DE4121696A1 - Novel prepn. of phosphite di:ester(s) - by reaction of phosphorous acid or its mono:ester with carboxylic anhydride and then alcohol - Google Patents
Novel prepn. of phosphite di:ester(s) - by reaction of phosphorous acid or its mono:ester with carboxylic anhydride and then alcoholInfo
- Publication number
- DE4121696A1 DE4121696A1 DE19914121696 DE4121696A DE4121696A1 DE 4121696 A1 DE4121696 A1 DE 4121696A1 DE 19914121696 DE19914121696 DE 19914121696 DE 4121696 A DE4121696 A DE 4121696A DE 4121696 A1 DE4121696 A1 DE 4121696A1
- Authority
- DE
- Germany
- Prior art keywords
- phosphorous acid
- ester
- alcohol
- iii
- reaction
- 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- Withdrawn
Links
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 14
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 title claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 10
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 title description 2
- 150000002148 esters Chemical class 0.000 title 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 phosphorous acid diesters Chemical class 0.000 claims abstract description 15
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 abstract description 4
- 150000005690 diesters Chemical class 0.000 abstract description 4
- 150000001348 alkyl chlorides Chemical class 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000003063 flame retardant Substances 0.000 abstract description 2
- 235000011007 phosphoric acid Nutrition 0.000 abstract 2
- 125000003710 aryl alkyl group Chemical group 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 abstract 1
- 239000004753 textile Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- ZLMKQJQJURXYLC-UHFFFAOYSA-N bis(2-ethylhexoxy)-oxophosphanium Chemical compound CCCCC(CC)CO[P+](=O)OCC(CC)CCCC ZLMKQJQJURXYLC-UHFFFAOYSA-N 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- XAKRTGZVYPZHCO-UHFFFAOYSA-O hydroxy-methoxy-oxophosphanium Chemical compound CO[P+](O)=O XAKRTGZVYPZHCO-UHFFFAOYSA-O 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000000047 product 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
- YIKVZDICBNEEOZ-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphite Chemical compound CCCCC(CC)COP(O)O YIKVZDICBNEEOZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- ZUNGGJHBMLMRFJ-UHFFFAOYSA-O ethoxy-hydroxy-oxophosphanium Chemical compound CCO[P+](O)=O ZUNGGJHBMLMRFJ-UHFFFAOYSA-O 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- C07F9/141—Esters of phosphorous acids
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)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Phosphorigsäurediestern. Phosphorigsäurediester sind Zwischenprodukte für die Herstellung von Wirkstoffen, Flammschutz- und Textilveredelungsmitteln.The invention relates to a method for producing Phosphoric acid diesters. Phosphorous acid diesters are intermediate products for the production of active ingredients, flame retardant and textile finishing agents.
Phosphorigsäurediester werden in technischem Maßstab durch Alkoholyse von Phosphor(III)-chlorid hergestellt (Gl. 1)Phosphoric acid diesters are produced on an industrial scale Alcoholysis of phosphorus (III) chloride produced (Eq. 1)
PCl₃+3 ROH → HP(O)(OR)₂+RCl+2 HCl (1)PCl₃ + 3 ROH → HP (O) (OR) ₂ + RCl + 2 HCl (1)
Der wesentliche Nachteil dieser Herstellungsweise besteht, wie aus Bruttogleichung (1) zu entnehmen ist, im Zwangsanfall von Salzsäure und Alkylchloriden, die umweltschonend aufgearbeitet werden müssen. Um diesen Nachteil zu überwinden, wurden Verfahren zur Herstellung von Phosphorigsäureestern aus Phosphor(III)-oxid entwickelt, das mit Alkoholen zu äquimolaren Gemischen aus Phosphorigsäuremono- und Phosphorigsäurediestern reagiert (Gl. 2).The main disadvantage of this method of production is as can be seen from the gross equation (1), in the case of forced attack of hydrochloric acid and alkyl chlorides that are environmentally friendly have to be worked up. To overcome this disadvantage were processes for the preparation of phosphorous acid esters developed from phosphorus (III) oxide with alcohols to equimolar mixtures of phosphoric acid mono- and phosphoric acid diesters reacts (Eq. 2).
