US3178368A - Process for basic sulfurized metal phenates - Google Patents
Process for basic sulfurized metal phenates Download PDFInfo
- Publication number
- US3178368A US3178368A US194996A US19499662A US3178368A US 3178368 A US3178368 A US 3178368A US 194996 A US194996 A US 194996A US 19499662 A US19499662 A US 19499662A US 3178368 A US3178368 A US 3178368A
- Authority
- US
- United States
- Prior art keywords
- alkyl
- amount
- alkaline earth
- earth metal
- temperatures
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 238000000034 method Methods 0.000 title claims description 21
- 229910052751 metal Inorganic materials 0.000 title description 20
- 239000002184 metal Substances 0.000 title description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 85
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 31
- 239000010687 lubricating oil Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- 239000011541 reaction mixture Substances 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 3
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 claims 1
- -1 alkyl substituent radicals Chemical class 0.000 description 58
- 239000000203 mixture Substances 0.000 description 35
- 235000019441 ethanol Nutrition 0.000 description 26
- 125000004432 carbon atom Chemical group C* 0.000 description 17
- 125000000217 alkyl group Chemical group 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 229910052791 calcium Inorganic materials 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- 238000013019 agitation Methods 0.000 description 9
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 150000003871 sulfonates Chemical class 0.000 description 7
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 6
- 239000000920 calcium hydroxide Substances 0.000 description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 6
- 229940087291 tridecyl alcohol Drugs 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 235000011116 calcium hydroxide Nutrition 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- 239000010688 mineral lubricating oil Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000158728 Meliaceae Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- YDLYQMBWCWFRAI-UHFFFAOYSA-N n-Hexatriacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC YDLYQMBWCWFRAI-UHFFFAOYSA-N 0.000 description 1
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OLTHARGIAFTREU-UHFFFAOYSA-N triacontane Natural products CCCCCCCCCCCCCCCCCCCCC(C)CCCCCCCC OLTHARGIAFTREU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G99/00—Subject matter not provided for in other groups of this subclass
- C07G99/002—Compounds of unknown constitution containing sulfur
- C07G99/0024—Overbased compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/06—Well-defined aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
-
- 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
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/104—Aromatic fractions
-
- 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
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/106—Naphthenic fractions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/286—Esters of polymerised unsaturated acids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
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- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
- C10M2219/088—Neutral salts
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
- C10M2219/089—Overbased salts
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- 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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/251—Alcohol-fuelled 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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline 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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
- C10N2040/28—Rotary engines
Definitions
- This invention pertains to a new process whereby highly basic sulfurized metal phenates are prepared.
- this process pertains to the manufacture of overbased sulfurized alkaline earth metal alkyl phenates.
- Basic sulfurized alkaline earth metal alkyl phenates are used as compounding agents in lubricating oils to neutralize harmful acids, to inhibit corrosion, piston ring sticking and gum formation in internal combustion engines resulting from oxidation of the lubricating oil and oxidation polymerization of the engine fuel residues.
- metal salts of phenolic materials have been used as additives for mineral lubricating oil compositions used in the lubrication of internal combustion engines.
- the metal phenates improve the detergency characteristics of the lubricating oil, reduce engine wear, minimize the formation of harmful deposits 011 engine parts, and improve the resistance of the oil to oxidation.
- normal sulfurized alkaline earth metal phenates refer to the metal phenates wherein the mole ratio of metal to the phenol nucleus is about 1:2, such as wherein R represents the alkyl substituent radicals on the benzene ring, and M is an alkaline earth metal.
- the sulfur (S) is attached to both of the benzene rings.
- sulfurized alkaline earth metal phenates refers to su-lfurizcd alkaline. earth metal phenates having base ratios in excess of 1.2; that is, the percent of the total alkaline earth metal to the metal of the normal phenate is greater than 20% in excess of the metal of the normal sulfurizecl alkaline earth metal phenates.
- a metal phenate having a base ratio of 1 is a neutral (a normal) phenate.
- overbased carbonated sulfurized alkaline earth metal phenates described herein are particularly useful when incorporated in lubricating oil compositions for diesel engines.
- oil-soluble overbased carbonated sulfurized alkaline earth metal phenates can be prepared by the reaction of alkyl phenols with alkaline earth metal oxides or hydroxides, followed by carbonation with CO in the presence of glycol, sulfonates, and a high molecular weight alcohol. It is essential to the process described herein that the reaction mixture contains (1) a sulfonate, (2) ethylene glycol, and (3) a high molecular weight alcohol.
- the final basic phenateoil blend contain the sulfonate, and it is desirable that the final oil blend contains a portion of the high molecular weight alcohol.
- the process of this invention comprises blending, then heating with agitation, a mixture of an alkyl phenol, a sulfonate, a high molecular weight alcohol, lubricating oil, and sulfur. Hydrated lime (or CaO) is then added to this blend. The mixture is then heated, and ethylene glycol is added. Water of reaction is removed; the mixture is cooled, and carbon dioxide is added. Uncombined CO is removethand the reaction vesesl is heated to remove ethylene glycol, water, and high molecular weight alcohol.
