US3652644A - Quaternary ammonium salts of esters of salicylic acid as rust inhibitors - Google Patents
Quaternary ammonium salts of esters of salicylic acid as rust inhibitors Download PDFInfo
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- US3652644A US3652644A US717971A US3652644DA US3652644A US 3652644 A US3652644 A US 3652644A US 717971 A US717971 A US 717971A US 3652644D A US3652644D A US 3652644DA US 3652644 A US3652644 A US 3652644A
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- US
- United States
- Prior art keywords
- quaternary ammonium
- salicylic acid
- percent
- arquad
- esters
- Prior art date
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- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 title abstract description 30
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 title abstract description 15
- 229960004889 salicylic acid Drugs 0.000 title abstract description 15
- 150000003242 quaternary ammonium salts Chemical class 0.000 title abstract description 9
- 239000003112 inhibitor Substances 0.000 title abstract description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title description 10
- 150000002148 esters Chemical class 0.000 title description 7
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000000295 fuel oil Substances 0.000 description 14
- 125000001453 quaternary ammonium group Chemical group 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 239000003921 oil Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000003760 tallow Substances 0.000 description 8
- IPNFHEWNDOORKH-UHFFFAOYSA-N 6-methylheptyl 2-hydroxybenzoate Chemical compound CC(C)CCCCCOC(=O)C1=CC=CC=C1O IPNFHEWNDOORKH-UHFFFAOYSA-N 0.000 description 7
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical class CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 125000003438 dodecyl group Chemical class [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 5
- 125000002347 octyl group Chemical class [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 125000002889 tridecyl group Chemical class [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])[H] 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 244000068988 Glycine max Species 0.000 description 3
- 235000010469 Glycine max Nutrition 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- -1 alkyltrimethylammonium chlorides Chemical class 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- NHLHASWXBVULGU-UHFFFAOYSA-N hexadecyl 2-hydroxybenzoate Chemical class CCCCCCCCCCCCCCCCOC(=O)C1=CC=CC=C1O NHLHASWXBVULGU-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 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 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 101100484930 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) VPS41 gene Proteins 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- UMUPSVNXWTUCEE-UHFFFAOYSA-N calcium;octyl 2-hydroxybenzoate Chemical compound [Ca].CCCCCCCCOC(=O)C1=CC=CC=C1O UMUPSVNXWTUCEE-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- ZCPCLAPUXMZUCD-UHFFFAOYSA-M dihexadecyl(dimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCC ZCPCLAPUXMZUCD-UHFFFAOYSA-M 0.000 description 1
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 1
- 239000004664 distearyldimethylammonium chloride (DHTDMAC) Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229960003921 octisalate Drugs 0.000 description 1
- WCJLCOAEJIHPCW-UHFFFAOYSA-N octyl 2-hydroxybenzoate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1O WCJLCOAEJIHPCW-UHFFFAOYSA-N 0.000 description 1
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
Definitions
- This invention relates to chemical compounds and to compositions containing said compounds.
- the chemical compounds of this invention are quaternary ammonium salts of esters of salicylic acid. These compounds have been found to exhibit high activity as rust inhibitors when present in a minor concentration in a hydrocarbon oil, such as fuel oil.
- the compounds of this invention are particularly eifective rust inhibitors when present in a hydrocarbon oil which is in contact with a water phase or is otherwise in a condition conducive to rust formation.
- the quaternary ammonium salts of esters of salicylic acid of this invention can be selected from compounds having the general structure wherein:
- R is a normal or iso alkyl, normal or iso alkenyl, aralkyl or cycloalkyl substituent containing 1 to 22 carbon atoms and can be substituted with substituents such as nitrogen, phosphorus, sulfur or oxygen,
- R may be absent or is a normal or iso alkyl, nor-mal or iso alkenyl, aralkyl or cycloalkyl substituent containing 1 to 22 carbon atoms and can be substituted with substituents such as nitrogen, phosphorus, sulfur or oxygen.
