15min. The stirred mixture was cooled to 30 ℃ over 15min. Next, 48.5 g CO was introduced at 0.95g/min over 51min 2 The temperature is increased from 30 ℃ to 35 ℃. 52 g CO was then introduced at 0.95g/min over 55min 2 The temperature is increased from 35 ℃ to 40 ℃.
The first distillation step was then started at atmospheric pressure by heating the reactor from 40 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 613.4 grams of 140N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products.
The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 170 ℃ and holding the product at 170 ℃ for 60min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 3
Diphenylamine
In example 3, after neutralization of the alkylhydroxybenzoic acid with lime, diphenylamine is introduced and reacted with CO 2 And (3) reacting.
The beaker was charged with 150 grams of methanol, 222.5 grams of xylene solvent, and 150 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. Then, 1820.4 g of alkylhydroxybenzoic acid (C14-16-18 alkylhydroxybenzoic acid) was introduced. The mixture was stirred at 40℃for 15min. 200 g of diphenylamine were then introduced into a glass reactor and the stirred mixture was cooled to 30℃over 15min. Next, 48.5 g CO was introduced over a period of 51min at 0.95g/min 2 The temperature is increased from 30 ℃ to 35 ℃. 52 g CO was then introduced at 0.95g/min over 55min 2 The temperature is increased from 35 ℃ to 40 ℃.
The first distillation step was then started at atmospheric pressure by heating the reactor from 40 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 613.4 grams of 140N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products.
The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 170 ℃ and holding the product at 170 ℃ for 60min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 4
Ethanolamine
In example 4, ethanolamine is introduced and reacted with CO after neutralization of alkylhydroxybenzoic acids with lime 2 And (3) reacting.
The beaker was charged with 130 grams of methanol, 222.5 grams of xylene solvent, and 130 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. Then, 1820.4 g of alkylhydroxybenzoic acid (C14-16-18 alkylhydroxybenzoic acid) was introduced. The mixture was stirred at 40℃for 15min. 70 g of ethanolamine were then introduced into the glass reactor and the stirred mixture was cooled to 30℃over 15min. Next, 25 g CO was introduced at 0.95g/min over 26min 2 The temperature is increased from 30 ℃ to 34 ℃. 51.3 g CO were then introduced at 0.95g/min over 54min 2 The temperature is increased from 34 ℃ to 40 ℃.
The first distillation step was then started at atmospheric pressure by heating the reactor from 40 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 613.4 grams of 140N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products.
The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 170 ℃ and holding the product at 170 ℃ for 60min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 5
N-phenyl-phenylenediamine
In example 5, N-phenyl-phenylenediamine is introduced and reacted with CO after neutralization of the alkylhydroxybenzoic acid with lime 2 And (3) reacting.
The beaker was charged with 85 grams of methanol, 222.5 grams of xylene solvent, and 85 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. Then, 1820.4 g of alkylhydroxybenzoic acid (C14-16-18 alkylhydroxybenzoic acid) was introduced. The mixture was stirred at 40℃for 15min. 200 g of N-phenylphenylenediamine are then introduced into a glass reactor and the stirred mixture is cooled to 30℃over 15min. Next, 16.4 g CO was introduced at 0.95g/min over 17min 2 The temperature is increased from 30 ℃ to 32 ℃. 47.8 g CO was then introduced at 0.95g/min over 55min 2 The temperature is increased from 32 ℃ to 40 ℃.
The first distillation step was then started at atmospheric pressure by heating the reactor from 40 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 613.4 grams of 140N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products.
The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 170 ℃ and holding the product at 170 ℃ for 60min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 6
Triethylenetetramine
In example 6 triethylenetetramine was introduced and reacted with CO after neutralization of the alkylhydroxybenzoic acid with lime 2 And (3) reacting.
The beaker was charged with 65 grams of methanol, 115.7 grams of xylene solvent, and 65 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a lime slurry at 350 is chargedStainless steel mechanical stirrer rotating at rpm and located directly above stirrer blades for addition of CO 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. Then, 1820.4 g of alkylhydroxybenzoic acid (C14-16-18 alkylhydroxybenzoic acid) was introduced. The mixture was stirred at 40℃for 15min. 50 g of triethylenetetramine was then introduced into the glass reactor and the stirred mixture was cooled to 30℃over 20 min. 15 g CO was then introduced at 0.95g/min over 16min 2 The temperature is increased from 30 ℃ to 35 ℃.
The beaker was charged with 60 grams of methanol, 106.8 grams of xylene solvent, 60 grams of calcium hydroxide and stirred for a few minutes to obtain a lime slurry. Lime slurry is charged to the reactor. 24.1 g CO was then introduced at 0.95g/min over 25min 2 The temperature is increased from 35 ℃ to 40 ℃. The first distillation step was then started at atmospheric pressure by heating the reactor from 40 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 613.4 grams of 140N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products. The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 170 ℃ and holding the product at 170 ℃ for 60min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 7
1, 4-diazabicyclo [2.2.2] octane
In example 7, 1, 4-diazabicyclo [2.2.2] is introduced after neutralization of the alkylhydroxybenzoic acid with lime]Octane and CO 2 And (3) reacting.