- Alkyl phenols which are usedherein in the reaction mixture are represented by the formula:
- A is an essentially hydrocarbon aromatic radical, preferably a benzene radical
- R is .a straight-chain or branched-chain, saturated or unsaturated essentially hydrocarbon radical having from 4 to 30 carbon atoms and a is a number having a value from 1 to 2.
- the total number of carbon atoms for R has a minimum value of 8. Thus, when a is 1, the minimum number of carbon atoms in R is 8.
- hydrocarbonaceous radicals examples include alkyl radicals, such as butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, eicosyl, tricontyl radicals; radicals derived from petroleum hydrocarbons, such as white oil, Wax, olefin polymers (e.g., polypropylene and polybutylene) etc. i
- the basic sulfonates used herein contain from 0% to 300% of metal in excess of the metal of normal sulfonates, that is, essentially neutral, metal sulfonates.
- the basic sulfonates used herein are derived from neutral sulfonates represented by the formula:
- R is a high molecular weight straight-chained or branched-chain saturated or unsaturated essentially hydrocarbonaceous radical having a molecular weight of about to about 800;
- A is an aromatic radical, such as benzene, naphthalene, anthracene, etc; a isa number having the value of 1 to 4; and
- M is an alkaline earth metal.
- alkaline earth metals includes preferably calcium, barium, and strontium; calcium is particularly preferred.
- hydrocarbonaceous radicals examples include the following: dodecane, hexadecane, eicosane, triacontane radicals; radicals derived from petroleum hydrocarbons such as white oil, wax, olefin polymers (e.g., polypropyleneand polybutylene, etc.).
- the sulfonic acids used in preparing the basic sulfonates of this invention also include the oil-soluble sulfonic acids obtained from petroleum, such as the mahogany acids, and the synthetic sulfonic acids prepared by various methods of synthesis (e.g., sulfonic' acids prepared by reacting a chlorinated white oil with benzene, using hydrofluoric acid as the catalyst, then treating the resulting white oil alkylated benzene with chlorosulfonic acid or fuming sulfuric acid to form a white oil benzene sulfonic acid).
- oil-soluble sulfonic acids obtained from petroleum, such as the mahogany acids
- synthetic sulfonic acids prepared by various methods of synthesis e.g., sulfonic' acids prepared by reacting a chlorinated white oil with benzene, using hydrofluoric acid as the catalyst, then treating the resulting white oil alkylated benzene with chlorosulfonic acid or fuming sulfuric
- the metal sulfonates are exemplified as follows: calcium white oil benzene sulfonate, barium white oil benzene sulfonate, calcium dipolypropylene benzene sulfonate, barium dipolypropylene benzene sulfonate, calcium mahogany petroleum sulfonate, barium mahogany petroleum sulfonate, calcium triacontyl benzene sulfonate, barium triacontyl benzene, etc.
- the high molecular weight alcohol which is used in amounts no more than 75% by weight of the alkyl phenol charged, preferably 10% to 50%, are those monohydric alcohols containing from 8 to 18 carbon atoms. These alcohols are exemplified as follows: octyl alcohol, decyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, cetyl alcohol, etc.
- a lubricating oil may be used as a reaction medium.
- oil concentrates of the desired highly basic carbonated sulfurized metal phenates can be obtained.
- Such lubricating oils include a wide variety of lubricating oils, such as naphthenic base, paraffin base and mixed base lubricating oils, other hydrocarbon lubricants, e.g., lubricating oils derived from coal products and the synthetic oils, e.g., alkylene polymers (such as polymers of propylene, butylene, etc., and the mixtures thereof); alkylene oxide type polymers, e.g., alkylene oxide polymers prepared by polymerizing the alkylene oxides, e.g., propylene oxide, etc., in the presence of water or alcohols (e.g., ethyl alcohol); carboxylic acid esters, for example, those which are prepared by esterifying such carboxylic acids as adipic acid,
- alcohols such as'butyl alcohol, hexyl alcohol, 2-ethylhexyl alcohol, and pentaerythritol; alkyl bcnzenes, polyphenyls; polymers of silicon; etc.
- alkyl phenol For each molal quantity of alkyl phenol, it is desirable to use from 0.01 mole to 1 mole of sulfonate, preferably 0.01 mole to 0.05 mole, and from 0.1 mole to 1.5 mole of high molecular weight alcohol, preferably tridecyl alcohol.
- the amount of elemental sulfur present in the reaction mixture is such that the mol ratio of sulfur to alkaline earth metal of the basic substance is from 0.25 to 4.0. It is preferred that the mol ratio is in the range of 0.5 to 1.5.
- the amount of alkaline earth metal oxide or hydroxide which is used is that amount which will be sufficient to give a base ratio of 1.2 to 4.5, preferably 1.5 to 3.5.
- the amount of alkaline earth metal oxides or hydroxide used in the reaction depends on the amount of metal desired in the product in excess of that of the normal phenate. Normally, in the preparation of basic carbonated sulfurized phenates a slight excess (e.g., 5 mole percent excess) of calcium oxide or hydroxide is used in the reaction mixture over that desired in the final basic phenate product.
- the carbon dioxide used is from 300 mole percent to mole percent, preferably 150 mole percent to 10 mole percent of the alkyl phenol charged.
- glycol In the process of this invention, it is preferred to use ethylene glycol.
- the amount of glycol used will depend upon the amount of calcium oxide or hydroxide used.
