US2716658A - Purification of tricresyl phosphate - Google Patents
Purification of tricresyl phosphate Download PDFInfo
- Publication number
- US2716658A US2716658A US307373A US30737352A US2716658A US 2716658 A US2716658 A US 2716658A US 307373 A US307373 A US 307373A US 30737352 A US30737352 A US 30737352A US 2716658 A US2716658 A US 2716658A
- Authority
- US
- United States
- Prior art keywords
- tricresyl phosphate
- solution
- wash
- purification
- mixture
- 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
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 title claims description 24
- 238000000746 purification Methods 0.000 title description 2
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 3
- 238000010936 aqueous wash Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000003518 caustics Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012476 oxidizable substance Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
- C07F9/025—Purification; Separation; Stabilisation; Desodorisation of organo-phosphorus compounds
-
- 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
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
Definitions
- This invention relates to a process for purifying tricresyl phosphate.
- the crude product ordinarily has a poor color and contains oxidizable substances, both of which lower its value. It has heretofore been the practice to purify tricresyl phosphate by treatment with an oxidizing agent such as potassium permanganate to improve the color and to remove substances susceptible to oxidation.
- tricresyl phosphate ordinarily has only two types of impurities.
- the first of these is of an acidic nature and consists primarily of free cresol and cresol acid phosphates; this type of impurity may be readily removed from the reaction mixture by an ordinary alkaline wash.
- the second type of impurity consists of oxidation and/0r polymerization products in which the hydroxyl group has lost its acidic nature, which prevents the impurity from being washed out by an alkaline wash.
- the second type of impurity may be removed by treating crude tricresyl phosphate with an alkaline aqueous solution in the presence of an amphoteric metal such as zinc, tin, aluminum and the like and which reacts with the alkali to produce hydrogen in the nascent state.
- an amphoteric metal such as zinc, tin, aluminum and the like and which reacts with the alkali to produce hydrogen in the nascent state.
- any caustic alkali may be employed in carrying out this process, but I prefer sodium hydroxide because of its low cost, ready availability and eflicient results. It is not necessary that a concentrated solution be used and I have found that a 1% to 3% aqueous solution of sodium hydroxide is entirely suitable.
- the treatment may be carried out at room temperature although higher temperatures may be preferred since the tricresyl phosphate is less viscous at the higher temperature and thus the alkaline solution is more easily mixed with it.
- the metal is added in a very finely divided form such as in the form of a metal dust.
- the amount of metal which is necessary is not large and ordinarily about 1% by weight of the tricresyl phosphate is sufiicient. In many instances, a smaller amount can be used.
- the quantity of the alkali solution which is used is not critical, but ordinarily about one volume of the alkaline solution per volume of the tricresyl phosphate will be found to be suitable.
- stirring is continued for about half an hour, the aqueous layer decanted and the alkaline wash repeated in presence of finely divided metal dust about three times, the duration of each wash being rather short, about 10-15 minutes.
Landscapes
- 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)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
United States Patent 2,716,658 PURIFICATION OF TRICRESYL PHOSPHATE Jacob Rosin, Maplewood, N. J., assignor to Montrose Chemical Company, a corporation of New Jersey No Drawing. Application August 30, 1952, Serial No. 307,373
3 Claims. (Cl. 260-461) This invention relates to a process for purifying tricresyl phosphate. When tricresyl phosphate is produced, the crude product ordinarily has a poor color and contains oxidizable substances, both of which lower its value. It has heretofore been the practice to purify tricresyl phosphate by treatment with an oxidizing agent such as potassium permanganate to improve the color and to remove substances susceptible to oxidation. This treatment, as it has been practiced in the past, has been expensive, both from the standpoint of the use of relatively costly reagents and the fact that the yield of tricresyl phosphate is reduced, since a portion of the tricresyl phosphate reacts with the potassium permanganate.
I have found that tricresyl phosphate ordinarily has only two types of impurities. The first of these is of an acidic nature and consists primarily of free cresol and cresol acid phosphates; this type of impurity may be readily removed from the reaction mixture by an ordinary alkaline wash. The second type of impurity consists of oxidation and/0r polymerization products in which the hydroxyl group has lost its acidic nature, which prevents the impurity from being washed out by an alkaline wash. 1 have found that the second type of impurity may be removed by treating crude tricresyl phosphate with an alkaline aqueous solution in the presence of an amphoteric metal such as zinc, tin, aluminum and the like and which reacts with the alkali to produce hydrogen in the nascent state. By such a treatment, the impurities are made alkali soluble and are thus removed in the alkaline wash.
Any caustic alkali may be employed in carrying out this process, but I prefer sodium hydroxide because of its low cost, ready availability and eflicient results. It is not necessary that a concentrated solution be used and I have found that a 1% to 3% aqueous solution of sodium hydroxide is entirely suitable. The treatment may be carried out at room temperature although higher temperatures may be preferred since the tricresyl phosphate is less viscous at the higher temperature and thus the alkaline solution is more easily mixed with it. Preferably, the metal is added in a very finely divided form such as in the form of a metal dust. The amount of metal which is necessary is not large and ordinarily about 1% by weight of the tricresyl phosphate is sufiicient. In many instances, a smaller amount can be used.
