CA2644961A1 - Method for the purification of triorganophosphites by treatment with a basic additive - Google Patents
Method for the purification of triorganophosphites by treatment with a basic additive Download PDFInfo
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- CA2644961A1 CA2644961A1 CA002644961A CA2644961A CA2644961A1 CA 2644961 A1 CA2644961 A1 CA 2644961A1 CA 002644961 A CA002644961 A CA 002644961A CA 2644961 A CA2644961 A CA 2644961A CA 2644961 A1 CA2644961 A1 CA 2644961A1
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- 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 System
- 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
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- 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 System
- C07F9/02—Phosphorus compounds
- C07F9/025—Purification; Separation; Stabilisation; Desodorisation of organo-phosphorus compounds
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- 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 System
- 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
- C07F9/1412—Polyol derivatives esterified at least twice by phosphorous acid groups
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- 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 System
- 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
- C07F9/142—Esters of phosphorous acids with hydroxyalkyl compounds without further substituents on alkyl
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- 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 System
- 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
- C07F9/144—Esters of phosphorous acids with cycloaliphatic alcohols
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- 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 System
- 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
- C07F9/145—Esters of phosphorous acids with hydroxyaryl compounds
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- 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 System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
Abstract
The invention provides a method for separating one or more triorganophosphite components from a crude phosphite mixture containing acidic hydrolysis products, the method comprising: contacting said crude phosphite mixture with a basic additive to produce a second mixture comprising a first phase and a second phase, wherein said first phase comprises the basic additive and one or more components independently selected from the group consisting of (R2O)(R3O)POH, (R1O)(HO)PO(H) and H3PO3, wherein R1, R2 and R3 are independently selected from the group consisting of C1 to C18 alkyl, C6 to C18 aryl and hydroxyaryl, and C3 to C18 cycloalkyl and hydroxyalkyl radicals, and wherein R2 and R3 can optionally be connected to each other directly by a chemical bond or through an intermediate divalent group R9; and said second phase comprises one or more triorganophosphite components independently selected from the group consisting of (R4O)(R5O)P(OR6) and ((R7O)(R8O)PO)nA, wherein R4, R5, R6, R7 and R8 are independently selected from the group consisting of C1 to C18 alkyl, C6 to C18 aryl and C3 to C18 cycloalkyl radicals, wherein each of R4, R5 and R6 can optionally be connected to one or both of the other two directly by a chemical bond or through an intermediate divalent group R10, wherein R7 and R8 can optionally be connected to each other directly by a chemical bond or through an intermediate divalent group R11, wherein A is an optionally substituted or unsubstituted aliphatic, aromatic or heteroaromatic radical, and wherein n is an integer greater than 1; and R9, R10, and R11 are independently selected from the group consisting of - O-, -S-, and -CH(R12)-, wherein R12 is selected from the group consisting of H, C6 to C18 aryl, and C1 to C18 alkyl.
Description
METHOD FOR THE PURIFICATION OF TRIORGANOPHOSPHITES BY
TREATMENT WITH A BASIC ADDITIVE
CROSS-REFERENCE TO RELATED APPLICATIONS
s This application claims benefit of priority from Provisional Application No.
60/783,462, filed March 17, 2006. This application hereby incorporates by ~-reference Provisional Application No. 60/783,462 in its entirety.
FIELD OF THE INVENTION
The invention relates to the field of preparation and use of triorganophosphite compounds. More specifically, the invention relates to the partial removal of phosphorus acids in triorganophosphite product streams by treatment with a basic additive. Because the phosphorus acids can act as catalysts for triorganophosphite hydrolysis, the treated triorganophosphite product streams can be stabilized against further hydrolysis when exposed to water.
BACKGROUND OF THE INVENTION
Triorganophosphites of the general structure (R40)(R$O)P(OR6) and ((R'O)(R8O)PO)nA, where "A" is an optionally substituted or unsubstituted aliphatic, aromatic, or heteroaromatic radical and n is an integer greater than 1, are used in a number of important commercial applications including their use as antioxidants, stabilizers, anti-wear additives and as ligands for various catalytic processes. Generally, triorganophosphites are produced from PX3 (X = Cl, Br, or I) and the corresponding alcohols (ROH). This reaction occurs stepwise by displacement of X with OR_ When X is Cl, the process can form phosphorodichloridite (R40)PCI2 and phosphorochloridite (R40)(R50)PCI
intermediates, triorganophosphites (R40)(R50)P(ORs) and acid HX.
Several methods for making organophosphites, for example those 3o described in Houben-Weyl, Bd. XXII/2 pages 12-17, G. Thieme Verlag, Stuttgart 1964, and supplement El, pages 413-421 Stuttgart, New York 1982, are known using readily available PCIs and the corresponding alcohols. The acid HX can be removed by physical separation or by acid-base reaction using organic or inorganic bases. In addition, US Patent No. 6,069,267, and US Patent No.
6,031,120 describe the use of triorganoamines to remove HCI followed by water washing at tow temperatures to remove the corresponding ammonium hydrochloride salts from the triorganophosphite mixture.
Houben-Weyl, Bd. XXII/2 Chapter I and pages 30-32, G. Thieme Verlag, Stuttgart 1964 teaches that triorganophosphites are easily hydrolyzed in the presence of water, especially in the presence of acidic compounds, to produce one or more of the compounds diorganohydrogenphosphite (R20)(R30)POH, io organodihydrogenphosphite (R'O)(HO)PO(H), and phosphorous acid H3P03.
Gerard, Hudson and Healy, respectively, (in G.M. Kosolapoff & L. Maier Eds., Organic Phosphorous Compounds, Vol. 5 pages 41-42, Wiley & Sons., New York, 1973; Healy et al. J. Inorg. Nucl. Chem., 1974, 36, 2579) teach that this hydrolysis reaction is autocatalytic due to the acidic properties of diorganohydrogenphosphite (R20)(R30)POH, organodihydrogenphosphite (R'O)(OH)PO(H) and H3PO3. Hydrolysis under basic conditions was found to be slower than hydrolysis in the presence of acids (Westheimer et al., J. Amer.
Chem. Soc. 1988, 110, 183). Without the removal of these acidic hydrolysis products, as a result of hydrolysis, there can be significant degradation and loss of the triorganophosphite product during downstream processing and storage. In order to at least partially address this effect, US Patent No. 3,553,298 teaches that nitrogen-containing compound additives such as amines and magnesium oxide can partially stabilize the triorganophosphites by retarding hydrolysis.
However, such additives can cause undesirable effects or be incompatible with the use of the triorganophosphites, for example during preparation of a transition metal-triorganophosphite catalyst or catalyst precursor for reactions such as hydrocyanation and hydroformylation, for example. It would, therefore, be desirable to have a method to stabilize triorganophosphites without using additives that may provide undesirable side effects.
TREATMENT WITH A BASIC ADDITIVE
CROSS-REFERENCE TO RELATED APPLICATIONS
s This application claims benefit of priority from Provisional Application No.
60/783,462, filed March 17, 2006. This application hereby incorporates by ~-reference Provisional Application No. 60/783,462 in its entirety.
FIELD OF THE INVENTION
The invention relates to the field of preparation and use of triorganophosphite compounds. More specifically, the invention relates to the partial removal of phosphorus acids in triorganophosphite product streams by treatment with a basic additive. Because the phosphorus acids can act as catalysts for triorganophosphite hydrolysis, the treated triorganophosphite product streams can be stabilized against further hydrolysis when exposed to water.
BACKGROUND OF THE INVENTION
Triorganophosphites of the general structure (R40)(R$O)P(OR6) and ((R'O)(R8O)PO)nA, where "A" is an optionally substituted or unsubstituted aliphatic, aromatic, or heteroaromatic radical and n is an integer greater than 1, are used in a number of important commercial applications including their use as antioxidants, stabilizers, anti-wear additives and as ligands for various catalytic processes. Generally, triorganophosphites are produced from PX3 (X = Cl, Br, or I) and the corresponding alcohols (ROH). This reaction occurs stepwise by displacement of X with OR_ When X is Cl, the process can form phosphorodichloridite (R40)PCI2 and phosphorochloridite (R40)(R50)PCI
intermediates, triorganophosphites (R40)(R50)P(ORs) and acid HX.
Several methods for making organophosphites, for example those 3o described in Houben-Weyl, Bd. XXII/2 pages 12-17, G. Thieme Verlag, Stuttgart 1964, and supplement El, pages 413-421 Stuttgart, New York 1982, are known using readily available PCIs and the corresponding alcohols. The acid HX can be removed by physical separation or by acid-base reaction using organic or inorganic bases. In addition, US Patent No. 6,069,267, and US Patent No.
6,031,120 describe the use of triorganoamines to remove HCI followed by water washing at tow temperatures to remove the corresponding ammonium hydrochloride salts from the triorganophosphite mixture.
Houben-Weyl, Bd. XXII/2 Chapter I and pages 30-32, G. Thieme Verlag, Stuttgart 1964 teaches that triorganophosphites are easily hydrolyzed in the presence of water, especially in the presence of acidic compounds, to produce one or more of the compounds diorganohydrogenphosphite (R20)(R30)POH, io organodihydrogenphosphite (R'O)(HO)PO(H), and phosphorous acid H3P03.
Gerard, Hudson and Healy, respectively, (in G.M. Kosolapoff & L. Maier Eds., Organic Phosphorous Compounds, Vol. 5 pages 41-42, Wiley & Sons., New York, 1973; Healy et al. J. Inorg. Nucl. Chem., 1974, 36, 2579) teach that this hydrolysis reaction is autocatalytic due to the acidic properties of diorganohydrogenphosphite (R20)(R30)POH, organodihydrogenphosphite (R'O)(OH)PO(H) and H3PO3. Hydrolysis under basic conditions was found to be slower than hydrolysis in the presence of acids (Westheimer et al., J. Amer.
Chem. Soc. 1988, 110, 183). Without the removal of these acidic hydrolysis products, as a result of hydrolysis, there can be significant degradation and loss of the triorganophosphite product during downstream processing and storage. In order to at least partially address this effect, US Patent No. 3,553,298 teaches that nitrogen-containing compound additives such as amines and magnesium oxide can partially stabilize the triorganophosphites by retarding hydrolysis.
However, such additives can cause undesirable effects or be incompatible with the use of the triorganophosphites, for example during preparation of a transition metal-triorganophosphite catalyst or catalyst precursor for reactions such as hydrocyanation and hydroformylation, for example. It would, therefore, be desirable to have a method to stabilize triorganophosphites without using additives that may provide undesirable side effects.
US Patent No. 6,069,267 Example 1 discloses a sequential treatment of a triorganophosphite reaction mixture in an organic solvent with 0.1 N aqueous HCI, 0.1 N aqueous NaOH, followed by distilled water.
US Patent No. 6,844,289 discloses a process for combining a crude ligand s mixture, prepared for example by the process of US Patent No. 6,069,267, with divalent nickel compounds and reducing agents to produce a catalyst which is a complex of nickel and a bidentate phosphorus compound. This patent discloses that such crude ligand mixture can contain byproducts which may affect the rate of formation of the nickel-containing catalyst. Disclosed therein are treatment io methods which include contacting crude ligand mixture with one or more of, for example, a weakly basic organic resin and a two phase solvent system for liquid-liquid extraction. The patent discloses that various treatments of crude ligand may overcome deleterious rate inhibiting effects of byproduct impurities which are present in the crude ligand.
SUMMARY OF THE INVENTION
As described above, triorganophosphites can be hydrolyzed in basic as well as acidic conditions, with base-catalyzed hydrolysis being slower than acid-catalyzed hydrolysis. In this regard, it has been discovered that hydrolysis 2o products can be removed by treatment with a strong base, so that the overall degradation of triorganophosphite may be decreased.
The present invention includes a method for separating one or more triorganophosphite components from a crude phosphite mixture containing acidic hydrolysis products by contacting the crude phosphite mixture with a basic additive to produce a second mixture comprising a first phase and a second phase. The first phase comprises the basic additive and one or more components independently selected from the group consisting of (R20)(R30)POH, (R'O)(HO)PO(H) and H3PO3 wherein R1, R2 and R3 are independently selected from the group consisting of Ct to C,s alkyl, C6 to C18 aryl 3o and hydroxyaryl, and C3 to C18 cycloalkyl and hydroxyalkyl radicals, and wherein R2 and R3 can optionally be connected to each other directly by a chemical bond or through an intermediate divalent group R9. R9 is selected from the group consisting -0-, -S-,*and -CH(R'2)-, wherein R12 is selected from the group comprising H, C6 to C18 aryl, and C, to C18 alkyl.