- a sufiicient amount of glycol is employed to bring the reactants into efficient contact for substantial reaction in a reasonably short time; that is, the amount of glycol used is sufiicient to dissolve a portion of each of the reactants and to cause substantial contact between said reactants.
- the alkaline earth metal-glycol mole ratio may vary from 2 to 1 to about 0.25 to 1.0; preferably from 1 to 1 to about 0.5 to 1.
- a blend consisting of an alkyl phenol, a sulfonate, a high molecular weight alcohol, and an oil of lubricating viscosity. This mixture is then heated with agitation to temperatures from 150 F. to 190 F., followed by the addition of the sulfur and calcium hydroxide (or oxide). Ths blend is then heated to temperatures in the range of 250 F. to 300 F., and that temperature is maintained while ethylene glycol is slowly added. The water of reaction liberated after the addition of the glycol is then removed by heating to temperatures of about 340 F. The reaction mixture is cooled slightly, followed by carbonation by means of carbon dioxide at temperatures from 250 F. to 350 F. Any uncombined CO is then removed.
- the reaction blend is then heated for 2 to 10 hours at temperatures ranging from 300 F. to 390 F., during which heating the absolute pressure is reduced to 4050 mm. Hg to remove glycol.
- some of the high molecular Weight alcohols may be removed along with the ethylene glycol.
- the resulting lubricating oil composition is highly effective for its intended purpose.
- the particularly preferred high molecular weight alcohol that is, tridecyl alcohol
- the final lubricating oil composition may contain from 30% to 50%, by weight, of the original charge of the tridecyl alcohol.
- the high molecular weight alcohol may be removed in its entirety or amounts up to of the initial charge may remain in the final composition.
- EXAMPLE I Preparation of basic sulfurized carbonated calcium alkyl phenate A mixture of 4,170 pounds of an alkyl phenol having a hydroxyl number of 184 wherein the alkyl radical was derived from a polypropylene having an average of 12 carbon atoms, 508 gallons of a California refined base oil having viscosities of SSU at 100 F., 436 pounds of a basic calcium sulfonate containing 40% calcium in excess of that amount for a neutral sulfonate (i.e., the base ratio was 1.421), and 1294 pounds of tridecyl alcohol was heated to F. with agitation. Sulfur, 854 pounds, was charged to the vessel with the temperature maintained at 180-190 F.
- the final lubricating oil composition have a high basicity.
- the initial amount of alkyl phenol be from 20% to 45%, by Weight, based on the final composition, preferably from 25% to 35%, by weight.
- the lubricating oil reaction medium is used in amounts from 15% to 50%, by weight, based on the finished composition, preferably from 20% to 30%, by weight.
- the metal sulfonate used in the example hereinabove was a concentrate consisting of 46.4% by weight of a mineral lubricating oil and 53.6% by weight of a calcium petroleum sulfonate wherein the petroleum radical was derived from a mineral oil having a viscosity of 500 SSU at 100 F.
- the calcium content of the oil concentrate was 11.4% by weight, and the base ratio was 1.4.
- a process of preparing sulfurized basic alkaline earth metal carbonated alkyl phenate comprising forming a blend comprising a petroleum lubricating oil, an alkyl phenol wherein said alkyl radical has from 4 to 30 carbon atoms and the total number of carbon atoms in the alkyl groups is at least 8, an alkaline earth metal alkyl aryl sulfonate in an amount of from 0.01 to 1 mol per mol of said alkyl phenol and an aliphatic saturated monohydric alcohol having from 8 to 18 carbon atoms in an amount of from to 75% by weight of said alkyl phenol, heating said blend to temperatures in the range of 150 F.
- a process of preparing a sulfurized basic alkaline earth metal carbonated alkyl phenate comprising forming a blend comprising a petroleum lubricating oil, an alkyl phenol wherein said alkyl radical is derived from a polypropylene having an average of 12 carbon atoms, an alkaline earth metal alkyl aryl sulfonate in an amount of from 0.01 to 1 mol per mol of said alkyl phenol, an aliphatic saturated monohydric alcohol having from 8 to 18 carbon atoms in amount of from 10% to 75% by weight of said alkyl phenol, heating with agitation to 130 F., while maintaining temperatures in the range of 180 to 190 F., adding thereto a basic substance selected from the group consisting of alkaline earth metal hy droxide and alkaline earth metal oxide in amount necessary to give a base ratio for the aforesaid carbonated alkylphenate of from 1.2 to 4.5 and sulfur in an amount such that the mol ratio of sulfur to al
- a process of preparing sulfurized basic alkaline earth metal carbonated alkyl phenate comprising forming a blend comprising from 20% to 30% by weight, based on the final composition, of a petroleum lubricating oil, from 20% to 45% by Weight of an alkyl phenol wherein said alkyl radical has from 4 to 30 carbon atoms and the total number of carbon atoms in the alkyl groups is at least 8, an alkaline earth metal alkyl aryl sulfonate in an amount of from 0.01 to 1 mol per mol of said alkyl phenol and an aliphatic saturated monohydric alcohol having from 8 to 18 carbon atoms in an amount of from 10% to 75% by Weight of said alkyl phenol,
- a process of preparing a sulfurized basic alkaline earth metal carbonated alkyl phenate comprising forming a blend comprising from 15% to 50% by weight, based on the final composition, of a lubricating oil, from 20% to 45% by weight of an alkyl phenol wherein said alkyl radical is derived from a polypropylene having an average of 12 carbon atoms, an alkaline earth metal alkyl aryl sulfonate in an amount of from 0.01 to 1 mol per mol of said alkyl phenol, an aliphatic saturated monohydric alcohol having from 8 to 18 carbon atoms in an amount of from 10% to 75 by weight of said alkyl phenol, heating with agitation to 180 F., and While maintaining the temperatures in the range of 180 to F., adding thereto a basic substance selected from the group consisting of alkaline earth metal hydroxide and alkaline earth metal oxide in amount necessary to give a base ratio for the aforesaid carbonated alkyl phenate of from
- the mol ratio of basic substance to ethylene glycol is from 2:1 to 0.25:1, heating said reaction mixture to a temperature of 340 F. to remove water of reaction, adding carbon dioxide at temperatures of from about 250 F. to about 300 F. in an amount of from 10 mol percent to 300 mol percent of said alkyl phenol, followed by heating to temperatures of 390 F. at reduced pressure to remove ethylene glycol and at least 50% by weight of the original charge of said monohydric alcohol.