The quantity of the alkali solution which is used is not critical, but ordinarily about one volume of the alkaline solution per volume of the tricresyl phosphate will be found to be suitable. In carrying out the invention, it is only necessary to stir together the tricresyl phosphate, the aqueous alkaline solution, and the finely divided metal. Preferably, stirring is continued for about half an hour, the aqueous layer decanted and the alkaline wash repeated in presence of finely divided metal dust about three times, the duration of each wash being rather short, about 10-15 minutes. It is important not to follow up the caustic washes with a series of water washes intended to wash out the alkali entirely, since some hydrolysis occurring during this long procedure may yield phenolic material which would not go into the aqueous layer because the pH of the water layer is not high enough at this stage. As soon as the last alkaline wash does not yield phenolic matter on acidification the batch is acidified to prevent hydrolysis, and then neutralized with an excess of calcium carbonate or magnesium oxide. Instead of acidification followed by neutralization, one may treat the washed tricresyl phosphate with magnesium sulfate which will neutralize the alkali without rendering the solution acid. The neutral tricresyl phosphate is then dried by heating in a vacuum or by treating with a dehydrating agent, and filtered.
It has been found that this treatment is extremely eifective and when a ten gram sample of tricresyl phosphate, treated in accordance with the present invention, is shaken vigorously for two minutes with 50 ml. of freshly prepared 0.01 N potassium permanganate solution, the solution keeps the purple color unchanged for at least thirty minutes. Further, the color of the treated tricresyl phosphate is entirely satisfactory.
The following working example illustrates the present preferred method of carrying out my invention.
Equivalent molar quantities of phosphorous oxychloride and cresol are heated together in presence of .catalysts such as aluminum chloride, zinc chloride, etc., until there is no further evolution of HCl from the reaction mixture. The reaction mixture is then washed with warm water, followed by a caustic wash with one volume, based on the quantity of the reaction mixture, of 2% sodium hydroxide solution. There is added to this caustic mixture 1% by weight based on tricresyl phosphate of zinc dust, and the mixture is stirred and kept at a temperature of about 20 C. for thirty minutes. The aqueous layer is then decanted and the alkaline wash repeated in presence of the metal powder for about ten minutes. This procedure is repeated until the alkaline wash does not show any phenolic matter on acidification. Then the tricresyl phosphate is acidified by addition of diluted sulfuric or hydrochloric acid, and the mixture is then neutralized by the addition of calcium carbonate. The mixture is then filtered, and dried by heating in a vacuum to produce tricresyl phosphate having a satisfactory color and being substantially free from oxidizable substances.
I claim:
1. The process for treating crude tricresyl phosphate, consisting of washing the reaction mixture with a dilute aqueous alkaline solution in the presence of about 1% based on the weight of tricresyl phosphate of an amphoteric metal until the aqueous wash is free from phenolic materials, neutralizing the mixture, drying and filtering it.
2. The process of claim 1 wherein the alkalizing solution used contains from about 1% to about 3% of sodium hydroxide.
3. The process of claim 1 wherein is finely divided zinc.
the amphoteric metal References Cited in the file of this patent UNITED STATES PATENTS 2,365,121 Traylor Dec. 12, 1944
Claims (1)
1. THE PROCESS FOR TREATING CRUDE TRICRESYL PHOSPHATE CONSISTING OF WASHING THE REACTION MIXTURE WITH A DILUTE AQUEOUS ALKALINE SOLUTION IN THE PRESENCE OF ABOUT 1% BASED ON THE WEIGHT OF TRICRESYL PHOSPHATE OF AN AMPHOTERIC METAL UNTIL THE AQUEOUS WASH IS FREE FROM PHENOLIC MATERIALS, NEUTRALIZING THE MIXTURE, DRYING AND FILTERING IT.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US307373A US2716658A (en) | 1952-08-30 | 1952-08-30 | Purification of tricresyl phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US307373A US2716658A (en) | 1952-08-30 | 1952-08-30 | Purification of tricresyl phosphate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2716658A true US2716658A (en) | 1955-08-30 |
Family
ID=23189473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US307373A Expired - Lifetime US2716658A (en) | 1952-08-30 | 1952-08-30 | Purification of tricresyl phosphate |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2716658A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4205023A (en) * | 1978-10-02 | 1980-05-27 | Stauffer Chemical Company | Process for removing soluble metallic salts from a phosphate ester functional fluid |
| US4264534A (en) * | 1978-10-02 | 1981-04-28 | Stauffer Chemical Company | Process for removing soluble metallic salts from a phosphate ester functional fluid and reclamation of said fluid |
| US20040149600A1 (en) * | 2003-01-17 | 2004-08-05 | Wolter Kevin E. | Coach's organization and travel bag |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2365121A (en) * | 1941-04-18 | 1944-12-12 | Hercules Powder Co Ltd | Refining of phenolic resins zn-nahso mixture |
-
1952
- 1952-08-30 US US307373A patent/US2716658A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2365121A (en) * | 1941-04-18 | 1944-12-12 | Hercules Powder Co Ltd | Refining of phenolic resins zn-nahso mixture |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4205023A (en) * | 1978-10-02 | 1980-05-27 | Stauffer Chemical Company | Process for removing soluble metallic salts from a phosphate ester functional fluid |
| US4264534A (en) * | 1978-10-02 | 1981-04-28 | Stauffer Chemical Company | Process for removing soluble metallic salts from a phosphate ester functional fluid and reclamation of said fluid |
| US20040149600A1 (en) * | 2003-01-17 | 2004-08-05 | Wolter Kevin E. | Coach's organization and travel bag |
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