The second phase comprises one or more triorganophosphite components independently selected from the group consisting of (R40)(R50)P(OR6) and ((R7O)(R80)PO)õA, wherein R4, R5, R6, R7 and R 8 are independently selected from the group consisting of C, to C18 alkyl, C6 to C18 aryl and C3 to C18 cycloalkyl radicals, and wherein each R4, R5 and R6 can optionally be connected to one or both of the other two directly by a chemical bond or io through an intermediate divalent group R10, and R' and Rg can optionally be connected to each other directly by a chemical bond or through an intermediate divalent group R". The intermediate divalent groups R10 and R" are independently selected from the group consisting of -0-, -S-, and -CH(R12)-, wherein R12 is selected from the group consisting of H, C6 to C18 aryl, and C, to 1s C18 alkyl. The substituent "A" is an optionally substituted or unsubstituted aliphatic, aromatic, or heteroaromatic radical and n is an integer greater than 1.
Examples of A include C1 to C18 aliphatic, C6 to C28 aromatic, or C3 to C28 heteroaromatic radicals.
The basic additive can comprise at least one compound selected from the 20 group consisting of NaOH, KOH, Na2CO3, K2CO3, Ca(OH)2, NH4OH, CaCO3, a strongly basic anion-exchange resin, and combinations thereof. In one embodiment, the basic additive comprises a strongly basic anion-exchange resin, for example a strongly basic anion-exchange resin comprising polymer-bound tetraorgano-ammonium hydroxide groups.
25 I n one embodiment of the present invention, the basic additive and the crude phosphite mixture are contacted at temperatures above about -25 C, for example at temperatures from about -10 C to about 30 C.
In yet another embodiment of the present invention, the first phase is maintained at or above a pH of about 13.5 throughout the contacting process.
30 The present invention also relates to a method for separating triorganophosphite components from a crude phosphite mixture containing acidic hydrolysis products which further comprises the step of contacting the crude phosphite mixture with water before contacting the crude phosphite mixture with the basic additive.
The present invention also relates to methods for separating triorganophosphite components from a crude phosphite mixture containing acidic hydrolysis products wherein the methods further comprise the steps of separating the first phase from the second phase, and contacting the second phase with the basic additive. In another embodiment the present invention includes contacting the second phase with a brine solution after contacting with io the basic additive.
Another embodiment of the present invention further comprises contacting the second phase with a transition metal or a transition metal compound to produce a transition metal-triorganophosphite catalyst or catalyst precursor.
Examples of transition metals or transition metal compounds that can be used include Ni(COD)2 (COD is 1,5-cyclooctadiene), Ni[P(O-o-C6H4CH3)3]3 and Ni[P(O-o-C6H4CH3)3]2(C2H4), all of which are known in the art. The resulting transition metal-triorganophosphite catalyst or catalyst precursor can be useful for reactions such as hydrocyanation or hydroformylation, for example.
The invention also relates to a method for preparing triorganophosphites, which comprises contacting an alcohol with PCl3 in the presence of a triorganoamine to produce a first reaction product comprising one or more organophosphites and triorganoamine hydrochloride; removing the triorganoamine hydrochloride from the first reaction product to produce a second reaction product optionally containing one or more triorganophosphites, diorganohydrogenphosphite (R 20)(R30)POH, organodihydrogenphosphite (R'O)(HO)PO(H) and H3PO3, wherein R1, R2 and R3 are independently selected from the group consisting of C, to C18 alkyl, C6 to Cl8 aryl and hydroxyaryl, and C3 to C18 cycloalkyl and hydroxyalkyl radicals, and wherein R2 and R3 can optionally be connected to each other directly by a chemical bond or through an intermediate divalent group R9, wherein R9 is selected from the group consisting of -0-, -S-, and -CH(R12)-, wherein R 12 is selected from the group consisting of H, Cs to C18 aryl, and C, to C1$ alkyl; and removing at least a portion of one or more of the compounds diorganohydrogenphosphite (R20)(R30)POH, organodihydrogenphosphite (R'O)(HO)PO(H) and H3P03by contacting the second reaction product with a basic additive.
BRIEF DESCRIPTION OF THE FIGURE
FIG. 1 is a graphical representation showing the fraction of hydrolysis products remaining in the organic phase after contact with a control (brine) as compared to contact with a basic additive.
DETAILED DESCRIPTION OF THE INVENTION
The present invention includes methods for purifying and stabilizing triorganophosphites by removing acidic impurities from the phase containing the triorganophosphites. For example, acidic impurities such as diorganohydrogenphosphite (R20)(R30)POH, organodihydrogenphosphite (R'O)(HO)PO(H), and H3PO3 can occur as a result of aqueous workup of crude triorganophosphites, such as (R40)(R50)P(OR), and ((R'O)(R8O)PO)õA, and from unconverted phosphorodichloridite (R40)PCI2 and phosphorochloridite (R 40)(R50)PCI intermediates used as components for the making of triorganophosphites. Furthermore, small amounts of the above-described acidic impurities can increase in concentration during storage of triorganophosphite materials by autocatalytic hydrolysis upon exposure to moisture, causing yield loss and undesirable effects with the use of triorganophosphites in applications such as catalysis. At least one of these disadvantages may be overcome by removal of acidic impurities by means of extraction with a basic additive.
In at least one embodiment falling within the scope of the present invention, a crude phosphite mixture comprising at least one triorganophosphite selected from the group consisting of (R40)(R5O)P(OR6), and ((R7O)(RSO)PO)r,A;
and one or more of the compounds diorganohydrogenphosphite (R20)(R30)POH, organodihydrogenphosphite (R'O)(HO)PO(H), and H3P03 is contacted with a basic additive to produce a second mixture. The second mixture comprises two phases - a first phase and a second phase. The first phase comprises the basic additive and at least a portion of one or more of the components consisting of diorganohydrogenphosphite (R20)(R30)POH, organodihydrogenphosphite (R'O)(HO)PO(H), and H3P03. The second phase comprises at least a portion of the organophosphites. The first phase of the second mixture can optionally be separated from the second phase, using general separation methods known by those skilled in the art. For example, if the basic phase is liquid, such as aqueous NaOH, a conventional mixer-settler can be used to contact the crude phosphite mixture and aqueous NaOH then io separate the second phase comprising the triorganophosphites from the first phase comprising the acidic impurities. If, instead, a basic ion-exchange resin is deployed, a decanter or filter may be used.
R1, R2, and R3 are independently selected from the group consisting of C, to C18 alkyl, C6 to Ci8 aryl and hydroxyaryl, and C3 to C18 cycloalkyl and hydr.oxyaikyl radicals; R2 and R3 can optionally be connected to each other directly by a chemical bond or through an intermediate divalent group R9. R9 is selected from the group consisting of -0-, -S-, and -CH(R12)-, wherein R12 is selected from the group consisting of H, C6 to Ci8 aryl, or C, to C18 alkyl.
R4, R5, R6, R', and R8 are independently selected from the group consisting of C1 to C18 alkyl, C6 to C18 aryl, and C3 to Cy8 cycloalkyl radicals.
Each of R4, R5, and Rs can optionally be connected to one or both of the other two directly by a chemical bond or through an intermediate divalent group R10.
and R8 can optionally be connected to each other directly by a chemical bond or through an intermediate divalent group R". R10 and R" are independently selected from the group consisting of -0-, -S-, and -CH(R'2)-, wherein R12 is selected from the group consisting of H, C6 to C,s aryl, and C, to C18 alkyl.
The substituent "A" is an optionally substituted or unsubstituted aliphatic, aromatic or heteroaromatic radical where n is an integer greater than 1.
The basic additive employed in the present invention can comprise one or more compositions comprising at least one basic compound and/or material.
The basic additive may, for example, comprise at least one compound selected from the group consisting of NaOH, KOH, Na2CO3, K2CO:3, Ca(OH)2, NH4OH, CaCO3, a strongly basic anion-exchange resin, and combinations thereof.
Examples of suitable strongly basic ion-exchange resins are resins comprising polymer-bound tetraorgano-ammonium hydroxide groups.
Since hydrolysis rates are dependent on temperature, the extraction temperature should ideally be as low as possible only restricted by physical limits. In the case of liquid-liquid extractions, a physical limit impacting the range-of suitable operation temperatures is, for example, the freezing point of the liquid phases. Since under commercial operation the temperature range achievable is io subject to the limits of the equipment available, temperatures above about -are generally preferred. An example of a non-limiting temperature range for this process is from about -10 C to about 30 C.
Ideally, the pH of the basic phase should remain at or above about 13.5 throughout the extraction process. This can be accomplished by using a 1 normal solution of a strong base in water or a strongly basic anion-exchange resin of equivalent strength. If the production of the triorganophosphite generates a salt constituting a weak acid such as a triorganoamine hydrochloride, the weak acid should be removed first to allow for an effective extraction process of the acidic diorganohydrogenphosphite (R 20)(R30)POH, organodihydrogenphosphite 2o (R'O)(HO)PO(H), and H3PO3 impurities with the basic additive.
Triorganoamine hydrochloride salt removal can be achieved by filtration and/or by water extraction prior to contacting with the basic additive as, for example, described in US Patent Nos. 6,069,267, and 6,031,120.
The total amount of molar equivalents of base to be used is, at least in part, a function of the total amount of molar equivalents of acidic diorganohydrogenphosphite (R20)(R30)POH, organodihydrogenphosphite (R'O)(HO)PO(H), and H3POs impurities that are present prior to the treatment with the basic additive. For example, a 10- to 1000-fold excess of the base can be suitable, provided that, in the case of a solution extraction, a minimum pH
of 3o about 13.5 of the basic solution is maintained throughout the extraction process, or, in the case of a resin treatment, an equivalent basicity is maintained.
US Patent No. 6,844,289 discloses a process for combining a crude ligand s mixture, prepared for example by the process of US Patent No. 6,069,267, with divalent nickel compounds and reducing agents to produce a catalyst which is a complex of nickel and a bidentate phosphorus compound. This patent discloses that such crude ligand mixture can contain byproducts which may affect the rate of formation of the nickel-containing catalyst. Disclosed therein are treatment io methods which include contacting crude ligand mixture with one or more of, for example, a weakly basic organic resin and a two phase solvent system for liquid-liquid extraction. The patent discloses that various treatments of crude ligand may overcome deleterious rate inhibiting effects of byproduct impurities which are present in the crude ligand.
SUMMARY OF THE INVENTION
As described above, triorganophosphites can be hydrolyzed in basic as well as acidic conditions, with base-catalyzed hydrolysis being slower than acid-catalyzed hydrolysis. In this regard, it has been discovered that hydrolysis 2o products can be removed by treatment with a strong base, so that the overall degradation of triorganophosphite may be decreased.
The present invention includes a method for separating one or more triorganophosphite components from a crude phosphite mixture containing acidic hydrolysis products by contacting the crude phosphite mixture with a basic additive to produce a second mixture comprising a first phase and a second phase. The first phase comprises the basic additive and one or more components independently selected from the group consisting of (R20)(R30)POH, (R'O)(HO)PO(H) and H3PO3 wherein R1, R2 and R3 are independently selected from the group consisting of Ct to C,s alkyl, C6 to C18 aryl 3o and hydroxyaryl, and C3 to C18 cycloalkyl and hydroxyalkyl radicals, and wherein R2 and R3 can optionally be connected to each other directly by a chemical bond or through an intermediate divalent group R9. R9 is selected from the group consisting -0-, -S-,*and -CH(R'2)-, wherein R12 is selected from the group comprising H, C6 to C18 aryl, and C, to C18 alkyl.
The second phase comprises one or more triorganophosphite components independently selected from the group consisting of (R40)(R50)P(OR6) and ((R7O)(R80)PO)õA, wherein R4, R5, R6, R7 and R 8 are independently selected from the group consisting of C, to C18 alkyl, C6 to C18 aryl and C3 to C18 cycloalkyl radicals, and wherein each R4, R5 and R6 can optionally be connected to one or both of the other two directly by a chemical bond or io through an intermediate divalent group R10, and R' and Rg can optionally be connected to each other directly by a chemical bond or through an intermediate divalent group R". The intermediate divalent groups R10 and R" are independently selected from the group consisting of -0-, -S-, and -CH(R12)-, wherein R12 is selected from the group consisting of H, C6 to C18 aryl, and C, to 1s C18 alkyl. The substituent "A" is an optionally substituted or unsubstituted aliphatic, aromatic, or heteroaromatic radical and n is an integer greater than 1.
Examples of A include C1 to C18 aliphatic, C6 to C28 aromatic, or C3 to C28 heteroaromatic radicals.