- a process of preparing a sulfurized basic calcium carbonated alkyl phenate comprising forming a blend comprising from 20% to 30% by weight, based on the final composition, of a petroleum lubricating oil, from 25% to 35% by weight of an alkyl phenol wherein said alkyl radical is derived from a polypropylene having an average of 12 carbon atoms, a calcium alkyl aryl sulfonate in an amount of from 0.01 to 0.05 mol per mol of said alkyl phenol, an aliphatic saturated monohydric alcohol having from 8 to 18 carbon atoms in an amount of from 10% to 50% by weight of said alkyl phenol, heating with agitation to 180 F., and While maintaining temperatures of 180 to 190 F., adding thereto a basic substance selected from the group consisting of calcium hydroxide and calcium oxide in amount necessary to give a base ratio for the aforesaid carbonated alkyl 340 F., to remove water of reaction, adding carbon dioxide at temperatures of from about 250 F
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
Description
United States Patent Ofiice 3,178,368 PRGCESS FOR BASIC SULFURIZED META PHENATES Walter W. Hannernan, El Cerrito, Califi, assignor to California Research Corporation, San Francisco, Cahfi,
a corporation of Delaware No Drawing. Filed May 15, 1962, Ser. No. 194,996
. 5 tilaims. (Cl. 252--33.4)
This invention pertains to a new process whereby highly basic sulfurized metal phenates are prepared. In particular, this process pertains to the manufacture of overbased sulfurized alkaline earth metal alkyl phenates.
Basic sulfurized alkaline earth metal alkyl phenates are used as compounding agents in lubricating oils to neutralize harmful acids, to inhibit corrosion, piston ring sticking and gum formation in internal combustion engines resulting from oxidation of the lubricating oil and oxidation polymerization of the engine fuel residues.
For many years, metal salts of phenolic materials have been used as additives for mineral lubricating oil compositions used in the lubrication of internal combustion engines. In combination with numerous other additives, the metal phenates improve the detergency characteristics of the lubricating oil, reduce engine wear, minimize the formation of harmful deposits 011 engine parts, and improve the resistance of the oil to oxidation.
Numerous attempts have been made to prepare oilsoluble sulfurize-d alkaline earth metal alkyl phenates which have the detergent characteristics of the metal phenates, and, in addition thereto, the property of neutralizing larger amounts of acidic bodies than possible with the presently available normal or basic sulfurized alkaline earth metal phenates. By the particular process described herein, it is possible to prepare overbased sulfurized alkaline earth metal alkyl phenates which can neutralize large amounts of acidity than possible with phenates available heretofore.
By the use of the term herein, normal sulfurized alkaline earth metal phenates refer to the metal phenates wherein the mole ratio of metal to the phenol nucleus is about 1:2, such as wherein R represents the alkyl substituent radicals on the benzene ring, and M is an alkaline earth metal. The sulfur (S) is attached to both of the benzene rings.
The term basic carbonated. sulfurized alkaline earth metal phenates refers to su-lfurizcd alkaline. earth metal phenates having base ratios in excess of 1.2; that is, the percent of the total alkaline earth metal to the metal of the normal phenate is greater than 20% in excess of the metal of the normal sulfurizecl alkaline earth metal phenates. A metal phenate having a base ratio of 1 is a neutral (a normal) phenate.
It is a particular advantage of this invention, that by the process described, basic carbonated sulfurized alka line earth metal phenateshaving metal contents greater than 20% in excess of the metal present in the corresponding sulfurized normal alkaline earth metal phenates can be prepared. In particular, the base ratios of the resulting basic phenates have values from 1.2 to 4.5 or higher.
The overbased carbonated sulfurized alkaline earth metal phenates described herein are particularly useful when incorporated in lubricating oil compositions for diesel engines.
It is a primary object of this'invention to set forth a new method of preparing highly over-based carbonated sulfurized alkaline earth metal phenates.