P₄O₆+6 ROH → 2 HP(O)(OR)₂+2 HOPH(O)OR (2)P₄O₆ + 6 ROH → 2 HP (O) (OR) ₂ + 2 HOPH (O) OR (2)
Die gleichzeitige Bildung von Mono- und Diester im Molverhältnis 1 : 1 ist ein erheblicher Nachteil dieser Verfahren, da der Bedarf für Diester wesentlich größer als der für Monoester ist. Weiterhin ist bekannt, Phosphorigsäurediester langkettiger Alkohole (C<5) durch Veresterung von phosphoriger Säure mit überschüssigem Alkohol herzustellen, indem das bei der Veresterung entstandene Wasser durch azeotrope Destillation laufend abgetrennt wird. Das Verfahren ist energieaufwendig und auf die Herstellung von Phosphorigsäurediestern langkettiger Alkohole eingeschränkt.The simultaneous formation of mono- and diesters in a molar ratio 1: 1 is a significant disadvantage of these methods, because the need for diesters is much greater than that is for monoester. It is also known phosphorous acid diester long chain alcohols (C <5) by esterification of to produce phosphorous acid with excess alcohol, by the water formed during the esterification through azeotropic distillation is continuously separated. The procedure is energy consuming and on the production of Phosphorous acid diesters of long-chain alcohols restricted.
Der Erfindung liegt die Aufgabe zugrunde, ein energetisch günstiges Verfahren zur Herstellung von Phosphorigsäurediestern zu entwickeln, das nicht mit Chlorwasserstoff und Alkylchloriden als Abprodukte belastet ist und das auch die Darstellung von Phosphorigsäurediestern von kurzkettigen Alkoholen (C<5) erlaubt.The invention is based, an energetic task favorable process for the preparation of phosphorous diesters to develop that not with hydrogen chloride and Alkyl chlorides are contaminated as waste products and that too Representation of short-chain phosphoric acid diesters Alcohols (C <5) allowed.
Erfindungsgemäß wird die Aufgabe dadurch gelöst, daß Phosphorigsäurediester durch Umsetzung von phosphoriger Säure mit einem Carbonsäureanhydrid, vorzugsweise Acetanhydrid, und einem Alkohol im Molverhältnis 1 : 2,0-3,0 : 2,0-2,5 entsprechend Bruttogleichung (3)According to the invention the object is achieved in that phosphorous diester by reacting phosphorous acid with a carboxylic anhydride, preferably acetic anhydride, and an alcohol in a molar ratio of 1: 2.0-3.0: 2.0-2.5 according to gross equation (3)
R¹=organischer Rest, R²=alkyl-, cycloalkyl-, aralkyl- oder durch Umsetzung von Phosphorigsäuremonoester mit einem Carbonsäureanhydrid und einem Alkohol im Molverhältnis 1 : 1,0-1,5 : 1,0-1,5 entsprechend Bruttogleichung (4) hergestellt werden.R¹ = organic radical, R² = alkyl-, cycloalkyl-, aralkyl- or by reacting phosphoric acid monoester with a Carboxylic anhydride and an alcohol in a molar ratio 1: 1.0-1.5: 1.0-1.5 according to gross equation (4) getting produced.
R¹=organischer Rest, R²=alkyl-, cycloalkyl-, aralkyl-R¹ = organic radical, R² = alkyl-, cycloalkyl-, aralkyl-
Die Umsetzung erfolgt durch Mischen der Reaktionskomponenten in der Reihenfolge P(III)-Verbindung, Carbonsäureanhydrid, Alkohol, gegebenenfalls unter Zusatz eines inerten Lösungsmittels, bei Temperaturen zwischen 20 und 50°C.The reaction is carried out by mixing the reaction components in the order P (III) compound, carboxylic anhydride, Alcohol, optionally with the addition of an inert solvent, at temperatures between 20 and 50 ° C.
Für die Herstellung von Phosphorigsäurediestern lassen sich als Ausgangsprodukte vorteilhaft Gemische aus phosphoriger Säure, Phosphorigsäuremono- und Phosphorigsäurediester ver wenden.For the production of phosphorous diesters as starting products advantageous mixtures of phosphorous Acid, phosphoric acid mono- and phosphoric acid diesters ver turn.
Die Trennung Carbonsäure/Phosphorigsäurediester erfolgt in bekannter Weise, z. B. durch Destillation.The separation of carboxylic acid / phosphorous diester takes place in known manner, e.g. B. by distillation.
Die Erfindung soll an nachfolgenden Beispielen näher erläutert werden.The invention is illustrated by the following examples will.
