US2851417A - Complex alkoxy metal salts of organic acids and lubricating and fuel compositions thereof - Google Patents
Complex alkoxy metal salts of organic acids and lubricating and fuel compositions thereof Download PDFInfo
- Publication number
- US2851417A US2851417A US348117A US34811753A US2851417A US 2851417 A US2851417 A US 2851417A US 348117 A US348117 A US 348117A US 34811753 A US34811753 A US 34811753A US 2851417 A US2851417 A US 2851417A
- Authority
- US
- United States
- Prior art keywords
- complex
- metal
- acid
- magnesium
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 85
- 239000002184 metal Substances 0.000 title claims description 85
- 150000003839 salts Chemical class 0.000 title claims description 40
- 150000007524 organic acids Chemical class 0.000 title claims description 26
- 239000000203 mixture Substances 0.000 title description 60
- 239000000446 fuel Substances 0.000 title description 17
- 125000003545 alkoxy group Chemical group 0.000 title description 15
- 235000005985 organic acids Nutrition 0.000 title description 5
- 230000001050 lubricating effect Effects 0.000 title description 4
- 239000003921 oil Substances 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 18
- 239000002480 mineral oil Substances 0.000 claims description 18
- 235000010446 mineral oil Nutrition 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 description 85
- 229910052749 magnesium Inorganic materials 0.000 description 85
- 235000001055 magnesium Nutrition 0.000 description 85
- 229940091250 magnesium supplement Drugs 0.000 description 85
- 239000002253 acid Substances 0.000 description 75
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 63
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 58
- 239000001993 wax Substances 0.000 description 55
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 54
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 42
- 229910052725 zinc Inorganic materials 0.000 description 29
- 239000011701 zinc Substances 0.000 description 29
- 229910052788 barium Inorganic materials 0.000 description 25
- 239000000047 product Substances 0.000 description 25
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 22
- 239000004927 clay Substances 0.000 description 22
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 20
- 239000011575 calcium Substances 0.000 description 20
- 229910052791 calcium Inorganic materials 0.000 description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 19
- 239000011541 reaction mixture Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 17
- 150000007513 acids Chemical class 0.000 description 17
- 239000011734 sodium Substances 0.000 description 17
- 229910052708 sodium Inorganic materials 0.000 description 17
- 238000003756 stirring Methods 0.000 description 17
- 239000000460 chlorine Substances 0.000 description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 15
- 229910052801 chlorine Inorganic materials 0.000 description 15
- 239000003350 kerosene Substances 0.000 description 15
- 239000002002 slurry Substances 0.000 description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 14
- 239000000295 fuel oil Substances 0.000 description 14
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 13
- DAEXGDSKPVNFGH-UHFFFAOYSA-N CO[Mg] Chemical class CO[Mg] DAEXGDSKPVNFGH-UHFFFAOYSA-N 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 239000003784 tall oil Substances 0.000 description 13
- 239000003502 gasoline Substances 0.000 description 12
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 12
- QKUNKVYPGIOQNP-UHFFFAOYSA-N 4,8,11,14,17,21-hexachlorotetracosane Chemical compound CCCC(Cl)CCCC(Cl)CCC(Cl)CCC(Cl)CCC(Cl)CCCC(Cl)CCC QKUNKVYPGIOQNP-UHFFFAOYSA-N 0.000 description 10
- 239000010687 lubricating oil Substances 0.000 description 10
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 9
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000012467 final product Substances 0.000 description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 9
- -1 aliphatic acids Chemical class 0.000 description 8
- 229940092714 benzenesulfonic acid Drugs 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- CQJXEKPVUKTVBG-UHFFFAOYSA-N dihydroxy-phenylsulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound OP(O)(=S)SC1=CC=CC=C1 CQJXEKPVUKTVBG-UHFFFAOYSA-N 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- VSIIELBPDODZGZ-UHFFFAOYSA-N (2-dodecylphenyl) dihydrogen phosphate Chemical compound CCCCCCCCCCCCC1=CC=CC=C1OP(O)(O)=O VSIIELBPDODZGZ-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000003599 detergent Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 235000006708 antioxidants Nutrition 0.000 description 5
- JWAZRIHNYRIHIV-UHFFFAOYSA-N beta-hydroxynaphthyl Natural products C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 5
- 239000010688 mineral lubricating oil Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- WIKSRXFQIZQFEH-UHFFFAOYSA-N [Cu].[Pb] Chemical compound [Cu].[Pb] WIKSRXFQIZQFEH-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000013556 antirust agent Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- GJRCAPGAPUNIHP-UHFFFAOYSA-N CO[Zn] Chemical class CO[Zn] GJRCAPGAPUNIHP-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- WFILLLWGTUFZSS-UHFFFAOYSA-N [H]C([H])([H])O[Ba] Chemical class [H]C([H])([H])O[Ba] WFILLLWGTUFZSS-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229950011260 betanaphthol Drugs 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RRSGNBPOYMCOPK-UHFFFAOYSA-N CO[Ca] Chemical class CO[Ca] RRSGNBPOYMCOPK-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000003118 aryl group Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000003017 phosphorus Chemical class 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 1
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical compound CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 description 1
- RYSXDTSXRRSZRO-UHFFFAOYSA-N C(CCCCCCCCCCC)OP(OCCCCCCCCCCCC)=S Chemical compound C(CCCCCCCCCCC)OP(OCCCCCCCCCCCC)=S RYSXDTSXRRSZRO-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000004129 EU approved improving agent Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HVWGGPRWKSHASF-UHFFFAOYSA-N Sulfuric acid, monooctadecyl ester Chemical compound CCCCCCCCCCCCCCCCCCOS(O)(=O)=O HVWGGPRWKSHASF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001552 barium Chemical class 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- NSAODVHAXBZWGW-UHFFFAOYSA-N cadmium silver Chemical compound [Ag].[Cd] NSAODVHAXBZWGW-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- KUFDFOXPFQCUST-UHFFFAOYSA-N dipentylphosphinic acid Chemical compound CCCCCP(O)(=O)CCCCC KUFDFOXPFQCUST-UHFFFAOYSA-N 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 description 1
- RAMRROOXFMYSNA-UHFFFAOYSA-N hexadecyl benzoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C1=CC=CC=C1 RAMRROOXFMYSNA-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 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
- 239000003209 petroleum derivative Substances 0.000 description 1
- 235000009048 phenolic acids Nutrition 0.000 description 1
- 150000007965 phenolic acids Chemical class 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- CUQOHAYJWVTKDE-UHFFFAOYSA-N potassium;butan-1-olate Chemical class [K+].CCCC[O-] CUQOHAYJWVTKDE-UHFFFAOYSA-N 0.000 description 1
- RLEFZEWKMQQZOA-UHFFFAOYSA-M potassium;octanoate Chemical compound [K+].CCCCCCCC([O-])=O RLEFZEWKMQQZOA-UHFFFAOYSA-M 0.000 description 1
- JTBKFHQUYVNHSR-UHFFFAOYSA-N propan-2-yloxyalumane Chemical class CC(C)O[AlH2] JTBKFHQUYVNHSR-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical class [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000003788 van Ess reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 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
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/26—Organic compounds containing phosphorus
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/414—Preparation of superbasic salts
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
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- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/30—Organic compounds compounds not mentioned before (complexes)
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
- C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/025—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with condensed rings
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/027—Neutral salts thereof
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/128—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/141—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings monocarboxylic
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/142—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings polycarboxylic
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/146—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings having carboxyl groups bound to carbon atoms of six-membeered aromatic rings having a hydrocarbon substituent of thirty or more carbon atoms
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/16—Naphthenic acids
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/18—Tall oil acids
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- 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
- C10M2219/042—Sulfate esters
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- 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
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
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- 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
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- C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
- C10M2223/065—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds containing sulfur
Definitions
- This invention relates to improved petroleum fractions, such as gasolines, fuels and lubricating oils. More particularly, it relates to a new class of multi-functional additives for such fractions and to a method for their prepara tion.
- agents which, when added to lubricating oils, are capable of inhibiting to a significant degree the corrosive effect of oxidation on the metal parts of engines. These agents are known as anti-oxidants. Agents are also known which have the ability to keep sedimentation and deposit-forming materials formed in fuel in storage or in a lubricating oil in use in suspension, thereby helping to keep the fuel burning equipment or the engine being lubricated clean and in good operating condition for extended periods of time.
- Such additives are known as detergents or dispersants. Still other agents are known which act to inhibit other deleterious eifects in oil fractions, such as anti-rust agents for gasoline and fuel oils. Ordinarily, a combination of such chemical agents must be utilized in a fuel or a lubricating oil in order to provide all the desired improving effects.
- the present invention provides a new class of metal organic addition agents which are multifunctional in their activity, i. e., they are capable of improving mineral oil fractions in several respects.
- the additives of the invention which may be designated as complex metal alkoxy salts of organic acids, are excellent detergents as well as highly effective anti-oxidants for lubricating oils. Furthermore, they act as stabilizers for fuel oils in that they prevent color degradation and sedimentation therein. Finally, these complex salts are excellent anti-rust and anti-screen clogging agents for gasolines and fuel oils.
- the complex alkoxy salts of the invention are high metal content complex salts prepared by the retion of an oil-soluble organic acid with a metal alcohote in a proportion such as to supply to the reaction 31',XCSS of metal alcoholate over that which would be equ *alent to the acid-hydrogen content of the organic
- the omplex alkoxy metal salts thus provided by the inventi n contain at least about 2 and up to about 6 equival nts of metal.
- the reaction is conducted by heat- U ther a solvent solution of the organic acid and an alcohol olution of the metal alcohlate reactant for several Q Temperatures suitable for the reaction range, from about 50 C.
- aHydrocarbon solvents other than mineral lubricating g1 may, of course, be utilized, such as light naphtha, ke sene, toluene, xylene or the like. These may or may not 'be removed from the complex salt product prior to addition to a petroleum fraction.
- the complex methoxy salt product from 2 and up to 6 equivalents of metal may be incorporated into the complex methoxy salt product depending upon the amount of metal alcoholate reactant used. From 2 to about 6 equivalents of metal alcoholate, based on the equivalents of acid-hydrogen in the organic acid, are, therefore, ordinarily used in the reaction. action is as follows: The organic acid reactant is dissolved in mineral lubricating oil. A slurry of the metal alcoholate reactant, in alcohol, is then prepared. This slurry is then added to the oil solution of the organic acid with constant stirring to form an intimate mixture of the reactants. When the addition is complete, the reaction with stirring to a temperature of, say, from about C. to about C. for from about one hour to about six hours in order to complete the reaction. Any excess alcohol remaining in the reaction mixture is then removed by further heating at a higher temperature and/or reduced pressure. The product, which is an oil solution of the complex alkoxy metal salt, is then filtered to remove any traces of insolubles.
- sucl therev may be mentioned aliphatic carboxylic aci as decanoic acid, lauric acid, stearic acid, olei linoleic acid, arachidic acid, abietic acid, etc.; at carboxylic acids, such as alkyl-substituted benzoi' cylic and phthalic. acids, where the-alkyl group or ,roups are attached to.
- carboxylic acids such as alkyl-substituted benzoi' cylic and phthalic. acids, where the-alkyl group or ,roups are attached to.
- the aryl nucleus-of the acid and c ntain atotal of at least about 10 carbon atoms such asg liamyl benzoic acid, hexadecyl-benzoic acid, wax benzo acid, etc.; and naphthenic acids, such as those derive petroleum.
- Phenolic acids such as alkyl-substituted p naphthols, resorcinols, catechols, hydroquinols,
- alkyl portion contains at lea bout 10 carbon atoms.
- acids there may be -mentioned diamyl phen wax phenol, dinonyl catechol, hexadecyl hydroquino wax pyrogallol, etc.
