GB2322373A - Preparation of ethane phosphonic acid diethyl ester - Google Patents
Preparation of ethane phosphonic acid diethyl ester Download PDFInfo
- Publication number
- GB2322373A GB2322373A GB9801960A GB9801960A GB2322373A GB 2322373 A GB2322373 A GB 2322373A GB 9801960 A GB9801960 A GB 9801960A GB 9801960 A GB9801960 A GB 9801960A GB 2322373 A GB2322373 A GB 2322373A
- Authority
- GB
- United Kingdom
- Prior art keywords
- peroxide
- producing
- diethyl ester
- acid diethyl
- ethylene
- 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.)
- Withdrawn
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- RRNPGLHPJFTKMV-UHFFFAOYSA-N C(C)OP(OCC)=O.CC Chemical compound C(C)OP(OCC)=O.CC RRNPGLHPJFTKMV-UHFFFAOYSA-N 0.000 title description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000005977 Ethylene Substances 0.000 claims abstract description 33
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- AATNZNJRDOVKDD-UHFFFAOYSA-N 1-[ethoxy(ethyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(CC)OCC AATNZNJRDOVKDD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000011541 reaction mixture Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- ZUNGGJHBMLMRFJ-UHFFFAOYSA-O ethoxy-hydroxy-oxophosphanium Chemical compound CCO[P+](O)=O ZUNGGJHBMLMRFJ-UHFFFAOYSA-O 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 3
- 150000001451 organic peroxides Chemical class 0.000 claims description 3
- FFHGJCBXRQUCED-UHFFFAOYSA-N 1-methyl-2-(2-methylphenyl)peroxybenzene Chemical compound CC1=CC=CC=C1OOC1=CC=CC=C1C FFHGJCBXRQUCED-UHFFFAOYSA-N 0.000 claims description 2
- QYLYCIMKTCNLGY-UHFFFAOYSA-N 11-methyldodecoxycarbonyloxy 11-methyldodecyl carbonate Chemical compound CC(C)CCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCC(C)C QYLYCIMKTCNLGY-UHFFFAOYSA-N 0.000 claims description 2
- SZFABAXZLWVKDV-UHFFFAOYSA-N 2-methyloctanoyl 2-methyloctaneperoxoate Chemical compound CCCCCCC(C)C(=O)OOC(=O)C(C)CCCCCC SZFABAXZLWVKDV-UHFFFAOYSA-N 0.000 claims description 2
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- -1 azo compound Chemical class 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 claims description 2
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 3
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 claims 2
- PCJGHYSTCBLKIA-UHFFFAOYSA-N (1-acetylcyclohexyl)sulfonyloxy 1-acetylcyclohexane-1-sulfonate Chemical compound C1CCCCC1(C(C)=O)S(=O)(=O)OOS(=O)(=O)C1(C(=O)C)CCCCC1 PCJGHYSTCBLKIA-UHFFFAOYSA-N 0.000 claims 1
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 claims 1
- RAWISQFSQWIXCW-UHFFFAOYSA-N 2-methylbutan-2-yl 2,2-dimethyloctaneperoxoate Chemical compound CCCCCCC(C)(C)C(=O)OOC(C)(C)CC RAWISQFSQWIXCW-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- GATNOFPXSDHULC-UHFFFAOYSA-N ethylphosphonic acid Chemical compound CCP(O)(O)=O GATNOFPXSDHULC-UHFFFAOYSA-N 0.000 claims 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- VGUWZCUCNQXGBU-UHFFFAOYSA-N 3-[(4-methylpiperazin-1-yl)methyl]-5-nitro-1h-indole Chemical compound C1CN(C)CCN1CC1=CNC2=CC=C([N+]([O-])=O)C=C12 VGUWZCUCNQXGBU-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a process for producing ethanephosphonic acid diethyl ester by the reaction of diethyl phosphite with ethylene at a temperature of less than 130‹C, in which acid formation is prevented and an almost acid-free ethanephosphonic acid diethyl ester is obtained.
Description
2322373 A process for Producing ethanephosphonic acid diethyl ester The
present invention relates to a process for producing ethanephosphonic acid diethyl ester.
Ethanephosphonic acid diethyl ester, or diethylethane phosphonate (termed DEEP), is used as a flame-retardant additive in polyurethane foam formulations. DEEP can be produced in a single-stage reaction, either by the Arbusow rearrangement of tnethyl phosphite or by the addition of diethyl phosphite to ethylene. In both cases, the reaction is conducted in the presence of a catalyst. The prior art is described in
Houben-Weyl, Methoden der Organischen Chemie, 4th Edition, Volume IWI, Stuttgart 1964, pages 423-522, particularly on pages 433-435 and pages 463-467.