The beaker was charged with 65 grams of methanol, 222.5 grams of xylene solvent, and 65 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. Then, 1820.4 g of alkylhydroxybenzoic acid (C14-16-18 alkylhydroxybenzoic acid) was introduced. The mixture was stirred for 15min at 40 ℃. 190 g of 1, 4-diazabicyclo [2.2.2]Octane was introduced into the glass reactor and the stirred mixture was cooled to 30 ℃ over 15 min. 74.5 g CO was then introduced at 0.95g/min (79 min) 2 The temperature is increased from 30 ℃ to 40 ℃. The first distillation step was then started at atmospheric pressure by heating the reactor from 40 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 613.4 grams of 140N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products. The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 170 ℃ and holding the product at 170 ℃ for 60min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 8
1, 4-diazabicyclo [2.2.2] octane
In example 8, 1, 4-diazabicyclo [2.2.2] octane was introduced after neutralization of the alkylhydroxybenzoic acid with lime and reacted with ethylene carbonate.
The beaker was charged with 65 grams of methanol, 222.5 grams of xylene solvent, and 65 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. Then, 1820.4 g of alkylhydroxybenzoic acid (C14-16-18 alkylhydroxybenzoic acid) was introduced. The mixture was stirred for 15min at 40 ℃. 200 g of 1, 4-diazabicyclo [2.2.2]Octane was introduced into the glass reactor and the stirred mixture was heated to 45 ℃ over 20 min. 314 grams of carbon were then introduced over 30 minutesThe temperature of the acid ethylene is increased to 45-50 ℃. The first distillation step was then started at atmospheric pressure by heating the reactor from 50 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 613.4 grams of 140N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products. The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 170 ℃ and holding the product at 170 ℃ for 60min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 9
1, 4-diazabicyclo [2.2.2] octane
In example 9, 1, 4-diazabicyclo [2.2.2] octane was introduced after neutralization of the alkylhydroxybenzoic acid with lime.
The beaker was charged with 65 grams of methanol, 222.5 grams of xylene solvent, and 65 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. 1820.4 g of alkylhydroxybenzoic acid (C14-16-18 alkylphenol) were then introduced. The mixture was stirred for 15min at 40 ℃. 190 g of 1, 4-diazabicyclo [2.2.2]Octane was introduced into the glass reactor and the stirred mixture was maintained at 40 ℃ for 15min. The first distillation step was then started at atmospheric pressure by heating the reactor from 40 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 613.4 grams of 140N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products. Liquid to be treated The body part was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 170 ℃ and holding the product at 170 ℃ for 60min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 10
1, 4-diazabicyclo [2.2.2] octane
In example 10, 1, 4-diazabicyclo [2.2.2] octane was introduced after neutralization of the alkylhydroxybenzoic acid with lime.
The beaker was charged with 65 grams of methanol, 222.5 grams of xylene solvent, and 65 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. 2007.5 g of alkylhydroxybenzoic acid (C20-24-23% branched alkylhydroxybenzoic acid) were then introduced. The mixture was stirred for 15min at 40 ℃. 190 g of 1, 4-diazabicyclo [2.2.2]Octane was introduced into the glass reactor and the stirred mixture was maintained at 40 ℃ for 30min. The first distillation step was then started at atmospheric pressure by heating the reactor from 40 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 613.4 grams of 140N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products. The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 170 ℃ and holding the product at 170 ℃ for 60min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 11
1, 4-diazabicyclo [2.2.2] octane
In example 11, 1, 4-diazabicyclo [2.2.2] is introduced after neutralization of the alkylhydroxybenzoic acid with lime]Octane and makeIt is combined with CO 2 And (3) reacting.
The beaker was charged with 62 grams of methanol, 115.7 grams of xylene solvent, and 62 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. 2007.5 g of alkylhydroxybenzoic acid (C20-24-23% branched alkylhydroxybenzoic acid) were then introduced. The mixture was stirred for 15min at 40 ℃. 170 g of 1, 4-diazabicyclo [2.2.2]Octane was introduced into the glass reactor and the stirred mixture was cooled to 30 ℃ over 15 min. 66.7 g CO was then introduced at 0.95g/min over 70min 2 The temperature is increased from 30 ℃ to 37 ℃.
The beaker was charged with 38 grams of methanol, 106.8 grams of xylene solvent, 38 grams of calcium hydroxide and stirred for a few minutes to obtain a lime slurry. Lime slurry is charged to the reactor. Then introducing 12.2 g CO at 0.95g/min over 13min 2 The temperature is increased from 37 ℃ to 40 ℃. The first distillation step was then started at atmospheric pressure by heating the reactor from 40 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 613.4 grams of 140N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products. The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 170 ℃ and holding the product at 170 ℃ for 60min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 12
Triethylenetetramine
In example 12 triethylenetetramine was introduced and reacted with ethylene carbonate after neutralization of the alkylhydroxybenzoic acid with lime.
The beaker was charged with 65 grams of methanol, 222.5 grams of xylene solvent, and 65 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. Then, 1820.4 g of alkylhydroxybenzoic acid (C14-16-18 alkylhydroxy acid) was introduced. The mixture was stirred for 15min at 40 ℃. 110 g of triethylenetetramine were then introduced into a glass reactor and the stirred mixture was heated to 45℃over 20 min. 132.5 g of ethylene carbonate were then introduced and the mixture was stirred for 30min and heated to 50 ℃. The first distillation step was then started at atmospheric pressure by heating the reactor from 50 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 613.4 grams of 140N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products. The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 170 ℃ and holding the product at 170 ℃ for 60min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 13
C9 alkylated diphenylamines
In example 13, after neutralization of the alkylhydroxybenzoic acid with lime, a C9 alkylated diphenylamine was introduced and reacted with CO 2 And (3) reacting.