- Organo-substituted phosphorus-containing acids i. e.., partial, esters of phosphorus acids, such as alkyl-, alkaryland aralkyl-substituted phosphoric, phosbhonic and phosphinic acids.
- Non-limiting examples 1 such acidsvv are dodecyl phenyl phosphoric acid, or adecyl phosphonic acid and diamyl phosphinic acid.
- Organo-substituted sulfur-containing acids i.e., partial esters of sulfonic acids, such as alkyl-, alkaryland aralkyl-substituted sulfonic acids and alkyl sulfuric acids.
- sulfonic acids such as alkyl-, alkaryland aralkyl-substituted sulfonic acids and alkyl sulfuric acids.
- examples of such acids are dodecyl phenyl sulfonic acid, wax benzene sulfOnic acid, petroleum sulfonic acid'and octadecyl sulfuric acid.
- the metal alcoholates which have beenfound to form alkoxy complex metal salts with the aforesaid acids are the alcoholates of the metals of Groups I, II', III and IV of M'endeleefls Periodic Table of the Elements.
- the alcoholates of potassium, calcium, barium, strontium, zinc, magnesium, aluminum and tin have been used successfully.
- the alcohols from which the metal alcoholates may be derived are monohydroxy alcohols, preferably the methoxy magnesium salt of aliphatic alcohols having from. 1 up to about. 20. carbon. atoms.
- Suitable metal alcoholates are, for example, sodium methylate, calcium methylate, barium methylate, magnesium methylate, aluminum isopropylate, calcium butylate, potassium caprylate, barium decylate, calcium dodecylate, magnesium tetradecylate, zinc hexadecylate and magnesium octadecylate.
- Example 1.C0mplex magnesium methoxy salt of tall oil acid containing two equivalents of magnesium Three hundred grams of facoil CB, a refined tall oil acid obtained from National Southern Products Corporation, having an acid number of about 165, and analyzing about 45.4% rosin. acids and. about 47.8% fatty acids, was blended with 60.0 grams of; a straight run kerosene of approximately 350 F. to 500 F. boiling range. The
- Example 2 C mplex magnesium methoxy salt" of tall oil acid containing three equivalents ofmagnesium
- Two hundred grams of Facoil CB (see. Example 1) was blended with 400 grams of a solvent-refined mineral oil having a Saybolt viscosity of 35 seconds at 210 F. and added to 21.5 grams of magnesium (three equivalents based on the acid number of the Facoil CE) in the form of a slurry of magnesium methylate in math anol.
- the temperature of the mixture was raised to about 120 C. to C. over a period of 5 to 6 hours followed by filtration through Hi-Flo clay.
- the oil blend of the produce analyzed 2.4% magnesium which was the theoretical magnesium content of a complex methoxy magnesium salt of Facoil CB containing three equivalents of magnesium..
- Example 3.-C0mplex magnesium methoxy salt of tall Oil acid containing four equivalents of magnesium Two hundred grams of Facoil CB (see Example 1) was blended with 600 grams of kerosene and added to 28 grams of magnesium (four equivalents based on acid number of Facoil CE) in the form of a slurry of magnesium methylate (see Example 1) in methanol. The temperature of the mixture was raised to about 120 C. to 125 C. over a period of 5 to 6 hours. Filtration through a layer of Hi-Flo clay yielded the final product which analyzed 3.5% magnesium in the kerosene blend. This analysis approximates the theoretical magnesium content of a complex methoxy magnesium salt of Facoil CB containing four equivalents of magnesium.
- Two hundred grams of Facoil CB (see Example 1) was blended with 800 grams of kerosene and added to 23.6 grams of calcium (two equivalents based on acid number of the Facoil CB) in the form of a slurry of calcium methylate (prepared from metallic calcium and methanol) in methanol. The temperature of the mixture was raised to about 120 C. to 125 C. over a period of 4 to 5 hours. Filtration through Hi-Flo clay yielded the final product analyzing 2.0% calcium in the kerosene blend, which approximates theoretical calcium content for a complex methoxy calcium salt of Facoil CB containing two equivalents of calcium.
- the reaction mixture was heated with stirring to about 125 C. over a period of about hours and filtered through Hi-Flo clay.
- the oil blend of the product analyzed 7.3% zinc which was the theoretical zinc content for a complex methoxy zinc salt of naphthenic acid containing two equivalents of zinc.
- Example 8 Complex zinc methoxy salt of naphthenic acid containing three equivalents of zinc in the form of sodi- K equivalents based on fined mineral oil having a Saybolt viscosity of 35 secondsat 210 F.
- the reaction mixture was heated to about 125 C. over a period of about 5 hours and filtered through Hi-Flo clay.
- the oil blend of the product analyzed 10.4% zinc which was the theoretical zinc content for a complex methoxy zinc salt of naphthenic acid containing three equivalents of zinc.
- Example 9.-C0mplex zinc methoxy salt of naphthenic acid containing four equivalents of zinc Utilizing the procedure of Example 6, a complex zinc methoxy salt of naphthenic acid (M. W. 300) containing four equivalents of zinc was prepared as follows: Sixty-six grams of sodium (four equivalents based on acid number of the naphthenic acid) in the form of sodium methylate was added to a methanol solution of 196 grains of anhydrous zinc chloride (four equivalents based on acid number of the naphthenic acid) and the mixture refluxed for 2 hours forming a methanol slurry of zinc methylate and sodium chloride.
- Example J0 Complex aluminum isopropoxy salt of naphthenic acid containing three equivalents of aluminum Seventy-three grams of aluminum isopropoxide (three acid number of the naphthenic acid) was dissolved in 400 grams of xylene by warming. The solution was added to 100 grams of naphthenic acid (see Example 9) and the mixture was heated with stirring to about 125 C. over a period of about 5 hours. The reaction mixture became clear and homogeneous at this point but was filtered through Hi-Flo clay as a precautionary measure to give the final product. The xylene blend of complex isopropoxy aluminum salt of naphthenic acid analyzed for 1.7% aluminum which was almost theoretical aluminum content for three equivalents of aluminum per equivalent of acid.
- Example 11 Complex barium methoxy salt of naphthenic acid containing two equivalents of barium
- the reaction mixture was heated to about 125 C. over a period of about 5 hours, then filtered through a layer of Hi-Flo clay.
- the barium analysis of the kerosene blend was 10.1% barium which approximates the theoretical barium content of a complex methoxy barium salt of naphthenic acid containing two equivalents of barium.
- Example 13 -C'0mplex magnesium methoxy salt of naphthenic acid containing three equivalents of magnesium
- the oil blend of the product analyzed 2.5% magnesium which was the theoretical magnesium content for a complex methoxy magnesium salt of naphthenic acid containing three equivalents of magnesium.
- the wax phenol (3-14) utilized. in this example was prepared as follows:
- a paraffin wax melting at approximately 120 F. and predominantly-comprised. of hydrocarbons, having at least 20 and an average of about 24 carbon atoms in. their molecules, is melted and heated to about 200 F., after which chlorine is bubbled therethrough until the wax has absorbed about 14%, by weight, of chlorine.
- a sufficient quantity of this chlorinated wax to provide 3 atomic proportions of chlorine is then heated to a temperature varying from just above its melting point to not over 150 F.
- One, mol of phenol (C H OH) is then mixed with the chlorowax. The mixture is then heatedto about 150 F. and a quantity of anhydrous aluminum chloride, corresponding, to about 3% of' the weight of the chlorowax in the mixture, is slowly added with active stirring.
- the rate of addition of the aluminum chloride should be sufficiently slow to avoid violent foaming and during the addition the temperature should be held at about 150 F.
- the temperature of the mixture may be increased slowly over a period of from 15 to 25 minutes to a temperature of about 250 F. and then should be more slowly increased to about 350 F.
- the temperature of the mixture is preferably raised from 250 F. to 350 F. at a rate of approximately one degree per minute; the whole heating operation occupying approximatelytwo hours from the time of adding the aluminum chloride. If the emission of HCl gas has not ceased when the final temperature is reached, the mixture may be held at 350 F. for a short time to allow completion of the reaction. However, to avoid possible cracking of the wax, the mixture should not be heated appreciably above 350 F., nor should it beheld at that temperature for any extended length of time.
- the product may then be treated with steam. This latter step will insure complete removal of the unreacted material. and also dry the product.
- wax phenol (3-14) a wax-substituted phenolprepared according tov the. above procedure in which a quantity of chlorowax containing 3 atomic proportionsofv chlorine and having a chlorine content of 14% is reacted with one mol of phenol is designated as wax phenol (3-14).
- .waxphenol (3-10) and wax phenol (1-10) may also be prepared by the reaction of sufficient. amounts. of chlorinated wax, containing 10%, by weight, of chlorine, to provide 3; atomic proportions and 1 atomic proportion of chlorine per mol of phenol, respectively,. the reaction: and are. useful in the invention.
- the. amount of chlorowax containing from about. 10% to 1 8%., by weight, of chlorine, used. inthe. reaction is suffi'cient to supply between 1 and 4 atomic proportions of chlorine per mol of phenol used.
- Twohundred grains of wax phenol (3-14) (-see Example 1.4)v was blended with- 600 grams of kerosene and added to 11.5 grams of sodium (two equivalents based onthe phenol contentofthe wax phenol [3-141) in the form of a butanol solution. of sodium but'ylate.
- Thereaction mixture washeated' with stirring to about C. to C. over. a period of about 5 hours and filtered through Hi-Flo clay.
- the kerosene blend of the final product analyzed 1.2% sodium which was the theoretical sodium content for a complex butoxy sodium salt of wax phenol (3 -14) containing twoequivalents of sodium.
- Example 16 Complex magnesium methoxy salt. of wax.- beta-naphthol (3-14 containing two equivalents of magnesium One; hundred. grams of wax alkylated betamaphthola (3-14.), preparedlby' the method. given in Example. 124 for the; preparation of wax phenol. (3-14), but; using beta-naphthol in place of phenoL. was blended with. 2001 grams of a, solvent refined oilhaving a Saybolt viscosity of 3.5.; seconds at 210 F. and added. to 3.1 grams oi mag, nesium (two equivalents based, on.
- action mixture was heated with stirring to about 150 C. over a period of about 5 hours and filtered through Hip Flo clay.
- the oil blend. of the final product analyzed 0.95% magnesium which approximates the theoretical magnesium content of a complex magnesium salt of waxbeta-napht-hol (3-14") containing two equivalents of magnesium.
- Example 10 7.-C0mplexbarium methoxy salt-0f petroleum sulfonic acid containing two equivalents'of barium Four hundred, and twenty-six grams of an aromatic petroleum stock sulfonic acid having an acid number of 32.8 was blended. with 426 grams of a solvent refined mineral oil having. a Saybolt viscosity of 35 seconds at 210 F. and the blend added to 34.2 grams of barium. (two equivalents. based on the acid number of the petroleurn sulfonic acid) in the form of a. barium methylate solution in methanol. The reaction mixture was heated with stirring to about 160 C. over a period of about 5 hours and filtered through Hi-Flo clay. The oil blend of the final product analyzed 3.7% barium which was the theoretical barium content for. a complex methoxy barium salt of the' particular petroleum sulfonic acidcontaining two equivalents of barium.
- Example 18 -Complex barium methox-y salt of wax benzene (2-12) sulfonic acid containing two equiva-. lents of barium Onehundredland'eighty-two grams of a wax-allcylated benzene, sulfonic acid-having anacid number of 77.0 was blended. with 3 64 grams of a solvent refined mineral oilhaving a Saybolt viscosity of 35 seconds at 210 F; and
- the wax benzene sulfonic acid utilized in this example was prepared as follows:
- a paraflin Wax having an average of 24 carbon atoms per molecule and a melting point of 126 F. was chlorinated at a. temperature of about 100 C. with chlorine gas until the weight of the wax had increased about 12%. The chlorowax thus obtained was then blown with nitrogen to remove any occluded chloride and hydrogen chlo ride.