- R,,, R R and R are each a normal or iso alkyl, normal or iso alkenyl, aralkyl or cycloalkyl substituent containing 1 to 22 carbon atoms which can be substituted with substituents such as oxygen, nitrogen, phosphorus, or sulfur, at least one of said groups containing at least four carbon atoms,
- N is nitrogen and can be the nitrogen of a heterocyclic nitrogen-containing ring such as imidazoline, pyridine, thiazine or piperazine, in which case 'R and R are members of the heterocyclic ring and at least one of the substituents R and R contains at least four carbon atoms,
- O is oxygen
- R R R and R generically encompass oxygen-containing substituents, compounds wherein R R R and R are hydrogen substituents which are free of hydroxyl groups with or without an ether polymer thereof unexpectedly possess dilferent utility from compounds wherein R,,, R R, and R have an hydroxyl group with or without an ether polymer thereof, and the latter group of compounds is covered specifically in application Ser. No. 476,666, filed Aug. 2, 1965, now Pat. No. 3,419,- 366.
- Preferred compounds of this invention include quaternary ammonium salts of octyl, dodecyl, tridecyl or hexadecyl salicylates where the quaternary ammonium group is selected from the following:
- Some commercial starting materials which can be utilized as the quaternary ammonium base are Arquad C, Arquad S, Arquad T, Arquad 12, Arquad 18, Arquad 2C, Arquad 2S, Arquad 2HT, Arquad T-2C, and Arquad S- 2C, all of which are commercial products.
- Arquad C, Arquad S, Arquad T, Arquad 12, and Arquad 18 are alkyltrimethylammonium chlorides wherein the symbols C, S and T indicate that the alkyl substituent comes from coco, soya bean oils or fats, or tallow, respectively, while in A'rquad 12 and Arquad 18 the alkyl substituent is essentially pure dodecyl or octadecyl, respectively.
- Arquad 2C, Arquad 2S and Arquad 2HT are dialkyldimethylammonium chlorides wherein the alkyl substituent is coco, soya' and hydrogenated tallow, respectively, and Arquad T2C and Arquad S-2C are mixtures of the indicated alkyltrimethylammonium chlorides and dialkyldimethylammonium chlorides.
- Salicylic acid is a convenient starting material in the preparation of the quaternary ammonium salicylates of this invention.
- Salicylic acid contains an hydroxyl radical and a carboxylic acid radical at ortho positions on a benzene ring.
- the reactant containing the quaternary ammonium cation is reacted with the hydroxyl radical of the salicylic acid rather than with the carboxylic radical so that the salt formed is a quaternary ammonium phenate rather than a quaternary ammonium carboxylate.
- the carboxylic acid radical is considerably more acidic and therefore more reactive with the quarternary ammonium cation than is the hydroxyl radical and in order for the quaternary ammonium cation to react with the hydroxyl radical rather than with the carboxylic acid radical the salicylic acid must be esterified prior to the reaction thereof with the quaternary ammonium compound. Therefore, the preparation of the quaternary ammonium salt of this invention is a two-step process in which the order of performance of the steps is critical, i.e. the salicylic acid starting material is first esterified by reaction with an alcohol and only after esterification is it converted to a quaternary salt.
- the more reactive carboxylic acid radical is first reacted with an alcohol to form an ester.
- a commercial quaternary ammonium chloride is converted to the corresponding quaternary ammonium hydroxide.
- the quaternary ammonium hydroxide is then reacted with the hydroxyl radical of the ester of salicylic acid to form a quarternary ammonium salt of salicylic acid ester.
- isooctyl salicylate contains 71.9 percent carbon, 8.8 percent hydrogen, and 19.2 percent oxygen, and has a molecular weight of 250.
- Step 2. Preparation of di(hydrogenated tallow)dimethylammonium isooctyl salicylate from isooctyl salicylate.