The basic additive can comprise at least one compound selected from the 20 group consisting of NaOH, KOH, Na2CO3, K2CO3, Ca(OH)2, NH4OH, CaCO3, a strongly basic anion-exchange resin, and combinations thereof. In one embodiment, the basic additive comprises a strongly basic anion-exchange resin, for example a strongly basic anion-exchange resin comprising polymer-bound tetraorgano-ammonium hydroxide groups.
25 I n one embodiment of the present invention, the basic additive and the crude phosphite mixture are contacted at temperatures above about -25 C, for example at temperatures from about -10 C to about 30 C.
In yet another embodiment of the present invention, the first phase is maintained at or above a pH of about 13.5 throughout the contacting process.
30 The present invention also relates to a method for separating triorganophosphite components from a crude phosphite mixture containing acidic hydrolysis products which further comprises the step of contacting the crude phosphite mixture with water before contacting the crude phosphite mixture with the basic additive.
The present invention also relates to methods for separating triorganophosphite components from a crude phosphite mixture containing acidic hydrolysis products wherein the methods further comprise the steps of separating the first phase from the second phase, and contacting the second phase with the basic additive. In another embodiment the present invention includes contacting the second phase with a brine solution after contacting with io the basic additive.
Another embodiment of the present invention further comprises contacting the second phase with a transition metal or a transition metal compound to produce a transition metal-triorganophosphite catalyst or catalyst precursor.
Examples of transition metals or transition metal compounds that can be used include Ni(COD)2 (COD is 1,5-cyclooctadiene), Ni[P(O-o-C6H4CH3)3]3 and Ni[P(O-o-C6H4CH3)3]2(C2H4), all of which are known in the art. The resulting transition metal-triorganophosphite catalyst or catalyst precursor can be useful for reactions such as hydrocyanation or hydroformylation, for example.
The invention also relates to a method for preparing triorganophosphites, which comprises contacting an alcohol with PCl3 in the presence of a triorganoamine to produce a first reaction product comprising one or more organophosphites and triorganoamine hydrochloride; removing the triorganoamine hydrochloride from the first reaction product to produce a second reaction product optionally containing one or more triorganophosphites, diorganohydrogenphosphite (R 20)(R30)POH, organodihydrogenphosphite (R'O)(HO)PO(H) and H3PO3, wherein R1, R2 and R3 are independently selected from the group consisting of C, to C18 alkyl, C6 to Cl8 aryl and hydroxyaryl, and C3 to C18 cycloalkyl and hydroxyalkyl radicals, and wherein R2 and R3 can optionally be connected to each other directly by a chemical bond or through an intermediate divalent group R9, wherein R9 is selected from the group consisting of -0-, -S-, and -CH(R12)-, wherein R 12 is selected from the group consisting of H, Cs to C18 aryl, and C, to C1$ alkyl; and removing at least a portion of one or more of the compounds diorganohydrogenphosphite (R20)(R30)POH, organodihydrogenphosphite (R'O)(HO)PO(H) and H3P03by contacting the second reaction product with a basic additive.
BRIEF DESCRIPTION OF THE FIGURE
FIG. 1 is a graphical representation showing the fraction of hydrolysis products remaining in the organic phase after contact with a control (brine) as compared to contact with a basic additive.
DETAILED DESCRIPTION OF THE INVENTION
The present invention includes methods for purifying and stabilizing triorganophosphites by removing acidic impurities from the phase containing the triorganophosphites. For example, acidic impurities such as diorganohydrogenphosphite (R20)(R30)POH, organodihydrogenphosphite (R'O)(HO)PO(H), and H3PO3 can occur as a result of aqueous workup of crude triorganophosphites, such as (R40)(R50)P(OR), and ((R'O)(R8O)PO)õA, and from unconverted phosphorodichloridite (R40)PCI2 and phosphorochloridite (R 40)(R50)PCI intermediates used as components for the making of triorganophosphites. Furthermore, small amounts of the above-described acidic impurities can increase in concentration during storage of triorganophosphite materials by autocatalytic hydrolysis upon exposure to moisture, causing yield loss and undesirable effects with the use of triorganophosphites in applications such as catalysis. At least one of these disadvantages may be overcome by removal of acidic impurities by means of extraction with a basic additive.
In at least one embodiment falling within the scope of the present invention, a crude phosphite mixture comprising at least one triorganophosphite selected from the group consisting of (R40)(R5O)P(OR6), and ((R7O)(RSO)PO)r,A;
and one or more of the compounds diorganohydrogenphosphite (R20)(R30)POH, organodihydrogenphosphite (R'O)(HO)PO(H), and H3P03 is contacted with a basic additive to produce a second mixture. The second mixture comprises two phases - a first phase and a second phase. The first phase comprises the basic additive and at least a portion of one or more of the components consisting of diorganohydrogenphosphite (R20)(R30)POH, organodihydrogenphosphite (R'O)(HO)PO(H), and H3P03. The second phase comprises at least a portion of the organophosphites. The first phase of the second mixture can optionally be separated from the second phase, using general separation methods known by those skilled in the art. For example, if the basic phase is liquid, such as aqueous NaOH, a conventional mixer-settler can be used to contact the crude phosphite mixture and aqueous NaOH then io separate the second phase comprising the triorganophosphites from the first phase comprising the acidic impurities. If, instead, a basic ion-exchange resin is deployed, a decanter or filter may be used.
R1, R2, and R3 are independently selected from the group consisting of C, to C18 alkyl, C6 to Ci8 aryl and hydroxyaryl, and C3 to C18 cycloalkyl and hydr.oxyaikyl radicals; R2 and R3 can optionally be connected to each other directly by a chemical bond or through an intermediate divalent group R9. R9 is selected from the group consisting of -0-, -S-, and -CH(R12)-, wherein R12 is selected from the group consisting of H, C6 to Ci8 aryl, or C, to C18 alkyl.
R4, R5, R6, R', and R8 are independently selected from the group consisting of C1 to C18 alkyl, C6 to C18 aryl, and C3 to Cy8 cycloalkyl radicals.
Each of R4, R5, and Rs can optionally be connected to one or both of the other two directly by a chemical bond or through an intermediate divalent group R10.
and R8 can optionally be connected to each other directly by a chemical bond or through an intermediate divalent group R". R10 and R" are independently selected from the group consisting of -0-, -S-, and -CH(R'2)-, wherein R12 is selected from the group consisting of H, C6 to C,s aryl, and C, to C18 alkyl.
The substituent "A" is an optionally substituted or unsubstituted aliphatic, aromatic or heteroaromatic radical where n is an integer greater than 1.
The basic additive employed in the present invention can comprise one or more compositions comprising at least one basic compound and/or material.
The basic additive may, for example, comprise at least one compound selected from the group consisting of NaOH, KOH, Na2CO3, K2CO:3, Ca(OH)2, NH4OH, CaCO3, a strongly basic anion-exchange resin, and combinations thereof.
Examples of suitable strongly basic ion-exchange resins are resins comprising polymer-bound tetraorgano-ammonium hydroxide groups.
Since hydrolysis rates are dependent on temperature, the extraction temperature should ideally be as low as possible only restricted by physical limits. In the case of liquid-liquid extractions, a physical limit impacting the range-of suitable operation temperatures is, for example, the freezing point of the liquid phases. Since under commercial operation the temperature range achievable is io subject to the limits of the equipment available, temperatures above about -are generally preferred. An example of a non-limiting temperature range for this process is from about -10 C to about 30 C.
Ideally, the pH of the basic phase should remain at or above about 13.5 throughout the extraction process. This can be accomplished by using a 1 normal solution of a strong base in water or a strongly basic anion-exchange resin of equivalent strength. If the production of the triorganophosphite generates a salt constituting a weak acid such as a triorganoamine hydrochloride, the weak acid should be removed first to allow for an effective extraction process of the acidic diorganohydrogenphosphite (R 20)(R30)POH, organodihydrogenphosphite 2o (R'O)(HO)PO(H), and H3PO3 impurities with the basic additive.
Triorganoamine hydrochloride salt removal can be achieved by filtration and/or by water extraction prior to contacting with the basic additive as, for example, described in US Patent Nos. 6,069,267, and 6,031,120.
The total amount of molar equivalents of base to be used is, at least in part, a function of the total amount of molar equivalents of acidic diorganohydrogenphosphite (R20)(R30)POH, organodihydrogenphosphite (R'O)(HO)PO(H), and H3POs impurities that are present prior to the treatment with the basic additive. For example, a 10- to 1000-fold excess of the base can be suitable, provided that, in the case of a solution extraction, a minimum pH
of 3o about 13.5 of the basic solution is maintained throughout the extraction process, or, in the case of a resin treatment, an equivalent basicity is maintained.
The volume of the basic phase can be determined by practical limitations, such as reactor size and separation capacity, by the pH limits, and by molar equivalent ratios of base to acidic impurities. For instance, in the case of an extraction using aqueous NaOH, the volume of the basic first phase can, for example, be between one-tenth and one-third of the product second phase volume. The amount of NaOH or polymer-bound tetraorgano-ammonium hydroxide can, for example, be between about 0.05 and about 1 equivalent of the total amount of phosphorus in the triorganophosphite solution phase.
The contact time is, at least in part, a function of scale, mixing equipment, io and hydrolysis rates of a specific organophosphite under conditions of basic extraction, and can, for example, be from about 15 minutes to about 5 hours.
For many processes using a basic additive, one or two extractions using a 10-fold excess of base to acid at a pH greater than 13 for about 15 to about minutes should be sufficient. In the case of a treatment with a strongly basic anion-exchange resin comprising polymer-bound tetraorgano-ammonium hydroxide groups, the phase containing the phosphorus compounds can be mixed with a predetermined amount of the resin or the foresaid phase can be passed through a column containing the resin. The amount of resin used is, at least in part, a function of the amount of acidic impurities to be removed.
For 2o example, when using a strongly basic anion-exchange resin, a one time treatment with an amount of resin equivalent to a 6-1 0 fold excess of base to acid may be sufficient. The resin may be regenerated using a basic aqueous solution of NaOH as known by those skilled in the art.
Typically, the extraction process is relatively insensitive to pressure and, in this regard, is usually limited only by practical considerations. For practical reasons, preferred reaction pressure ranges can, for example, be from about 10 psia (69 kPa) to about 50 psia (345 kPa).
In the case of a liquid-liquid extraction, the basic solution may contain a soluble salt, such as NaCi, to aid the separation process.
To avoid further triorganophosphite hydrolysis, contact with the basic additive should ideally be done soon after the production of the crude phosphite mixture and preferably before further concentration and or heat exposure of the crude phosphite product mixture.
Acidic compounds to be removed may include, but are not restricted to, diorganohydrogenphosphite (R20)(R30)POH, organodihydrogenphosphite (R'O)(HO)PO(H), H3P03, aromatic alcohols, and ammoniumhydrochlorides and ammoniumhydrobromides.
Examples The following non-limiting examples further illustrate embodiments of the io present invention.
Examples of the invention were prepared from crude phosphite mixtures containing one or more components having the following chemical structures:
diorganohydrogenphosphite 5, organodihydrogenphosphite 6, monodentate triorganophosphites 7 and 8, phosphorochloridite 7, phosphorodichloridite 4, biphenol 2, and bidentate triorganophosphite 3.
Cl I ~ I~ Cl p-, OH OH ~ Q O P' CI
O\ O-p P_O
OH \PH / ~ O
4 p\ 0, \ pH O - p-The following example shows that acidic diorganohydrogenphosphite 5, organodihydrogenphosphite G and H3POs representing primary hydrolysis products of triorganophosphites 7, phosphorochloridite 1 and phosphorodichloridite 4 can be significantly reduced or quantitatively removed from a solution containing the monodentate and bidentate triorganophosphites 7, and 3 by extraction with an aqueous solution of a strong base. Results are summarized in Table 1 and reported graphically in FIG. 1. For quantitative NMR
analysis, 0.250 mL of the organic phase and 0.600 mL of a 0.01 molar triphenylphosphine oxide (TPPO) in C6D6 were combined and analyzed by 31P
NMR (T1 = 5 sec.). Unless stated otherwise, the term brine refers to a saturated aqueous NaCi solution (about 26 wt% NaCI).
lo Example A
Synthesis of a Crude Phosphorochloridite '1 Containing Reaction Mixture:
A temperature controlled 2000 mL baffled flask equipped with an overhead stirrer was charged with 400 mL of 1.0 molar PCI3 in toluene and 4.0 mL 2.0 molar triethylamine in toluene. Under vigorous stirring, a solution of mL 2.0 molar triethylamine in toluene and a solution of 411 mL 2.0 molar 2,4-xylenol in toluene were added separately and concurrently via peristaltic pump at 2.3 mUmin. During the addition period, the reaction temperature was maintained at 5 C. The 31P NMR analysis exhibited transformation to the corresponding 2o phosphorochloridite 1 (31P NMR chemical shift 162 ppm) in 90% selectivity.