In einem Reaktionsgefäß, versehen mit Rührer, Thermometer und Tropftrichter, wurden 0,5 mol (41,0 g) kristalline phosphorige Säure vorgelegt und unter Rühren bei T=25°C 1,5 mol (153,1 g) Essigsäureanhydrid zugegeben. Die phosphorige Säure löste sich. Die homogene, farblose Reaktionslösung wurde 1 Stunde gerührt und danach unter Kühlen und Rühren 1,1 mol (35,2 g) Methanol tropfenweise so zugegeben, daß die Temperatur unter 50°C blieb. Die Reaktionslösung wurde 2 Stunden nachgerührt.In a reaction vessel, equipped with a stirrer, thermometer and dropping funnel, became 0.5 mol (41.0 g) of crystalline Phosphorous acid presented and with stirring at T = 25 ° C. 1.5 mol (153.1 g) of acetic anhydride was added. The phosphorous Acid dissolved. The homogeneous, colorless reaction solution was stirred for 1 hour and then with cooling and Stirring 1.1 mol (35.2 g) of methanol added dropwise so that the temperature remained below 50 ° C. The reaction solution was stirred for 2 hours.
Aus dem ³¹P-NMR-Spektrum der Reaktionslösung war zu entnehmen,
daß die vorgelegte phosphorige Säure quantitativ
zu Dimethylphosphit umgesetzt wurde.
Dimethylphosphit ³¹P-NMR
δ = 8,86 ppm
JPH = 718,0 Hz
JPCH = 12,0 HzFrom the 31 P-NMR spectrum of the reaction solution it could be seen that the phosphorous acid introduced was converted quantitatively to dimethyl phosphite.
Dimethyl phosphite 31 P NMR
δ = 8.86 ppm
J PH = 718.0 Hz
J PCH = 12.0 Hz
In einer Reaktionsanordnung, wie unter Beispiel 1 beschrieben,
wurden zu 0,25 mol (20,5 g) kristalliner phosphoriger
Säure 0,625 mol (63,81 g) Acetanhydrid gegeben. Nach Lösen
der phosphorigen Säure und 1stündigem Rühren wurden dann
unter Kühlung und Rühren 0,55 mol (71,5 g) 2-Ethylhexanol
tropfenweise so zugegeben, daß die Temperatur unter 50°C
blieb. Die Reaktionslösung wurde 2 Stunden nachgerührt.
Aus dem ³¹P-NMR-Spektrum der Reaktionslösung war ersichtlich,
daß das Reaktionsprodukt zu 96% aus Di-2-ethylhexylphosphit
und zu 4% aus Mono-2-ethylhexylphosphit bestand.
Di-2-ethylhexylphosphit ³¹P-NMR
δ = 8,95 ppm
JPH = 712,2 Hz
JPCH = 7,4 Hz
In a reaction arrangement as described in Example 1, 0.625 mol (63.81 g) of acetic anhydride was added to 0.25 mol (20.5 g) of crystalline phosphorous acid. After dissolving the phosphorous acid and stirring for 1 hour, 0.55 mol (71.5 g) of 2-ethylhexanol were then added dropwise with cooling and stirring in such a way that the temperature remained below 50.degree. The reaction solution was stirred for 2 hours. From the 31 P-NMR spectrum of the reaction solution, it was seen that the reaction product was 96% di-2-ethylhexyl phosphite and 4% mono-2-ethylhexyl phosphite.
Di-2-ethylhexyl phosphite 31 P NMR
δ = 8.95 ppm
J PH = 712.2 Hz
J PCH = 7.4 Hz
In 0,4 mol eines Gemisches, bestehend aus 51,5% Monoethylphosphit und 48,5% Dimethylphosphit in Benzen als Lösungsmittel wurden unter Rühren und Kühlen 0,3 mol (30,6 g) Acetanhydrid zugegeben. Die Reaktionslösung wurde 1 Stunde gerührt, anschließend wurden unter Rühren und Kühlen 0,24 mol (7,7 g) Methanol so zugegeben, daß die Temperatur nicht über 50°C anstieg. Das Molverhältnis Monomethylphosphit : Acetanhydrid : Methanol betrug 1 : 1,5 : 1,2. Die Reaktionsmischung wurde 3 Stunden nachgerührt.In 0.4 mol of a mixture consisting of 51.5% monoethyl phosphite and 48.5% dimethyl phosphite in benzene as a solvent 0.3 mol (30.6 g) Acetic anhydride added. The reaction solution was 1 hour stirred, then with stirring and cooling 0.24 mol (7.7 g) methanol added so that the temperature did not exceed 50 ° C rise. The molar ratio of monomethyl phosphite: acetic anhydride : Methanol was 1: 1.5: 1.2. The reaction mixture was stirred for 3 hours.