One particular industrial embodiment is described in DE-A 2 043 520, and diffiers with regard to product purity, freedom from oligomers and reaction rate from the previous prior art (US 2 957 931, US 2 478 390, US 2 724 718, and AR. Stiles, W.E.
Vaughan et al., J. Am. Chem. Soc. 80 714 (1958). DE-A 2 043 520 teaches that the reaction of dialkylphosphites with ethylene or propylene has to be conducted at HO'C to 23 MC, preferably at 15WC to 195C. The reaction is conducted at 17WC in the example given. According to DE-A 2 043 520, unsatisfactory results are obtained at lower temperatures. The prior German Patent Application 1 963 014 also explains that temperatures of 1SO'C to 195'C are necessary for the reaction of olefines with dialkyl phosphites.
In the polyurethane formulations in which DEEP is preferably used, basic reaction accelerators are also used in catalytic amounts, namely in small amounts, in addition to other substances. To prevent uncontrollable losses of these reaction accelerators it is necessary that the DEEP used contains as little acid as possible. As shown in comparative example 1, this requirement is only fulfilled to an inadequate extent by DEEP which has been produced according to the prior art.
The object of the present invention was therefore to provide a process for producing DEEP in which acid formation is prevented as far as possible and an almost acid-firee DEEP is thus obtained.
Le A 32 25 1 -Foreign Countries Surprisingly, it has been possible to achieve this object by employing lower temperatures than those of the prior art for the production of DEEP, in fact below HO'C, without losses in yield thereby arising.
The present invention relates to a process for producing ethanephosphonic acid diethyl ester by the addition of diethyl phosphite to ethylene, wherein ethylene is added in the presence of a radical-forming catalyst to diethyl phosphite placed in a reaction vessel, characterised in that, in order to obtain a low-acid grade of ethane phosphonic acid diethyl ester, production is effected at a temperature below HO'C, preferably of 80T to 125'C, most preferably of WC to 120'C.
The process according to the invention not only results in a product which is almost acid-free, but also provides high yields.
Organic peroxides are preferably used as radical-forming catalysts; azo compounds and other known radical-forMing catalysts are also suitable, however. Catalysts which are particularly suitable are those which have a half-life (HL) of a few minutes within the temperature range of the synthesis. e.g. those which have an HL of I minute or less at 125T. In particular. these catalysts comprise tert.-butyl peroctoate, diisotri decyl peroxydicarbonate and other dialkyl peroxydicarbonates, tert.-arnyl perneo decanoate, tert.-butyl perpivalate, mono-tert.-butyl permaleate, tert.- butyl periso butyrate, didecanoyl peroxide, dioctanoyl peroxide, isononanoyl peroxide, succinyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis(2,4-dicWorobenzoyl) peroxide, bis(o-toluyl) peroxide and acetyl-cyclohexanesulphonyi-peroxide.
Liquid peroxy compounds are preferred which are added as such or as a solution in diethyl phosphite to the reaction mixture. Solutions of solid peroxy compounds in diethyl phosphite can also be used, however, as can solutions of solid or liquid peroxy J compounds in other solvents or with the aid of other, inert solvents.
The selection of suitable radical-forming catalysts enables an increased space-time yield to be achieved due to an increased reaction rate, so that the durations of reaction Le A 3 2 25 1 -Foreign Countries are determined only by the rate of addition of the components and the possibility of dissipating heat, and the requisite reaction time after addition is not more than 5 to 10 minutes.
In order to suppress the polymerisation of ethylene and the formation of oligo- or polyethylene phosphonates, ethylene should be used in stoichiometric amounts at most, and preferably as a deficit, and the ethylene should be introduced into diethyl phosphite placed in a reaction vessel. The molar ratio of ethylene to diethyl phosphite is preferably 0.3 to 0.8. FEgher molar ratios up to 1.0 are also possible, depending on the requirement for uniformity of the synthesis product. Introduction of ethylene into the reaction mixture is preferably effected with intensive, thorough mixing of the reaction mixture.
The principle of adding ethylene to diethyl phosphite placed in a reaction vessel can be applied both to batch-wise and continuous modes of conducting the reaction.
Work-up of the synthesis solution can be effected in the usual manner by distillation.
In the course of this procedure, the low-boiling excess of diethyl phosphite is distilled from the DEEP. In order to prevent excessive thermal loading of the product, reduced pressure is preferably employed. The excess diethyl phosphite can be recycled to the process. The DEEP which remains behind can either be used directly or subjected to further purification steps, e.g. to a distillation step, according to need. An almost acid ftee DEEP is obtained in high yield.