- wax benzene prepared according to the foregoing procedure in which a quantity of chlorowax containing 2 atomic proportions of chlorine and having a chlorine content of 12% is reacted with 1 mol of benzene is designated wax benzene (212).
- wax benzene (3l0) and wax benzene (110) may also be prepared by the reaction of sufficient amounts of chlorinated wax, containing by weight of chlorine, to provide 3 atomic proportions and 1 atomic proportion of chlorine per mol of benzene, respectively, in the reaction and are useful in the invention.
- Example 19 Complex calcium methoxy salt of wax benzene (2-12) sulfonic acid containing two equivaalents of calcium
- a wax alkylated benzene sulfonic acid (2--12) prepared as described in Example 18, having an acid number of 84.0 was blended with 200 grams of a solvent refined mineral oil having a Sayboltviscosity of 35 seconds at 210 F. and added to 6.0 grams of calcium (two equivalents based on the acid number of the sulfonic acid)l..in the form of a slurryv of calcium methylate in methanol.
- the reaction mixture was heated with stirring to about C. over a period of about 5 hours and filtered through Hi-Flo clay.
- the oil blend of the product analyzed 2.1% calcium which was the theoretical calcium content for a complex methoxy calcium salt of the wax-alkylated benzene sulfonic acid containing two equivalents of calcium.
- Example 2 Complex magnesium methoxy salt of wax benzene (2]2) sulfonic acid containing two equivalents of magnesium
- Two hundred grams of a wax-alkylated benzene sulfonic acid (2-l2), prepared as in Example 18, having an acid number of 77.0 was blended with 400 grams of a solvent refined mineral oil having a Saybolt viscosity of 35 seconds at 210 F. and added to 6.6 grams of magnesium (two equivalents based on the acid number of the sulfonic acid) in the form of a slurry of magnesium methylate in methanol.
- the reaction mixture was heated with stirring to about 150 C. over a period of about 5 hours and filtered through Hi-Flo clay.
- the oil blend of the product analyzed 0.95% magnesium which approximates the theoretical magnesium content of a complex methoxy magnesium salt of the wax alkylated benzene sulfonic acid containing two equivalents of magnesium.
- Example 22 Complex potassium butoxy salt of wax benzene (2J2) sulfonic acid containing two equivalents of potassium
- Two hundred and fifty-three grams of a wax-alkylated benzene sulfonic acid (2-12), prepared as in Example 18,- having an acid number of 88.0 was blended with 506 grams of a solvent refined mineral oil having a Saybolt viscosity of 35 seconds at 210 F. and added to 44.6 grams of potassium hydroxide (two equivalents based on the acid number of the sulfonic acid) in the form of a butanol solution of the potassium hydroxide.
- the reaction mixture was heated with stirring to about C. over a period of about 5 hours and filtered through Hi- Flo clay.
- the oil blend of the product analyzed 4.0% potassium which was the theoretical potassium content for a complex butoxy potassium salt of the wax-alkylated benzene sulfonic acid containing two equivalents of potassium.
- Example 23 Complex magnesium methoxy salt of dodecylphenyl phosphoric acid containing two equivalents of magnesium
- a dodecyclphenyl phosphoric acid having an acid number of 162 was blended with 200 grams of a solvent refined mineral oil having a Saybolt viscosity of 35 seconds at 210 F. and added to 7.0 grams of magnesium (two equivalents based on the acid number of the phosphoric acid) in the form of a slurry of magnesium methylate in methanol.
- the reaction mixture was heated with stirring to about 150 C. over a period of about 5 hours and filtered through Hi-Flo clay.
- the oil blend of the product analyzed 2.3% magnesium which was the theoretical magnesium content for. a. complex methoxy magnesium salt of the dodecylphenyl phosphoric acid containing two equivalents of magnesium.
- the dodecylphenyl phosphoric acid used in this example was prepared as follows: Two thousand grams of a dodecylphenol was stirred with 321 grams of phosphorus pentoxide' and heated to 150 C. The reaction mixture was stirred at 150 C. for 3 hours and. then filtered through Hi-Flo clay to give the finished dodecylphenyl phosphoric acid.
- Example 24 -Cm lex magnesium methoxy salt of wax phenyl dithiophosphoric acid containing threeequivalents of magnesium
- Two hundred grams of a wax phenyl dithiophosphoric acid having an acid number of 46 was blended with 400 grams of a solvent. refined. mineral oil having a. Saybolt viscosity of35 seconds at 210" F. and added to 610 grams of magnesium (three equivalents based on the acid number of the dithiophosphoric acid) in the form of. a slurry of magnesium methylate in methanol.
- the reaction mixture was heated with stirring to about 150 C. over a period of about hours and filtered through Hi- Flo clay.
- the oil blend of the product analyzed 0.9% magnesium which approximates the. theoretical magnesium content of a complex methoxy magnesium salt of the wax phenyl dithiophosphoric acid containing three equivalents of magnesium.
- test oil' are placed in a tall form (127 x 70 mm.) beaker and a cylindrical polished steel specimen is suspended and soaked in the oil under test at 140 F; for 30 minutes. Thirty cc. of distilled water are added and the mixture is stirred at 1000'R. P. M. After 48 hours, the steelspecimen is removed and examined for evidence of rust thereon. The specifications require the complete absence of rust, even pin points of rust, and the absence of dark stain. The fuel used was the same as that used in the fuel storage tests of Table I. The products have also been tested as anti-rust agents in gasoline and'lubricating. oil and found to give good results.
- the fuel used is a controlled. Mobilgas Special. type: blend gasoline (40% thermal, catalytically cracked and 30% straight. run, plus 2.5 cc. TEL/gal). duration of. the test is l00hours.
- the fuel used is a controlled Mobilgas Special type blend (40% thermal, 30% catalytically cracked and 30% straight run, plus 2.5 cc. TEL/gal.).
- the complex metal alkoxy salts of the invention which are actually concentrated solutions containing from about 20% to about 50% of the complex metal salts, are effective improving agents petroleum oil fractions in concentrations ranging from as little as 0.01% (i. e., 100 parts per million) as anti-rust agents in gasoline to from 0.5% to 2.0% as anti-oxidants and detergents in lubricating oils.
- the complex salts may be used in greater or lesser amounts than shown herein depending upon the particular oil fraction and the use for which it is intended. Thus, amounts of from as little as 0.001% up to about 10% comprise the eifective concentration range.
- the petroleum oil fractions may, of course, contain other addition agents along with the complex metal alkoxy salts of the invention, such as viscosity index improvers, extreme pressure agents, and pour point depres sants, which it may be found desirable to add to said fraction.
- other addition agents such as viscosity index improvers, extreme pressure agents, and pour point depres sants, which it may be found desirable to add to said fraction.
- complex salts of this invention are intended primarily for use as additives for various petroleum oil fractions, they also find application in the manufacture of detergent soaps, dispersants, etc.
- a mineral oil fraction containing a minor proportion, sufiicient to stabilize said oil fraction against oxidation, of a complex alkoxy metal salt of an organic acid prepared by the method which comprises: reacting a hydrocarbon solution containing 1 equivalent proportion of a hydrocarbon-soluble organic acid having a molecular weight of from about 200 to about 1000 with from at least about 2 and up to about 6 equivalent proportions of a metal alcoholate derived from an aliphatic monohydroxy alcohol having from 1 up to about 20 carbon atoms and the metal constituent of which is selected from the metals of Groups I and II of Mendeleetfs Periodic Table of the Elements, at a temperature of from about 50 C.
- the complex salt so produced having combined therein about 2 equivalents of metal per equivalent of organic acid where the metal of the metal alcoholate used in the reaction is a metal of group I and from about 3 to about 6 equivalents of metal where the metal of the metal alcoholate used in the reaction is a metal of group II.
- a mineral lubricating oil containing a minor proportion, sufficient to stabilize said oil fraction against oxidation, of a complex alkoxy metal salt of an organic acid prepared by the method which comprises: reacting a hydrocarbon solution containing 1 equivalent proportion of a hydrocarbon-soluble organic acid having a molecular weight of from about 200 to about 1000 with from at least about 2 and up to about 6 equivalent proportions of a metal alcoholate derived from an aliphatic monohydroxy alcohol having from 1 up to about 20 carbon atoms and the metal constituent of which is selected from the metals of Groups I and II of Mendeleetfs Periodic Table of the Elements, at a temperature of from about 50 C.
- the complex salt so produced having combined therein about 2 equivalents of metal per equivalent of organic acid where the metal of the metal alcoholate used in the reaction is a metal of group I and from about 3 to about 6 equivalents of metal Where the metal of the metal alcoholate used in the reaction is a metal of group II.
- a mineral lubricating oil containing a minor proportion, sufficient to stabilize said oil against oxidation, of a complex methoxy magnesium salt' of a naphthenic acid prepared by the method which comprises: reacting an oil solution containing 1 equivalent proportion of an oil-soluble naphthenic acid having a molecular Weight of from about 200 to about 1000 with from at least about 2 and up to about 6 equivalents of magnesium methylate, at a temperature of from about 50 C. to about 200 C., the complex salt so produced having combined therein from about 3 to about 6 equivalents of magnesium per equivalent of naphthenic acid.
- molecular weight of from about 200 to about 1000 with from at least about 2 and up to about 6 equivalent proportions of potassum methylate, at a temperature of from about 50 C. to about 200 C., the complex salt so produced having combined therein about 2 equivalents of potassium per equivalent of wax-benzene sulfonic acid.
- a fuel oil containing a minor proportion, sufficient to stabilize said fuel oil against oxidation, of a complex alkoxy metal salt of an organic acid prepared by the method which comprises: reacting a hydrocarbon solution containing 1 equivalent proportion of a hydrocarbon soluble organic acid having a molecular weight of from about 200 to about 1000' with from at least about 2 and up to about 6' equivalent proportions of a metal alcoholate derived from an aliphatic monohydroxy alcohol hav ing from 1 up to about 20 carbon atoms and the metal constituent ofwhich is selected from the-metals of Groups I and II of'Mencleleefifs Periodic Table of the Elements, at a temperature of from about 50 C. to about 200C, the complex salt so produced having.
- a fuel oil containing a minor proportion, suflicient to stabilize said oil against oxidation, of a complex methoxy magnesium salt of a tall oil acid prepared by the method which comprises: reacting an oil. solution containing 1 equivalent proportion of an oil-soluble tall oil acid having a molecular weight of from about 200 to about 1000 with from at least about 2 and up to about 6 equivalent proportions of magnesium methylate, at a temperature of from about 50 C. to about 200 C., the complex salt so produced having combined therein from about 3 to about 6 equivalents of magnesium per equivalent of tall oil acid.
- a fuel oil containing a minor proportion, sufficient to stabilize said oil against oxidation, of a complex rnethoxy zine salt of a naphthenic acid prepared by the method which comprises: reacting an oil solution containing 1 equivalent proportion of an oil-soluble naphthenic acid having a molecular weight of from about 200 to about 1000 with from at least about 2 and up to about 6 equivalent proportions of zinc methylate, at a temperature of from about 50 C. to about 200 C., the complex salt so produced having combined therein from about 3 to about 6 equivalents of zinc per equivalent of naphthenic acid.
- the complex salt so produced having combined therein about 2 equivalents of metal per equivalent of organic acid where the metal of the metal alcoholate used in the reaction is a metal of group I and from about 3 to about 6 equivalents of metal where the metal of the metal alcoholate used in the reaction is a metal of group II.