Other phosphorus containing components were triorganophosphite 7(9%) and phosphorodichloridite 4(1 %) representing the crude solution of phosphorochloridite 1 used in the Water Extraction (Control Experiment) as well as Examples Al and A2.
Water Extraction (Control Experiment):
Under nitrogen, 25 mL of the crude solution of phosphorochloridite 1 in toluene (0.56 molar) was combined with 14 mmol of triethylamine (Et3N) and 10 mL of water (H20). The mixture was stirred vigorously for 5 minutes before the two phases were separated. 31P NMR analysis of the organic phase indicated complete hydrolysis of phosphorochloridite 1 (162 ppm) to a mixture of the corresponding diorganohydrogenphosphite 5, organodihydrogenphosphite 6, and traces of H3POs (3'P NMR chemical shifts -2 to + 2 ppm). Subsequently, the organic phase was contacted with two successive portions of 10 mL 13 wt /a brine and one portion of 10 mL 26 wt% brine by vigorous mixing for 5 minutes each, and subsequent separation of the two phases. Quantitative 31P NMR
analysis of the organic phase was conducted after each treatment with brine, but no significant reduction of hydrolysis products in the organic phase was observed at any time.
1o Example Al (Aqueous KOH Treatment):
Under nitrogen, 25 mL of a 0.56 molar solution of phosphorochloridite 1 in toluene was combined with 14 mmol of Et3N and 10 mL of H20. The mixture was stirred vigorously for 5 minutes before the two phases were separated. 31P NMR
analysis of the organic phase indicated complete hydrolysis of phosphorochloridite 1(31 P NMR chemical shift 162 ppm) to a mixture of the corresponding diorganohydrogenphosphite 5, organodihydrogenphosphite s, and traces of H3PO3 (31P NMR chemical shift -2 to + 2 ppm). Subsequently, the organic phase was contacted with two successive portions of 10 mL 1 molar aqueous KOH and one portion of 10 mL 26 wt% brine by vigorous mixing for 5 2o minutes each, and subsequent separation of the two phases. Quantitative 31 P
NMR analysis of the organic phase after each treatment with aqueous KOH was conducted indicating a significant reduction of hydrolysis products by the aqueous KOH treatment.
Example A2 (Aqueous NaOH Treatment):
Under nitrogen, 25 mL of a 0.56 molar solution of phosphorochloridite 1 in toluene were combined with 14 mmol of Et3N and 10 mL of H20. The mixture was stirred vigorously for 5 minutes before the two phases were separated. 31P
NMR analysis of the organic phase indicated complete hydrolysis of phosphorochloridite 1 to a mixture of the corresponding diorganohydrogenphosphite 5, organodihydrogenphosphite 6 and traces of H3PO3 (31 P NMR chemical shift -2 to + 2 ppm). Subsequently, the organic phase was contacted with two successive portions of 10 mL 1 molar aqueous NaOH
and one portion of 10 mL 26 wt% brine by vigorous mixing for 5 minutes each, and subsequent separation of the two phases. Quantitative 3'P NMR analysis of the organic phase after each treatment was conducted indicating quantitative removal of hydrolysis products by the aqueous NaOH treatment.
Table 1 Fraction of Acidic Hydrolysis Products Diorganohydrogenphosphite 5, Organodihydrogenphosphite 6, and H3PO3 Remaining in the Organic Phase as Determined by 31P NMR.
Experiment Step / Treatment Remaining fraction of acidic hydrolysis products in organic phase (% mol) Water 10 mL water, 8 mmol 100%
Extraction(control) Et3N
The contact time is, at least in part, a function of scale, mixing equipment, io and hydrolysis rates of a specific organophosphite under conditions of basic extraction, and can, for example, be from about 15 minutes to about 5 hours.
For many processes using a basic additive, one or two extractions using a 10-fold excess of base to acid at a pH greater than 13 for about 15 to about minutes should be sufficient. In the case of a treatment with a strongly basic anion-exchange resin comprising polymer-bound tetraorgano-ammonium hydroxide groups, the phase containing the phosphorus compounds can be mixed with a predetermined amount of the resin or the foresaid phase can be passed through a column containing the resin. The amount of resin used is, at least in part, a function of the amount of acidic impurities to be removed.
For 2o example, when using a strongly basic anion-exchange resin, a one time treatment with an amount of resin equivalent to a 6-1 0 fold excess of base to acid may be sufficient. The resin may be regenerated using a basic aqueous solution of NaOH as known by those skilled in the art.
Typically, the extraction process is relatively insensitive to pressure and, in this regard, is usually limited only by practical considerations. For practical reasons, preferred reaction pressure ranges can, for example, be from about 10 psia (69 kPa) to about 50 psia (345 kPa).
In the case of a liquid-liquid extraction, the basic solution may contain a soluble salt, such as NaCi, to aid the separation process.
To avoid further triorganophosphite hydrolysis, contact with the basic additive should ideally be done soon after the production of the crude phosphite mixture and preferably before further concentration and or heat exposure of the crude phosphite product mixture.
Acidic compounds to be removed may include, but are not restricted to, diorganohydrogenphosphite (R20)(R30)POH, organodihydrogenphosphite (R'O)(HO)PO(H), H3P03, aromatic alcohols, and ammoniumhydrochlorides and ammoniumhydrobromides.
Examples The following non-limiting examples further illustrate embodiments of the io present invention.
Examples of the invention were prepared from crude phosphite mixtures containing one or more components having the following chemical structures:
diorganohydrogenphosphite 5, organodihydrogenphosphite 6, monodentate triorganophosphites 7 and 8, phosphorochloridite 7, phosphorodichloridite 4, biphenol 2, and bidentate triorganophosphite 3.
Cl I ~ I~ Cl p-, OH OH ~ Q O P' CI
O\ O-p P_O
OH \PH / ~ O
4 p\ 0, \ pH O - p-The following example shows that acidic diorganohydrogenphosphite 5, organodihydrogenphosphite G and H3POs representing primary hydrolysis products of triorganophosphites 7, phosphorochloridite 1 and phosphorodichloridite 4 can be significantly reduced or quantitatively removed from a solution containing the monodentate and bidentate triorganophosphites 7, and 3 by extraction with an aqueous solution of a strong base. Results are summarized in Table 1 and reported graphically in FIG. 1. For quantitative NMR
analysis, 0.250 mL of the organic phase and 0.600 mL of a 0.01 molar triphenylphosphine oxide (TPPO) in C6D6 were combined and analyzed by 31P
NMR (T1 = 5 sec.). Unless stated otherwise, the term brine refers to a saturated aqueous NaCi solution (about 26 wt% NaCI).
lo Example A
Synthesis of a Crude Phosphorochloridite '1 Containing Reaction Mixture:
A temperature controlled 2000 mL baffled flask equipped with an overhead stirrer was charged with 400 mL of 1.0 molar PCI3 in toluene and 4.0 mL 2.0 molar triethylamine in toluene. Under vigorous stirring, a solution of mL 2.0 molar triethylamine in toluene and a solution of 411 mL 2.0 molar 2,4-xylenol in toluene were added separately and concurrently via peristaltic pump at 2.3 mUmin. During the addition period, the reaction temperature was maintained at 5 C. The 31P NMR analysis exhibited transformation to the corresponding 2o phosphorochloridite 1 (31P NMR chemical shift 162 ppm) in 90% selectivity.
Other phosphorus containing components were triorganophosphite 7(9%) and phosphorodichloridite 4(1 %) representing the crude solution of phosphorochloridite 1 used in the Water Extraction (Control Experiment) as well as Examples Al and A2.
Water Extraction (Control Experiment):
Under nitrogen, 25 mL of the crude solution of phosphorochloridite 1 in toluene (0.56 molar) was combined with 14 mmol of triethylamine (Et3N) and 10 mL of water (H20). The mixture was stirred vigorously for 5 minutes before the two phases were separated. 31P NMR analysis of the organic phase indicated complete hydrolysis of phosphorochloridite 1 (162 ppm) to a mixture of the corresponding diorganohydrogenphosphite 5, organodihydrogenphosphite 6, and traces of H3POs (3'P NMR chemical shifts -2 to + 2 ppm). Subsequently, the organic phase was contacted with two successive portions of 10 mL 13 wt /a brine and one portion of 10 mL 26 wt% brine by vigorous mixing for 5 minutes each, and subsequent separation of the two phases. Quantitative 31P NMR
analysis of the organic phase was conducted after each treatment with brine, but no significant reduction of hydrolysis products in the organic phase was observed at any time.
1o Example Al (Aqueous KOH Treatment):
Under nitrogen, 25 mL of a 0.56 molar solution of phosphorochloridite 1 in toluene was combined with 14 mmol of Et3N and 10 mL of H20. The mixture was stirred vigorously for 5 minutes before the two phases were separated. 31P NMR
analysis of the organic phase indicated complete hydrolysis of phosphorochloridite 1(31 P NMR chemical shift 162 ppm) to a mixture of the corresponding diorganohydrogenphosphite 5, organodihydrogenphosphite s, and traces of H3PO3 (31P NMR chemical shift -2 to + 2 ppm). Subsequently, the organic phase was contacted with two successive portions of 10 mL 1 molar aqueous KOH and one portion of 10 mL 26 wt% brine by vigorous mixing for 5 2o minutes each, and subsequent separation of the two phases. Quantitative 31 P
NMR analysis of the organic phase after each treatment with aqueous KOH was conducted indicating a significant reduction of hydrolysis products by the aqueous KOH treatment.
Example A2 (Aqueous NaOH Treatment):
Under nitrogen, 25 mL of a 0.56 molar solution of phosphorochloridite 1 in toluene were combined with 14 mmol of Et3N and 10 mL of H20. The mixture was stirred vigorously for 5 minutes before the two phases were separated. 31P
NMR analysis of the organic phase indicated complete hydrolysis of phosphorochloridite 1 to a mixture of the corresponding diorganohydrogenphosphite 5, organodihydrogenphosphite 6 and traces of H3PO3 (31 P NMR chemical shift -2 to + 2 ppm). Subsequently, the organic phase was contacted with two successive portions of 10 mL 1 molar aqueous NaOH
and one portion of 10 mL 26 wt% brine by vigorous mixing for 5 minutes each, and subsequent separation of the two phases. Quantitative 3'P NMR analysis of the organic phase after each treatment was conducted indicating quantitative removal of hydrolysis products by the aqueous NaOH treatment.
Table 1 Fraction of Acidic Hydrolysis Products Diorganohydrogenphosphite 5, Organodihydrogenphosphite 6, and H3PO3 Remaining in the Organic Phase as Determined by 31P NMR.
Experiment Step / Treatment Remaining fraction of acidic hydrolysis products in organic phase (% mol) Water 10 mL water, 8 mmol 100%
Extraction(control) Et3N
10 mL 13 wt% brine 99%
10 mL 13 wt% brine 98%
10 mL 26wt% brine 100%
Example Al 10 mL water, 8 mmol 100%
Et3N
10mL1 MKOH 46%
10mL1 MKOH 7%
10 mL 26 wt% brine 5%
Exampte A2 10 mL water, 8 mmol 100%
Et3N
10mL1 MNaOH 34%
10 mL 1 M NaOH 4%
10 mL 26 wt% brine 0%
FIG. 1 illustrates the results from Table 1 in graphical form.
The following Example and Table 2 show the benefit of strongly basic anion-exchange resin treatment for the purity and stability of the crude bidentate triorganophosphite 3 under exposure to water over an extended period of time, for example, under certain storage conditions.
AmberlystTM A26-OH (Rohm and Haas Company) is a strong base, type 1, anionic, macroreticular polymeric resin based on crosslinked styrene divinylbenzene copolymer containing quaternary ammonium hydroxide groups; d = 675 g/L, concentration of active sites = 0.80 equiv/L.
Example B
Synthesis of a Crude Bidentate Triorganophosphite 3 Reaction Mixture:
A temperature controlled 500 mL baffled flask equipped with an overhead stirrer was charged with 200 mL of 1.0 molar PCI3 in toluene. Under vigorous stirring, a solution of 203.6 mL 2.0 molar triethylamine in toluene and a solution of 203.6 mL 2.0 molar 2,4-xylenol in toluene were added separately and concurrently via peristaltic pump at 2.9 mUmin. During the addition period, the reaction temperature was maintained at 5 C. The 31P NMR analysis exhibited transformation to the corresponding phosphorochloridite 1(31P NMR chemical shift 162 ppm) in 90% selectivity. Under vigorous stirring, 252.8 mmol of Et3N
was added at 20 C, followed by a solution of 84.6 mL of 1.0 molar biphenol 2 via a peristaltic pump at 2 mUmin. The reaction mixture was vigorously contacted with 150 mL H20. Quantitative 31 P NMR analysis of the organic phase revealed a phosphorus distribution of 81 mol% bidentate triorganophosphite 3, 4 mol%
monodentate triorganophosphite 8, 12 mol% monodentate triorganophosphite 7, and hydrolysis products 5 6 and H3PO3 equaling 3 mol % of the total phosphorus content. This solution represents the crude bidentate triorganophosphite 3 reaction mixture used in the Brine Treatment (Control 3o Experiment) and Example B1.