3,l?8,3t8 Patented Apr. 13, 1965 In accordance with this invention, it has been discovered that oil-soluble overbased carbonated sulfurized alkaline earth metal phenates can be prepared by the reaction of alkyl phenols with alkaline earth metal oxides or hydroxides, followed by carbonation with CO in the presence of glycol, sulfonates, and a high molecular weight alcohol. It is essential to the process described herein that the reaction mixture contains (1) a sulfonate, (2) ethylene glycol, and (3) a high molecular weight alcohol. Furthermore, for the satisfactory use as a lubricating oil additive of the final overbased sulfurized alkaline earth metal phenates, it is essential that the final basic phenateoil blend contain the sulfonate, and it is desirable that the final oil blend contains a portion of the high molecular weight alcohol.
Briefly, the process of this invention comprises blending, then heating with agitation, a mixture of an alkyl phenol, a sulfonate, a high molecular weight alcohol, lubricating oil, and sulfur. Hydrated lime (or CaO) is then added to this blend. The mixture is then heated, and ethylene glycol is added. Water of reaction is removed; the mixture is cooled, and carbon dioxide is added. Uncombined CO is removethand the reaction vesesl is heated to remove ethylene glycol, water, and high molecular weight alcohol.
Alkyl phenols which are usedherein in the reaction mixture are represented by the formula:
wherein A is an essentially hydrocarbon aromatic radical, preferably a benzene radical, R is .a straight-chain or branched-chain, saturated or unsaturated essentially hydrocarbon radical having from 4 to 30 carbon atoms and a is a number having a value from 1 to 2. The total number of carbon atoms for R has a minimum value of 8. Thus, when a is 1, the minimum number of carbon atoms in R is 8.
Examples of suitable hydrocarbonaceous radicals include alkyl radicals, such as butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, eicosyl, tricontyl radicals; radicals derived from petroleum hydrocarbons, such as white oil, Wax, olefin polymers (e.g., polypropylene and polybutylene) etc. i
The basic sulfonates used herein contain from 0% to 300% of metal in excess of the metal of normal sulfonates, that is, essentially neutral, metal sulfonates. The basic sulfonates used herein are derived from neutral sulfonates represented by the formula:
wherein R is a high molecular weight straight-chained or branched-chain saturated or unsaturated essentially hydrocarbonaceous radical having a molecular weight of about to about 800; A is an aromatic radical, such as benzene, naphthalene, anthracene, etc; a isa number having the value of 1 to 4; and M is an alkaline earth metal.
As the metal, the term alkaline earth metals, includes preferably calcium, barium, and strontium; calcium is particularly preferred. Y
Examples of suitable hydrocarbonaceous radicals are the following: dodecane, hexadecane, eicosane, triacontane radicals; radicals derived from petroleum hydrocarbons such as white oil, wax, olefin polymers (e.g., polypropyleneand polybutylene, etc.). The sulfonic acids used in preparing the basic sulfonates of this invention also include the oil-soluble sulfonic acids obtained from petroleum, such as the mahogany acids, and the synthetic sulfonic acids prepared by various methods of synthesis (e.g., sulfonic' acids prepared by reacting a chlorinated white oil with benzene, using hydrofluoric acid as the catalyst, then treating the resulting white oil alkylated benzene with chlorosulfonic acid or fuming sulfuric acid to form a white oil benzene sulfonic acid).
The metal sulfonates are exemplified as follows: calcium white oil benzene sulfonate, barium white oil benzene sulfonate, calcium dipolypropylene benzene sulfonate, barium dipolypropylene benzene sulfonate, calcium mahogany petroleum sulfonate, barium mahogany petroleum sulfonate, calcium triacontyl benzene sulfonate, barium triacontyl benzene, etc.
The high molecular weight alcohol, which is used in amounts no more than 75% by weight of the alkyl phenol charged, preferably 10% to 50%, are those monohydric alcohols containing from 8 to 18 carbon atoms. These alcohols are exemplified as follows: octyl alcohol, decyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, cetyl alcohol, etc.
In the process described herein, a lubricating oil may be used as a reaction medium. Thus, by such use of a lubricating oil, oil concentrates of the desired highly basic carbonated sulfurized metal phenates can be obtained. Such lubricating oils include a wide variety of lubricating oils, such as naphthenic base, paraffin base and mixed base lubricating oils, other hydrocarbon lubricants, e.g., lubricating oils derived from coal products and the synthetic oils, e.g., alkylene polymers (such as polymers of propylene, butylene, etc., and the mixtures thereof); alkylene oxide type polymers, e.g., alkylene oxide polymers prepared by polymerizing the alkylene oxides, e.g., propylene oxide, etc., in the presence of water or alcohols (e.g., ethyl alcohol); carboxylic acid esters, for example, those which are prepared by esterifying such carboxylic acids as adipic acid, azelaic acid, subaric acid, sebacic acid, alkenyl succinic acid, fumaric acid, maleic acid, etc. with alcohols such as'butyl alcohol, hexyl alcohol, 2-ethylhexyl alcohol, and pentaerythritol; alkyl bcnzenes, polyphenyls; polymers of silicon; etc.
The several components which are used in this process are used in certain proportions with respect to each other. For each molal quantity of alkyl phenol, it is desirable to use from 0.01 mole to 1 mole of sulfonate, preferably 0.01 mole to 0.05 mole, and from 0.1 mole to 1.5 mole of high molecular weight alcohol, preferably tridecyl alcohol.