- a gasoline containing a minor proportion, sufficient to stabilize said gasoline against oxidation and inhibit the formation of rust therein, of a complex methoxy magnesium salt of a tall oil acid prepared by the method which comprises: reacting an oil solution containing 1 equivalent proportion of an oil-soluble tall oil acid having a molecular weight of from about 200 to about 1000 with from at least about 2 and up to about 6 equivalent proportions of magnesium methylate, at a temperature of from about 50 C. to about 200 C., the complex salt so produced having combined therein from about 3 to about 6 equivalents of magnesium per equivalent of tall oil acid.
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Description
' or fuel oil.
51,417 i atented Sept. 9, 1958 haw.
COWLEX ALKOXY METAL SALTS OF ORGANIC ACIDS AND LUBRICATING AND FUEL CUP/ilPOSITIONS THEREOF Harry J. Andress, .l'ra, Pittman, N. 3., assignor to $ocony Mobil Oil Company, Inc, a corporation of New York No Drawing. Application April 10, 1953 Seriai No. 348,117
9 Claims. Cl. 252--3$) This invention relates to improved petroleum fractions, such as gasolines, fuels and lubricating oils. More particularly, it relates to a new class of multi-functional additives for such fractions and to a method for their prepara tion.
it is well known that substantially all mineral oil fractions refined for their various uses are suceptible to oxidation. The manner in which this oxidation manifests itself varies with the particular oil fraction, the manner of its refinement and the conditions under which it is stored or used. Thus, mineral lubricating oils are subject to oxidative deterioration, particularly under conditions of high temperature and pressure encountered in use in internal combustion engines. This oxidation produces acidic bodies in the oil which are corrosive to the metal parts of the engine, particularly to certain types of alloys, such as copper-lead and cadmium-silver alloys, utilied in present day engines. This oxidative deterioration is also attended by deposition of carbonaceous sludge, lacquer and resinous materials which accumulate in the engine, particularly around the piston ring skirts and grooves, so that the operating efiiciency of the engine is impaired.
Another problem encountered .with gasolines and fuel oils in pipe lines and in storage is the rusting of the pipe line and container walls, the fuel oil or gasoline thereby being contaminated with lust which produces an undesirable sediment therein. Oxidation in storage also causes color degradation and sediment formation in the gasoline This rust and oxidation sediment causes plugging of filter screens, orifices, etc. in engines or heating units in which the gasoline or fuel oil is used.
in order to overcome, insofar as possible, the various deleterious effects of oxidation in mineral oil fractions, it has become the practice in the art to add to said fractions minor amounts of chemical agents, which have the ability to minimize these efiects. Thus, agents are known which, when added to lubricating oils, are capable of inhibiting to a significant degree the corrosive effect of oxidation on the metal parts of engines. These agents are known as anti-oxidants. Agents are also known which have the ability to keep sedimentation and deposit-forming materials formed in fuel in storage or in a lubricating oil in use in suspension, thereby helping to keep the fuel burning equipment or the engine being lubricated clean and in good operating condition for extended periods of time. Such additives are known as detergents or dispersants. Still other agents are known which act to inhibit other deleterious eifects in oil fractions, such as anti-rust agents for gasoline and fuel oils. Ordinarily, a combination of such chemical agents must be utilized in a fuel or a lubricating oil in order to provide all the desired improving effects. The present invention, however, provides a new class of metal organic addition agents which are multifunctional in their activity, i. e., they are capable of improving mineral oil fractions in several respects. Thus, the additives of the invention, which may be designated as complex metal alkoxy salts of organic acids, are excellent detergents as well as highly effective anti-oxidants for lubricating oils. Furthermore, they act as stabilizers for fuel oils in that they prevent color degradation and sedimentation therein. Finally, these complex salts are excellent anti-rust and anti-screen clogging agents for gasolines and fuel oils.
As far as is known, the complex salts herein contemplated have not been prepared heretofore and they are, therefore, considered to be new compositions of matter.
it is, therefore, an object of this invention to provide a new class of complex alkoxy metal salts. It is a further object to provide lubricating oil compositions containing relatively small amounts of these new complex alkoxy metal salts, which compositions are improved with respect to their anti-corrosive and detergents properties. It is also. an object to provide gasoline and fuel oil compositiof containing minor amounts of these salts whereby such co. positions are improved in their anti-oxidant, antiscreen clogging and anti-rust properties. Other and further 0 facts will become apparent from the following detailed ibscription of the invention.
Broa fly stated, the complex alkoxy salts of the invention are high metal content complex salts prepared by the retion of an oil-soluble organic acid with a metal alcohote in a proportion such as to supply to the reaction 31',XCSS of metal alcoholate over that which would be equ *alent to the acid-hydrogen content of the organic The omplex alkoxy metal salts thus provided by the inventi n contain at least about 2 and up to about 6 equival nts of metal. The reaction is conducted by heat- U ther a solvent solution of the organic acid and an alcohol olution of the metal alcohlate reactant for several Q Temperatures suitable for the reaction range, from about 50 C. up to about 200 C., the paremperature utilized in any case being that sufii- :tfect the removal of the alcohol from the reaction iixtui by distillation, in the course of the reaction, but not ,fl, enough to remove the solvent, which is generally a hyd arbon solution, preferably a mineral lubricating oil this Way, a fluid-concentrate of the complex -oholate salt is obtained, which is readily filtered e insolubles and which 18 adaptable for addition to the articular oil fraction which it is desired to improve. aHydrocarbon solvents other than mineral lubricating g1 may, of course, be utilized, such as light naphtha, ke sene, toluene, xylene or the like. These may or may not 'be removed from the complex salt product prior to addition to a petroleum fraction.
As aforesaid, from 2 and up to 6 equivalents of metal may be incorporated into the complex methoxy salt product depending upon the amount of metal alcoholate reactant used. From 2 to about 6 equivalents of metal alcoholate, based on the equivalents of acid-hydrogen in the organic acid, are, therefore, ordinarily used in the reaction. action is as follows: The organic acid reactant is dissolved in mineral lubricating oil. A slurry of the metal alcoholate reactant, in alcohol, is then prepared. This slurry is then added to the oil solution of the organic acid with constant stirring to form an intimate mixture of the reactants. When the addition is complete, the reaction with stirring to a temperature of, say, from about C. to about C. for from about one hour to about six hours in order to complete the reaction. Any excess alcohol remaining in the reaction mixture is then removed by further heating at a higher temperature and/or reduced pressure. The product, which is an oil solution of the complex alkoxy metal salt, is then filtered to remove any traces of insolubles.
A general procedure for conducting the re-- THE ORGANIC ACID REACTANT As. far as is: known, all organic acids will react with the -metal, alcoholates; in. accordance with the invention to.-form high: metal content complex. salts of the type herein contemplated. The, acids. particularly cOntem-- plated herein, however, are the oil-soluble organic acids. Thesehave. relatively high molecular weights, i.e., about ZOO/or above. Those. acids having-molecular W ights of from. about 300 to about,1000are'particularly pr: erred. More specifically, the following types of acids ave particularly contemplated herein- ,3-
(G): Carboxylic acids of. the aliphatic, aror'l'fi glc or naphthenic type, the aliphatic acids'having at lea'l about 10. and up.- to about 24 carbon atoms and the lmatic acids and. naphthenic. acids having aliphatic sul gtituent groups containing at least about and up to a carbon. atoms. As non-limiting examples of sucl therev may be mentioned aliphatic carboxylic aci as decanoic acid, lauric acid, stearic acid, olei linoleic acid, arachidic acid, abietic acid, etc.; at carboxylic acids, such as alkyl-substituted benzoi' cylic and phthalic. acids, where the-alkyl group or ,roups are attached to. the aryl nucleus-of the acid and c ntain atotal of at least about 10 carbon atoms, such asg liamyl benzoic acid, hexadecyl-benzoic acid, wax benzo acid, etc.; and naphthenic acids, such as those derive petroleum.
(b) Phenolic acids, such as alkyl-substituted p naphthols, resorcinols, catechols, hydroquinols,
101, etc., wherein the alkyl portion contains at lea bout 10 carbon atoms. As non-limiting examples such acids, there may be -mentioned diamyl phen wax phenol, dinonyl catechol, hexadecyl hydroquino wax pyrogallol, etc.
('c) Organo-substituted phosphorus-containing acids, i. e.., partial, esters of phosphorus acids, such as alkyl-, alkaryland aralkyl-substituted phosphoric, phosbhonic and phosphinic acids. Non-limiting examples 1 such acidsvv are dodecyl phenyl phosphoric acid, or adecyl phosphonic acid and diamyl phosphinic acid.
((1) Organo-substituted sulfur-containing acids, i.e., partial esters of sulfonic acids, such as alkyl-, alkaryland aralkyl-substituted sulfonic acids and alkyl sulfuric acids. Examples of such acids are dodecyl phenyl sulfonic acid, wax benzene sulfOnic acid, petroleum sulfonic acid'and octadecyl sulfuric acid.
(e) Organo-substituted phosphorusand sulfur-containing acids, i.e., partial esters of phosphorusand sulfur-containing acids, such as alkylr, alkaryland aralkylsubstituted thiophosphoric, thiophosphonic and thiophosphinic acids. Examples of these types of acids are the following: wax phenyl dithiophosphoric acid, didodecyl thiophosphonic acid anddihexadecyl phosphinic acid.
THE METAL ALCOHOLATE REACTANT The metal alcoholates which have beenfound to form alkoxy complex metal salts with the aforesaid acids are the alcoholates of the metals of Groups I, II', III and IV of M'endeleefls Periodic Table of the Elements. Thus, the alcoholates of potassium, calcium, barium, strontium, zinc, magnesium, aluminum and tin have been used successfully. The alcohols from which the metal alcoholates may be derived are monohydroxy alcohols, preferably the methoxy magnesium salt of aliphatic alcohols having from. 1 up to about. 20. carbon. atoms. Suitable metal alcoholates are, for example, sodium methylate, calcium methylate, barium methylate, magnesium methylate, aluminum isopropylate, calcium butylate, potassium caprylate, barium decylate, calcium dodecylate, magnesium tetradecylate, zinc hexadecylate and magnesium octadecylate.
in order to fully illustrate the nature and mannerof preparation of our complex metal alkOxy salts and their ability as additives for fuels and lubricating oils, the following examples and test results are presented.
Example 1.C0mplex magnesium methoxy salt of tall oil acid containing two equivalents of magnesium Three hundred grams of facoil CB, a refined tall oil acid obtained from National Southern Products Corporation, having an acid number of about 165, and analyzing about 45.4% rosin. acids and. about 47.8% fatty acids, was blended with 60.0 grams of; a straight run kerosene of approximately 350 F. to 500 F. boiling range. The
erosene blend of tall. oil wasadded to 21.5 grams of magnesium (two equivalents based on acid number of Faco-il CB) in the form of aslurry of magnesium methylate (prepared from metallic magnesium and methanol) in methanol. The reaction mixture was heated with stirring to about -125 C. over a period of 4 to 5 hours, in which time all the methanol was removed leaving a clear solution of the complex methoxy magnesium salt of Facoil CB in kerosene. The final product was.
filtered through.Hi-Flo (a diatomaceous clay filter-aid) to remove any traces of unreacted material. The product analyzed 2.4% magnesium in the kerosene blend which approximates theoretical magnesium for a complex Facoil CB" containing two equivalents of magnesium.
Example 2.C mplex magnesium methoxy salt" of tall oil acid containing three equivalents ofmagnesium Two hundred grams of Facoil CB (see. Example 1) was blended with 400 grams of a solvent-refined mineral oil having a Saybolt viscosity of 35 seconds at 210 F. and added to 21.5 grams of magnesium (three equivalents based on the acid number of the Facoil CE) in the form of a slurry of magnesium methylate in math anol. The temperature of the mixture was raised to about 120 C. to C. over a period of 5 to 6 hours followed by filtration through Hi-Flo clay. The oil blend of the produce analyzed 2.4% magnesium which was the theoretical magnesium content of a complex methoxy magnesium salt of Facoil CB containing three equivalents of magnesium..