- di(hydrogenated tallow) dimethylammonium chloride was dissolved in 200 milliliters of benzene.
- the composition of the 75 weight percent of the paste which consisted of di(hydrogenated tallow)dimethylammonium chloride was 75 percent by weight distearyldimethylammonium chloride, 1 percent by weight dioctadecenyldimethylammonium chloride, and 24 percent by weight dihexadecyldimethylammonium chloride.
- a warm solution containing 10.1 grams (0.153 mole) of potassium hydroxide (assay 85%) in absolute ethanol was added to the benzene solution.
- the precipitated potassium chloride was removed by filtration.
- To the filtrate was added 38.4 grams (0.153 mole) of isooctyl salicylate.
- Solvent was removed.
- the calculated nitrogen content of di(hydrogenated tallow)dimethylammonium octyl salicylate is 1.75 percent.
- Tests were conducted to illustrate the high rust arresting effectiveness of the compounds of this invention as compared to a control fuel oil sample without additives and as compared to a control fuel oil sample containing calcium octyl salicylate.
- a test solution was prepared by placing a mixture of 80 percent by volume of fuel oil or fuel oil plus additive with percent by volume of distilled water into a 4-ounce jar and shaking vigorously for one minute.
- a clean specimen of SAE 1020 steel was immersed nearly vertically into 4 each test jar and the jar was stored at room temperature. The steel specimens were inspected and rated after 1 day, 3 days and 7 days, respectively, and the results of the inspection are shown in the following table.
- the quaternary ammonium salicylates of this invention are oil soluble and can be present in hydrocarbon oils over a wide range of concentrations. For example, they can be generally present in hydrocarbon oils over a concentration range of about 0.002 up to about 10 percent by weight, the higher region of the range being especially useful when preparing a concentrate, or preferably, over a concentration range of about 0.005 to about 0.1 percent by weight.
- the quaternary ammonium salicylates of this invention are especially useful in fuel oils, such as blends of straight run and catalytically cracked fuel oils.
- the compounds of this invention are primarily useful for rust inhibition in oils which are in contact with an aqueous phase.
- a quaternary ammonium phenate-type salt of octyl, dodecyl, tridecyl or hexadecyl salicylate wherein of the four groups on the quaternary ammonium radical two or three are methyl groups and the remaining are derived from coco, soya bean oils or fats or tallow.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
QUATERNARY AMMONIUM SALTS OF ESTERS OF SALICYLIC ACID ARE USED AS RUST INHIBITORS IN HYDROCARBON OIL.
Description
United States Patent 3,652,644 QUATERNARY AMMONIUM SALTS OF ESTERS OF SALICYLIC ACID AS RUST INHIBITORS Elizabeth L. Fareri, Pittsburgh, Robert J. McGuire, Monroeville, and Harold O. Strange, Penn Hills Township, Allegheny County, Pa., assignors to Gulf Research & Development Company, Pittsburgh, Pa.
No Drawing. Original application Aug. 2, 1965, Ser. No. 476,717, now Patent No. 3,433,607, dated Mar. 18, 1969. Divided and this application Apr. 1, 1968, Ser.
Int. Cl. C07c 101/42 US. Cl. 260-471 R 4 Claims ABSTRACT OF THE DISCLOSURE Quaternary ammonium salts of esters of salicylic acid are used as rust inhibitors in hydrocarbon oil.
This application is a division of Ser. No. 476,717, filed Aug. 2, 1965, now Pat. No. 3,433,607.
This invention relates to chemical compounds and to compositions containing said compounds.
The chemical compounds of this invention are quaternary ammonium salts of esters of salicylic acid. These compounds have been found to exhibit high activity as rust inhibitors when present in a minor concentration in a hydrocarbon oil, such as fuel oil. The compounds of this invention are particularly eifective rust inhibitors when present in a hydrocarbon oil which is in contact with a water phase or is otherwise in a condition conducive to rust formation.