The amount of elemental sulfur present in the reaction mixture is such that the mol ratio of sulfur to alkaline earth metal of the basic substance is from 0.25 to 4.0. It is preferred that the mol ratio is in the range of 0.5 to 1.5.
The amount of alkaline earth metal oxide or hydroxide which is used is that amount which will be sufficient to give a base ratio of 1.2 to 4.5, preferably 1.5 to 3.5. The amount of alkaline earth metal oxides or hydroxide used in the reaction depends on the amount of metal desired in the product in excess of that of the normal phenate. Normally, in the preparation of basic carbonated sulfurized phenates a slight excess (e.g., 5 mole percent excess) of calcium oxide or hydroxide is used in the reaction mixture over that desired in the final basic phenate product.
The carbon dioxide used is from 300 mole percent to mole percent, preferably 150 mole percent to 10 mole percent of the alkyl phenol charged.
In the process of this invention, it is preferred to use ethylene glycol. The amount of glycol used will depend upon the amount of calcium oxide or hydroxide used.
A sufiicient amount of glycol is employed to bring the reactants into efficient contact for substantial reaction in a reasonably short time; that is, the amount of glycol used is sufiicient to dissolve a portion of each of the reactants and to cause substantial contact between said reactants. For this purpose it is beneficial to use certain ratios by weight of the alkaline earth metal oxide or hydroxide to glycol. The alkaline earth metal-glycol mole ratio may vary from 2 to 1 to about 0.25 to 1.0; preferably from 1 to 1 to about 0.5 to 1. i
According to the process described herein, there is first formed a blend consisting of an alkyl phenol, a sulfonate, a high molecular weight alcohol, and an oil of lubricating viscosity. This mixture is then heated with agitation to temperatures from 150 F. to 190 F., followed by the addition of the sulfur and calcium hydroxide (or oxide). Ths blend is then heated to temperatures in the range of 250 F. to 300 F., and that temperature is maintained while ethylene glycol is slowly added. The water of reaction liberated after the addition of the glycol is then removed by heating to temperatures of about 340 F. The reaction mixture is cooled slightly, followed by carbonation by means of carbon dioxide at temperatures from 250 F. to 350 F. Any uncombined CO is then removed. The reaction blend is then heated for 2 to 10 hours at temperatures ranging from 300 F. to 390 F., during which heating the absolute pressure is reduced to 4050 mm. Hg to remove glycol. In certain instances, some of the high molecular Weight alcohols may be removed along with the ethylene glycol. However, whether or not any or all of the high molecular weight alcohol is removed, the resulting lubricating oil composition is highly effective for its intended purpose. When the particularly preferred high molecular weight alcohol is used, that is, tridecyl alcohol, it is beneficial that at least 50%, by weight, remain in the lubricating oil composition. However, with this preferred alcohol, the final lubricating oil composition may contain from 30% to 50%, by weight, of the original charge of the tridecyl alcohol. Thus, the high molecular weight alcohol may be removed in its entirety or amounts up to of the initial charge may remain in the final composition.
The examples hereinbelow illustrate the process of this invention.
EXAMPLE I Preparation of basic sulfurized carbonated calcium alkyl phenate A mixture of 4,170 pounds of an alkyl phenol having a hydroxyl number of 184 wherein the alkyl radical was derived from a polypropylene having an average of 12 carbon atoms, 508 gallons of a California refined base oil having viscosities of SSU at 100 F., 436 pounds of a basic calcium sulfonate containing 40% calcium in excess of that amount for a neutral sulfonate (i.e., the base ratio was 1.421), and 1294 pounds of tridecyl alcohol was heated to F. with agitation. Sulfur, 854 pounds, was charged to the vessel with the temperature maintained at 180-190 F. Hydrated lime, 1974 pounds, was added to the blend. The temperature of the reaction mixture was increased to 260 F. Unheated ethylene glycol, 134 gallons, was added slowly to the reaction mixture, which was kept at a temperature of 260-270 F. for the glycol addition. The reaction mixture was then heated to 340 F. to remove water.
With rapid agitation of the reaction mixture 574 pounds of CO was added at a rate of 100 pounds per hour at an initial temperature of 330 F. Uncombined CO was removed. The mixture was heated to 390 F. at an absolute pressure of approximately 40 mm. Hg to remove, by distillation, water, ethylene glycol, and tridecyl alcohol. The remaining lubricating oil blend contained 9.72%, by weight, calcium.
As noted hereinabove, it is desirable that the final lubricating oil composition have a high basicity. In the process described, it is desirable that the initial amount of alkyl phenol be from 20% to 45%, by Weight, based on the final composition, preferably from 25% to 35%, by weight. The lubricating oil reaction medium is used in amounts from 15% to 50%, by weight, based on the finished composition, preferably from 20% to 30%, by weight.
The metal sulfonate used in the example hereinabove was a concentrate consisting of 46.4% by weight of a mineral lubricating oil and 53.6% by weight of a calcium petroleum sulfonate wherein the petroleum radical was derived from a mineral oil having a viscosity of 500 SSU at 100 F. The calcium content of the oil concentrate was 11.4% by weight, and the base ratio was 1.4.