Example 3.-C0mplex magnesium methoxy salt of tall Oil acid containing four equivalents of magnesium Two hundred grams of Facoil CB (see Example 1) was blended with 600 grams of kerosene and added to 28 grams of magnesium (four equivalents based on acid number of Facoil CE) in the form of a slurry of magnesium methylate (see Example 1) in methanol. The temperature of the mixture was raised to about 120 C. to 125 C. over a period of 5 to 6 hours. Filtration through a layer of Hi-Flo clay yielded the final product which analyzed 3.5% magnesium in the kerosene blend. This analysis approximates the theoretical magnesium content of a complex methoxy magnesium salt of Facoil CB containing four equivalents of magnesium.
Example 4.C0mplex magnesium methoxy salt of tall oil acid containing six equivalents of magnesium Example 5.Complex calcium methoxy salt of tall oil acid containing two equivalents of calcium Two hundred grams of Facoil CB (see Example 1) was blended with 800 grams of kerosene and added to 23.6 grams of calcium (two equivalents based on acid number of the Facoil CB) in the form of a slurry of calcium methylate (prepared from metallic calcium and methanol) in methanol. The temperature of the mixture Was raised to about 120 C. to 125 C. over a period of 4 to 5 hours. Filtration through Hi-Flo clay yielded the final product analyzing 2.0% calcium in the kerosene blend, which approximates theoretical calcium content for a complex methoxy calcium salt of Facoil CB containing two equivalents of calcium.
Example 6.Cmplex magnesium methoxy salt of tall oil acid containing four equivalents of magnesium A complex methoxy magnesium salt of Facoil CB containing four equivalents of magnesium (similar to that of Example 3) was prepared by the following alternative procedure:
Fifty-four grams of sodium (four equivalents based on acid number of the Facoil CB um methylate was added to a methanol solution of 113 grams of anhydrous magnesium chloride (four equivalents based on acid number of Facoil CB) and the mixture refluxed for 2 hours forming a methanol slurry of magnesium methylate and sodium chloride. To this slurry was added a blend of 200 grams of Facoil CB and 600 grams of kerosene. The reaction mixture was heated with stirring to about 120 C. to 125 C. over a period of 4 to 6 hours. Filtration through Hi-Flo clay yielded the final product analyzing 3.4% magnesium in the kerosene blend which approximates the theoretical magnesium content of Example 3.
'Example 7.Complex zinc methoxy salt of naphthenic acid containing two equivalents of zinc Thirty-three grams of sodium (two equivalents based on acid number of the naphthenic acid) in the form of sodium methylate was added to a methanol solution of 98 grams of anhydrous zinc chloride (two equivalents based on the acid number of the naphthenic acid) and the mixture refluxed for two hours forming a methanol slurry of zinc methylate and sodium chloride. To this slurry was added a blend of 200 grams of naphthenic acid with an acid number of about 200 and 400 grams of a solvent refined mineral oil having a Saybolt viscosity of 35 seconds at 210 F. The reaction mixture was heated with stirring to about 125 C. over a period of about hours and filtered through Hi-Flo clay. The oil blend of the product analyzed 7.3% zinc which was the theoretical zinc content for a complex methoxy zinc salt of naphthenic acid containing two equivalents of zinc.
Example 8.Complex zinc methoxy salt of naphthenic acid containing three equivalents of zinc in the form of sodi- K equivalents based on fined mineral oil having a Saybolt viscosity of 35 secondsat 210 F. The reaction mixture was heated to about 125 C. over a period of about 5 hours and filtered through Hi-Flo clay. The oil blend of the product analyzed 10.4% zinc which was the theoretical zinc content for a complex methoxy zinc salt of naphthenic acid containing three equivalents of zinc.
Example 9.-C0mplex zinc methoxy salt of naphthenic acid containing four equivalents of zinc Utilizing the procedure of Example 6, a complex zinc methoxy salt of naphthenic acid (M. W. 300) containing four equivalents of zinc was prepared as follows: Sixty-six grams of sodium (four equivalents based on acid number of the naphthenic acid) in the form of sodium methylate was added to a methanol solution of 196 grains of anhydrous zinc chloride (four equivalents based on acid number of the naphthenic acid) and the mixture refluxed for 2 hours forming a methanol slurry of zinc methylate and sodium chloride. To this slurry was added a blend of 200 grams of petroleum derived naphthenic acid, having an acid number of about 200, and 600 grams of kerosene. The reaction mixture was heated with stirring to about C. to C. over a period of about 5 hours, then filtered through Hi-Flo clay. The kerosene blend of the product anlyzed 10.6% zinc which approximates the theoretical zinc content of a complex methoxy zinc salt of naphthenic acid containing four equivalents of zinc.
Example J0.Complex aluminum isopropoxy salt of naphthenic acid containing three equivalents of aluminum Seventy-three grams of aluminum isopropoxide (three acid number of the naphthenic acid) was dissolved in 400 grams of xylene by warming. The solution was added to 100 grams of naphthenic acid (see Example 9) and the mixture was heated with stirring to about 125 C. over a period of about 5 hours. The reaction mixture became clear and homogeneous at this point but was filtered through Hi-Flo clay as a precautionary measure to give the final product. The xylene blend of complex isopropoxy aluminum salt of naphthenic acid analyzed for 1.7% aluminum which was almost theoretical aluminum content for three equivalents of aluminum per equivalent of acid.
Example 11.Complex barium methoxy salt of naphthenic acid containing two equivalents of barium One hundred grams of naphthenic acid (see Example 9)';was blended with 300 grams of kerosene and added to -50 grams of barium (two equivalents based on acid number of the naphthenic acid) in the form of a barium methylate solution (prepared from barium oxide and methanol) in methanol. The reaction mixture was heated to about 125 C. over a period of about 5 hours, then filtered through a layer of Hi-Flo clay. The barium analysis of the kerosene blend was 10.1% barium which approximates the theoretical barium content of a complex methoxy barium salt of naphthenic acid containing two equivalents of barium.
Example 12.Complex magnesium methoxy salt of naphthenic acid containing two equivalents of magnesium Two hundred grams of naphthenic acid (acid number-=200) was blended with 400 grams of oil and reacted with 17.5 grams of magnesium (two equivalents based on acid number of naphthenic acid) using the procedure described in Example 1. The oil blend of the product analyzed 2.0% magnesium which was the theoretical magnesium content for a complex methoxy magnesium salt of naphthenic acid containing two equivalents of magnesium.
Example 13.-C'0mplex magnesium methoxy salt of naphthenic acid containing three equivalents of magnesium Two hundred grams of napht-henic acid (acid number =200.) was blended with 600 grams of oil and reacted with- 26.0 grams of magnesium (three equivalents based on acid number of naphthenic acid), using the procedure described in Example 1. The oil blend of the product analyzed 2.5% magnesium which was the theoretical magnesium content for a complex methoxy magnesium salt of naphthenic acid containing three equivalents of magnesium.
Example 141-Complex magnesium methoxy salt of wax phenol (3-1'4) containing two equivalents of mag nesium magnesium. :salt of wax phenol (3-1.4) containing two equivalents of magnesium.
The wax phenol (3-14) utilized. in this example was prepared as follows:
A paraffin wax melting at approximately 120 F. and predominantly-comprised. of hydrocarbons, having at least 20 and an average of about 24 carbon atoms in. their molecules, is melted and heated to about 200 F., after which chlorine is bubbled therethrough until the wax has absorbed about 14%, by weight, of chlorine. A sufficient quantity of this chlorinated wax to provide 3 atomic proportions of chlorine is then heated to a temperature varying from just above its melting point to not over 150 F. One, mol of phenol (C H OH) is then mixed with the chlorowax. The mixture is then heatedto about 150 F. and a quantity of anhydrous aluminum chloride, corresponding, to about 3% of' the weight of the chlorowax in the mixture, is slowly added with active stirring. The rate of addition of the aluminum chloride should be sufficiently slow to avoid violent foaming and during the addition the temperature should be held at about 150 F. After the aluminum chloride has been added, the temperature of the mixture may be increased slowly over a period of from 15 to 25 minutes to a temperature of about 250 F. and then should be more slowly increased to about 350 F. To control the evolution of HCl gas. the temperature of the mixture is preferably raised from 250 F. to 350 F. at a rate of approximately one degree per minute; the whole heating operation occupying approximatelytwo hours from the time of adding the aluminum chloride. If the emission of HCl gas has not ceased when the final temperature is reached, the mixture may be held at 350 F. for a short time to allow completion of the reaction. However, to avoid possible cracking of the wax, the mixture should not be heated appreciably above 350 F., nor should it beheld at that temperature for any extended length of time.
It is important that all unreacted, or, non-alkylated,
phenol remaining in the reaction mixture, as well as aluminum chloride, be removed. This can be conveniently effected by. washing. the product; several. times with a mixture of water and an alcohol, such as butanol, preferably at elevated temperature, say 175 F. The product may then be treated with steam. This latter step will insure complete removal of the unreacted material. and also dry the product.
It will be understood that a wax-substituted phenolprepared according tov the. above procedure in which a quantity of chlorowax containing 3 atomic proportionsofv chlorine and having a chlorine content of 14% is reacted with one mol of phenol is designated as wax phenol (3-14)." Similarly, .waxphenol (3-10) and wax phenol (1-10) may also be prepared by the reaction of sufficient. amounts. of chlorinated wax, containing 10%, by weight, of chlorine, to provide 3; atomic proportions and 1 atomic proportion of chlorine per mol of phenol, respectively,. the reaction: and are. useful in the invention. 'In genera-1,, the. amount of chlorowax, containing from about. 10% to 1 8%., by weight, of chlorine, used. inthe. reaction is suffi'cient to supply between 1 and 4 atomic proportions of chlorine per mol of phenol used.
Example Iii-Complex. sodium. butoxy. salt. 0 wax phenol (3-14) containing," two equivalents of sodiumv Twohundred grains of wax phenol (3-14) (-see Example 1.4)v was blended with- 600 grams of kerosene and added to 11.5 grams of sodium (two equivalents based onthe phenol contentofthe wax phenol [3-141) in the form of a butanol solution. of sodium but'ylate. Thereaction mixture washeated' with stirring to about C. to C. over. a period of about 5 hours and filtered through Hi-Flo clay. The kerosene blend of the final product analyzed 1.2% sodium which was the theoretical sodium content for a complex butoxy sodium salt of wax phenol (3 -14) containing twoequivalents of sodium.
Example 16.-Complex magnesium methoxy salt. of wax.- beta-naphthol (3-14 containing two equivalents of magnesium One; hundred. grams of wax alkylated betamaphthola (3-14.), preparedlby' the method. given in Example. 124 for the; preparation of wax phenol. (3-14), but; using beta-naphthol in place of phenoL. was blended with. 2001 grams of a, solvent refined oilhaving a Saybolt viscosity of 3.5.; seconds at 210 F. and added. to 3.1 grams oi mag, nesium (two equivalents based, on. the beta-naphthol con.- tent of wax-betamaphthol [3-14]) in the form of a slurry of magnesium methylate in, methanol. action mixture was heated with stirring to about 150 C. over a period of about 5 hours and filtered through Hip Flo clay. The oil blend. of the final product analyzed 0.95% magnesium which approximates the theoretical magnesium content ofa complex magnesium salt of waxbeta-napht-hol (3-14") containing two equivalents of magnesium.