Brine Treatment (Control Experiment):
About 200 mL of the crude bidentate triorganophosphite 3 reaction mixture representing 67 mmol phosphorus was contacted with 50 mL of 26 wt% brine.
Approximately 20% of the solvent was removed in vacuo at 40 C over 30 minutes. The remaining solvent was removed in vacuo at 55 C over one hour.
Quantitative 31 P NMR analysis of the organic phase was conducted after the contact with brine, and of the concentrated sample, but no significant reduction of hydrolysis products in the organic phase was observed at any time.
The crude mixture was diluted with toluene to about 80 mL resulting in a io 33 wt% mixture. To 40 mL of this mixture, representing about 34 mmol phosphorus, was added 0.4 mL of water and the mixture stirred vigorously for 6 days while monitoring the content of phosphorus compounds by 31 P NMR.
Quantitative 31P NMR analysis of the organic layer was conducted after 2 hours, 1 day, 2 days, 3 days, and 6 days. Results are summarized in Table 2 and indicate relatively fast hydrolysis of all the triorganophosphites.
Example B1 (Resin Treatment):
About 200 mL of the crude bidentate triorganophosphite 3 reaction mixture representing 67 mmol phosphorus was stirred with 11.5 g (13.6 mmol hydroxy anion equivalent) of AmberlystTM A26-OH resin for two days. After the resin was removed, approximately 20% of the solvent was evaporated in vacuo at 40 C
over 30 minutes. The remaining solvent was removed in vacuo at 55 C over one hour. Quantitative 3'P NMR analysis of the organic layer was conducted after treating with resin for two hours and two days. The results summarized in Table 2 indicate that all hydrolysis products were removed quantitatively after 2 hours of treatment, and no hydrolysis of the triorganophosphites was observed after prolonged treatment with resin over 2 days.
The crude mixture was diluted with toluene to about 80 mL resulting in a 33 wt% mixture. To 40 mL of this mixture, representing about 34 mmol phosphorus, was added 0.4 mL of water and the mixture stirred vigorously for day's. Quantitative 31P NMR analysis of the organic layer was conducted after hours, 1 day, 2 days, 3 days, 6 days and 13 days. In contrast to the control experiment without AmberlystTM A26-OH resin treatment, no significant increase in hydrolysis products was observed at any time.
Table 2 Fraction of Acidic Hydrolysis Products Diorganohydrogenphosphite 5, Organodihydrogenphosphite 6, and H3P03 Compared to Bidentate Triorganophosphite 3 Remaining in the Organic Phase as Determined by 31P NMR.
Acidic hydrolysis Bidentate Experiment Step / Treatment Products (mof % Triorganophosphite Phosphorus) 3 (mol % Phos horus Brine Experiment H2O wash 3 81 (control) Brine treatment 3 81 After concentrating 3 81 2 hours with H20 4 81 1 day with H2O 5 80 2 days with H20 11 75 3 days with H20 64 16 6 days with H20 66 15 Example B1 H20 wash 3 81 Resin 2 hours 0 84 Resin 2 days 0 84 2 hours with H20 0 85 1 day with H2O 0 85 2 days with H20 0 85 3 days with H20 0 85 6 days with H20 0 85 13 days with H20 0 85 Additional Examples The following Examples demonstrate the removal of 3 mol% of total io phosphorus and 6 mol% of total phosphorus, respectively, of acidic hydrolysis products diorganohydrogenphosphite 5, organodihydrogenphosphite 67 and H3PO3 by treatment with aqueous NaOH during the workup of a crude bidentate triorganophosphite 3.
Example 1 Synthesis of a Crude Bidentate Triorganophosphite 3 Reaction Mixture:
A temperature controlled 2000 mL baffled flask equipped with an overhead stirrer was charged with 400 mL of 1.0 molar PCI3 in toluene and 4.0 mL 2.0 molar triethylamine in toluene. Under vigorous stirring, a solution of mL 2.0 molar triethylamine in toluene and a solution of 411 mL 2.0 molar 2,4-xylenol in toluene were added separately and concurrently via a peristaltic pump at 2.3 mUmin. During the addition period, the reaction temperature was maintained at 5 C. The 31P NMR analysis exhibited transformation to the corresponding phosphorochloridite 1(31P NMR chemical shift 162 ppm) in 90%
selectivity. Unde.r vigorous stirring, 600 mmol of Et3N were added at 20 C
io followed by a solution of 87.9 mL of 1.0 molar biphenol 2 via a peristaltic pump at a rate of 1.2 mUmin.
Workup:
After the completion of reaction, the reaction mixture was contacted with 300 mL of 13 wt% brine under vigorous stirring to remove triethylamine hydr chloride salts. Quantitative 31P NMR of the organic phase (Table 3) indicated hydrolysis products (31P NMR chemical shift -2 to +2 ppm), equivalent to 3 mol % of the total phosphorus content. After separating, the organic phase was contacted with 300 mL of 20 wt% brine containing 8 mmol of NaOH (pH 12) 2o followed by 300 mL of 26 wt% brine. Quantitative 31P NMR analysis of the organic phase indicated hydrolysis products equivalent to 3 mol % of total phosphorus (31 P NMR chemical shift -2 to +2 ppm) indicating that the amount of base used was not sufficient to remove the acidic impurities. Subsequently, the organic phase was contacted successively with 300 mL of 1 molar NaOH (pH 14) and 300 mL 26 wt% brine. Quantitative 31P NMR analysis of the organic phase indicated quantitative removal of the hydrolysis products. The molar distribution of phosphorus in the organic phase was 82% bidentate triorganophosphite 3 and 18 % monodentate triorganophosphites 7 and 8 at 31P NMR chemical shifts of 133, 132, and 136 ppm, respectively.
Table 3 Phosphorus Distribution During Aqueous Workup with NaOH (Example 1) Acidic Hydrolysis Bidentate Step / Treatment Products (mol % Trio rganophosphite 3 Phos horus (mol % Phos horus 13 % wt. brine 3 78 20 % wt. Brine + 8 mmol NaO 2 79 followed by 26 % wt. brine 1 M NaOH followed by 26 % 0 82 wt. brine Example 2 Synthesis of a Crude Bidentate Triorganophosphite 3 Reaction Mixture:
A temperature controlled 500 mL baffled flask equipped with an overhead stirrer was charged with 100 mL of 1.0 molar PCl3 in toluene and 1.0 mL 2.0 1o molar triethylamine in toluene. Under vigorous stirring, a solution of 100 mL 2.0 molar triethylamine in toluene and a solution of 100 mL 2.0 molar 2,4-xylenol in toluene were added separately and concurrently via a peristaltic pump at 2.9 mUmin. During the addition period, the reaction temperature was maintained at 45 C. The 31P NMR analysis exhibited transformation to the corresponding phosphorochloridite 1(31P NMR chemical shift 162 ppm) in 89% selectivity.
Under vigorous stirring, 130 mmol of Et3N was added at 20 C followed by a solution of 37.5 mL of 1.0 molar biphenol 2 via a peristaltic pump at 2 mUmin.
Workup:
The reaction mixture was vigorously contacted with 75 mL H20.
Quantitative 31P NMR analysis of the organic phase indicated hydrolysis products equaling 6 mol % of the total phosphorus content (Table 4). After separating the aqueous phase, the organic phase was contacted successively with two portions of 75 mL 1 molar aqueous NaOH followed by 75 mL of 26 wt% brine.
Quantitative 31P NMR analysis of the organic phase indicated quantitative removal of hydrolysis products. The molar distribution of phosphorus in the organic phase was 76 % bidentate triorganophosphite 3 and 23 % monodentate triorganophosphites 7 and 8 at 31P NMR chemical shifts of 133, 132, and 136 ppm, respectively.
Table 4 Phosphorus Distribution During Aqueous Workup with NaOH (Example 2) Acidic Hydrolysis Bidentate Step / Treatment Products (mol % Triorganophosphite 3 Phos horus (mol % Phos horus 1 S 1 M NaOH 4 74 2" 1 M NaOH 0 76 Many modifications and other embodiments of the inventions set forth io herein will come to mind to one skilled in the art to which these inventions pertain having the benefit of the teachings presented in the foregoing descriptions and the associated Figure. Therefore; it is to be understood that the inventions are not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the is appended claims.
10 mL 13 wt% brine 98%
10 mL 26wt% brine 100%
Example Al 10 mL water, 8 mmol 100%
Et3N
10mL1 MKOH 46%
10mL1 MKOH 7%
10 mL 26 wt% brine 5%
Exampte A2 10 mL water, 8 mmol 100%
Et3N
10mL1 MNaOH 34%
10 mL 1 M NaOH 4%
10 mL 26 wt% brine 0%
FIG. 1 illustrates the results from Table 1 in graphical form.
The following Example and Table 2 show the benefit of strongly basic anion-exchange resin treatment for the purity and stability of the crude bidentate triorganophosphite 3 under exposure to water over an extended period of time, for example, under certain storage conditions.
AmberlystTM A26-OH (Rohm and Haas Company) is a strong base, type 1, anionic, macroreticular polymeric resin based on crosslinked styrene divinylbenzene copolymer containing quaternary ammonium hydroxide groups; d = 675 g/L, concentration of active sites = 0.80 equiv/L.
Example B
Synthesis of a Crude Bidentate Triorganophosphite 3 Reaction Mixture:
A temperature controlled 500 mL baffled flask equipped with an overhead stirrer was charged with 200 mL of 1.0 molar PCI3 in toluene. Under vigorous stirring, a solution of 203.6 mL 2.0 molar triethylamine in toluene and a solution of 203.6 mL 2.0 molar 2,4-xylenol in toluene were added separately and concurrently via peristaltic pump at 2.9 mUmin. During the addition period, the reaction temperature was maintained at 5 C. The 31P NMR analysis exhibited transformation to the corresponding phosphorochloridite 1(31P NMR chemical shift 162 ppm) in 90% selectivity. Under vigorous stirring, 252.8 mmol of Et3N
was added at 20 C, followed by a solution of 84.6 mL of 1.0 molar biphenol 2 via a peristaltic pump at 2 mUmin. The reaction mixture was vigorously contacted with 150 mL H20. Quantitative 31 P NMR analysis of the organic phase revealed a phosphorus distribution of 81 mol% bidentate triorganophosphite 3, 4 mol%
monodentate triorganophosphite 8, 12 mol% monodentate triorganophosphite 7, and hydrolysis products 5 6 and H3PO3 equaling 3 mol % of the total phosphorus content. This solution represents the crude bidentate triorganophosphite 3 reaction mixture used in the Brine Treatment (Control 3o Experiment) and Example B1.
Brine Treatment (Control Experiment):
About 200 mL of the crude bidentate triorganophosphite 3 reaction mixture representing 67 mmol phosphorus was contacted with 50 mL of 26 wt% brine.
Approximately 20% of the solvent was removed in vacuo at 40 C over 30 minutes. The remaining solvent was removed in vacuo at 55 C over one hour.
Quantitative 31 P NMR analysis of the organic phase was conducted after the contact with brine, and of the concentrated sample, but no significant reduction of hydrolysis products in the organic phase was observed at any time.
The crude mixture was diluted with toluene to about 80 mL resulting in a io 33 wt% mixture. To 40 mL of this mixture, representing about 34 mmol phosphorus, was added 0.4 mL of water and the mixture stirred vigorously for 6 days while monitoring the content of phosphorus compounds by 31 P NMR.
Quantitative 31P NMR analysis of the organic layer was conducted after 2 hours, 1 day, 2 days, 3 days, and 6 days. Results are summarized in Table 2 and indicate relatively fast hydrolysis of all the triorganophosphites.
Example B1 (Resin Treatment):
About 200 mL of the crude bidentate triorganophosphite 3 reaction mixture representing 67 mmol phosphorus was stirred with 11.5 g (13.6 mmol hydroxy anion equivalent) of AmberlystTM A26-OH resin for two days. After the resin was removed, approximately 20% of the solvent was evaporated in vacuo at 40 C
over 30 minutes. The remaining solvent was removed in vacuo at 55 C over one hour. Quantitative 3'P NMR analysis of the organic layer was conducted after treating with resin for two hours and two days. The results summarized in Table 2 indicate that all hydrolysis products were removed quantitatively after 2 hours of treatment, and no hydrolysis of the triorganophosphites was observed after prolonged treatment with resin over 2 days.