The quaternary ammonium salts of esters of salicylic acid of this invention can be selected from compounds having the general structure wherein:
R is a normal or iso alkyl, normal or iso alkenyl, aralkyl or cycloalkyl substituent containing 1 to 22 carbon atoms and can be substituted with substituents such as nitrogen, phosphorus, sulfur or oxygen,
R may be absent or is a normal or iso alkyl, nor-mal or iso alkenyl, aralkyl or cycloalkyl substituent containing 1 to 22 carbon atoms and can be substituted with substituents such as nitrogen, phosphorus, sulfur or oxygen.
"ice
R,,, R R and R, are each a normal or iso alkyl, normal or iso alkenyl, aralkyl or cycloalkyl substituent containing 1 to 22 carbon atoms which can be substituted with substituents such as oxygen, nitrogen, phosphorus, or sulfur, at least one of said groups containing at least four carbon atoms,
N is nitrogen and can be the nitrogen of a heterocyclic nitrogen-containing ring such as imidazoline, pyridine, thiazine or piperazine, in which case 'R and R are members of the heterocyclic ring and at least one of the substituents R and R contains at least four carbon atoms,
C is carbon, and
O is oxygen.
Although R R R and R generically encompass oxygen-containing substituents, compounds wherein R R R and R are hydrogen substituents which are free of hydroxyl groups with or without an ether polymer thereof unexpectedly possess dilferent utility from compounds wherein R,,, R R, and R have an hydroxyl group with or without an ether polymer thereof, and the latter group of compounds is covered specifically in application Ser. No. 476,666, filed Aug. 2, 1965, now Pat. No. 3,419,- 366.
Preferred compounds of this invention include quaternary ammonium salts of octyl, dodecyl, tridecyl or hexadecyl salicylates where the quaternary ammonium group is selected from the following:
Alkyltrimethylammonium wherein the alkyl group is a C to C substituent; dialkyldimethylammonium wherein the alkyl groups are C to C substituents; or mixtures of said monoalkyltrimethylammonium and said dialkyldimethylammonium groups.
Some commercial starting materials which can be utilized as the quaternary ammonium base are Arquad C, Arquad S, Arquad T, Arquad 12, Arquad 18, Arquad 2C, Arquad 2S, Arquad 2HT, Arquad T-2C, and Arquad S- 2C, all of which are commercial products. Arquad C, Arquad S, Arquad T, Arquad 12, and Arquad 18 are alkyltrimethylammonium chlorides wherein the symbols C, S and T indicate that the alkyl substituent comes from coco, soya bean oils or fats, or tallow, respectively, while in A'rquad 12 and Arquad 18 the alkyl substituent is essentially pure dodecyl or octadecyl, respectively. Arquad 2C, Arquad 2S and Arquad 2HT are dialkyldimethylammonium chlorides wherein the alkyl substituent is coco, soya' and hydrogenated tallow, respectively, and Arquad T2C and Arquad S-2C are mixtures of the indicated alkyltrimethylammonium chlorides and dialkyldimethylammonium chlorides.
Salicylic acid is a convenient starting material in the preparation of the quaternary ammonium salicylates of this invention. Salicylic acid contains an hydroxyl radical and a carboxylic acid radical at ortho positions on a benzene ring. In preparing the quaternary ammonium salts of this invention, the reactant containing the quaternary ammonium cation is reacted with the hydroxyl radical of the salicylic acid rather than with the carboxylic radical so that the salt formed is a quaternary ammonium phenate rather than a quaternary ammonium carboxylate. However, the carboxylic acid radical is considerably more acidic and therefore more reactive with the quarternary ammonium cation than is the hydroxyl radical and in order for the quaternary ammonium cation to react with the hydroxyl radical rather than with the carboxylic acid radical the salicylic acid must be esterified prior to the reaction thereof with the quaternary ammonium compound. Therefore, the preparation of the quaternary ammonium salt of this invention is a two-step process in which the order of performance of the steps is critical, i.e. the salicylic acid starting material is first esterified by reaction with an alcohol and only after esterification is it converted to a quaternary salt.
