USRE29098E - Preparation of aliphatic phosphates - Google Patents
Preparation of aliphatic phosphates Download PDFInfo
- Publication number
- USRE29098E USRE29098E US05/655,648 US65564876A USRE29098E US RE29098 E USRE29098 E US RE29098E US 65564876 A US65564876 A US 65564876A US RE29098 E USRE29098 E US RE29098E
- Authority
- US
- United States
- Prior art keywords
- phosphite
- oxidation
- peroxide
- oxygen
- phosphates
- 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
- -1 aliphatic phosphates Chemical class 0.000 title claims abstract description 24
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 17
- 235000021317 phosphate Nutrition 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 3
- 238000000034 method Methods 0.000 claims abstract description 25
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 9
- 150000002978 peroxides Chemical class 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- KJWHEZXBZQXVSA-UHFFFAOYSA-N tris(prop-2-enyl) phosphite Chemical group C=CCOP(OCC=C)OCC=C KJWHEZXBZQXVSA-UHFFFAOYSA-N 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 16
- 230000003647 oxidation Effects 0.000 abstract description 13
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract description 8
- 239000003999 initiator Substances 0.000 abstract description 4
- 239000007789 gas Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 9
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000002081 peroxide group Chemical group 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QEDNBHNWMHJNAB-UHFFFAOYSA-N tris(8-methylnonyl) phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OCCCCCCCC(C)C QEDNBHNWMHJNAB-UHFFFAOYSA-N 0.000 description 2
- PVSKJBDIJJFTBV-UHFFFAOYSA-N 1,1-ditert-butyl-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(C(C)(C)C)(C(C)(C)C)C1 PVSKJBDIJJFTBV-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001491 aromatic compounds Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- YQLIHRFKJJQBAF-UHFFFAOYSA-N tris(3-methylbutyl) phosphate Chemical compound CC(C)CCOP(=O)(OCCC(C)C)OCCC(C)C YQLIHRFKJJQBAF-UHFFFAOYSA-N 0.000 description 1
- FSLSJTZWDATVTK-UHFFFAOYSA-N tris(6-methylheptyl) phosphate Chemical compound CC(C)CCCCCOP(=O)(OCCCCCC(C)C)OCCCCCC(C)C FSLSJTZWDATVTK-UHFFFAOYSA-N 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 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
- C07F9/09—Esters of phosphoric acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/123—Ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M2223/042—Metal salts thereof
Definitions
- This invention relates to a process for the preparation of aliphatic phosphates by means of the oxidation of certain trialkenyl phosphites or trialkyl phosphites. More particularly, it relates to such a process which avoids high temperatures and yet results in very good yields.
- the aliphatic phosphates made available by this invention are useful as plasticizers, gasolines additives, lubricant additives and flame-retarding additives.
- the trialkenyl phosphates are excellent cross-linking agents in the curing of ethylene polymers such as low density polyethylene or EPDM polymers.
- tertiary phosphites to the corresponding phosphates via oxidation affords a convenient method of synthesis of these desirable products. They can also be prepared by the reaction of phosphorus oxychloride with the appropriate alcohol, and this synthesis has been used, but it involves the elimination of large amounts of hydrogen chloride which is both wasteful of chlorine and corrosive, requiring special equipment.
- the oxidation of phosphites is a preferred method.
- Hodan et al., U.S. Pat. No. 3,136,804, and Baranauckas et al., U.S. Pat. No. 3,136,805, show the oxidation of trialkenyl and trialkyl phosphites, respectively, to the corresponding phosphates by the action of oxygen in an anhydrous medium, using a metal oxide such as aluminum oxide as a catalyst, yields of 88-96% are obtained and losses due to hydrolysis are avoided because of the absence of water in the oxidation mixture.
- the oxidations are carried out at temperatures between 60° C and 180° C, preferably between 100° C and 125° C, and for a period of time ranging from two to seven hours.
- Still another method of oxidizing tertiary olefinic phosphites to the corresponding phosphates by means of air is shown in Hodan et al., U.S. Pat. No. 3,334,158.