I claim:
1. A process of preparing sulfurized basic alkaline earth metal carbonated alkyl phenate comprising forming a blend comprising a petroleum lubricating oil, an alkyl phenol wherein said alkyl radical has from 4 to 30 carbon atoms and the total number of carbon atoms in the alkyl groups is at least 8, an alkaline earth metal alkyl aryl sulfonate in an amount of from 0.01 to 1 mol per mol of said alkyl phenol and an aliphatic saturated monohydric alcohol having from 8 to 18 carbon atoms in an amount of from to 75% by weight of said alkyl phenol, heating said blend to temperatures in the range of 150 F. to 190 F., adding thereto a basic substance selected from the group consisting of alkaline earth metal hydroxide and alkaline earth metal oxide in amount necessary to give a base ratio of from 1.2 to 4.5 for said basic alkaline earth metal carbonated alkyl phenate, and sulfur in an of sulfur to basic substance has a value from 0.25 to 4, heating said blend to temperatures in the range of 250 F. to 300 F., and at that temperature, adding unheated ethylene glycol thereto in amount such that the mole ratio of basicsubstance to ethylene glycol is from about 2:1 to about 0.25:1, removing the resulting Water of reaction by heating to temperatures of about 340 F while maintaining temperatures no lower than 250 adding carbon dioxide 300 mol percent of temperature of the reaction mixture at temperatures of 3100 F. to 390 F. at reduced pressure to remove ethylene g ycol.
2. A process of preparing a sulfurized basic alkaline earth metal carbonated alkyl phenate comprising forming a blend comprising a petroleum lubricating oil, an alkyl phenol wherein said alkyl radical is derived from a polypropylene having an average of 12 carbon atoms, an alkaline earth metal alkyl aryl sulfonate in an amount of from 0.01 to 1 mol per mol of said alkyl phenol, an aliphatic saturated monohydric alcohol having from 8 to 18 carbon atoms in amount of from 10% to 75% by weight of said alkyl phenol, heating with agitation to 130 F., while maintaining temperatures in the range of 180 to 190 F., adding thereto a basic substance selected from the group consisting of alkaline earth metal hy droxide and alkaline earth metal oxide in amount necessary to give a base ratio for the aforesaid carbonated alkylphenate of from 1.2 to 4.5 and sulfur in an amount such that the mol ratio of sulfur to alkyl phenol has a value from 0.25 to 4, heating with agitation to 260 F., and while maintaining the reaction mixture at temperatures of 260270 R, adding unheated ethylene glycol thereto in amount such that the mol ratio of basic substance to ethylene glycol is from 2:1 to about 0.25:1, heating to a temperature of about 340 F. to remove Water of reaction, adding carbon dioxide in an amount of from 10 mol percent to 300 mol percent of said alkyl phenol, followed by heating to temperatures of 390 F. at reduced pressure to remove ethylene glycol and at least 50% of the original charge of said alcohol.
3. A process of preparing sulfurized basic alkaline earth metal carbonated alkyl phenate comprising forming a blend comprising from 20% to 30% by weight, based on the final composition, of a petroleum lubricating oil, from 20% to 45% by Weight of an alkyl phenol wherein said alkyl radical has from 4 to 30 carbon atoms and the total number of carbon atoms in the alkyl groups is at least 8, an alkaline earth metal alkyl aryl sulfonate in an amount of from 0.01 to 1 mol per mol of said alkyl phenol and an aliphatic saturated monohydric alcohol having from 8 to 18 carbon atoms in an amount of from 10% to 75% by Weight of said alkyl phenol,
F. in amount of 10 mol percent to said alkyl phenol, maintaining the amount such that the mol ratio ing said blend to temperatures in the range of 250 F.
to 300 F., and at that temperature, adding unheated ethylene glycol thereto in amount such that the mole ratio of basic substance to ethylene glycol is from about 2:1 to about 0.25:1, removing the resulting water of reaction by heating to temperatures of about 340 F., while maintaining temperatures no lower than 250 F. adding carbon dioxide in amount of 10 mol percent to 300 mol percent of said alkyl phenol, maintaining the temperature of the reaction mixture at temperatures of 300 F. to 390 F. at reduced pressure to remove ethylene glycol.
4. A process of preparing a sulfurized basic alkaline earth metal carbonated alkyl phenate comprising forming a blend comprising from 15% to 50% by weight, based on the final composition, of a lubricating oil, from 20% to 45% by weight of an alkyl phenol wherein said alkyl radical is derived from a polypropylene having an average of 12 carbon atoms, an alkaline earth metal alkyl aryl sulfonate in an amount of from 0.01 to 1 mol per mol of said alkyl phenol, an aliphatic saturated monohydric alcohol having from 8 to 18 carbon atoms in an amount of from 10% to 75 by weight of said alkyl phenol, heating with agitation to 180 F., and While maintaining the temperatures in the range of 180 to F., adding thereto a basic substance selected from the group consisting of alkaline earth metal hydroxide and alkaline earth metal oxide in amount necessary to give a base ratio for the aforesaid carbonated alkyl phenate of from 1.2 to 4.5, and a sulfur in an amount such that the mol ratio of sulfur to alkyl phenol has a value from 0.25 to 4, heating said mixture with agitation to 260 F., and, while maintaining the reaction mixture at temperatures of 260270 F., adding ethylene glycol thereto in amount such that. the mol ratio of basic substance to ethylene glycol is from 2:1 to 0.25:1, heating said reaction mixture to a temperature of 340 F. to remove water of reaction, adding carbon dioxide at temperatures of from about 250 F. to about 300 F. in an amount of from 10 mol percent to 300 mol percent of said alkyl phenol, followed by heating to temperatures of 390 F. at reduced pressure to remove ethylene glycol and at least 50% by weight of the original charge of said monohydric alcohol.
