US3228925A - Process for preparing o, o-dihydrocarbon phosphoric acids - Google Patents
Process for preparing o, o-dihydrocarbon phosphoric acids Download PDFInfo
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- US3228925A US3228925A US127476A US12747661A US3228925A US 3228925 A US3228925 A US 3228925A US 127476 A US127476 A US 127476A US 12747661 A US12747661 A US 12747661A US 3228925 A US3228925 A US 3228925A
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- United States
- Prior art keywords
- dihydrocarbon
- acid
- phosphoric
- dithiophosphoric
- dithiophosphoric acid
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- Expired - Lifetime
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- 150000003016 phosphoric acids Chemical class 0.000 title claims description 18
- 235000011007 phosphoric acid Nutrition 0.000 title description 35
- 238000004519 manufacturing process Methods 0.000 title description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 38
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 claims description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- -1 ANTHRACYL Chemical class 0.000 claims description 9
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical class [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 150000007513 acids Chemical class 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 229910052770 Uranium Inorganic materials 0.000 description 4
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 4
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- BFBJAIUYHVCZNN-UHFFFAOYSA-N hydroxy-methoxy-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound COP(O)(S)=S BFBJAIUYHVCZNN-UHFFFAOYSA-N 0.000 description 1
- SPSVMKCHKRWZKC-UHFFFAOYSA-N hydroxy-octadecoxy-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(S)=S SPSVMKCHKRWZKC-UHFFFAOYSA-N 0.000 description 1
- QPPQHRDVPBTVEV-UHFFFAOYSA-N isopropyl dihydrogen phosphate Chemical compound CC(C)OP(O)(O)=O QPPQHRDVPBTVEV-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 229920000570 polyether Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
Definitions
- Dihydrocarbon phosphoric acids including the dialkyl phosphoric acids, diaryl phosphoric acids, dicycloalkyl phosphoric acids, and the like, are well known in the art. Such compounds are useful as surface-ignition suppressors in motor fuels, such as gasoline, and may be useful in extracting uranium from uranium-bearing ores.
- the dihydrocarbon phosphoric acids are prepared -by reacting an alcohol with phosphorus pentoxide but the resulting product contains substantial amounts of monohydrocarbon phosphoric acids. Often it is desirable or necessary to obtain high purity dihydrocarbon phosphoric acids in the substantial absence of the monohydrocarbon phosphoric acids.
- the dihydrocarbon phosphoric acid is the active species in suppression of surface ignition.
- the monohydrocarbon phosphoric acid often attacks zinc surfaces in gasoline and supply lines and forms an insoluble zinc salt; the Zinc salt of the dihydrocarbon phosphoric acid is soluble in gasoline.
- Insoluble zinc monohydrocarbon phosphoric acids precipitate and clog feed lines, valves and the like. Furthermore, in the extraction of uranium from ores, it is necessary to use substantially pure dihydrocarbon phosphoric acid in the absence of monohydrocarbon phosphoric acid for elfective extraction.
- the process of the present invention produces 0,0-dihydrocarbon phosphoric acids in high purity.
- 0,0-dihydrocarbo-n dithiophosphoric acids are converted to the corresponding 0,0- dihydrocarbon phosphoric acids by reaction with 2 mols of water per mol of the dihydrocarbon dithiophosphoric acid at a temperature in the range of from about 100 F. to 400 F.
- the resulting product is dihydrocarbon phosphoric acid in high purity and in the substantial absence of monohydrocarbon phosphoric acid the reaction may be carried out at higher or lower temperatures but such temperatures are not advantageous. At lower temperatures, e.g. 70 F., the reaction may take weeks or months for completion and such reactions are impractical. At higher than about 400 F., degradation of the product may result.
- the above process may be used in combination with the formation of the dihydrocarbon dithiophosphoric acid. Accordingly, phosphorus pentasulfide is reacted with an alcohol to form the dihydrocarbon dithiophosphoric acid which is then converted by the above process step to the dihydrocarbon phosphoric acid.
- hydrocarbon groups are not critical with respect to this invention and although the process is applicable to the formation of any dihydrocarbon phosphoric acid, where the hydrocarbon (i.e. at least one of the hydrocarbon groups) has less than 8 carbon atoms, e.g. 1-5 carbon atoms, it has been found advantageous to carry the reaction out at a temperature in the range of 150 to 250 F. and preferably about 200 F. Similarly, where the hydrocarbon contains about 8 carbon atoms, it has been found advantageous to conduct the reaction at a temperature in the range of 200 to 300 F. and preferably about 220 to 240 F. Additionally, where the hydrocarbon groups contain more than 8 carhon atoms, it is advantageous to conduct the reaction at a temperature in the range of 200 to 350 F. and preferably 220 to 300 F.