- the method involves a short residence time, i.e., less than 20 minutes and preferably less than 5 minutes, in the reaction zone.
- the temperature is above 100° C, preferably between 130° C and 190° C.
- the reaction zone is a column packed with protruded stainless steel.
- Another object is to provide such a process which is effective at relatively low temperatures.
- Still another object is to provide such a process which results in good yields of trialkyl or trialkenyl phosphates.
- a process for preparing aliphatic phosphates comprising introducing oxygen into a mixture of a trialkenyl or trialkyl phosphite and a source of free radicals, at a temperature below about 80° C and in the presence of light of wavelength of 2000-4000A°. Yields of tertiary phosphate are very good, i.e., virtually quantitative in most cases, and the process requires no unusual attention.
- trialkenyl or trialkyl phosphite may be defined in terms of a structural formula, as follows:
- R is alkyl or alkenyl, each containing 1-20 carbon atoms.
- Illustrative alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-amyl, sec-amyl, n-hexyl, isohexyl, 2-methylamyl-4, 2-ethylhexyl, n-octyl, isooctyl, n-dodecyl, n-tetradecyl, n-octadecyl, and eicosyl.
- Illustrative alkenyl radicals include allyl, methallyl, crotyl, pentenyl-2,3, 3-dimethyl and 2,3-dimethallyl.
- the oxygen may be used as such, i.e., without dilution, or it may be diluted, as in air. Ordinarily the oxygen is bubbled into the phosphite, either neat or in a solvent, until the mixture is completely oxidized. This end point is shown by testing with iodine which is reactive with any unreacted phosphite, and a negative test indicates completion of the reaction.
- the reactor vessel may be evacuated to about 5 mm. Hg and oxygen fed in on demand, i.e., oxygen is introduced only as fast as it is consumed by the oxidation reaction.
- a solvent may be used but it is not necessary.
- Heptane is a suitable solvent.
- the source of free radicals is a class of compounds generally known as non-oxidizing initiators. They include principally organic peroxides and azo compounds having less than 30 carbon atoms, and of these the aliphatic initiators are preferred. Illustrative examples of such peroxides include di-tert-butyl peroxide, alpha, alpha-bis (tert-butylperoxy) diisopropylbenzene, diacetone alcohol peroxide, dicumyl peroxide, 1,1-di-tert-butyl-3,3,5-trimethylcyclohexane, and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane.
- aliphatic as used to describe these peroxides defines the peroxide linkages, i.e., the carbon atoms to which the peroxide group is attached. These carbon atoms are aliphatic carbon atoms. Thus, as illustrative above, an "aliphatic" peroxide may or may not contain aromatic groups. Dicumyl peroxide, for example, although it is an aromatic compound, is herein classified as an aliphatic peroxide because the carbon atoms to which ##STR1## the peroxide group is attached are aliphatic carbon atoms.
- Illustrative examples of preferred azo compounds include alpha-cyano azo compounds, conforming to the structural formula ##STR2## where R are the same or different alkyl or phenyl radicals having 1-6 carbon atoms.
- Bis-azo isobutyronitrile (where all four R's are methyl) is particularly illustrative.
- the temperature of the oxidation reaction mixture may range from about 0° C to about 80° C. Higher temperatures are wholly unnecessary and, in fact, the oxidation proceeds quite satisfactorily, with near-quantitative yields, at lower temperatures than 80° C.
- the oxidiation temperature is within the range of from about 10° C to about 60° C, and in most instances a range of from about 10° C to about 50° C is suitable. The oxidation is exothermic and it is necessary to cool the reaction mixture to maintain the temperature at a desired level.
- the amount of peroxide or azo compound used in the oxidation reaction may range from about 0.01% to about 5.0%. More than 5.0% can of course be used with no harmful effect, but with no added advantage. Ordinarily it is preferred to use from about 0.1% to about 2.0% of the peroxide or azo compound.
- the reaction must be carried out in the presence of ultraviolet light, i.e., light having wavelength between 2000A° and 4000A°. Light of wavelength between 2000A° and 2500A° is especially effective.