The beaker was charged with 65 grams of methanol, 115.7 grams of xylene solvent, and 65 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser.Then, 1820.4 g of alkylhydroxybenzoic acid (C14-16-18 alkylhydroxybenzoic acid) was introduced. The mixture was stirred for 15min at 40 ℃. 570 g of C9 alkylated diphenylamine were then introduced into a glass reactor and the stirred mixture was cooled to 30℃over 20 min. 67.5 g CO was then introduced at 0.95g/min over 71min 2 The temperature is increased from 30 ℃ to 36 ℃. 110.8 g of methanol, 106.8 g of xylene solvent, 110.8 g of calcium hydroxide were charged in a beaker and stirred for several minutes to obtain a lime slurry. Lime slurry is charged to the reactor. Then 56.4 g CO was introduced at 0.95g/min over 59min 2 The temperature is increased from 36 ℃ to 40 ℃. The first distillation step was then started at atmospheric pressure by heating the reactor from 40 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 600 grams of 140N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products. The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 170 ℃ and holding the product at 170 ℃ for 60min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 14
C9 alkylated diphenylamines
In example 14, after neutralization of the alkylhydroxybenzoic acid with lime, a C9 alkylated diphenylamine was introduced and reacted with CO 2 And (3) reacting.
The beaker was charged with 62 grams of methanol, 115.7 grams of xylene solvent, and 62 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. 2007.5 g of alkylhydroxybenzoic acid (C20-24-branched to 23%) were then introduced. The mixture was stirred for 15min at 40 ℃. 570 g of C9 alkylatedAniline was introduced into the glass reactor and the stirred mixture was cooled to 30 ℃ over 20 min. 67.5 g CO was then introduced at 0.95g/min over 71min 2 The temperature is increased from 30 ℃ to 36 ℃. The beaker was charged with 113.8 grams of methanol, 106.8 grams of xylene solvent, 113.8 grams of calcium hydroxide and stirred for a few minutes to obtain a lime slurry. Lime slurry is charged to the reactor. Then 56.4 g CO was introduced at 0.95g/min over 59min 2 The temperature is increased from 36 ℃ to 40 ℃. The first distillation step was then started at atmospheric pressure by heating the reactor from 40 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 500 grams of 140N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products. The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 170 ℃ and holding the product at 170 ℃ for 60min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 15
C9 alkylated diphenylamines
In example 15, the C9 alkylated diphenylamine was introduced after neutralization of the alkylhydroxybenzoic acid with lime.
The beaker was charged with 62 grams of methanol, 115.7 grams of xylene solvent, and 62 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. 2007.5 g of alkylhydroxybenzoic acid (C20-24-branched to 23%) were then introduced. The mixture was stirred for 15min at 40 ℃. 1100 g of C9 alkylated diphenylamine were then introduced into a glass reactor and the stirred mixture was cooled to 30℃over 15 min. 113.8 g of methanol, 106.8 g of xylene solvent and 113.8 g of calcium hydroxide are placed in a beaker and stirred for a few minutesClock to obtain lime slurry. Lime slurry is charged to the reactor. Then 56.4 g CO was introduced at 0.95g/min over 59min 2 The temperature is increased from 30 ℃ to 40 ℃. The first distillation step was then started at atmospheric pressure by heating the reactor from 40 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 500 grams of 140N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products. The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 170 ℃ and holding the product at 170 ℃ for 60min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 16
Benzylamine
In example 16, benzylamine was introduced and reacted with CO after neutralization of the alkylhydroxybenzoic acid with lime 2 And (3) reacting.
The beaker was charged with 65 grams of methanol, 222.5 grams of xylene solvent, and 65 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. Then, 1820.4 g of alkylhydroxybenzoic acid (C14-16-18 alkylhydroxybenzoic acid) was introduced. The mixture was stirred for 15min at 40 ℃. 400 g of benzylamine were then introduced into the glass reactor and the stirred mixture was cooled to 30℃over 20 min. 164.3 g CO was then introduced at 0.95g/min over 173min 2 The temperature is increased from 30 ℃ to 40 ℃. The first distillation step was then started at atmospheric pressure by heating the reactor from 40 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. In this distillation step At the end, 613.4 grams of 140N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products. The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 170 ℃ and holding the product at 170 ℃ for 60min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 17
Urea
In example 17, urea is introduced and reacted with CO after neutralization of the alkylhydroxybenzoic acid with lime 2 And (3) reacting.
The beaker was charged with 65 grams of methanol, 222.5 grams of xylene solvent, and 65 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. Then, 1820.4 g of alkylhydroxybenzoic acid (C14-16-18 alkylhydroxybenzoic acid) was introduced. The mixture was stirred for 15min at 40 ℃. 85 g of urea were then introduced into the glass reactor and the stirred mixture was cooled to 30℃over 15 min. 62.3 g CO was then introduced at 0.95g/min over 67min 2 The temperature is increased from 30 ℃ to 40 ℃. The first distillation step was then started at atmospheric pressure by heating the reactor from 40 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 613.4 grams of 140N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products. The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 170 ℃ and holding the product at 170 ℃ for 60min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 18
Dimethyl piperazine
In example 18, dimethyl piperazine was introduced and reacted with CO after neutralization of the alkylhydroxybenzoic acid with lime 2 And (3) reacting.
A beaker was charged with 100 grams of methanol, 222.5 grams of xylene solvent, and 100 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. 2007.5 g of alkylhydroxybenzoic acid (C20-24-23% isomerised alkylhydroxybenzoic acid) were then introduced. The mixture was stirred for 15min at 40 ℃. 150 g of dimethylpiperazine were then introduced into the glass reactor and the stirred mixture was maintained at 40℃for 15min and cooled to 30℃over 20 min. 11.6 g CO was then introduced at 0.95g/min over 13min 2 The temperature is increased from 30 ℃ to 36 ℃. 57.8 g CO was then introduced at 0.95g/min over 61min 2 The temperature is increased from 36 ℃ to 60 ℃. The first distillation step was then started at atmospheric pressure by heating the reactor from 60 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 613.4 grams of 140N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products. The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 170 ℃ and holding the product at 170 ℃ for 60min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 19
Dimethyl piperazine
In example 19, dimethylpiperazine was introduced after neutralization of the alkylhydroxybenzoic acid with lime.