- a solvent in the case Where the hydrocarbon group is less than C
- Such solvent may be diluent capable of thinning the reaction mixture, e.g. ketone (acetone), ether, dioxane, isooctyl, hexyl, etc.; the solvent may be an excess of the alcohol used in the formation of the dihydrocarbon dithiophosphoric acid.
- the hydrocarbon group is about a C it is advantageous to use in addition to a solvent, an emulsification agent to mix the water and dithiophosphoric acid phase.
- Such emulsification composition may be non-ionic, e.g. an ester, amid-e or polyether ethanol detergent, or may be cationic, e.-g. quaternary ammonium chlorides or nitrites, or may be anionic, e.g. sodium dodecyl phenyl sulfonate. Where the hydrocarbon group is higher than C the alcohol solvent and detergent or emulsification agent are also employed.
- the reaction of this invention 2 mols of water are reacted with the dihydrocarbon dithiophosphoric acid to produce the corresponding dihydrocarbon phosphoric acid. It is preferred that an excess of the water he used, e.g. 2 to 3 mols of Water per mol of dithiophosphoric acid during the reaction.
- the dihydrocarbon phosphoric acid product is recovered as the non-aqueous phase where it is water-insoluble or may be recovered by evaporation of excess Water where it is water-soluble.
- dihydrocarbon dithiophosphoric acids which may be used in the present process include the di(C to C hydrocarbon dithiophosphoric acids, e.g. the dialkyl, diaryl, diaralkyl, dicycloalkyl, etc., dithiophosphoric acids, such as 0,0-dimethyl dithiophosphoric acid, O-butyl, O-octadecyl dithiophosphoric acid, 0,0-dibutyl dithiophosphoric acid, 0,0-diisooctyl dithiophosphoric acid, 0,0-didodecyl, 0,0-diisopropyl dithiophosphoric acid, 0,0-dihexyldecyl dithiophosphoric acid, 0,0- dioctadecyl dithiophosphoric acid, 0,0didocosyl, 0,0-diphenyl dithiophosphoric acid, 0,0-ditoluyl dithiophosphoric acid, 0,0-dinaphthyl dithiophosphoric acid,
- the dihydrocarbon dithiophosphoric acid may be produced as a first step in an em bodiment of this invention. Accordingly, the corresponding alcohol is reacted with the phosphorus pentasulfide. Four mols of the alcohol are included in the reaction mixture per mol of phosphorus pentasulfide (P 8 and the reaction may be carried out at a temperature in the range of from about to 400 F.
- Useable alcohols are evident from the above examples of dihyd-rocarbon dithiophosphoric acids, such useable alcohols including, for example, the corresponding hydroxy substituted hydrocarbons of the hydrocarbon radicals disclosed as O- substituted in the dithiophosphoric acids, e.g. methyl alcohol, isopropanol, phenol and the like.
- 144 g. of isopropyl alcohol are added gradually to 111 g. of phosphorus pentasulfide at a temperature in the range of F. to F. and reacted at that temperature for 1 hour. Thereafter, 36 g. of Water are added and the reaction mixture is maintained at a temperature of 170 F. for 16 hours.
- the resulting product is d-iisopropyl phosphoric acid containing no more than trace amounts of monoisopropyl phosphoric acid.
- 144 g. of isooctyl alco- 1101 are reacted with 56 g. of P 3 in 44 g. SAE 5 oil as a diluent.
- the reaction mixture is maintained at a temperature of 240 to 260 F. for 2 hours.
- 18 g. of water are then added and the mixture is maintained in the 220 to 240 F. range for about 24 hours.
- the product is diisooctyl phosphoric acid.
- the dihydrocarbon phosphoric acids in substantially pure form as produced by the present process may be 1 used, in addition to use assurface ignition suppressors and uranium extraction agents, as'intermediate in the produc tion of addition agents and especially addition agents for use in gasoline.
- the product may be used to form the amine salt which may be used as a de-icing agent in gasoline.
- the acid is completely tied up and'the resulting composition would be substantially non-corrosive to Zinc parts.