The crude mixture was diluted with toluene to about 80 mL resulting in a 33 wt% mixture. To 40 mL of this mixture, representing about 34 mmol phosphorus, was added 0.4 mL of water and the mixture stirred vigorously for day's. Quantitative 31P NMR analysis of the organic layer was conducted after hours, 1 day, 2 days, 3 days, 6 days and 13 days. In contrast to the control experiment without AmberlystTM A26-OH resin treatment, no significant increase in hydrolysis products was observed at any time.
Table 2 Fraction of Acidic Hydrolysis Products Diorganohydrogenphosphite 5, Organodihydrogenphosphite 6, and H3P03 Compared to Bidentate Triorganophosphite 3 Remaining in the Organic Phase as Determined by 31P NMR.
Acidic hydrolysis Bidentate Experiment Step / Treatment Products (mof % Triorganophosphite Phosphorus) 3 (mol % Phos horus Brine Experiment H2O wash 3 81 (control) Brine treatment 3 81 After concentrating 3 81 2 hours with H20 4 81 1 day with H2O 5 80 2 days with H20 11 75 3 days with H20 64 16 6 days with H20 66 15 Example B1 H20 wash 3 81 Resin 2 hours 0 84 Resin 2 days 0 84 2 hours with H20 0 85 1 day with H2O 0 85 2 days with H20 0 85 3 days with H20 0 85 6 days with H20 0 85 13 days with H20 0 85 Additional Examples The following Examples demonstrate the removal of 3 mol% of total io phosphorus and 6 mol% of total phosphorus, respectively, of acidic hydrolysis products diorganohydrogenphosphite 5, organodihydrogenphosphite 67 and H3PO3 by treatment with aqueous NaOH during the workup of a crude bidentate triorganophosphite 3.
Example 1 Synthesis of a Crude Bidentate Triorganophosphite 3 Reaction Mixture:
A temperature controlled 2000 mL baffled flask equipped with an overhead stirrer was charged with 400 mL of 1.0 molar PCI3 in toluene and 4.0 mL 2.0 molar triethylamine in toluene. Under vigorous stirring, a solution of mL 2.0 molar triethylamine in toluene and a solution of 411 mL 2.0 molar 2,4-xylenol in toluene were added separately and concurrently via a peristaltic pump at 2.3 mUmin. During the addition period, the reaction temperature was maintained at 5 C. The 31P NMR analysis exhibited transformation to the corresponding phosphorochloridite 1(31P NMR chemical shift 162 ppm) in 90%
selectivity. Unde.r vigorous stirring, 600 mmol of Et3N were added at 20 C
io followed by a solution of 87.9 mL of 1.0 molar biphenol 2 via a peristaltic pump at a rate of 1.2 mUmin.
Workup:
After the completion of reaction, the reaction mixture was contacted with 300 mL of 13 wt% brine under vigorous stirring to remove triethylamine hydr chloride salts. Quantitative 31P NMR of the organic phase (Table 3) indicated hydrolysis products (31P NMR chemical shift -2 to +2 ppm), equivalent to 3 mol % of the total phosphorus content. After separating, the organic phase was contacted with 300 mL of 20 wt% brine containing 8 mmol of NaOH (pH 12) 2o followed by 300 mL of 26 wt% brine. Quantitative 31P NMR analysis of the organic phase indicated hydrolysis products equivalent to 3 mol % of total phosphorus (31 P NMR chemical shift -2 to +2 ppm) indicating that the amount of base used was not sufficient to remove the acidic impurities. Subsequently, the organic phase was contacted successively with 300 mL of 1 molar NaOH (pH 14) and 300 mL 26 wt% brine. Quantitative 31P NMR analysis of the organic phase indicated quantitative removal of the hydrolysis products. The molar distribution of phosphorus in the organic phase was 82% bidentate triorganophosphite 3 and 18 % monodentate triorganophosphites 7 and 8 at 31P NMR chemical shifts of 133, 132, and 136 ppm, respectively.
Table 3 Phosphorus Distribution During Aqueous Workup with NaOH (Example 1) Acidic Hydrolysis Bidentate Step / Treatment Products (mol % Trio rganophosphite 3 Phos horus (mol % Phos horus 13 % wt. brine 3 78 20 % wt. Brine + 8 mmol NaO 2 79 followed by 26 % wt. brine 1 M NaOH followed by 26 % 0 82 wt. brine Example 2 Synthesis of a Crude Bidentate Triorganophosphite 3 Reaction Mixture:
A temperature controlled 500 mL baffled flask equipped with an overhead stirrer was charged with 100 mL of 1.0 molar PCl3 in toluene and 1.0 mL 2.0 1o molar triethylamine in toluene. Under vigorous stirring, a solution of 100 mL 2.0 molar triethylamine in toluene and a solution of 100 mL 2.0 molar 2,4-xylenol in toluene were added separately and concurrently via a peristaltic pump at 2.9 mUmin. During the addition period, the reaction temperature was maintained at 45 C. The 31P NMR analysis exhibited transformation to the corresponding phosphorochloridite 1(31P NMR chemical shift 162 ppm) in 89% selectivity.
Under vigorous stirring, 130 mmol of Et3N was added at 20 C followed by a solution of 37.5 mL of 1.0 molar biphenol 2 via a peristaltic pump at 2 mUmin.
Workup:
The reaction mixture was vigorously contacted with 75 mL H20.
Quantitative 31P NMR analysis of the organic phase indicated hydrolysis products equaling 6 mol % of the total phosphorus content (Table 4). After separating the aqueous phase, the organic phase was contacted successively with two portions of 75 mL 1 molar aqueous NaOH followed by 75 mL of 26 wt% brine.
Quantitative 31P NMR analysis of the organic phase indicated quantitative removal of hydrolysis products. The molar distribution of phosphorus in the organic phase was 76 % bidentate triorganophosphite 3 and 23 % monodentate triorganophosphites 7 and 8 at 31P NMR chemical shifts of 133, 132, and 136 ppm, respectively.
Table 4 Phosphorus Distribution During Aqueous Workup with NaOH (Example 2) Acidic Hydrolysis Bidentate Step / Treatment Products (mol % Triorganophosphite 3 Phos horus (mol % Phos horus 1 S 1 M NaOH 4 74 2" 1 M NaOH 0 76 Many modifications and other embodiments of the inventions set forth io herein will come to mind to one skilled in the art to which these inventions pertain having the benefit of the teachings presented in the foregoing descriptions and the associated Figure. Therefore; it is to be understood that the inventions are not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the is appended claims.
Claims (13)
1. A method for separating one or more triorganophosphite components from a crude phosphite mixture containing acidic hydrolysis products, said method comprising:
contacting said crude phosphite mixture with a basic additive to produce a second mixture comprising a first phase and a second phase, wherein said first phase comprises the basic additive and one or more components independently selected from the group consisting of (R2O)(R3O)POH, (R1O)(HO)PO(H) and H3PO3, wherein R1, R2 and R3 are independently selected from the group consisting of C1 to C18 alkyl, C6 to C18 aryl and hydroxyaryl, and C3 to C18 cycloalkyl and hydroxyalkyl radicals, and wherein R2 and R3 can optionally be connected to each other directly by a chemical bond or through an intermediate divalent group R9; and said second phase comprises one or more triorganophosphite components independently selected from the group consisting of (R4O)(R5O)P(OR6) and ((R7O)(R8O)PO)n A, wherein R4, R5, R6, R7 and R8 are independently selected from the group consisting of C1 to C18 alkyl, C6 to C18 aryl and C3 to C18 cycloalkyl radicals, wherein each of R4, R5 and R6 can optionally be connected to one or both of the other two directly by a chemical bond or through an intermediate divalent group R10, wherein R7 and R8 can optionally be connected to each other directly by a chemical bond or through an intermediate divalent group R11, wherein A is an optionally substituted or unsubstituted aliphatic, aromatic or heteroaromatic radical, wherein n is an integer greater than 1; and wherein R9, R10, and R11 are independently selected from the group consisting of -O-, -S-, and -CH(R12)-, wherein R12 is selected from the group consisting of H, C6 to C18 aryl, and C1 to C18 alkyl.
contacting said crude phosphite mixture with a basic additive to produce a second mixture comprising a first phase and a second phase, wherein said first phase comprises the basic additive and one or more components independently selected from the group consisting of (R2O)(R3O)POH, (R1O)(HO)PO(H) and H3PO3, wherein R1, R2 and R3 are independently selected from the group consisting of C1 to C18 alkyl, C6 to C18 aryl and hydroxyaryl, and C3 to C18 cycloalkyl and hydroxyalkyl radicals, and wherein R2 and R3 can optionally be connected to each other directly by a chemical bond or through an intermediate divalent group R9; and said second phase comprises one or more triorganophosphite components independently selected from the group consisting of (R4O)(R5O)P(OR6) and ((R7O)(R8O)PO)n A, wherein R4, R5, R6, R7 and R8 are independently selected from the group consisting of C1 to C18 alkyl, C6 to C18 aryl and C3 to C18 cycloalkyl radicals, wherein each of R4, R5 and R6 can optionally be connected to one or both of the other two directly by a chemical bond or through an intermediate divalent group R10, wherein R7 and R8 can optionally be connected to each other directly by a chemical bond or through an intermediate divalent group R11, wherein A is an optionally substituted or unsubstituted aliphatic, aromatic or heteroaromatic radical, wherein n is an integer greater than 1; and wherein R9, R10, and R11 are independently selected from the group consisting of -O-, -S-, and -CH(R12)-, wherein R12 is selected from the group consisting of H, C6 to C18 aryl, and C1 to C18 alkyl.
2. The method of claim 1 wherein the basic additive comprises at least one compound selected from the group consisting of NaOH, KOH, Na2CO3, K2CO3, Ca(OH)2, NH4OH, CaCO3, a strongly basic anion-exchange resin, and combinations thereof.
3. The method of claim 1 wherein the basic additive comprises a strongly basic anion-exchange resin.
4. The method of claim 3 wherein said strongly basic anion-exchange resin comprises polymer-bound tetraorgano-ammonium hydroxide groups.
5. The method of claim 1 wherein said basic additive and said crude phosphite mixture are contacted at a temperature of from about -10 °C
to about 30 °C.
to about 30 °C.
6. The method of claim 1 wherein said first phase is maintained at or above a pH of about 13.5.
7. The method of claim 1 further comprising the step of contacting said crude phosphite mixture with water before contacting the crude phosphite mixture with said basic additive.
8. The method of claim 1 further comprising the steps of:
b) separating said first phase from said second phase; and c) contacting said second phase with the basic additive.
b) separating said first phase from said second phase; and c) contacting said second phase with the basic additive.
9. The method of claim 8 further comprising the step of:
d) contacting the second phase with a brine solution.
d) contacting the second phase with a brine solution.
10. The method of claim 1 further comprising contacting the second phase with a transition metal or a transition metal compound to produce a transition metal-triorganophosphite catalyst or catalyst precursor.
11. A method for preparing triorganophosphites, said method comprising:
a) contacting an alcohol with PCI3 in the presence of a triorganoamine to produce a first reaction product comprising one or more organophosphites and triorganoamine hydrochloride;
b) removing the triorganoamine hydrochloride from the first reaction product to produce a second reaction product optionally containing one or more triorganophosphites, diorganohydrogenphosphite (R2O)(R3O)POH, organodihydrogenphosphite (R1O)(HO)PO(H) and H3PO3, wherein R1, R2 and R3 are independently selected from the group consisting of C1 to C18 alkyl, C6 to aryl and hydroxyaryl, and C3 to C18 cycloalkyl and hydroxyalkyl radicals, and wherein R2 and R3 can optionally be connected to each other directly by a chemical bond or through an intermediate divalent group R9, wherein R9 is selected from the group consisting of -O-, -S-, and -CH(R12)-, wherein R12 is selected from the group consisting of H, C6 to C18 aryl, and C1 to C18 alkyl;
and c) removing at least a portion of one or more of the compounds diorganohydrogenphosphite (R2O)(R3O)POH, organodihydrogenphosphite (R1O)(HO)PO(H) and H3PO3 by contacting the second reaction product with a basic additive.
a) contacting an alcohol with PCI3 in the presence of a triorganoamine to produce a first reaction product comprising one or more organophosphites and triorganoamine hydrochloride;
b) removing the triorganoamine hydrochloride from the first reaction product to produce a second reaction product optionally containing one or more triorganophosphites, diorganohydrogenphosphite (R2O)(R3O)POH, organodihydrogenphosphite (R1O)(HO)PO(H) and H3PO3, wherein R1, R2 and R3 are independently selected from the group consisting of C1 to C18 alkyl, C6 to aryl and hydroxyaryl, and C3 to C18 cycloalkyl and hydroxyalkyl radicals, and wherein R2 and R3 can optionally be connected to each other directly by a chemical bond or through an intermediate divalent group R9, wherein R9 is selected from the group consisting of -O-, -S-, and -CH(R12)-, wherein R12 is selected from the group consisting of H, C6 to C18 aryl, and C1 to C18 alkyl;
and c) removing at least a portion of one or more of the compounds diorganohydrogenphosphite (R2O)(R3O)POH, organodihydrogenphosphite (R1O)(HO)PO(H) and H3PO3 by contacting the second reaction product with a basic additive.