5. A process of preparing a sulfurized basic calcium carbonated alkyl phenate comprising forming a blend comprising from 20% to 30% by weight, based on the final composition, of a petroleum lubricating oil, from 25% to 35% by weight of an alkyl phenol wherein said alkyl radical is derived from a polypropylene having an average of 12 carbon atoms, a calcium alkyl aryl sulfonate in an amount of from 0.01 to 0.05 mol per mol of said alkyl phenol, an aliphatic saturated monohydric alcohol having from 8 to 18 carbon atoms in an amount of from 10% to 50% by weight of said alkyl phenol, heating with agitation to 180 F., and While maintaining temperatures of 180 to 190 F., adding thereto a basic substance selected from the group consisting of calcium hydroxide and calcium oxide in amount necessary to give a base ratio for the aforesaid carbonated alkyl 340 F., to remove water of reaction, adding carbon dioxide at temperatures of from about 250 F. to about 300 F. in an amount of from 10 mol percent to 150 mol percent of said alkyl phenol, followed by heating to temperatures of 390 F. at reduced pressure to remove ethylene glycol and at least 50% by Weight of the original charge of said alcohol.
References Cited by the Examiner UNITED STATES PATENTS 2,119,114 5/38 Richardson et al 25252 2,409,687 10/46 Rogers et a1. 25242.7 2,409,726 10/46 Winning et al. 25252 0 0 2,483,505 10/49 Rogers et al 252-427 2,680,096 1/54 Walker et a1. 252-42.7 2,766,291 10/ 56 Weissberg et al 252-42] X 3,036,971 5/62 Otto 25242.7
' FOREIGN PATENTS 727,655 4/55 Great Britain. 776,455 6/57 Great Britain. 821,397 10/59 Great Britain.
DANIEL E. WYMAN, Primary Examiner.
JULIUS GREENWALD, Examiner.
Claims (1)
1. A PROCESS OF PREPARING SULFURIZED BASIC ALKALINE EARTH METAL CARBONATED ALKYL PENATE COMPRISING FORMING A BLEND COMPRISING A PETROLEUM LUBRICATING OIL, AN ALKYL PHENOL WHEREIN SAID ALKYL RADICAL HAS FROM 4 TO 30 CARBON ATOMS AND THTE TOTAL NUMBER OF CARBON ATOMS IN THE ALKYL GROUPS IS AT LEAST 8, AN ALKALINE EARTH MEAL ALKYL ARYL SULFONATE IN AN AMOUNT OF FROM 0.01 TO 1 MOL PER MOL OF SAID ALKYL PHENOL AND AN ALIPATIC SATURATED MONOHYDRIC ALCOHOL HAVING FROM 8 TO 18 CARBON ATOMS IN AN AMOUNT OF FROM 10 TO 75% BY WEIGHT OF SAID ALKYL PHENOL, HEATING SAID BLEND TO TEMPERATURES N THE RANGE OF 150*F. TO 190*F., ADDING THERETO A BASIC SUBSTANCE SELECTED FROM THE GROUP CONSISITNG OF ALKALINE EARTH METAL HYDROXIDE AND ALKALINE EARTH MEATAL OXIDE IN AMOUNT NECESARY TO GIVE A BASE RATIO OF FROM 1.2 TO 4.5 FOR SAID BASIC ALKALINE EARTH METAL CARBONATED ALKYL PHENATE, AND SULFUR IN AN AMOUNT SUCH TAHT THE MOL RATIO OF SULFUR TO BASIC SUBSTANCE HAS A VALUE FROM 0.25 TO 4, HEATING SAID BLEND TO TEMPERATURES IN THE RANGE OF 250*F. TO 300*F., AND AT THAT TEMPERATURE, ADDING UNHEATED ETHYLENE GLYCOL THERETO IN AMOUNT SUCH TAHT THE MOLE RATIO OF BASIC SUBSTANCE TO ETHYLENE GLYCOL IS FROM ABOUT 2:1 TO ABOUT 0.25:1, REMOVING THE RESULTING WATER OF REACTION BY HEATING TO TEMPERATURES OF ABOUT 340*F., WHILE MAINTAINING TEMEPRATURES NO LOWER THAN 250*F. ADDING CARBON DIOXIDE IN AMOUNT OF 10 MOL PERCENT TO 300 MOL PERCENT OF SAID ALKYL PHENOL, MAINTAINING THE TEMPERATURE OF THE REACTION MIXTURE AT TEMPERATURES OF 300*F. TO 390*F. AT REDUCED PRESSURE TO REMOVE ETHYLENE GLYCOL.
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