The beaker was charged with 62 grams of methanol, 222.5 grams of xylene solvent, and 62 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. 2007.5 g of alkylhydroxybenzoic acid (C20-24-23% isomerised alkylhydroxybenzoic acid) were then introduced. The mixture was stirred for 15min at 40 ℃. 150 g of dimethylpiperazine were then introduced into the glass reactor and the stirred mixture was maintained at 40℃for 15min and heated to 50℃over 30 min. The first distillation step was then started at atmospheric pressure by heating the reactor from 50 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 425 grams of 140N lube oil were charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products. The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 170 ℃ and holding the product at 170 ℃ for 60min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 20
N-ethyl butylamine
In example 20, N-ethylbutylamine is introduced after neutralization of the alkylhydroxybenzoic acid with lime and is reacted with CO 2 And (3) reacting.
A beaker was charged with 100 grams of methanol, 222.5 grams of xylene solvent, and 100 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. 2007.5 g of alkylhydroxybenzoic acid (C20-24-23% isomerised alkylhydroxybenzoic acid) were then introduced. Stirring the mixtureStirring for 15min at 40 ℃. 200 g of N-ethylbutylamine were then introduced into the glass reactor and cooled to 30℃over 20 min. 11.6 g CO was then introduced at 0.95g/min over 12min 2 The temperature is increased from 30 ℃ to 34 ℃. Then 87 g CO was introduced at 0.95g/min over 92min 2 The temperature is increased from 34 ℃ to 60 ℃. The first distillation step was then started at atmospheric pressure by heating the reactor from 60 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 613.4 grams of 140N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products. The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 170 ℃ and holding the product at 170 ℃ for 60min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 21
N-ethyl butylamine
In example 21, N-ethylbutylamine was introduced after neutralization of the alkylhydroxybenzoic acid with lime and reacted with ethylene carbonate.
A beaker was charged with 100 grams of methanol, 222.5 grams of xylene solvent, and 100 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. 2007.5 g of alkylhydroxybenzoic acid (C20-24-23% isomerised alkylhydroxybenzoic acid) were then introduced. The mixture was stirred for 15min at 40 ℃. 200 g of N-ethylbutylamine were then introduced into the glass reactor and the mixture was maintained at 40℃for 15min. 433.9 g of ethylene carbonate are then introduced over 30 min-the temperature is increased from 40℃to 50 ℃. The mixture was then maintained at 50℃for 15min. Then by heating the reactor from 50℃to 65℃over 15min, then at 60miThe first distillation step was started at atmospheric pressure by heating from 65 ℃ to 93 ℃ in n and then from 93 ℃ to 128 ℃ in 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 613.4 grams of 140N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products. The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 170 ℃ and holding the product at 170 ℃ for 60min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 22
N-ethyl butylamine
In example 22, N-ethylbutylamine was introduced after neutralization of the alkylhydroxybenzoic acid with lime.
The beaker was charged with 65 grams of methanol, 222.5 grams of xylene solvent, and 65 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. 2007.5 g of alkylhydroxybenzoic acid (C20-24-23% isomerised alkylhydroxybenzoic acid) were then introduced. The mixture was stirred for 15min at 40 ℃. 290 g of N-ethylbutylamine were then introduced into the glass reactor and the mixture was maintained at 40℃for 15min. The temperature was increased from 40 ℃ to 50 ℃ over 30 min. The first distillation step was then started at atmospheric pressure by heating the reactor from 50 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 613.4 grams of 140N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products. The liquid fraction was charged into a 4 liter round bottom reactor and the product was heated to 170 ℃ and the product was heated to 17 mm Hg under vacuum Xylene was distilled at 0deg.C for 60 min. The vacuum was broken with air and cooled to ambient temperature.
Example 23
Isopropyl methylamine
In example 23, isopropylmethylamine was introduced after neutralization of the alkylhydroxybenzoic acid with lime.
The beaker was charged with 62 grams of methanol, 222.5 grams of xylene solvent, and 62 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. 2007.5 g of alkylhydroxybenzoic acid (C20-24-23% isomerised alkylhydroxybenzoic acid) were then introduced. The mixture was stirred for 15min at 40 ℃. 250 g of isopropylmethylamine were then introduced into a glass reactor and the mixture was maintained at 40℃for 15min. The temperature was increased from 40 ℃ to 50 ℃ over 30 min. The first distillation step was then started at atmospheric pressure by heating the reactor from 50 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 613.4 grams of 140N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products. The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 170 ℃ and holding the product at 170 ℃ for 60min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 24
C9 alkylated diphenylamines
In example 24, a C9 alkylated diphenylamine is introduced and reacted with CO after neutralization of an alkyl or alkenyl aromatic sulfonic acid with lime 2 And (3) reacting.