In order to carry out the process according to the invention, diethyl phosphite is preferably placed in a reaction vessel and is heated to a temperature of preferably 100'C to 125'C. Ethylene is then fed in approximately in accordance (namely as it is consumed), with a radicalforming catalyst. Foreign eases are most preferably removed before the addition of ethylene, or during the feeding of ethylene if foreign gases are introduced with 30 the ethylene. The removal of foreign gases can be effected, for example, by the evacuation of the diethyl phosphite and/or of the reaction mixture, by passing ethylene through, and/or by the partial outward transfer of the gas phase, cyclically or continuously. Ethylene can be fed on to or below the surface of the reaction mixture. The radical-forming catalyst is Le A 3 2 25 1 -Foreign Countries preferably supplied in admixture with diethyl phosphite. Ethylene is subsequently fed into the reaction vessel approximately corresponding to the consumption of ethylene in the reaction. The reaction is preferably conducted at constant pressure, wherein this pressure can be below, at, or above atmospheric pressure, even though pressure variations do not have a negative effect on the reaction.
The invention is explained in more detail with reference to the following examples.
Examples
Example 1 (according to the invention) 230 g diethyl phosphite, containing 0.007 % by weight monoethyl phosphite as the acid, were placed in a vacuum-tight, stirred apparatus, evacuated to 4 mbar and brought to normal pressure with nitrogen, whilst being simultaneously heated to 120'C. Ethylene and a solution of diethyl phosphite/tertAutyl peroctoate (46 g/3 g) were added in parallel, with intensive stirring. 28 g ethylene were introduced in total.
The acid content in the reaction mixture, as determined by titration with 0. 1 N sodium methylate solution in methanol, was 0. 5 6 % by weight, calculated as monoethyl phosphite.
As measured by gas chromatographic analysis, the 301 g of reaction mixture contained 45.8 % diethyl phosphite and 53.1 % ethanephosphonic acid diethyl ester, corresponding to a yield of 96.4 % theoretical.
Example 2 (procedure according to DE-A 2 043 520) 230 g diethyl phosphite, containing 0.007 % by weight monoethyl phosphite as the acid, were placed in a vacuum-tight, stirred apparatus, evacuated to 4 mbar and brought to normal pressure with nitrogen, whilst being simultaneously heated to 17WC. Ethylene and a solution of diethyl phosphiteldi-tertAutyl peroxide (46 g/3 g) were added in parallel, with intensive stirring. 28 g ethylene were introduced in total.
Le A 3 2 2 5 1 -Foreijzn Countries The acid content in the reaction mixture, deternfined as in example 1, was 1.44 % by weight, calculated as monoethyl phosphite.
As measured by gas chromatographic analysis, the 299 g of reaction mixture contained 46.1 % diethyl phosphite and 52.8 % ethanephosphorfic acid diethyl ester, corresponding to a yield of 95 % theoretical.
Example 3
230 g diethyl phosphite, containing 0.007 % by weight monoethyl phosphite as the acid, were placed in a vacuum-tight, stirred apparatus, evacuated to 4 mbar and brought to 400 mbar with ethylene, whilst being simultaneously heated to 120'C. Ethylene and a solution of diethyl phosphitehertAutyl peroctoate (40 g/2.8 g) were added in paraUe with intensive stirring. 28 g ethylene were introduced in total.
After the feeding-in of ethylene was complete, the batch was stirred for a finther 5 minutes, held at 120'C, and the remainder of the diethyl phosphite/peroxide solution (about 6 g) was added drop-wise. The rapid decrease in pressure indicated that the consumption of ethylene was proceeding rapidly.
The acid content in the reaction mix:ture, determined as in example 1, was 0.63 % by weight calculated as monoethyl phosphite.
As measured by gas chromatographic analysis, the 302 g of reaction mixture contained 45.7 % diethyl phosphite and 53.3) % ethanephosphonic acid diethyl ester, corresponding to a yield of 96.9 % theoretical.