- a process for making 0,0-dihydrocarbon phosphoric acids which process comprises reacting 0,0-dihydrocarbon dithiophosphoric acid wherein the dihydrocarbon group is selected from the class consisting of alkyl, phenyl, alkylphenyl, dialkylphenyl, naphthyl, anthracyl and naphthylalkyl radicals with two mols of water per mol of said acid at a temperature in the range of from about F. to about 400 F. and recovering the resulting corresponding dihydrocarbon phosphoric acid in the substantial absence of corresponding monohydrocarbon phosphoric acid.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Description
United States Patent 3,228,925 PROCESS FOR PREPARING QO-DIHYDRQCUN PHOSPHURIC AQHDS Fred K. Kawahara, Parlr Forest, Iii, assignor to Standard Oil Company, Chicago, Ill., a corporation of Indiana No Drawing. Filed .ln'iy 28, 1961, Ser. No. 127,476 4 Claims. (Cl. 260-971) This invention rel-ates to a process for preparing dihydrocarbon phosphoric acids in high purity.
Dihydrocarbon phosphoric acids, including the dialkyl phosphoric acids, diaryl phosphoric acids, dicycloalkyl phosphoric acids, and the like, are well known in the art. Such compounds are useful as surface-ignition suppressors in motor fuels, such as gasoline, and may be useful in extracting uranium from uranium-bearing ores.
However, it has been difficult, if not often impossible, to prepare the dihydrocarbon phosphoric acids in high purity. Usually, the dihydrocarbon phosphoric acids are prepared -by reacting an alcohol with phosphorus pentoxide but the resulting product contains substantial amounts of monohydrocarbon phosphoric acids. Often it is desirable or necessary to obtain high purity dihydrocarbon phosphoric acids in the substantial absence of the monohydrocarbon phosphoric acids. For example, the dihydrocarbon phosphoric acid is the active species in suppression of surface ignition. Furthermore, the monohydrocarbon phosphoric acid often attacks zinc surfaces in gasoline and supply lines and forms an insoluble zinc salt; the Zinc salt of the dihydrocarbon phosphoric acid is soluble in gasoline. Insoluble zinc monohydrocarbon phosphoric acids precipitate and clog feed lines, valves and the like. Furthermore, in the extraction of uranium from ores, it is necessary to use substantially pure dihydrocarbon phosphoric acid in the absence of monohydrocarbon phosphoric acid for elfective extraction.
The process of the present invention produces 0,0-dihydrocarbon phosphoric acids in high purity. In accordance with the present process, 0,0-dihydrocarbo-n dithiophosphoric acids are converted to the corresponding 0,0- dihydrocarbon phosphoric acids by reaction with 2 mols of water per mol of the dihydrocarbon dithiophosphoric acid at a temperature in the range of from about 100 F. to 400 F. The resulting product is dihydrocarbon phosphoric acid in high purity and in the substantial absence of monohydrocarbon phosphoric acid the reaction may be carried out at higher or lower temperatures but such temperatures are not advantageous. At lower temperatures, e.g. 70 F., the reaction may take weeks or months for completion and such reactions are impractical. At higher than about 400 F., degradation of the product may result.
The above process may be used in combination with the formation of the dihydrocarbon dithiophosphoric acid. Accordingly, phosphorus pentasulfide is reacted with an alcohol to form the dihydrocarbon dithiophosphoric acid which is then converted by the above process step to the dihydrocarbon phosphoric acid.
Although the nature and size of the hydrocarbon groups are not critical with respect to this invention and although the process is applicable to the formation of any dihydrocarbon phosphoric acid, where the hydrocarbon (i.e. at least one of the hydrocarbon groups) has less than 8 carbon atoms, e.g. 1-5 carbon atoms, it has been found advantageous to carry the reaction out at a temperature in the range of 150 to 250 F. and preferably about 200 F. Similarly, where the hydrocarbon contains about 8 carbon atoms, it has been found advantageous to conduct the reaction at a temperature in the range of 200 to 300 F. and preferably about 220 to 240 F. Additionally, where the hydrocarbon groups contain more than 8 carhon atoms, it is advantageous to conduct the reaction at a temperature in the range of 200 to 350 F. and preferably 220 to 300 F.
In addition to the above variances in advantageous temperature ranges for reactions to form dihydrocarbon phosphoric acids wherein the size of the hydrocarbon group varies, it has been found advantageous to employ a solvent in the case Where the hydrocarbon group is less than C Such solvent may be diluent capable of thinning the reaction mixture, e.g. ketone (acetone), ether, dioxane, isooctyl, hexyl, etc.; the solvent may be an excess of the alcohol used in the formation of the dihydrocarbon dithiophosphoric acid. Where the hydrocarbon group is about a C it is advantageous to use in addition to a solvent, an emulsification agent to mix the water and dithiophosphoric acid phase. Such emulsification composition may be non-ionic, e.g. an ester, amid-e or polyether ethanol detergent, or may be cationic, e.-g. quaternary ammonium chlorides or nitrites, or may be anionic, e.g. sodium dodecyl phenyl sulfonate. Where the hydrocarbon group is higher than C the alcohol solvent and detergent or emulsification agent are also employed.