The beaker was charged with 21 grams of methanol, 147.5 grams of xylene solvent and 21 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. 313.4 g of an alkyl or alkenyl aromatic sulfonic acid (C20-24 alkyl or alkenyl aromatic sulfonic acid) were then introduced over 15 minutes up to 30 ℃. The mixture was then maintained at 30℃for 15min. 570 g of C9 alkylated diphenylamine was then introduced into a glass reactor and the stirred mixture was maintained at 30℃for 40min. 67.5 g CO was then introduced at 1.0g/min over 68min 2 The temperature is increased from 30 ℃ to 36 ℃. The beaker was charged with 90 grams of methanol, 200 grams of xylene solvent, and 90 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry. The glass reactor was charged with lime slurry previously prepared in a beaker. 48.8 g CO was then introduced at 1.0g/min over 49min 2 The temperature is increased from 36 ℃ to 40 ℃. The first distillation step was then started at atmospheric pressure by heating the reactor from 40 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 400 grams of 600N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products. The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 204 ℃ and holding the product at 204 ℃ for 10min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 25
C9 alkylated diphenylamines
In example 25, the C9 alkylated diphenylamine was introduced after neutralization of the alkyl or alkenyl aromatic sulfonic acid with lime.
A beaker was charged with 211 grams of methanol, 347.5 grams of xylene solvent, and 211 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
Reverse to glassLime slurry was charged into a reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades for addition of CO 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. 311.2 g of an alkyl or alkenyl aromatic sulfonic acid (C20-24 alkyl or alkenyl aromatic sulfonic acid) were then introduced over 15 minutes up to 30 ℃. The mixture was then maintained at 30℃for 15min. 800 grams of C9 alkylated diphenylamine was then introduced into the glass reactor and the stirred mixture was maintained at 30℃for 40 minutes. 92.8 g CO was then introduced at 1.0g/min over 93min 2 The temperature is increased from 30 ℃ to 40 ℃.
The first distillation step was then started at atmospheric pressure by heating the reactor from 40 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 390 grams of 600N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products. The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 204 ℃ and holding the product at 204 ℃ for 10min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 26
1, 4-diazabicyclo [2.2.2] octane
In example 26, 1, 4-diazabicyclo [2.2.2] octane was introduced after neutralization of the alkyl or alkenyl aromatic sulfonic acid with lime.
The beaker was charged with 21 grams of methanol, 247.5 grams of xylene solvent, and 21 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. 305.8 g of an alkyl or alkenyl aromatic sulfonic acid (C20-24 alkyl)Or alkenyl aromatic sulfonic acid) up to 30 ℃. The temperature of the mixture was then increased from 30 ℃ to 40 ℃ over 20min. 160 g of 1, 4-diazabicyclo [2.2.2]Octane was introduced into the glass reactor and the stirred mixture was maintained at 40 ℃ for 20min.
The first distillation step was then started at atmospheric pressure by heating the reactor from 40 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 400 grams of 600N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products. The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 204 ℃ and holding the product at 204 ℃ for 10min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 27
Alkylated diphenylamines
In example 27, the C9 alkylated diphenylamine was introduced after the formation of calcium carbonate and after neutralization of the alkyl or alkenyl aromatic sulfonic acid with lime 。
A beaker was charged with 211 grams of methanol, 347.5 grams of xylene solvent, and 211 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. 311.2 g of an alkyl or alkenyl aromatic sulfonic acid (C20-24 alkyl or alkenyl aromatic sulfonic acid) were then introduced over 15 minutes up to 32 ℃. The mixture was then cooled to 25 ℃. 92.8 g CO was then introduced at 1.0g/min over 93min 2 The temperature is increased from 25 ℃ to 32 ℃.
800 grams of C9 alkylated diphenylamine was then introduced into a glass reactor over 15 minutes and the reactor cooled to 30 ℃.
Then take 1 in 95min94.7 g CO was introduced at 0g/min 2 The temperature is increased from 30 ℃ to 41 ℃.
The first distillation step was then started at atmospheric pressure by heating the reactor from 41 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 390 grams of 600N lube oil was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products. The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 204 ℃ and holding the product at 204 ℃ for 10min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 28
2-phenoxyethylamine
In example 28, 2-phenoxyethylamine was introduced after neutralization of the alkylhydroxybenzoic acid with lime.
The beaker was charged with 12.7 grams of methanol, 54.7 grams of xylene, and 19.3 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
Lime slurry was charged to a 1L glass reactor equipped with heating capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for CO addition 2 A claisen adapter and a condenser. 200 g of alkylhydroxybenzoic acid (C20-24-23% isomerised alkylhydroxybenzoic acid) were then introduced dropwise over 15 minutes. The mixture was stirred for 15min at 40 ℃. 23.9 g of 2-phenoxyethylamine were then introduced into the glass reactor and the mixture was maintained at 40℃for 15min. During this hold time, a mixture of 30.7 grams methanol, 121.3 grams xylene, and 46.4 grams calcium hydroxide was stirred in a beaker to obtain a second lime slurry. During the next 156 minutes, this slurry was dropped into the glass reactor by a peristaltic pump while 29.2 grams of CO was injected through a glass injector as follows 2 Feeding into the reaction: 1.7 g were fed at 40℃over 11 minutes, 14.5 g were fed at 40℃to 53℃over 76 minutes, and finally at 40℃to 53℃in the course of the following steps 13.0 g are fed at 53℃to 58℃over 69 minutes.
The first distillation step was then started at atmospheric pressure by heating the reactor from 58 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 69.2 grams of 100R lube was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 10000RPM to separate insoluble solid products. The liquid portion was returned to the 1L reactor and xylene was distilled by heating the product to 170 ℃ and holding the product at 170 ℃ for 60min under 30 mmhg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 29
C20-24 alkylated 2-phenoxyethylamine
In example 29, C20-24 alkylated phenoxyethylamine was introduced after neutralization of the alkylhydroxybenzoic acid with lime.