Le A 3 2 2 5 1 -Foreign Countries
Claims (1)
- ClaimsA process for producing ethanephosphonic acid dlethyl ester, the process comprising the steps of.a) b) charging a reaction vessel with diethyl phosphite., adding ethylene and a radical-forming catalyst to the diethyl phosphite in the reaction vessel; wherein the process is carried out a temperature of below about HO'C.The process for producing ethanephosphonic acid diethyl ester according to claim 1, wherein the temperature is held between about WC and 125'C.3.The process for producing ethanephosphonic acid diethyl ester according to claim 1, wherein the radical-forming catalyst comprises an organic peroxide or an azo compound.4. The process for producing ethanephosphonic acid diethyl ester according to claim 4, wherein the organic peroxide catalyst comprises a dialkyl peroxydicarbonate, tert-butyl peroctaoate, tert-amyl perneodecanoate, tertbutyl perpivalate, mono-tert-butyl permaleate, tert-butyl perisobutyrate, didecanoyl peroxide, dioctanoyl peroxide, isononanoyl peroxide, succinyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2,4-dichlorobenzoyl) peroxide, bic (o-toluyl) peroxide, acetylcyclohexanesulphonyl peroxide, or a mixture thereof 5. The process for producing ethanephosphonic acid diethyl ester according to claim 6, wherein the dialkyl peroxydicarbonate comprises diisotridecyl peroxydicarbonate.6. The process for producing ethanephosphonic acid diethyl ester according to claim 1, wherein the process is carried out under reduced pressure.Le A 3 2 2 5 1 -Foreign Countries 7. The process for producing ethanephosphonic acid diethyl ester according to claim 1, wherein the ethylene is used in a stoichiometric amount or less than stoichiometric amount of ethylene to diethyl phosphite.8. The process for producing ethanephosphonic acid diethyl ester according to claim 9, wherein the ethylene is used in a molar ratio amount of ethylene to diethyl phosphite of about 0.3 to 0.8.9. The process for producing ethanephosphonic acid diethyl ester according to claim 1, wherein the reaction vessel comprises a reaction mixture of ethanephosphonic acid diethyl ester and diethyl phosphite.10. The process for producing ethanephosphonic acid diethyl ester according to claim 12, wherein the low acid grade value of the reaction mixture is less than or equal to 0.63% by weight, calculated as monoethyl phosphite.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1997106384 DE19706384C1 (en) | 1997-02-19 | 1997-02-19 | Process for the preparation of diethyl ethanephosphonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB9801960D0 GB9801960D0 (en) | 1998-03-25 |
| GB2322373A true GB2322373A (en) | 1998-08-26 |
Family
ID=7820724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9801960A Withdrawn GB2322373A (en) | 1997-02-19 | 1998-01-29 | Preparation of ethane phosphonic acid diethyl ester |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE19706384C1 (en) |
| GB (1) | GB2322373A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001068656A1 (en) * | 2000-03-13 | 2001-09-20 | Japan Science And Technology Corporation | Processes for the preparation of phosphonic esters |
| WO2014062411A1 (en) * | 2012-10-18 | 2014-04-24 | Dow Global Technologies Llc | Phosphorous-containing aluminum carboxylate salt flame retardants |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB694772A (en) * | 1948-07-10 | 1953-07-29 | Us Rubber Co | Improvements in phosphonic acid esters |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2043520A1 (en) * | 1970-09-02 | 1972-03-09 | Farbwerke Hoechst AG vormals Meister Lucius & Brüning, 6000 Frankfurt | Alkane phosphonic acid di-esters prepn |
| US5268393A (en) * | 1992-07-17 | 1993-12-07 | Blount David H | Flame-retardant polyurethane foam produced without additional blowing agents |
-
1997
- 1997-02-19 DE DE1997106384 patent/DE19706384C1/en not_active Expired - Fee Related
-
1998
- 1998-01-29 GB GB9801960A patent/GB2322373A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB694772A (en) * | 1948-07-10 | 1953-07-29 | Us Rubber Co | Improvements in phosphonic acid esters |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001068656A1 (en) * | 2000-03-13 | 2001-09-20 | Japan Science And Technology Corporation | Processes for the preparation of phosphonic esters |
| US6765107B2 (en) | 2000-03-13 | 2004-07-20 | National Institute Of Advanced Industrial Science And Technology | Method for manufacturing phosphonate esters |
| US7166737B2 (en) | 2000-03-13 | 2007-01-23 | Japan Science And Technology Corporation | Method for manufacturing phosphonate esters |
| WO2014062411A1 (en) * | 2012-10-18 | 2014-04-24 | Dow Global Technologies Llc | Phosphorous-containing aluminum carboxylate salt flame retardants |
| US9353246B2 (en) | 2012-10-18 | 2016-05-31 | Dow Global Technologies Llc | Phosphorous-containing aluminum carboxylate salt flame retardants |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19706384C1 (en) | 1998-07-23 |
| GB9801960D0 (en) | 1998-03-25 |
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