12. The method of claim 11, wherein the basic additive comprises at least one compound selected from the group consisting of NaOH, KOH, Na2CO3, K2CO3, Ca(OH)2, NH4OH, CaCO3, a basic ion-exchange resin, and combinations thereof.
13. The method of claim 11, wherein step c) is repeated.
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| US60/783,462 | 2006-03-17 | ||
| PCT/US2007/006242 WO2007109005A2 (en) | 2006-03-17 | 2007-03-09 | Method for the purification of triorganophosphites by treatment with a basic additive |
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| US3496217A (en) | 1967-05-23 | 1970-02-17 | Du Pont | Hydrocyanation of olefins |
| DE1625989A1 (en) * | 1967-08-31 | 1971-01-21 | Messerschmitt Boelkow Blohm | Double-acting, redundant hydraulic cylinder system, preferably for aircraft and space vehicles |
| US3553298A (en) | 1967-10-20 | 1971-01-05 | Hooker Chemical Corp | Hydrolytic stabilized phosphite esters |
| US3775461A (en) | 1967-11-06 | 1973-11-27 | Du Pont | Hydrocyanation of olefins |
| US3551474A (en) | 1967-11-06 | 1970-12-29 | Du Pont | Process of isomerizing 3-pentenenitrile to 4-pentenenitrile |
| US3579560A (en) | 1967-11-06 | 1971-05-18 | Du Pont | Isomerization of nitriles |
| NL6815746A (en) | 1967-11-06 | 1969-05-08 | ||
| US3694485A (en) | 1967-11-06 | 1972-09-26 | Du Pont | Hydrocyanation of olefins |
| US3522288A (en) | 1967-11-06 | 1970-07-28 | Du Pont | Hydrocyanation of olefins |
| JPS4943924Y1 (en) | 1967-12-13 | 1974-12-02 | ||
| US3547972A (en) | 1968-04-01 | 1970-12-15 | Du Pont | Addition of hydrogen cyanide to butadiene |
| US3526654A (en) | 1968-05-17 | 1970-09-01 | Du Pont | Isomerization of 2-pentenenitrile to 3-pentenenitrile |
| US3564040A (en) | 1968-06-14 | 1971-02-16 | Du Pont | Removal of trans-2-pentenenitrile from 3- and 4-pentenenitrile |
| US3641107A (en) | 1968-10-21 | 1972-02-08 | Du Pont | Purification process for unsaturated organic nitriles |
| US3563698A (en) | 1969-03-14 | 1971-02-16 | Du Pont | Process for preparing zinc cyanide |
| US3652641A (en) | 1969-08-04 | 1972-03-28 | Du Pont | Hydrocyanation of olefins |
| US3538142A (en) | 1969-08-04 | 1970-11-03 | Du Pont | Process of isomerizing 3-pentenenitrile to 4-pentenenitrile |
| US3542847A (en) | 1969-09-15 | 1970-11-24 | Du Pont | Process for isomerizing 3-pentenenitrile to 4-pentenenitrile |
| US3655723A (en) | 1969-10-31 | 1972-04-11 | Du Pont | Hydrocyanation of olefins |
| BE757731A (en) | 1969-11-13 | 1971-04-01 | Du Pont | OLEFINS CYANURATION PROCESS |
| US3651146A (en) | 1970-02-25 | 1972-03-21 | Du Pont | Process for the preparation of triarylboranes |
| US3631191A (en) | 1970-04-08 | 1971-12-28 | Du Pont | Synthesis of zero valent nickel-tetrakis triaryl phosphite complexes |
| US3676481A (en) | 1970-06-29 | 1972-07-11 | Du Pont | Catalytic isomerization of 2-methyl-3-butenenitrile to linear pentenenitriles in the presence of certain metal salt and/or tri(hydrocarbyl)boron promoters |
| US3752839A (en) | 1970-07-02 | 1973-08-14 | Du Pont | Hydrocyanation olefins |
| US3676475A (en) | 1970-07-06 | 1972-07-11 | Du Pont | Hydrides of nickel coordination compounds |
| US3739011A (en) | 1971-04-30 | 1973-06-12 | Du Pont | Catalytic isomerization of 2-methyl-3-butenenitrile to linear pentenenitriles |
| US3766241A (en) | 1971-05-26 | 1973-10-16 | Du Pont | Removal of metal cations from solution in nitriles |
| US3798256A (en) | 1971-08-02 | 1974-03-19 | Du Pont | Hydrocyanation of olefins |
| US3925445A (en) | 1971-08-02 | 1975-12-09 | Du Pont | Hydrocyanation of olefins |
| US3766231A (en) | 1971-08-02 | 1973-10-16 | Du Pont | Compounds of zero valent nickel containing n bonded nitriles |
| US3766237A (en) | 1972-01-25 | 1973-10-16 | Du Pont | Hydrocyanation of olefins |
| US3773809A (en) | 1972-06-28 | 1973-11-20 | Du Pont | Separation of organic phosphorus compounds and their metal complexes from organic nitriles in the hydrocyanation of olefins |
| US3853754A (en) | 1972-07-20 | 1974-12-10 | Du Pont | Membrane separation of homogeneous catalysts from nitrile solutions |
| US3818067A (en) | 1972-07-20 | 1974-06-18 | Du Pont | Preparation of organic dinitriles |
| GB1429651A (en) | 1972-07-31 | 1976-03-24 | Ici Ltd | Manufacture of organic nitriles |
| GB1429169A (en) | 1972-09-07 | 1976-03-24 | Ici Ltd | Manufacture of organic nitriles |
| US3847959A (en) | 1972-10-25 | 1974-11-12 | Du Pont | Process of preparing a zerovalent nickel complex with organic phosphorus compounds |
| US3846461A (en) | 1972-10-25 | 1974-11-05 | Du Pont | Process of preparing a zerovalent nickel complex with organic phosphorus compounds |
| US3859327A (en) | 1972-10-25 | 1975-01-07 | Du Pont | Process for recovery of nickel from a deactivated hydrocyanation catalyst |
| US3818068A (en) | 1973-01-19 | 1974-06-18 | Du Pont | Removal of deactivated catalyst species from a hydrocyanation product fluid |
| US3865865A (en) | 1973-02-15 | 1975-02-11 | Du Pont | Selective removal of 2-pentenenitrile and 2-methyl-2-butenenitrile from 3-pentenenitrile |
| US3884997A (en) | 1973-05-02 | 1975-05-20 | Du Pont | Process for preparation of aromatic phosphorus compounds |
| US3903120A (en) | 1973-06-19 | 1975-09-02 | Du Pont | Preparation of zerovalent nickel complexes from elemental nickel |
| US3852325A (en) | 1973-08-29 | 1974-12-03 | Du Pont | Selective isomerization of pentenenitriles |
| US3852327A (en) | 1973-08-29 | 1974-12-03 | Du Pont | Selective cis/trans isomerization of 2-pentenenitrile in a solution of pentenenitrile isomers |
| JPS5053926U (en) | 1973-09-11 | 1975-05-23 | ||
| US3852328A (en) | 1973-09-26 | 1974-12-03 | Du Pont | Catalytic isomerization of 2-methyl-3-butenenitrile to a linear pentenenitrile |
| US3850973A (en) | 1973-09-26 | 1974-11-26 | Du Pont | Hydrocyanation of conjugated diolefins |
| US3846474A (en) | 1973-10-02 | 1974-11-05 | Du Pont | Process for hydrocyanation of olefinic compounds |
| US3852329A (en) | 1973-10-02 | 1974-12-03 | Du Pont | Process for isomerization of 2-methyl-3-butene-nitrile to a linear pentenenitrile |
| JPS5059324U (en) | 1973-10-09 | 1975-06-02 | ||
| GB1482909A (en) | 1973-10-31 | 1977-08-17 | Ici Ltd | Manufacture of organic nitriles |
| US3947487A (en) | 1974-01-17 | 1976-03-30 | Imperial Chemical Industries Ltd. | Manufacture of organic nitriles |
| US3864380A (en) | 1974-01-17 | 1975-02-04 | Du Pont | Hydrocyanation of Olefins |
| FR2259104B1 (en) * | 1974-01-25 | 1976-11-26 | Rhone Poulenc Ind | |
| US3920721A (en) | 1974-09-18 | 1975-11-18 | Du Pont | Hydrocyanation of olefins |
| US3927056A (en) | 1974-04-04 | 1975-12-16 | Du Pont | Hydrido(nitrile)tris(triaryl phosphite)cobalt complexes |
| DE2512839A1 (en) | 1974-04-04 | 1975-10-30 | Du Pont | PROCESS FOR THE HYDROCYANATION OF OLFINICALLY UNSATURATED COMPOUNDS |
| JPS517649A (en) | 1974-07-08 | 1976-01-22 | Otis Elevator Japan | SHOKOKITSURIAIOMORINO DATSUREER UKENSHUTSUSOCHI |
| US3983011A (en) | 1974-07-11 | 1976-09-28 | E. I. Du Pont De Nemours And Company | Removal of chloride impurities from an adiponitrile feed by distillation in the presence of a high boiling amine |
| GB1429621A (en) | 1975-01-20 | 1976-03-24 | Mcmullin T A | Display systems |
| US4147717A (en) | 1975-08-26 | 1979-04-03 | Du Pont Of Canada Limited | Process for purifying adiponitrile |
| US3997579A (en) | 1975-10-15 | 1976-12-14 | E. I. Du Pont De Nemours And Company | Selected phosphorus complexes of zerovalent iron |
| US4045495A (en) | 1975-11-12 | 1977-08-30 | E. I. Du Pont De Nemours And Company | Process for the preparation of triarylboranes |
| US4046815A (en) | 1975-11-12 | 1977-09-06 | E. I. Du Pont De Nemours And Company | Process for the preparation of triarylborane |
| US4076756A (en) | 1975-11-12 | 1978-02-28 | E. I. Du Pont De Nemours And Company | Process for the preparation of triarylborane |
| FR2338253A1 (en) | 1976-01-13 | 1977-08-12 | Rhone Poulenc Ind | PROCESS FOR HYDROCYANATION OF UNSATURATED ORGANIC COMPOUNDS CONTAINING AT LEAST A DOUBLE ETHYLENIC BOND |
| US4080374A (en) | 1977-02-23 | 1978-03-21 | E. I. Du Pont De Nemours And Company | Product recovery |
| US4082811A (en) | 1977-02-23 | 1978-04-04 | E. I. Du Pont De Nemours And Company | Recovery of metal and triarylborane catalyst components from olefin hydrocyanation residue |
| US4120917A (en) | 1977-03-28 | 1978-10-17 | Mobil Oil Corporation | Process for preparing tertiary alkylphosphorodichloridites |
| GB1565443A (en) | 1977-03-28 | 1980-04-23 | Ici Ltd | Manufacture of organic nitriles |
| GB1594694A (en) | 1977-04-04 | 1981-08-05 | Ici Ltd | Manufacture of organic nitriles by hydrocyanation of olefins |
| US4134923A (en) | 1977-09-02 | 1979-01-16 | E. I. Du Pont De Nemours And Company | Process for producing a metal hydroxide adduct of a triarylborane |
| WO1979000193A1 (en) | 1977-10-11 | 1979-04-19 | Ici Ltd | Organic nitriles |
| DE2861674D1 (en) | 1977-11-07 | 1982-04-15 | Ici Plc | Reactivation of spent catalysts |
| GB2007521B (en) | 1977-11-07 | 1982-06-23 | Ici Ltd | Reactivation of spent catalysts |
| US4177215A (en) | 1978-07-17 | 1979-12-04 | E. I. Du Pont De Nemours And Company | Recovery of triarylboranes |
| US4347193A (en) | 1979-04-20 | 1982-08-31 | E. I. Du Pont De Nemours And Company | Aryl borane complexes |
| JPS5916132B2 (en) | 1979-09-21 | 1984-04-13 | 株式会社日立製作所 | Runner-shaft vibration reduction device |
| US4251468A (en) | 1979-12-21 | 1981-02-17 | E. I. Du Pont De Nemours And Company | Recovery of triarylboranes |
| JPS56152863A (en) | 1980-04-28 | 1981-11-26 | Adeka Argus Chem Co Ltd | Synthetic resin composition |
| US4298546A (en) | 1980-08-05 | 1981-11-03 | E. I. Du Pont De Nemours And Company | Isomerization of 2-methyl-3-butenenitrile |
| US4336110A (en) | 1981-02-05 | 1982-06-22 | E. I. Du Pont De Nemours And Company | Separation of benzene from cyclohexane |
| US4328172A (en) | 1981-02-24 | 1982-05-04 | E. I. Du Pont De Nemours And Company | Hydrocyanation of olefins |