The beaker was charged with 12.7 grams of methanol, 54.7 grams of xylene, and 19.3 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
Lime slurry was charged to a 1L glass reactor equipped with heating capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for CO addition 2 A claisen adapter and a condenser. 200 g of alkylhydroxybenzoic acid (C20-24-23% isomerised alkylhydroxybenzoic acid) were then introduced dropwise over 15 minutes. The mixture was stirred for 15min at 40 ℃. 74.9 g of C20-24 alkylated 2-phenoxyethylamine was then introduced into the glass reactor and the mixture was maintained at 40℃for 15min. During this hold time, a mixture of 30.7 grams methanol, 121.3 grams xylene, and 46.4 grams calcium hydroxide was stirred in a beaker to obtain a second lime slurry. During the next 156 minutes, this slurry was dropped into the glass reactor by a peristaltic pump while 29.2 grams of CO was injected through a glass injector as follows 2 Feeding into the reaction: 1.7 g were fed at 40℃over 11 minutes and 14.5 g were fed at 40℃to 53℃over 76 minutesAnd finally 13.0 g are fed over 69 minutes at 53 to 58 ℃.
The first distillation step was then started at atmospheric pressure by heating the reactor from 58 ℃ to 65 ℃ over 15min, then from 65 ℃ to 93 ℃ over 60min, then from 93 ℃ to 128 ℃ over 30 min. During this step, methanol, water and some meta-xylene are evaporated. At the end of this distillation step, 69.2 grams of 100R lube was charged to the reactor. The product was then loaded into a laboratory centrifuge operating at 10000RPM to separate insoluble solid products. The liquid portion was returned to the 1L reactor and xylene was distilled by heating the product to 170 ℃ and holding the product at 170 ℃ for 60min under 30 mmhg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Example 30
C9 alkylated diphenylamines and glycine
In example 30, the alkyl hydroxybenzoic acid was neutralized with lime. Then, after neutralization of benzoic acid, 16 g glycine was introduced into the reactor. Then introducing C9 alkylated diphenylamine.
The beaker was charged with 70 grams of methanol, 130.6 grams of xylene solvent, and 70 grams of calcium hydroxide. The mixture was stirred for a few minutes to obtain a lime slurry.
A glass reactor equipped with heating and cooling capacity and equipped with a stainless steel mechanical stirrer rotating at 350rpm, located directly above the stirrer blades, for adding CO, was charged with lime slurry 2 An air inlet pipe (2 mm inner diameter), a distillation column and a condenser. 2007.5 g of alkylhydroxybenzoic acid (C20-24-branched to 23%) were then introduced. The mixture was stirred for 15min at 40 ℃. 16 g glycine were then introduced. The reactor was maintained at 43℃for 15min. 835 g of C9 alkylated diphenylamine were then introduced into the glass reactor and the stirred mixture was cooled to 30℃over 15min. The beaker was charged with 113.8 grams of methanol, 106.8 grams of xylene solvent, 113.8 grams of calcium hydroxide and stirred for a few minutes to obtain a lime slurry. Lime slurry is charged to the reactor. Then 56.4 g CO was introduced at 0.95g/min over 59min 2 The temperature is increased from 30 ℃ to 40 ℃. Then by placing the reactor inThe first distillation step was started at atmospheric pressure by heating from 40 ℃ to 65 ℃ in 15min, then from 65 ℃ to 93 ℃ in 60min, then from 93 ℃ to 128 ℃ in 30 min. During this step, methanol, water and some meta-xylene are evaporated. The product was then loaded into a laboratory centrifuge operating at 35000G to separate insoluble solid products. The liquid fraction was charged to a 4 liter round bottom reactor and xylene was distilled by heating the product to 170 ℃ and holding the product at 170 ℃ for 60min under 30 millimeter Hg vacuum. The vacuum was broken with air and cooled to ambient temperature.
Comparative examples A to B
Comparative example a is calcium salicylate (TBN 175) without amine treatment.
Comparative example B is calcium salicylate (TBN 421) without amine treatment.
Tables 1-2 summarize the disclosed embodiments.
Table 3 summarizes the seal test results for comparative example A and examples 3, 9 and 13 in formulated engine oils (grade 15W-40). To ensure proper testing, samples were formulated to contain the same TBN level and the same SOAP content (a measure of the organic acid metal salt content).
TABLE 1
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HTCBT ASTM D6594
ASTM D6594 HTCBT testing is used to test diesel engine lubricants to determine their propensity to corrode various metals, particularly the alloys of lead and copper commonly used in cam followers and bearings. Four metal samples of copper, lead, tin and phosphor bronze were immersed in a measured amount of engine oil. The oil at elevated temperature (170 ℃) was blown with air (5 l/h) for a period of time (168 h). When the test is completed, the copper sample and the pressurized oil are inspected to detect corrosion and corrosion products, respectively. Corresponding changes in copper, lead and tin concentrations in the new and pressed oils are reported. For pass, the lead concentration should not exceed 120ppm and the copper concentration should not exceed 20ppm.
TABLE 2
TABLE 3 Table 3
For brevity, only certain ranges are explicitly disclosed herein. However, a range from any lower limit may be combined with any upper limit to list a range not explicitly listed, and a range from any lower limit may be combined with any other lower limit to list a range not explicitly listed, and a range from any upper limit may be combined with any other upper limit to list a range not explicitly listed in the same manner. Furthermore, each point or individual value between the endpoints of the range is included within the range, even if not explicitly recited. Thus, each point or individual value may serve as its own lower or upper limit to be combined with any other point or individual value or any other lower or upper limit to enumerate ranges not explicitly recited.