Example] 7.-C0mplexbarium methoxy salt-0f petroleum sulfonic acid containing two equivalents'of barium Four hundred, and twenty-six grams of an aromatic petroleum stock sulfonic acid having an acid number of 32.8 was blended. with 426 grams of a solvent refined mineral oil having. a Saybolt viscosity of 35 seconds at 210 F. and the blend added to 34.2 grams of barium. (two equivalents. based on the acid number of the petroleurn sulfonic acid) in the form of a. barium methylate solution in methanol. The reaction mixture was heated with stirring to about 160 C. over a period of about 5 hours and filtered through Hi-Flo clay. The oil blend of the final product analyzed 3.7% barium which was the theoretical barium content for. a complex methoxy barium salt of the' particular petroleum sulfonic acidcontaining two equivalents of barium.
Example 18.-Complex barium methox-y salt of wax benzene (2-12) sulfonic acid containing two equiva-. lents of barium Onehundredland'eighty-two grams of a wax-allcylated benzene, sulfonic acid-having anacid number of 77.0 was blended. with 3 64 grams of a solvent refined mineral oilhaving a Saybolt viscosity of 35 seconds at 210 F; and
added to 34.2 grams of barium (two equivalents based 7 The re-.
r the reaction is sufficient to clay. The oil blend of the product analyzed 5.34% arium which was the theoretical barium content for a complex methoxy barium salt of the wax-alkylated benzene sulfonic acid containing two equivalents of barium.
. The wax benzene sulfonic acid utilized in this example was prepared as follows:
A paraflin Wax having an average of 24 carbon atoms per molecule and a melting point of 126 F. was chlorinated at a. temperature of about 100 C. with chlorine gas until the weight of the wax had increased about 12%. The chlorowax thus obtained was then blown with nitrogen to remove any occluded chloride and hydrogen chlo ride.
A IOOO-gram portion of the chlorowax was then mixed with 500 grams of benzene in a 3-necked flask equipped with a stirrer, reflux condenser and a thermometer. The mixture was heated to a temperature of 60 C. Aluminum chloride was then added slowly over a period of two hours. The addition of aluminum chloride was accompanied by a vigorous evolution of hydrogen chloride. The temperature was then raised to a temperature of 80 C. and held there for one hour. The excess benzene was then removed by inverting the reflux condenser and heating to a temperature of 116 C. Two hundred milliliters of benzene were thus recovered. The mixture was cooled to a temperature of 60 C. and then another 1000 grams of chlorowax were added slowly. After completing the addition of this chlorowax, the temperature was raised to 100 C. and held there for one hour. The product was allowed to stand overnight at a temperature of about 60 C., and then was separated from the sludge by decantation and filtered by suction through clay.
Seventen hundred and thirt -eight grams of wax benzenethus obtained were placed in a 3-necked flask equipped with a stirrer and a thermometer and heated to a temperature of 40 C. Eight hundred and sixty-nine grams of oleum (15% S were added slowly to the wax benzene from a dropping funnel at a rate regulated to maintain the temperature below 50 C. The addition of oleum consumed about 3 hours. The mixture was then stirred for an additional hour to ensure complete reaction. The mixture was then poured into 1000 milliliters of water and subsequently 1810 grams of mineral oil were added to the mixture. The mixture thus obtained was stirred thoroughly and then allowed to stand until the water separated into a layer. The water layer was then drained ofi. The product thus obtained was approximately a 50% blend of wax benzene sulfonic acid in mineral oil and had a neutralization number of 40.7.
It will be understood that a wax benzene prepared according to the foregoing procedure in which a quantity of chlorowax containing 2 atomic proportions of chlorine and having a chlorine content of 12% is reacted with 1 mol of benzene is designated wax benzene (212). Similarly, wax benzene (3l0) and wax benzene (110) may also be prepared by the reaction of sufficient amounts of chlorinated wax, containing by weight of chlorine, to provide 3 atomic proportions and 1 atomic proportion of chlorine per mol of benzene, respectively, in the reaction and are useful in the invention. In general, the amount of chlorowax containing from about 10% to about 18% by weight of chlorine used in supply between land 4 atomic proportions of chlorine per mol of benzene used.
Example 19.Complex calcium methoxy salt of wax benzene (2-12) sulfonic acid containing two equivaalents of calcium One hundred grams of a wax alkylated benzene sulfonic acid (2--12), prepared as described in Example 18, having an acid number of 84.0 was blended with 200 grams of a solvent refined mineral oil having a Sayboltviscosity of 35 seconds at 210 F. and added to 6.0 grams of calcium (two equivalents based on the acid number of the sulfonic acid)l..in the form of a slurryv of calcium methylate in methanol. The reaction mixture was heated with stirring to about C. over a period of about 5 hours and filtered through Hi-Flo clay. The oil blend of the product analyzed 2.1% calcium which was the theoretical calcium content for a complex methoxy calcium salt of the wax-alkylated benzene sulfonic acid containing two equivalents of calcium.
Example 20.Complex sodium methoxy salt of wax benzene (212) sulfonic acid containing two equivalents of sodium Two hundred and twenty grams of a wax-alkylated benzene sulfonic acid (2-12), prepared as in Example 18, having an acid number of 80.0 was blended with 440 grams of a solvent refined mineral oil having a Saybolt viscosity of 35 seconds at 210 F. and added to 14.5 grams of sodium (two equivalents based on the acid ntunber of the sulfonic acid) in the form of a sodium methylate solution in methanol. The reaction mixture was heated with stirring to about 150 C. over a period of about 5 hours and filtered through Hi-Flo clay. The oil blend of the product analyzed 2.1% sodium which was the theoretical sodium content for a complex methoxy sodium salt of the wax alkylated benzene sulfonic acid containing two equivalents of sodium.
Example 2].Complex magnesium methoxy salt of wax benzene (2]2) sulfonic acid containing two equivalents of magnesium Two hundred grams of a wax-alkylated benzene sulfonic acid (2-l2), prepared as in Example 18, having an acid number of 77.0 was blended with 400 grams of a solvent refined mineral oil having a Saybolt viscosity of 35 seconds at 210 F. and added to 6.6 grams of magnesium (two equivalents based on the acid number of the sulfonic acid) in the form of a slurry of magnesium methylate in methanol. The reaction mixture was heated with stirring to about 150 C. over a period of about 5 hours and filtered through Hi-Flo clay. The oil blend of the product analyzed 0.95% magnesium which approximates the theoretical magnesium content of a complex methoxy magnesium salt of the wax alkylated benzene sulfonic acid containing two equivalents of magnesium.
Example 22.Complex potassium butoxy salt of wax benzene (2J2) sulfonic acid containing two equivalents of potassium Two hundred and fifty-three grams of a wax-alkylated benzene sulfonic acid (2-12), prepared as in Example 18,- having an acid number of 88.0 was blended with 506 grams of a solvent refined mineral oil having a Saybolt viscosity of 35 seconds at 210 F. and added to 44.6 grams of potassium hydroxide (two equivalents based on the acid number of the sulfonic acid) in the form of a butanol solution of the potassium hydroxide. The reaction mixture was heated with stirring to about C. over a period of about 5 hours and filtered through Hi- Flo clay. The oil blend of the product analyzed 4.0% potassium which was the theoretical potassium content for a complex butoxy potassium salt of the wax-alkylated benzene sulfonic acid containing two equivalents of potassium.
Example 23.Complex magnesium methoxy salt of dodecylphenyl phosphoric acid containing two equivalents of magnesium One hundred grams of a dodecyclphenyl phosphoric acid having an acid number of 162 was blended with 200 grams of a solvent refined mineral oil having a Saybolt viscosity of 35 seconds at 210 F. and added to 7.0 grams of magnesium (two equivalents based on the acid number of the phosphoric acid) in the form of a slurry of magnesium methylate in methanol. The reaction mixture was heated with stirring to about 150 C. over a period of about 5 hours and filtered through Hi-Flo clay.
The oil blend of the product analyzed 2.3% magnesium which was the theoretical magnesium content for. a. complex methoxy magnesium salt of the dodecylphenyl phosphoric acid containing two equivalents of magnesium.
The dodecylphenyl phosphoric acid used in this example was prepared as follows: Two thousand grams of a dodecylphenol was stirred with 321 grams of phosphorus pentoxide' and heated to 150 C. The reaction mixture was stirred at 150 C. for 3 hours and. then filtered through Hi-Flo clay to give the finished dodecylphenyl phosphoric acid.
Example 24.-Cm lex magnesium methoxy salt of wax phenyl dithiophosphoric acid containing threeequivalents of magnesium Two hundred grams of a wax phenyl dithiophosphoric acid having an acid number of 46 was blended with 400 grams of a solvent. refined. mineral oil having a. Saybolt viscosity of35 seconds at 210" F. and added to 610 grams of magnesium (three equivalents based on the acid number of the dithiophosphoric acid) in the form of. a slurry of magnesium methylate in methanol. The reaction mixture was heated with stirring to about 150 C. over a period of about hours and filtered through Hi- Flo clay. The oil blend of the product analyzed 0.9% magnesium which approximates the. theoretical magnesium content of a complex methoxy magnesium salt of the wax phenyl dithiophosphoric acid containing three equivalents of magnesium.
The Wax phenyl dithiophosphoric acid used in this example was prepared as follows. An oil blend containing 387 gramsof wax phenol (4-18) and 77.4 grams of the mineral oil describedv in Example 24 was stirred with 55.5 grams of phosphorus pentasulfide. The temperature of the reaction mixture was raised to 170 C.. and held there for 5 hours. The final product was a wax phenyl dithiophosphoric acid having an acid number of about 46.
EVALUATION OF PRODUCTS Test results showing the utility of the complex metal alkoxy salts as stabilizing agents for fuels and oils are presented in Tables I to IV. The effectiveness of the salts as color stabilizers and sludge inhibitors in a typical fuel oil in storage is shown by the data in Table I. It will be noted that sedimentation was substantially inhibited by the incorporation of the complex salt products in the oil and particularly so by the salts. containing the higher equivalents of metal. The fuel used was comprised of 70% catalytically cracked fuel and 30% straight 12 1 The test used was that described in A. S. T. M. Standards on Petroleum Products and Lubricants, September 1945, Test No. D665-44T. In this test, 350 cc. of test oil' are placed in a tall form (127 x 70 mm.) beaker and a cylindrical polished steel specimen is suspended and soaked in the oil under test at 140 F; for 30 minutes. Thirty cc. of distilled water are added and the mixture is stirred at 1000'R. P. M. After 48 hours, the steelspecimen is removed and examined for evidence of rust thereon. The specifications require the complete absence of rust, even pin points of rust, and the absence of dark stain. The fuel used was the same as that used in the fuel storage tests of Table I. The products have also been tested as anti-rust agents in gasoline and'lubricating. oil and found to give good results.
TABLE. II.-A. S. '1. MI. RUST. TEST leum Sultonic Acid. (Ex. 17).
The ability of the compounds of theinvention aslubricating oil detergents was tested by the Lauson D-4A Detergency' Test, Thistest determines. the effectiveness of the lubricating oil in preventing foulingas measuredzby the cleanliness of rings, lands, ring grooves and piston; skirts. A single cylinder, 4-cycle, liquid cooled. Lauson engine with splash lubrication and having a. copper-lead bearing is used. The operating conditions areasfollows.-
Oil temperature 225' F. Jacket temperature 275 F. Speed 1825 RzP; M. Brake load 1.6 l-F. P:
One-half throttle. 13-1 air-fuel rat-i0. Oil added every hours- (one-gallon sample used).
The fuel used is a controlled. Mobilgas Special. type: blend gasoline (40% thermal, catalytically cracked and 30% straight. run, plus 2.5 cc. TEL/gal). duration of. the test is l00hours.
run fuel and had a bOlllIlg range of 0 F. to 0 F. 50 An SAE 20 solvent-refined Pennsylvania oil was used TABLE I Six Weeks Storage Metal Concn., F. Compound Added Equiva- Lb./1,000
lents Bbls.
N. P. A. Sediment,
MgJl.