In the reaction of this invention, 2 mols of water are reacted with the dihydrocarbon dithiophosphoric acid to produce the corresponding dihydrocarbon phosphoric acid. It is preferred that an excess of the water he used, e.g. 2 to 3 mols of Water per mol of dithiophosphoric acid during the reaction. The dihydrocarbon phosphoric acid product is recovered as the non-aqueous phase where it is water-insoluble or may be recovered by evaporation of excess Water where it is water-soluble.
Examples of dihydrocarbon dithiophosphoric acids which may be used in the present process include the di(C to C hydrocarbon dithiophosphoric acids, e.g. the dialkyl, diaryl, diaralkyl, dicycloalkyl, etc., dithiophosphoric acids, such as 0,0-dimethyl dithiophosphoric acid, O-butyl, O-octadecyl dithiophosphoric acid, 0,0-dibutyl dithiophosphoric acid, 0,0-diisooctyl dithiophosphoric acid, 0,0-didodecyl, 0,0-diisopropyl dithiophosphoric acid, 0,0-dihexyldecyl dithiophosphoric acid, 0,0- dioctadecyl dithiophosphoric acid, 0,0didocosyl, 0,0-diphenyl dithiophosphoric acid, 0,0-ditoluyl dithiophosphoric acid, 0,0-dinaphthyl dithiophosphoric acid, 0,0- dianthryl dithiophosphoric acid, 0,0-dixylyl dithiophosphoric acid, 0,0-dicyclohexyl dithiophosphoric acid, 0,0- dicyclopropyl dithiophosphoric acid, 0,0-dicyclooctyl dithiophosphoric acid, 0,0-isopropyl, 0,0-decyl dithiophosphoric acid, 0,0-isopropyl, 0,0-isooctyl, 0,0-octadecyl, 0,0-tolyl dithiophosphoric acid, 0,0-cyclohexyl O-hexyl, O-Z-naphthylethyl, O-methyl dithiophosphoric acid, 0- methyl O-amyl dithiophosphoric acid, 0,0-diamyl dithiophosphoric acid, and the like.
As disclosed hereinabove, the dihydrocarbon dithiophosphoric acid may be produced as a first step in an em bodiment of this invention. Accordingly, the corresponding alcohol is reacted with the phosphorus pentasulfide. Four mols of the alcohol are included in the reaction mixture per mol of phosphorus pentasulfide (P 8 and the reaction may be carried out at a temperature in the range of from about to 400 F. Useable alcohols are evident from the above examples of dihyd-rocarbon dithiophosphoric acids, such useable alcohols including, for example, the corresponding hydroxy substituted hydrocarbons of the hydrocarbon radicals disclosed as O- substituted in the dithiophosphoric acids, e.g. methyl alcohol, isopropanol, phenol and the like.
In order to illustrate the process of the present invention, 144 g. of isopropyl alcohol are added gradually to 111 g. of phosphorus pentasulfide at a temperature in the range of F. to F. and reacted at that temperature for 1 hour. Thereafter, 36 g. of Water are added and the reaction mixture is maintained at a temperature of 170 F. for 16 hours. The resulting product is d-iisopropyl phosphoric acid containing no more than trace amounts of monoisopropyl phosphoric acid.
As another example of a preparation in accordance with the process of this invention, 144 g. of isooctyl alco- 1101 are reacted with 56 g. of P 3 in 44 g. SAE 5 oil as a diluent. The reaction mixture is maintained at a temperature of 240 to 260 F. for 2 hours. 18 g. of water are then added and the mixture is maintained in the 220 to 240 F. range for about 24 hours. The product is diisooctyl phosphoric acid.
The dihydrocarbon phosphoric acids in substantially pure form as produced by the present process may be 1 used, in addition to use assurface ignition suppressors and uranium extraction agents, as'intermediate in the produc tion of addition agents and especially addition agents for use in gasoline. As an intermediate, the product may be used to form the amine salt which may be used as a de-icing agent in gasoline. In the form of the amine salt, the acid is completely tied up and'the resulting composition would be substantially non-corrosive to Zinc parts.