Also, the term "comprising" is considered synonymous with the term "including". Likewise, whenever a composition, an element, or a group of elements is preceded by the transitional phrase "comprising," it is understood that we also contemplate the same composition or group of elements having the transitional phrase "consisting essentially of … …," consisting of … …, "" selected from the group consisting of or "yes" prior to the recitation of the composition, an element, or a plurality of elements, and vice versa.
The terms "a" and "an" and "the" as used herein are to be understood to cover both the plural and the singular.
Various terms have been defined above. If a term used in a claim is not defined above, that term should be given the broadest definition persons in the pertinent art have given that term as reflected in at least one printed publication or issued patent. Furthermore, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent such disclosure is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted.
The foregoing description of the present disclosure illustrates and describes the present disclosure. Furthermore, the disclosure shows and describes only the preferred embodiments, but as mentioned above, it is to be understood that the disclosure is capable of use in various other combinations, modifications, and environments and is capable of changes or modifications within the scope of the concept as expressed herein, commensurate with the above teachings and/or the skill or knowledge of the relevant art. While the foregoing is directed to embodiments of the present disclosure, other and further embodiments of the disclosure may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (27)
1. A process for preparing a low ash detergent, the process comprising:
a surfactant composition comprising a hydroxybenzoate, sulfonate or phosphonate detergent is mixed with an ashless nitrogen-containing compound to enhance the base number of the hydroxybenzoate, sulfonate or phosphonate detergent.
2. The process of claim 1, wherein the mixing is performed in the presence of carbon dioxide or ethylene carbonate.
3. The process of claim 1, wherein the mixing neutralizes the hydroxybenzoate, sulfonate, or phosphonate detergent.
4. The process of claim 1, wherein the hydroxybenzoate, sulfonate or phosphonate detergent is neutralized with a metal base prior to or during the mixing.
5. The process of claim 4, wherein the metal base is Ca (OH) 2 Or MgO.
6. The process of claim 1, wherein the nitrogen-containing compound is an alkylated amine, a hydrocarbyl amine, an ethylene amine, an aromatic amine, ethanolamine, urea, diphenylamine, an alkylated diphenylamine, a benzyl amine, piperazine, an alkylpiperazine, a dialkylpiperazine, a phenoxy amine, a benzamide, an aniline, a phthalimide, or an amino acid.
7. The process of claim 1, wherein the nitrogen-containing compound is C9 diphenylamine, 2-ethylhexyl (tallow) methylamine, ethylhexylamine, octylamine, ethylenediamine, N-methylethanolamine, 1-dimethylethylenediamine, 2-methoxyethylamine, diethanolamine, N-methylpropylenediamine, tetramethylurea, N-phenylphenylenediamine, triethylenetetramine, triethanolamine, 1, 4-diazabicyclo [2.2.2] octane, N' -bis (3-aminopropyl) ethylenediamine, 2-phenoxyethylamine, C20-C24 alkyl-2-phenoxyamine, 2- (2-aminoethoxy) naphthalene, N- (3- (dimethylamino) propyl) benzamide, phenylpropylamine, N- (2-hydroxyethyl) phthalimide, N- (2-aminoethyl) phthalimide, N- (3-hydroxypropyl) phthalimide, N- (2- (methylamino) ethyl) phthalimide, N- (3-carbamimidopropyl) phthalimide, N- (2- (methylamino) ethyl) phthalimide, N- (3- (methylamino) propyl) phthalimide, N- (2-carbamimidopropyl) phthalimide, or glycine.
8. The process of claim 1, wherein the surfactant is a salt of an alkyl hydroxybenzoic acid, an alkyl aromatic sulfonic acid, or an alkenyl aromatic sulfonic acid.
9. The process of claim 1, wherein the mixing occurs before or after formation of the metal carbonate.
10. A process for preparing a low ash detergent, the process comprising:
mixing a hydroxybenzoate, sulfonate or phosphonate detergent with an amine or amine derivative, wherein the amine or amine derivative is added in order to overbase the hydroxybenzoate, sulfonate or phosphonate detergent or to enhance the base number of the hydroxybenzoate, sulfonate or phosphonate detergent.
11. The process of claim 10, wherein the mixing is performed in the presence of carbon dioxide.
12. The process of claim 10, wherein the mixing neutralizes the hydroxybenzoate, sulfonate, or phosphonate detergent.
13. The process of claim 10, wherein the hydroxybenzoate, sulfonate or phosphonate detergent is neutralized with a metal base prior to or during the mixing.
14. The process of claim 13, wherein the metal base is Ca (OH) 2 Or MgO.
15. The process of claim 10, wherein the amine or amine derivative is an alkylated amine, a hydrocarbyl amine, an ethylene amine, an aromatic amine, ethanolamine, urea, diphenylamine, an alkylated diphenylamine, a benzyl amine, piperazine, an alkylpiperazine, a dialkylpiperazine, a phenoxy amine, a benzamide, an aniline, a phthalimide, or an amino acid.
16. The process of claim 10, wherein the amine or amine derivative is C9 diphenylamine, 2-ethylhexyl (tallow) methylamine, ethylhexylamine, octylamine, ethylenediamine, N-methylethanolamine, 1, -dimethylethylenediamine, 2-methoxyethylamine, diethanolamine, N-methylpropylenediamine, tetramethylurea, N-phenylphenylenediamine, triethylenetetramine, triethanolamine, 1, 4-diazabicyclo [2.2.2] octane, N' -bis (3-aminopropyl) ethylenediamine, 2-phenoxyethylamine, C20-C24 alkyl-2-phenoxyamine, 2- (2-aminoethoxy) naphthalene, N- (3- (dimethylamino) propyl) benzamide, phenylpropylamine, N- (2-hydroxyethyl) phthalimide, N- (2-aminoethyl) phthalimide, N- (3-hydroxypropyl) phthalimide, N- (2- (methylamino) ethyl) phthalimide, N- (3-aminopropyl) phthalimide, N- (2- (methylamino) ethyl) phthalimide, N- (3- (methylamino) propyl) phthalimide, N- (2-dicarboximide, N- (dimethylamino) propyl) phthalimide, or glycine.