Non 0 8 Complex Magnesium Methoxy Salt of "Facoil CB (Exam- 2 5 Complex Magnesium Methoxy Salt of Facoil CB" (Exam- 4 p 50 D6 9 Complex Magnesium Methoxy Salt of Facoil CB" (Examp e 6 50 D6 9 Complex Calcium-Methoxy Salt of Facoil CB" (Example 5) 2 100 8 22 Complex Zinc Methoxy Salt of N aphthenic Acid (Example 7 2 50 L236 13. Complex Aluminum Isopropyl Salt of Naphthenlc Acid I (Example 10).-. 3 50 8 42 Complex Barium Methoxy Salt of Naphthenic Acid (Exampic 11) 2 50 8 15 Complex Magnesium Methoxy Salt of Wax Phenol (Example 14) 2 50 8 29 Complex Sodium Methoxy Salt of Wax Phenol (Example 15) 2 113% 27 Complex Barium Methoxy Salt of Petroleum Suliom'c Acid (Example 17).. 2 100 L7 24 Table 11' shows the effectiveness of the compounds of the invention as anti-rust agents in a typical fuel oil. 7 erence oil' as the reference oil and various oiI blends of. the refand the compounds of the invention were The for various 13 tested in the engine separately. At the end of each run, e piston of the engine was examined and rated for lacquer and sludge deposits, an E. C. (Engine Cleanliness) Rating of 100 indicating a perfectly clean piston and lower ratings indicating increasing amounts of deposits. The test results are presented in Table III.
TABLE III.LAUSON D4 PISTON DETERGENCY TEST Metal Concn., E.C
Compound Added equiva- Wt. Rating lents percent K None 62 Complex Magn Methoxy Salt of Facoil CB (Ex. 1) 2 1 67 Complex Magnesium Methoxy Salt of Facoil CB (Ex. 2) 3 1 74 Complex Zinc Methoxy Salt of Naphthenlc Acid (Ex. 7) 2 2 76 Complex Magnesium Methoxy Salt of Naphthenic Acid (Ex. 12) 2 1 79 Complex Magnesium Methoxy Salt of Naphthenic Acid (Ex. 13) 3 1 77 Complex Magnesium Methoxy Salt of N aphthenic Acid 4 1 SR Complex Magnesium Methoxy Salt of Wax Phenol (Ex. 14) 2 1 77 Complex Magnesium Methoxy Salt of Wax- B-Naphthol (Ex. 16) 2 1 76 Complex Barium Methoxy Salt of Wax Benzene Sulfonic Acid (Ex. 1 2 1 77 Complex Calcium Methoxy Salt of Wax Benzene Sulfonic Acid (Ex. 19) 1 87 Complex Sodium Methoxy Salt of Wax Benzene Sulfonic Acid (Ex. 20) 2 1 84 Complex Magnesium Methoxy Salt of Wax I Benzene Snlfonic Acid (Ex. 21) 2 l 86 Complex Potassium Eutoxy Salt of Wax Benzene Sulfonic Acid (Ex. 22) 2 1 80 Complex Magnesium Methoxy Salt of Dodecyl Phenyl Phosphoric Acid (Ex. 23) 2 1 75 Complex Magnesium Methoxy Salt of Wax Phenyl Dithiophosphoric Acid (Ex. 24) 3 l 73 The anti-oxidant character of the compounds of the invention in lubricating oil was demonstrated by means of the Lauson 0S2 Oxidation Stability Test. In this test a Lauson single cylinder, 4-cycle, liquid cooled engine with splash lubrication and a copper-lead bearing is operated at an oil temperature of 270 F. and a jacket temperature of 212 F. at 1825 R. P. M. at /2 throttle and a 13 to l air-fuel ratio for 100 hours, oil being added every 20 hours. The fuel used is a controlled Mobilgas Special type blend (40% thermal, 30% catalytically cracked and 30% straight run, plus 2.5 cc. TEL/gal.).
As in the D4-A test, an SAE 20 solvent-refined Pennsylvania oil was used as the reference oil and various oil blends of the reference oil and the compounds of the in vention were tested in the engine separately. The copper-lead engine bearing was accurately weighed before and after each test run to determine the Weight loss thereof resulting from corrosion. The results of the several tests are given in Table IV.
TABLE IV.LAUSON 0S2 OXIDATION STABILITY TEST Metal Concn., Bearing Compound Added equiva- Wt. Wt.
rents percent loss, mg.
None 0 0 450 Complex Zinc Methoxy Salt of Facoil CB" (Ex. 2) 3 0. 75 82 Complex Zinc Methoxy Salt of Naphthenic Acid (Ex. 7) 2 1.0 87 Complex Zinc Methoxy Salt of Naphthenic Acid (Ex. 8) 3 1.0 61 Complex Zinc Methoxy Salt of Naphthenic Acid (Ex. 9) 4 0. 49
- Complex Magnesium Methoxy Salt of Naphthenic Acid (Ex. 12) 2 1. 0 400 Complex Magnesium Methoxy Salt of Wax Phenyl Dithiophosphoric Acid (Ex. 24) -t 3 1.0 130 As demonstrated herein, the complex metal alkoxy salts of the invention, which are actually concentrated solutions containing from about 20% to about 50% of the complex metal salts, are effective improving agents petroleum oil fractions in concentrations ranging from as little as 0.01% (i. e., 100 parts per million) as anti-rust agents in gasoline to from 0.5% to 2.0% as anti-oxidants and detergents in lubricating oils. However, the complex salts may be used in greater or lesser amounts than shown herein depending upon the particular oil fraction and the use for which it is intended. Thus, amounts of from as little as 0.001% up to about 10% comprise the eifective concentration range.
The petroleum oil fractions may, of course, contain other addition agents along with the complex metal alkoxy salts of the invention, such as viscosity index improvers, extreme pressure agents, and pour point depres sants, which it may be found desirable to add to said fraction.
Although the complex salts of this invention are intended primarily for use as additives for various petroleum oil fractions, they also find application in the manufacture of detergent soaps, dispersants, etc.
Although the principles of the invention have been i1- lustrated herein by means of certain specific examples and tests, it is not intended that the scope of the invention be limited thereby, but only as indicated in the appended claims.
What is claimed is:
1. A mineral oil fraction containing a minor proportion, sufiicient to stabilize said oil fraction against oxidation, of a complex alkoxy metal salt of an organic acid prepared by the method which comprises: reacting a hydrocarbon solution containing 1 equivalent proportion of a hydrocarbon-soluble organic acid having a molecular weight of from about 200 to about 1000 with from at least about 2 and up to about 6 equivalent proportions of a metal alcoholate derived from an aliphatic monohydroxy alcohol having from 1 up to about 20 carbon atoms and the metal constituent of which is selected from the metals of Groups I and II of Mendeleetfs Periodic Table of the Elements, at a temperature of from about 50 C. to about 200 C., the complex salt so produced having combined therein about 2 equivalents of metal per equivalent of organic acid where the metal of the metal alcoholate used in the reaction is a metal of group I and from about 3 to about 6 equivalents of metal where the metal of the metal alcoholate used in the reaction is a metal of group II.
2. A mineral lubricating oil containing a minor proportion, sufficient to stabilize said oil fraction against oxidation, of a complex alkoxy metal salt of an organic acid prepared by the method which comprises: reacting a hydrocarbon solution containing 1 equivalent proportion of a hydrocarbon-soluble organic acid having a molecular weight of from about 200 to about 1000 with from at least about 2 and up to about 6 equivalent proportions of a metal alcoholate derived from an aliphatic monohydroxy alcohol having from 1 up to about 20 carbon atoms and the metal constituent of which is selected from the metals of Groups I and II of Mendeleetfs Periodic Table of the Elements, at a temperature of from about 50 C. to about 200 C., the complex salt so produced having combined therein about 2 equivalents of metal per equivalent of organic acid where the metal of the metal alcoholate used in the reaction is a metal of group I and from about 3 to about 6 equivalents of metal Where the metal of the metal alcoholate used in the reaction is a metal of group II.
3. A mineral lubricating oil containing a minor proportion, sufficient to stabilize said oil against oxidation, of a complex methoxy magnesium salt' of a naphthenic acid prepared by the method which comprises: reacting an oil solution containing 1 equivalent proportion of an oil-soluble naphthenic acid having a molecular Weight of from about 200 to about 1000 with from at least about 2 and up to about 6 equivalents of magnesium methylate, at a temperature of from about 50 C. to about 200 C., the complex salt so produced having combined therein from about 3 to about 6 equivalents of magnesium per equivalent of naphthenic acid.
molecular weight of from about 200 to about 1000 with from at least about 2 and up to about 6 equivalent proportions of potassum methylate, at a temperature of from about 50 C. to about 200 C., the complex salt so produced having combined therein about 2 equivalents of potassium per equivalent of wax-benzene sulfonic acid.
5. A fuel oil containing a minor proportion, sufficient to stabilize said fuel oil against oxidation, of a complex alkoxy metal salt of an organic acid prepared by the method which comprises: reacting a hydrocarbon solution containing 1 equivalent proportion of a hydrocarbon soluble organic acid having a molecular weight of from about 200 to about 1000' with from at least about 2 and up to about 6' equivalent proportions of a metal alcoholate derived from an aliphatic monohydroxy alcohol hav ing from 1 up to about 20 carbon atoms and the metal constituent ofwhich is selected from the-metals of Groups I and II of'Mencleleefifs Periodic Table of the Elements, at a temperature of from about 50 C. to about 200C, the complex salt so produced having. combined therein about 2 equivalents of metal per equivalent of. organic acid where the metal of the metal aleoholate used in the reaction is a metal of group I and from about 3 to about 6 equivalents of metal where the metal of the metal alcoholate used in the reaction is a metal of group II.
6. A fuel oil containing a minor proportion, suflicient to stabilize said oil against oxidation, of a complex methoxy magnesium salt of a tall oil acid prepared by the method which comprises: reacting an oil. solution containing 1 equivalent proportion of an oil-soluble tall oil acid having a molecular weight of from about 200 to about 1000 with from at least about 2 and up to about 6 equivalent proportions of magnesium methylate, at a temperature of from about 50 C. to about 200 C., the complex salt so produced having combined therein from about 3 to about 6 equivalents of magnesium per equivalent of tall oil acid.
7. A fuel oil containing a minor proportion, sufficient to stabilize said oil against oxidation, of a complex rnethoxy zine salt of a naphthenic acid prepared by the method which comprises: reacting an oil solution containing 1 equivalent proportion of an oil-soluble naphthenic acid having a molecular weight of from about 200 to about 1000 with from at least about 2 and up to about 6 equivalent proportions of zinc methylate, at a temperature of from about 50 C. to about 200 C., the complex salt so produced having combined therein from about 3 to about 6 equivalents of zinc per equivalent of naphthenic acid.
8. A gasoline containing a minor proportion, sufficient to stabilize said gasoline against oxidation and inhibit the formation of rust therein, of a complex alkoxy metal salt of an organic acid and prepared by the method which comprises: reacting a hydrocarbon solution containing 1 equivalent proportion of a hydrocarbon-soluble organic acid having a molecular weight of from about 200 to about 1000 with from at least about 2 and up to about 6 equivalent proportions of a metal alcoholate derived from an aliphatic monohydroxy alcohol having from 1 up to about 20 carbon atoms and the metal constituent of which is selected from the metals of Group I and II of Mendeleeffs Periodic Table of the Elements, at a tem perature of from about 50 C. to about 200 C., the complex salt so produced having combined therein about 2 equivalents of metal per equivalent of organic acid where the metal of the metal alcoholate used in the reaction is a metal of group I and from about 3 to about 6 equivalents of metal where the metal of the metal alcoholate used in the reaction is a metal of group II.