Nach ³¹P-NMR-Messungen lagen in der Reaktionslösung 96%
des Phosphors als Dimethylphosphit und 4% als Monomethylphosphit
vor. Die Isolierung des Diesters erfolgte in bekannter
Weise durch Vakuumdestillation.
Dimethylphosphit ³¹P-NMR
δ = 8,86 ppm
JPH = 718,0 Hz
JPCH = 12,0 HzAccording to 31 P-NMR measurements, 96% of the phosphorus was present as dimethyl phosphite and 4% as monomethyl phosphite in the reaction solution. The diester was isolated in a known manner by vacuum distillation.
Dimethyl phosphite 31 P NMR
δ = 8.86 ppm
J PH = 718.0 Hz
J PCH = 12.0 Hz
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19914121696 DE4121696A1 (en) | 1991-06-29 | 1991-06-29 | Novel prepn. of phosphite di:ester(s) - by reaction of phosphorous acid or its mono:ester with carboxylic anhydride and then alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19914121696 DE4121696A1 (en) | 1991-06-29 | 1991-06-29 | Novel prepn. of phosphite di:ester(s) - by reaction of phosphorous acid or its mono:ester with carboxylic anhydride and then alcohol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE4121696A1 true DE4121696A1 (en) | 1993-01-07 |
Family
ID=6435141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19914121696 Withdrawn DE4121696A1 (en) | 1991-06-29 | 1991-06-29 | Novel prepn. of phosphite di:ester(s) - by reaction of phosphorous acid or its mono:ester with carboxylic anhydride and then alcohol |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE4121696A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010136565A1 (en) * | 2009-05-28 | 2010-12-02 | Straitmark Holding Ag | Method for the manufacture of dialkylphosphites |
| WO2010136575A1 (en) * | 2009-05-28 | 2010-12-02 | Straitmark Holding Ag | Method for the manufacture of dialkyl phosphites |
| JP2012528122A (en) * | 2009-05-28 | 2012-11-12 | ストレイトマーク・ホールディング・アーゲー | Process for the production of dialkyl phosphites |
| EP2581378A1 (en) | 2011-10-13 | 2013-04-17 | Straitmark Holding AG | Method for the esterification of P-O components |
| CN109912647A (en) * | 2019-03-20 | 2019-06-21 | 山东泰和水处理科技股份有限公司 | A kind of synthetic method of dimethylphosphite |
-
1991
- 1991-06-29 DE DE19914121696 patent/DE4121696A1/en not_active Withdrawn
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010136565A1 (en) * | 2009-05-28 | 2010-12-02 | Straitmark Holding Ag | Method for the manufacture of dialkylphosphites |
| WO2010136575A1 (en) * | 2009-05-28 | 2010-12-02 | Straitmark Holding Ag | Method for the manufacture of dialkyl phosphites |
| CN102448973A (en) * | 2009-05-28 | 2012-05-09 | 施里特马克控股公司 | Method for the manufacture of dialkyl phosphites |
| CN102448971A (en) * | 2009-05-28 | 2012-05-09 | 施里特马克控股公司 | Method for the manufacture of dialkylphosphites |
| JP2012528122A (en) * | 2009-05-28 | 2012-11-12 | ストレイトマーク・ホールディング・アーゲー | Process for the production of dialkyl phosphites |
| JP2012528123A (en) * | 2009-05-28 | 2012-11-12 | ストレイトマーク・ホールディング・アーゲー | Process for the production of dialkyl phosphites |
| US8802883B2 (en) | 2009-05-28 | 2014-08-12 | Straitmark Holding Ag | Method for the manufacture of dialkylphosphites |
| US8829222B2 (en) | 2009-05-28 | 2014-09-09 | Straitmark Holding Ag | Process for the manufacture of dialkylphosphites |
| EP2581378A1 (en) | 2011-10-13 | 2013-04-17 | Straitmark Holding AG | Method for the esterification of P-O components |
| WO2013053939A1 (en) | 2011-10-13 | 2013-04-18 | Straitmark Holding Ag | Method for the esterification of p-o components |
| CN109912647A (en) * | 2019-03-20 | 2019-06-21 | 山东泰和水处理科技股份有限公司 | A kind of synthetic method of dimethylphosphite |
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