- the light serves to activate the free radical source, i.e., it causes decomposition of the non-oxidizing initiator to yield a free radical which in turn catalyzes oxidation of the trialkenyl phosphite.
- Ordinary sunlight will serve the purpose and in many instances is satisfactory.
- an ultraviolet lamp is positioned alongside the reactor to provide relatively intense ultraviolet irradiation.
- the reaction involves simply contacting the trialkenyl or trialkyl phosphite with oxygen as above, with or without a solvent such as heptane, and then isolating the phosphate product. Where no solvent is employed, it may be unnecessary to isolate the product inasmuch as the product mixture consists almost entirely of phosphate and may be sufficiently pure for the particular purpose.
- a mixture of 0.5 ml. of di-tert-butyl peroxide and 120 ml. of triisoctyl phosphite are placed in a vertical cylindrical vessel surrounded with 16 high-intensity ultraviolet lamps, and containing internal cooling coils and a gas inlet tube fitted with a fritted disc opening. Water at 50° C is circulated through the cooling coils while oxygen is bubbled in through the gas inlet tube for 2.5 hours. The resulting product is substantially pure triisooctyl phosphate comprising a yield of greater than 99% of the theory.
- a mixture of 0.5 g. of bis-azo isobutyronitrile and 120 ml. of triisoamyl phosphite are placed in the above reactor and treated as there described, except that the temperature of the circulating water is such as to maintain the temperature of the oxidation mixture at 35°-40° C.
- the yield of substantially pure triisoamyl phosphate is about 99% of the theory.
- Triallyl phosphite is converted to triallyl phosphate quantitatively by the method of Example 1.
- Trimethyl phosphite is converted to trimethyl phosphate by the method of Example 1.
- the yield is 97% of the theory.
- Triisodecyl phosphite is converted to triisodecyl phosphate by the method of Example 1.
- the yield is 95% of the theory.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
Abstract
Description
______________________________________ O - R P O - R O - R ______________________________________
Claims (7)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/655,648 USRE29098E (en) | 1974-09-20 | 1976-02-06 | Preparation of aliphatic phosphates |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US507632A US3923620A (en) | 1974-09-20 | 1974-09-20 | Preparation of aliphatic phosphates |
US05/655,648 USRE29098E (en) | 1974-09-20 | 1976-02-06 | Preparation of aliphatic phosphates |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US507632A Reissue US3923620A (en) | 1974-09-20 | 1974-09-20 | Preparation of aliphatic phosphates |
Publications (1)
Publication Number | Publication Date |
---|---|
USRE29098E true USRE29098E (en) | 1977-01-04 |
Family
ID=27055924
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/655,648 Expired - Lifetime USRE29098E (en) | 1974-09-20 | 1976-02-06 | Preparation of aliphatic phosphates |
Country Status (1)
Country | Link |
---|---|
US (1) | USRE29098E (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4108746A (en) | 1977-09-08 | 1978-08-22 | The United States Of America As Represented By The Secretary Of The Army | Method of oxidative degradation of phosphorous esters |
CN107175060A (en) * | 2017-07-27 | 2017-09-19 | 洛阳市三诺化工有限公司 | A kind of reactor agitating device for producing TBP calcium phosphate+ forage agent |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2736695A (en) * | 1951-06-05 | 1956-02-28 | Allied Chem & Dye Corp | Process for preparing trichloroacetyl chloride |
-
1976
- 1976-02-06 US US05/655,648 patent/USRE29098E/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2736695A (en) * | 1951-06-05 | 1956-02-28 | Allied Chem & Dye Corp | Process for preparing trichloroacetyl chloride |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4108746A (en) | 1977-09-08 | 1978-08-22 | The United States Of America As Represented By The Secretary Of The Army | Method of oxidative degradation of phosphorous esters |
CN107175060A (en) * | 2017-07-27 | 2017-09-19 | 洛阳市三诺化工有限公司 | A kind of reactor agitating device for producing TBP calcium phosphate+ forage agent |
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