It is evident from the foregoing that I have provided a process for making dihydrocarbon phosphoric acids in the substantial absence of the monohydrocarbon phosphoric acid.
I claim:
1. A process for making 0,0-dihydrocarbon phosphoric acids which process comprises reacting 0,0-dihydrocarbon dithiophosphoric acid wherein the dihydrocarbon group is selected from the class consisting of alkyl, phenyl, alkylphenyl, dialkylphenyl, naphthyl, anthracyl and naphthylalkyl radicals with two mols of water per mol of said acid at a temperature in the range of from about F. to about 400 F. and recovering the resulting corresponding dihydrocarbon phosphoric acid in the substantial absence of corresponding monohydrocarbon phosphoric acid.
2. The process of claim 1 wherein said reacting is carried out in the presence of a solvent for said 0,0-dihydrocarbon dithiophosphoric acid, and said Water and 0,0- dihydrocarbon dithiophosphoric acid are present in the reaction mixture in the form of an emulsion.
3. The process of claim 1 wherein the 0,0-dihydrocarbon groups of the 0,0-dihydrocarbon dithiophosphoric acid and the resulting phosphoric acid are diisopropyl groups and acid reaction temperature is in the range of t0 250 F,
References Cited by the Examiner UNITED STATES PATENTS 2,7 15, 136 8/1955 Toy et al. =260-461 2,863,902 12/ 1958 Santay 260-'46-1 2,996,533 8/1961 Millikan et al. 260-461 3,073,857 1/'1963 Millikan et al. 260-461 OTHER REFERENCES Pishchimuka: Chem. Abst., vol. 20, p. 2816 (1926).
CHARLES B. PARKER, Primary Examiner.
NORRIS LIEBMAN, IRVING MARCUS, Examiners.
Claims (1)
1. A PROCESS FOR MAKING O,O-DIHYDROCARBON PHOSPHORIC ACIDS WHICH PROCESS COMPRISES REACTING O,O-DIHYDROCARBON DITHIOPHOSPHORIC ACID WHEREIN THE DIHYDROCARBON GROUP IS SELECTED FROM THE CLASS CONSISTING OF ALKYL, PHENYL, ALKYLPHENYL, DIALKYLPHENYL, NAPHTHYL, ANTHRACYL AND NAPHTHYLALKYL RADICALS WITH TWO MOLS OF WATER PER MOL OF SAID ACID AT A TEMPERATURE IN THE RANGE OF FROM ABOUT 100*F. TO ABOUT 400*F. AND RECOVERING THE RESULTING CORRESPONDING DIHYDROCARBON PHOSPHORIC ACID IN THE SUBSTANTIAL ABSENCE OF CORRESPONDING MONOHYDROCARBON PHOSPHORIC ACID.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US127476A US3228925A (en) | 1961-07-28 | 1961-07-28 | Process for preparing o, o-dihydrocarbon phosphoric acids |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US127476A US3228925A (en) | 1961-07-28 | 1961-07-28 | Process for preparing o, o-dihydrocarbon phosphoric acids |
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| Publication Number | Publication Date |
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| US3228925A true US3228925A (en) | 1966-01-11 |
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| US127476A Expired - Lifetime US3228925A (en) | 1961-07-28 | 1961-07-28 | Process for preparing o, o-dihydrocarbon phosphoric acids |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2715136A (en) * | 1949-04-29 | 1955-08-09 | Victor Chemical Works | Method of preparing dialkyl thionochlorophosphates |
| US2863902A (en) * | 1954-09-08 | 1958-12-09 | American Cyanamid Co | Preparation of phosphate esters |
| US2996533A (en) * | 1958-05-28 | 1961-08-15 | Pure Oil Co | Preparation of phosphoro thioate diesters |
| US3073857A (en) * | 1959-12-28 | 1963-01-15 | Pure Oil Co | Method of preparing phosphorotetrathioate esters |
-
1961
- 1961-07-28 US US127476A patent/US3228925A/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2715136A (en) * | 1949-04-29 | 1955-08-09 | Victor Chemical Works | Method of preparing dialkyl thionochlorophosphates |
| US2863902A (en) * | 1954-09-08 | 1958-12-09 | American Cyanamid Co | Preparation of phosphate esters |
| US2996533A (en) * | 1958-05-28 | 1961-08-15 | Pure Oil Co | Preparation of phosphoro thioate diesters |
| US3073857A (en) * | 1959-12-28 | 1963-01-15 | Pure Oil Co | Method of preparing phosphorotetrathioate esters |
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