In the following specific example for the preparation of the compounds of this invention from salicylic acid, the more reactive carboxylic acid radical is first reacted with an alcohol to form an ester. Thereupon, a commercial quaternary ammonium chloride is converted to the corresponding quaternary ammonium hydroxide. The quaternary ammonium hydroxide is then reacted with the hydroxyl radical of the ester of salicylic acid to form a quarternary ammonium salt of salicylic acid ester.
EXAMPLE Step 1.Preparation of isooctyl salicylate from salicylic acid A mixture containing 900 grams of salicylic acid, 1300 grams (10 moles) of isooctyl alcohol, 30 grams of ptoluenesulfonic acid and 1000 milliliters of toluene was heated at reflux in a -liter flask fitted with a Dean and Stark trap. Reflux was continued until no more Water collected in the trap. The solution was cooled to room temperature and extracted with one liter of water, then with one liter of percent sodium bicarbonate solution followed by a washing with one liter of water. The extracted solution was dried over anhydrous sodium sulfate, filtered and vacuum-distilled. After distillation of toluene and excess isooctyl alcohol, 1568 grams of a clear oil was collected at 150-l-60 C. and 3.2 millimeters presssure. Analysis of the product showed 72.21 percent carbon, 8.90 percent hydrogen, 18.21 percent oxygen and a molecular weight of 265. Theoretically, isooctyl salicylate contains 71.9 percent carbon, 8.8 percent hydrogen, and 19.2 percent oxygen, and has a molecular weight of 250.
Step 2.Preparation of di(hydrogenated tallow)dimethylammonium isooctyl salicylate from isooctyl salicylate Ninety grams (0.154 mole) of di(hydrogenated tallow) dimethylammonium chloride as a 75 weight percent paste containing isopropanol and a small amount of water, was dissolved in 200 milliliters of benzene. The composition of the 75 weight percent of the paste which consisted of di(hydrogenated tallow)dimethylammonium chloride was 75 percent by weight distearyldimethylammonium chloride, 1 percent by weight dioctadecenyldimethylammonium chloride, and 24 percent by weight dihexadecyldimethylammonium chloride. With stirring, a warm solution containing 10.1 grams (0.153 mole) of potassium hydroxide (assay 85%) in absolute ethanol was added to the benzene solution. The precipitated potassium chloride was removed by filtration. To the filtrate was added 38.4 grams (0.153 mole) of isooctyl salicylate. Solvent was removed. The product, a brown oil which solidified on cooling, contained 1.81 percent of nitrogen. The calculated nitrogen content of di(hydrogenated tallow)dimethylammonium octyl salicylate is 1.75 percent.
Tests were conducted to illustrate the high rust arresting effectiveness of the compounds of this invention as compared to a control fuel oil sample without additives and as compared to a control fuel oil sample containing calcium octyl salicylate. In conducting these tests, a test solution was prepared by placing a mixture of 80 percent by volume of fuel oil or fuel oil plus additive with percent by volume of distilled water into a 4-ounce jar and shaking vigorously for one minute. A clean specimen of SAE 1020 steel was immersed nearly vertically into 4 each test jar and the jar was stored at room temperature. The steel specimens were inspected and rated after 1 day, 3 days and 7 days, respectively, and the results of the inspection are shown in the following table. A rating of 0 signifies no rust; l signifies 1 to 5 percent of the surface area rusted; 2 signifies 6 to 25 percent of the surface area rusted; 3 signifies 26 to 50 percent of the surface area rusted; and 4 signifies greater than 50 percent of the surface area rusted. The results of the tests are presented in the following table.
1 Heavy red and black corrosion where water droplets cling to or creep over portion of steel specimen in the fuel 01113112159.
h Typical fuel oil inspections:
Gravity: API, ASTM D287 Viscosity SUV; See, ASIM D446, F. Flash, P-M: F., ASTM D93 ,A-sTM D97 2a Distillation, ASTM D158:
Over point: F. End point:
10% lat: F.