9. A gasoline containing a minor proportion, sufficient to stabilize said gasoline against oxidation and inhibit the formation of rust therein, of a complex methoxy magnesium salt of a tall oil acid prepared by the method which comprises: reacting an oil solution containing 1 equivalent proportion of an oil-soluble tall oil acid having a molecular weight of from about 200 to about 1000 with from at least about 2 and up to about 6 equivalent proportions of magnesium methylate, at a temperature of from about 50 C. to about 200 C., the complex salt so produced having combined therein from about 3 to about 6 equivalents of magnesium per equivalent of tall oil acid.
ReferencesCited' in the file of this patent UNITED STATES PATENTS 2,113,243 Scottet a1. Apr. 5, 1938 2,225,197 Stagner Dec. 17, 1940 2,469,041 Jones May 3, 1949 2,528,803 Unkefer Nov. 7, 1950 2,610,982. Hutcheson Sept. 16, 1952 2,582,833 Hunn Jan. 15, 1952 2,585,520 Van Ess et a1. Feb. 12, 1952 OTHER REFERENCES Richters Organic Chemistry Vol. 11 3rd Ed., Nordemann Pub: Co, New York, N. Y., page 350 (1939).
Steele-4r. America-n Chem. Soc-Vol 44, page 1337 (1922).
Sloane-J r. Oil and Colour Chem.Vol. 5, pages 323- 324 (1922).
Hasselstrom et al., Jr. American Chem. Soc. vol. 61 (1939) page 1229.
Fieser and Fieser, Org. Chem. 2nd Ed., D. C. Heath and Co., Boston, Mass, page 126.
Claims (1)
1. A MINERAL OIL FRACTION CONTAINING A MINOR PROPORTION, SUFFICIENT TO STABILIZE SAID OIL FRACTION AGAINST OXIDATION, OF A COMPLEX ALKOXY METAL SALT OF AN ORGANIC ACID PREPARED BY THE METHOD WHICH COMPRISES: REACTING A HYDROCARBON SOLUTION CONTAINING 1 EQUIVALENT PROPORTION OF A HYDROCARBON-SOLUBLE ORGANIC ACID HAVING A MOLECULAR WEIGHT OF FROM ABOUT 200 TO ABOUT 1000 WITH FROM AT LEAST ABOUT 2 AND UP TO ABOUT 6 EQUIVALENT PROPORTIONS OF A METAL ALCOHOLATE DERIVED FROM AN ALIPHATIC MONOHYDROXY ALCOHOL HAVING FROM 1 UP TO ABOUT 20 CARBON ATOMS AND THE METAL CONSTITUENT OF WHICH IS SELECTED FROM THE METALS OF GROUPS I AND II OF MENDELEEFF''S PERIODIC TABLE OF THE ELEMENTS, AT A TEMPERATURE OF FROM ABOUT 50*C. TO ABOUT 200*C., THE COMPLEX SALT SO PRODUCED HAVING COMBINED THEREIN ABOUT 2 EQUIVALENTS OF METAL PER EQUIVALENT OF ORGANIC ACID WHERE THE METAL OF THE METAL ALCOHOLATE USED IN THE REACTION IS A METAL OF GROUP I AND FROM ABOUT 3 TO ABOUT 6 EQUIVALENTS OF METAL WHERE THE METAL OF THE METAL ALCOHOLATE USED IN THE REACTION IS A METAL OF GROUP II.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US348117A US2851417A (en) | 1953-04-10 | 1953-04-10 | Complex alkoxy metal salts of organic acids and lubricating and fuel compositions thereof |
GB6896/54A GB774119A (en) | 1953-04-10 | 1954-03-09 | Complex alkoxy metal salts of organic acids and lubricating and fuel compositions thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US348117A US2851417A (en) | 1953-04-10 | 1953-04-10 | Complex alkoxy metal salts of organic acids and lubricating and fuel compositions thereof |
Publications (1)
Publication Number | Publication Date |
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US2851417A true US2851417A (en) | 1958-09-09 |
Family
ID=23366710
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US348117A Expired - Lifetime US2851417A (en) | 1953-04-10 | 1953-04-10 | Complex alkoxy metal salts of organic acids and lubricating and fuel compositions thereof |
Country Status (2)
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US (1) | US2851417A (en) |
GB (1) | GB774119A (en) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3014868A (en) * | 1958-04-24 | 1961-12-26 | Socony Mobil Oil Co Inc | Lubricating oil compositions containing complex metal salts of alkylphenolaldehyde condensation products |
US3021280A (en) * | 1956-12-17 | 1962-02-13 | Continental Oil Co | Method of dispersing barium hydroxide in a non-volatile carrier |
US3061419A (en) * | 1958-10-02 | 1962-10-30 | Continental Oil Co | Fuel additive for jet propulsion engines |
US3088815A (en) * | 1958-03-27 | 1963-05-07 | Sinclair Research Inc | Fuel oil |
US3131677A (en) * | 1959-01-14 | 1964-05-05 | British Petroleum Co | Fuels for internal combustion piston engines and to the operation of such engines |
US3264075A (en) * | 1962-07-06 | 1966-08-02 | Mobil Oil Corp | Metal salts of succinamic acids in distillate fuel oil |
US3320042A (en) * | 1962-11-21 | 1967-05-16 | Sun Oil Co | Color stable fuel oil |
US3406115A (en) * | 1965-04-02 | 1968-10-15 | Dow Chemical Co | Method of lessening friction in moving oil-base liquids |
US3471403A (en) * | 1967-03-07 | 1969-10-07 | Lubrizol Corp | Basic metal carboxylate complex |
US3635686A (en) * | 1969-05-19 | 1972-01-18 | Mobil Oil Corp | Mineral oil compositions metal alkyl ester tetrapropenylsuccinates |
US3791804A (en) * | 1969-10-10 | 1974-02-12 | Standard Oil Co | Fuel and lubricating oil additives transition metal complexes |
US3791805A (en) * | 1969-10-10 | 1974-02-12 | Standard Oil Co | Transition metal complexes as fuel and motor oil additives |
US3856688A (en) * | 1972-07-25 | 1974-12-24 | Us Agriculture | Ether-containing dibasic fatty acid metal soap thickened greases |
US5266080A (en) * | 1989-10-11 | 1993-11-30 | The Standard Oil Company | Methanol fuel containing flame luminosity agent |
US5290825A (en) * | 1985-05-17 | 1994-03-01 | Lazar Warren G | Composition and method for inhibiting the cure of cyanoacrylate adhesives and cure inhibited cyanoacrylate adhesive compositions |
US5800731A (en) * | 1991-11-28 | 1998-09-01 | Rwe-Dea Aktiengesellschaft Fur Mineraloel Und Chemie | Homogeneous electroviscous fluids using aluminum compounds |
US20040065002A1 (en) * | 2001-02-01 | 2004-04-08 | Shibin Hu | Fuel oil additive and fuel oil products containing the fuel oil additive |
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US2113243A (en) * | 1935-09-25 | 1938-04-05 | Du Pont | Production of abietic alcohol |
US2225197A (en) * | 1939-05-15 | 1940-12-17 | Stanger Bert Allen | Addition and stabilizer agent for lubricating oils and hydrocarbon liquids |
US2469041A (en) * | 1946-09-02 | 1949-05-03 | Standard Vacuum Oil Company | Methods for preparing aluminum soaps and certain classes of useful compositions containing aluminum soaps |
US2528803A (en) * | 1947-08-01 | 1950-11-07 | Harshaw Chem Corp | Preparation of metallic soaps |
US2582833A (en) * | 1950-07-12 | 1952-01-15 | Sherwin Williams Co | Method for the preparation of aluminum and magnesium soaps |
US2585520A (en) * | 1948-12-03 | 1952-02-12 | Shell Dev | Lubricating compositions containing highly basic metal sulfonates |
US2610982A (en) * | 1950-02-11 | 1952-09-16 | Texas Co | Manufacture of magnesium salts of high molecular weight alkylated hydroxy aromatic copounds and their use in lubricating oils |
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US2113243A (en) * | 1935-09-25 | 1938-04-05 | Du Pont | Production of abietic alcohol |
US2225197A (en) * | 1939-05-15 | 1940-12-17 | Stanger Bert Allen | Addition and stabilizer agent for lubricating oils and hydrocarbon liquids |
US2469041A (en) * | 1946-09-02 | 1949-05-03 | Standard Vacuum Oil Company | Methods for preparing aluminum soaps and certain classes of useful compositions containing aluminum soaps |
US2528803A (en) * | 1947-08-01 | 1950-11-07 | Harshaw Chem Corp | Preparation of metallic soaps |
US2585520A (en) * | 1948-12-03 | 1952-02-12 | Shell Dev | Lubricating compositions containing highly basic metal sulfonates |
US2610982A (en) * | 1950-02-11 | 1952-09-16 | Texas Co | Manufacture of magnesium salts of high molecular weight alkylated hydroxy aromatic copounds and their use in lubricating oils |
US2582833A (en) * | 1950-07-12 | 1952-01-15 | Sherwin Williams Co | Method for the preparation of aluminum and magnesium soaps |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3021280A (en) * | 1956-12-17 | 1962-02-13 | Continental Oil Co | Method of dispersing barium hydroxide in a non-volatile carrier |
US3088815A (en) * | 1958-03-27 | 1963-05-07 | Sinclair Research Inc | Fuel oil |
US3014868A (en) * | 1958-04-24 | 1961-12-26 | Socony Mobil Oil Co Inc | Lubricating oil compositions containing complex metal salts of alkylphenolaldehyde condensation products |
US3061419A (en) * | 1958-10-02 | 1962-10-30 | Continental Oil Co | Fuel additive for jet propulsion engines |
US3131677A (en) * | 1959-01-14 | 1964-05-05 | British Petroleum Co | Fuels for internal combustion piston engines and to the operation of such engines |
US3264075A (en) * | 1962-07-06 | 1966-08-02 | Mobil Oil Corp | Metal salts of succinamic acids in distillate fuel oil |
US3320042A (en) * | 1962-11-21 | 1967-05-16 | Sun Oil Co | Color stable fuel oil |
US3406115A (en) * | 1965-04-02 | 1968-10-15 | Dow Chemical Co | Method of lessening friction in moving oil-base liquids |
US3471403A (en) * | 1967-03-07 | 1969-10-07 | Lubrizol Corp | Basic metal carboxylate complex |
US3635686A (en) * | 1969-05-19 | 1972-01-18 | Mobil Oil Corp | Mineral oil compositions metal alkyl ester tetrapropenylsuccinates |
US3791804A (en) * | 1969-10-10 | 1974-02-12 | Standard Oil Co | Fuel and lubricating oil additives transition metal complexes |
US3791805A (en) * | 1969-10-10 | 1974-02-12 | Standard Oil Co | Transition metal complexes as fuel and motor oil additives |
US3856688A (en) * | 1972-07-25 | 1974-12-24 | Us Agriculture | Ether-containing dibasic fatty acid metal soap thickened greases |
US5290825A (en) * | 1985-05-17 | 1994-03-01 | Lazar Warren G | Composition and method for inhibiting the cure of cyanoacrylate adhesives and cure inhibited cyanoacrylate adhesive compositions |
US5266080A (en) * | 1989-10-11 | 1993-11-30 | The Standard Oil Company | Methanol fuel containing flame luminosity agent |
US5800731A (en) * | 1991-11-28 | 1998-09-01 | Rwe-Dea Aktiengesellschaft Fur Mineraloel Und Chemie | Homogeneous electroviscous fluids using aluminum compounds |
US20040065002A1 (en) * | 2001-02-01 | 2004-04-08 | Shibin Hu | Fuel oil additive and fuel oil products containing the fuel oil additive |
US20070266622A1 (en) * | 2001-02-01 | 2007-11-22 | Jinzhou Shengtong Chemical Co., Ltd. | Fuel oil additive and fuel oil products containing said fuel oil additive |
Also Published As
Publication number | Publication date |
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GB774119A (en) | 1957-05-08 |
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