17. The process of claim 10, wherein the surfactant is a salt of an alkyl hydroxybenzoic acid, an alkyl aromatic sulfonic acid, or an alkenyl aromatic sulfonic acid.
18. The process of claim 10, wherein the mixing occurs before or after formation of the metal carbonate.
19. A lubricating oil composition, the lubricating oil composition comprising:
a major amount of an oil of lubricating viscosity; and
a minor amount of a low ash detergent made by a process comprising:
mixing a hydroxybenzoate, sulfonate or phosphonate detergent with an amine or amine derivative, wherein the amine or amine derivative is added in order to overbase the hydroxybenzoate, sulfonate or phosphonate detergent or to enhance the base number of the hydroxybenzoate, sulfonate or phosphonate detergent.
20. The lubricating oil composition of claim 19, wherein the mixing is performed in the presence of carbon dioxide.
21. The lubricating oil composition of claim 19, wherein the blending neutralizes the hydroxybenzoate, sulfonate, or phosphonate detergent.
22. The lubricating oil composition of claim 19, wherein the hydroxybenzoate, sulfonate or phosphonate detergent is neutralized with a metal base prior to or during the mixing.
23. The lubricating oil composition of claim 19, wherein the metal base is Ca (OH) 2 Or MgO.
24. The lubricating oil composition of claim 19, wherein the amine or amine derivative is an alkylated amine, a hydrocarbyl amine, an ethylene amine, an aromatic amine, ethanolamine, urea, diphenylamine, an alkylated diphenylamine, a benzyl amine, piperazine, an alkyl piperazine, a dialkyl piperazine, a phenoxy amine, a benzamide, an aniline, a phthalimide, or an amino acid.
25. The lubricating oil composition of claim 19, wherein the amine or amine derivative is C9 diphenylamine, 2-ethylhexyl (tallow) methylamine, ethylhexyl amine, octylamine, ethylenediamine, N-methylethanolamine, 1, -dimethylethylenediamine, 2-methoxyethylamine, diethanolamine, N-methylpropylenediamine, tetramethylurea, N-phenylphenyldiamine, triethylenetetramine, triethanolamine, 1, 4-diazabicyclo [2.2.2] octane, N' -bis (3-aminopropyl) ethylenediamine, 2-phenoxyethylamine, C20-C24 alkyl-2-phenoxyamine, 2- (2-aminoethoxy) naphthalene, N- (3- (dimethylamino) propyl) benzamide, phenylpropylamine, N- (2-hydroxyethyl) phthalimide, N- (2-aminoethyl) phthalimide, N- (3-hydroxypropyl) phthalimide, N- (2- (methylamino) ethyl) phthalimide, N- (3-aminopropyl) phthalimide, N- (2- (methylamino) ethyl) phthalimide, N- (3- (methylamino) propyl) phthalimide, N- (2- (dimethylamino) propyl) phthalimide, or N- (2-diamino) propyl) phthalimide.
26. The lubricating oil composition of claim 19, wherein the surfactant is a salt of an alkyl hydroxybenzoic acid, an alkyl aromatic sulfonic acid, or an alkenyl aromatic sulfonic acid.
27. The lubricating oil composition of claim 19, wherein the mixing occurs before or after formation of the metal carbonate.
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| US202163209097P | 2021-06-10 | 2021-06-10 | |
| US63/209,097 | 2021-06-10 | ||
| PCT/IB2022/055364 WO2022259193A1 (en) | 2021-06-10 | 2022-06-09 | Amine-boosted detergent |
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| CN117597421A true CN117597421A (en) | 2024-02-23 |
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| US (1) | US20240209278A1 (en) |
| EP (1) | EP4352188A1 (en) |
| JP (1) | JP2024520810A (en) |
| KR (1) | KR20240021861A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3492230A (en) * | 1966-05-27 | 1970-01-27 | Standard Oil Co | Method of preparing alkaline earth sulfonates of high alkalinity |
| US4179385A (en) * | 1978-05-03 | 1979-12-18 | Tenneco Chemicals, Inc. | Process for the production of overbased manganese salts of organic acids |
| FR2588269B1 (en) * | 1985-10-03 | 1988-02-05 | Elf France | PROCESS FOR THE PREPARATION OF HIGHLY BASIC, HIGHLY FLUID BASED ADDITIVES AND COMPOSITION CONTAINING SAID ADDITIVES |
| EP1059301B1 (en) | 1999-06-10 | 2003-05-21 | Chevron Chemical S.A. | Alkaline earth alkylaryl sulfonates, their application as an additive for lubricating oil, and methods of preparation |
| US8030258B2 (en) | 2005-07-29 | 2011-10-04 | Chevron Oronite Company Llc | Overbased alkaline earth metal alkylhydroxybenzoates having low crude sediment |
| US8076272B2 (en) | 2009-11-19 | 2011-12-13 | Chevron Oronite Company Llc | Method of making a synthetic alkylaryl sulfonate |
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- 2022-06-09 KR KR1020247000718A patent/KR20240021861A/en unknown
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