It is seen from the above table that in the test with the fuel oil control sample without additives and in the test with the fuel oil control sample plus calcium isooctyl salicylate there was rusting over more than 50 percent of the surface area of the steel specimen in the Water phase and also heavy corrosion in the steel specimen in the fuel oil phase where water droplets clung to or crept over the portion of the specimen in the fuel oil phase. In contrast, the table shows that in the test with the fuel oil sample plus di(hydr-ogenated tallow)dimethylammonium isooctyl salicylate there was rusting over only 1 to 5 percent of the surface area of the steel specimen in the water phase, while there was no rust in the portion of the steel specimen in the fuel oil phase.
The quaternary ammonium salicylates of this invention are oil soluble and can be present in hydrocarbon oils over a wide range of concentrations. For example, they can be generally present in hydrocarbon oils over a concentration range of about 0.002 up to about 10 percent by weight, the higher region of the range being especially useful when preparing a concentrate, or preferably, over a concentration range of about 0.005 to about 0.1 percent by weight. Although useful in a wide variety of hydrocarbon oils such as gasoline, jet fuels, diesel fuels, etc., the quaternary ammonium salicylates of this invention are especially useful in fuel oils, such as blends of straight run and catalytically cracked fuel oils. Also, the compounds of this invention are primarily useful for rust inhibition in oils which are in contact with an aqueous phase.
Various changes and modifications can be made without departing from the spirit of this invention or the scope thereof as defined in the following claims.
We claim:
1. A quaternary ammonium phenate-type salt of octyl, dodecyl, tridecyl or hexadecyl salicylate wherein of the four groups on the quaternary ammonium radical two or three are methyl groups and the remaining are derived from coco, soya bean oils or fats or tallow.
6 2. A quaternary ammonium phenate-type salt of octyl, dodecyl, tridecyl or hexadecyl salicylate wherein of the References Cted four groups on the quaternary ammonium radical two or Final, I. L. Organic Chemistry, volume one (1963),
three are methyl groups and the remaining are dodecyl pub. by LongmansLondon, page 318 relied on. or octadecyl groups. 5
3. The distearyldimethyl quaternary ammonium phe- LORRAINE WEINBERGER, Primary Examine?! nalte-type salt of octyl, dodecyl, tridecyl or hexadecyl L A THAXTON Assistant Examiner sa icylate.
4. The dihexadecyldimethyl quaternary ammonium Us Cl XR phenate-type salt of octyl, dodecyl, tridecyl or hexadecyl 10 salicylate 260-268 R, 294.8 G, 295 R, 302 R, 309.6, 470
*zg gg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,652,644 Dated March 28, 1972 E. L. Fareri, R. J. McGuire and H. 0. Strange It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 1, line 61, delete "R and substitute therefor R'- Signed and sealed this 29th day of August 1972.
(SEAL) Attest:
ROBERT GOTTSCHALK Commissioner of Patents FDWARD M.FLETCHER.JR.
Attesting Officer
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US47671765A | 1965-08-02 | 1965-08-02 | |
| US71797168A | 1968-04-01 | 1968-04-01 |
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| Publication Number | Publication Date |
|---|---|
| US3652644A true US3652644A (en) | 1972-03-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US717971A Expired - Lifetime US3652644A (en) | 1965-08-02 | 1968-04-01 | Quaternary ammonium salts of esters of salicylic acid as rust inhibitors |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4787916A (en) * | 1986-10-31 | 1988-11-29 | Exxon Research And Engineering Company | Method and fuel composition for reducing octane requirement increase |
-
1968
- 1968-04-01 US US717971A patent/US3652644A/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4787916A (en) * | 1986-10-31 | 1988-11-29 | Exxon Research And Engineering Company | Method and fuel composition for reducing octane requirement increase |
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