| US4330483A (en) | 1981-02-24 | 1982-05-18 | E. I. Du Pont De Nemours And Company | Hydrocyanation of olefins |
| JPS6129611Y2 (en) | 1981-03-26 | 1986-09-01 | ||
| JPS57156454U (en) | 1981-03-26 | 1982-10-01 | ||
| US4339395A (en) | 1981-04-15 | 1982-07-13 | E. I. Du Pont De Nemours And Company | Treatment of olefin hydrocyanation products |
| US4387056A (en) | 1981-04-16 | 1983-06-07 | E. I. Du Pont De Nemours And Company | Process for separating zero-valent nickel species from divalent nickel species |
| JPS57179144U (en) | 1981-05-11 | 1982-11-13 | ||
| US4385007A (en) | 1981-09-24 | 1983-05-24 | E. I. Du Pont De Nemours And Company | Preparation of zerovalent nickel complexes |
| US4382038A (en) | 1981-10-01 | 1983-05-03 | E. I. Du Pont De Nemours And Company | Hydrocyanation of olefins |
| JPS5867658U (en) | 1981-10-30 | 1983-05-09 | 日産自動車株式会社 | Tightening jig |
| US4394321A (en) | 1981-11-12 | 1983-07-19 | E. I. Du Pont De Nemours And Company | Triarylboraneisocy ano metal compounds |
| US4416824A (en) | 1981-12-21 | 1983-11-22 | E. I. Du Pont De Nemours & Co. | Recovery of triarylboranes by forming boron-containing metal compounds |
| US4371474A (en) | 1982-01-13 | 1983-02-01 | E. I. Du Pont De Nemours And Company | Hydrocyanation of olefins |
| US4416825A (en) | 1982-02-23 | 1983-11-22 | E. I. Du Pont De Nemours & Co. | Preparation of zerovalent nickel complexes |
| JPS58126892U (en) | 1982-02-23 | 1983-08-29 | 株式会社タイト− | Electronic game board with clock |
| JPS58159452U (en) | 1982-04-20 | 1983-10-24 | セイレイ工業株式会社 | Water heater pipe freeze damage prevention device |
| JPS5912303U (en) | 1982-07-16 | 1984-01-25 | 技研発泡工業株式会社 | Body integration device |
| US4434316A (en) | 1983-03-25 | 1984-02-28 | E. I. Du Pont De Nemours & Co. | Separation of alkenes from alkadienes |
| US4510327A (en) | 1983-04-06 | 1985-04-09 | E. I. Du Pont De Nemours And Company | Process for making alkali-metal tetraorganylborates |
| US4521628A (en) | 1983-07-11 | 1985-06-04 | E. I. Du Pont De Nemours And Company | Recovery of arylboranes |
| JPS6044295A (en) | 1983-08-15 | 1985-03-09 | ナスコ株式会社 | Controller for reciprocating travelling |
| US4539302A (en) | 1984-04-30 | 1985-09-03 | E. I. Du Pont De Nemours And Company | Recovery of zerovalent nickel complexes |
| US4749801A (en) | 1986-06-04 | 1988-06-07 | E. I. Du Pont De Nemours And Company | [Hexakis(pentenenitrilo)nickel II]bis-[μ-(cyano) bis(triphenylborane) (I)], its method of preparation and its use |
| US4774353A (en) | 1986-06-05 | 1988-09-27 | E. I. Du Pont De Nemours And Company | Triorganotin catalyst promoters for hydrocyanation |
| JPS639819A (en) | 1986-06-30 | 1988-01-16 | Yokogawa Electric Corp | Displacement transducing device |
| US4705881A (en) | 1986-11-17 | 1987-11-10 | E. I. Du Pont De Nemours And Company | Continuous hydrocyanation process using zinc halide promoter |
| US4714773A (en) | 1987-01-09 | 1987-12-22 | E. I. Du Pont De Nemours And Company | Hydrocyanation of butadiene |
| JPS63135363U (en) | 1987-02-27 | 1988-09-06 | ||
| US4783546A (en) | 1987-06-02 | 1988-11-08 | E. I. Du Pont De Nemours And Company | Preparation of 4-pentenenitrile by isomerization |
| US4810815A (en) | 1987-11-04 | 1989-03-07 | E. I. Du Pont De Nemours And Company | Acceleration of diene hydrocyanation |
| JPH01251521A (en) | 1987-12-16 | 1989-10-06 | Yazaki Corp | Grommet |
| JPH01209830A (en) | 1988-02-17 | 1989-08-23 | Sony Corp | Data communication equipment |
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| JPH0412248Y2 (en) | 1988-11-10 | 1992-03-25 | ||
| JPH03205587A (en) | 1990-01-06 | 1991-09-09 | Yuuseishiyou Tsushin Sogo Kenkyusho | Determining method for generation area by mutual correlation of volcanic slight tremor |
| JPH03285878A (en) | 1990-03-30 | 1991-12-17 | Nippon Steel Chem Co Ltd | Production of lightweight concrete board |
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| US4990645A (en) * | 1990-06-27 | 1991-02-05 | E. I. Du Pont De Nemours And Company | Hydrocyanation process |
| JPH04166155A (en) | 1990-10-30 | 1992-06-12 | Toto Ltd | Jetting nozzle structure of bubble generating bath tub |
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| TW226345B (en) | 1991-06-10 | 1994-07-11 | Carrier Corp | |
| JPH0725841Y2 (en) | 1991-08-30 | 1995-06-07 | 日本マランツ株式会社 | Cassette tape recorder |
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| US5302756A (en) | 1992-12-23 | 1994-04-12 | E. I. Du Pont De Nemours And Company | Ammonolysis of nylon |
| US5312959A (en) * | 1993-07-12 | 1994-05-17 | E. I. Du Pont De Nemours And Company | Purification of 2-methylglutaronitrile or adiponitrile |
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| CN1035312C (en) | 1994-06-21 | 1997-07-02 | 许伸光 | Positioning method for bottle rotation printing and positioning structure |
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| US5449807A (en) | 1994-11-18 | 1995-09-12 | E. I. Du Pont De Nemours And Company | Catalyzed vapor phase hydrocyanation of diolefinic compounds |
| JPH08157795A (en) | 1994-12-02 | 1996-06-18 | Sekisui Chem Co Ltd | Acrylic pressure-sensitive adhesive composition |
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| US5773637A (en) | 1995-09-20 | 1998-06-30 | E. I. Du Pont De Nemours And Company | Perfluoroalkyl sulfonates, their preparation and use |
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| US5709841A (en) | 1996-02-23 | 1998-01-20 | E.I. Du Pont De Nemours And Company | Waste stream treatment |
| CN1047044C (en) | 1996-03-06 | 1999-12-01 | 潘之凯 | New remote control and telecommunication method |
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| KR100193851B1 (en) | 1996-11-05 | 1999-06-15 | 윤종용 | Small antenna of portable radio |
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| US5847191A (en) | 1997-07-29 | 1998-12-08 | E. I. Du Pont De Nemours And Company | Process for the hydrocyanation of monoolefins using bidentate phosphite ligands and zero-valent nickel |
| US6121184A (en) | 1997-07-29 | 2000-09-19 | E. I. Du Pont De Nemours And Company | Supported bis(phosphorus) ligands |
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| US6031120A (en) | 1997-07-29 | 2000-02-29 | E. I. Du Pont De Nemours And Company | Selective synthesis of organodiphosphite compounds |
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| US6077979A (en) * | 1999-02-18 | 2000-06-20 | E. I. Du Pont De Nemours And Company | Manufacture of 3,3',5,5'-tetramethyl-2,2'-biphenol |
| US6048996A (en) * | 1999-08-26 | 2000-04-11 | E. I. Du Pont De Nemours And Company | Insoluble promoters for nickel-catalyzed hydrocyanation of monoolefins |
| US6284865B1 (en) | 1999-09-20 | 2001-09-04 | E. I. Du Pont De Nemours And Company | Polymeric phosphite composition and hydrocyanation of unsaturated organic compounds and the isomerization of unsaturated nitriles |
| US6307107B1 (en) * | 1999-09-20 | 2001-10-23 | E.I. Du Pont De Nemours And Company | Hydroformylation of acyclic monoethylenically unsaturated compounds to corresponding terminal aldehydes |
| US6420611B1 (en) * | 1999-09-20 | 2002-07-16 | E. I. Du Pont De Nemours And Company | Composition comprising polymeric phosphite |
| US6380421B1 (en) * | 1999-09-20 | 2002-04-30 | E. I. Du Pont De Nemours And Company | Multidentate phosphite ligands, catalytic compositions containing such ligands and catalytic processes utilizing such catalytic compositions |
| DE19953058A1 (en) | 1999-11-03 | 2001-05-10 | Basf Ag | Phosphites |
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| AU2000270441A1 (en) | 2000-07-28 | 2002-02-13 | Anna Borisovna Mulin | Advertising method |
| DE10038037A1 (en) | 2000-08-02 | 2002-04-18 | Basf Ag | Catalyst suitable for the production of nitriles and process for the production of nitriles |
| US6461481B1 (en) | 2000-08-31 | 2002-10-08 | E. I. Du Pont De Nemours And Company | Process for removing water from organoborane compounds |
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-
2007
- 2007-03-09 US US11/716,133 patent/US7629484B2/en not_active Expired - Fee Related
- 2007-03-09 BR BRPI0709313-6A patent/BRPI0709313A2/en not_active Application Discontinuation
- 2007-03-09 EP EP11172673.3A patent/EP2395010B1/en active Active
- 2007-03-09 MX MX2008011640A patent/MX2008011640A/en not_active Application Discontinuation
- 2007-03-09 KR KR1020087022558A patent/KR20080104315A/en not_active Application Discontinuation
- 2007-03-09 SK SK5082-2008A patent/SK50822008A3/en unknown
- 2007-03-09 CZ CZ20080547A patent/CZ2008547A3/en unknown
- 2007-03-09 CN CNA2007800092938A patent/CN101405292A/en active Pending
- 2007-03-09 WO PCT/US2007/006242 patent/WO2007109005A2/en active Application Filing
- 2007-03-09 EP EP07752908.9A patent/EP1996598B1/en active Active
- 2007-03-09 JP JP2009500416A patent/JP2009530278A/en active Pending
- 2007-03-09 PL PL387008A patent/PL387008A1/en not_active Application Discontinuation
- 2007-03-09 CA CA002644961A patent/CA2644961A1/en not_active Abandoned
- 2007-03-15 TW TW096108961A patent/TW200740837A/en unknown
- 2007-03-17 SA SA07280109A patent/SA07280109B1/en unknown
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- 2009-10-29 US US12/608,044 patent/US8178711B2/en not_active Expired - Fee Related
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|---|---|
| WO2007109005A3 (en) | 2007-11-15 |
| JP2009530278A (en) | 2009-08-27 |
| KR20080104315A (en) | 2008-12-02 |
| EP1996598B1 (en) | 2013-10-16 |
| BRPI0709313A2 (en) | 2011-07-05 |
| US8178711B2 (en) | 2012-05-15 |
| EP2395010B1 (en) | 2016-07-13 |
| SK50822008A3 (en) | 2009-11-05 |
| TW200740837A (en) | 2007-11-01 |
| EP2395010A1 (en) | 2011-12-14 |
| US7629484B2 (en) | 2009-12-08 |
| US20100076212A1 (en) | 2010-03-25 |
| EP1996598A2 (en) | 2008-12-03 |
| PL387008A1 (en) | 2009-05-11 |
| US20070219386A1 (en) | 2007-09-20 |
| SA07280109B1 (en) | 2010-10-23 |
| MX2008011640A (en) | 2008-09-22 |
| WO2007109005A2 (en) | 2007-09-27 |
| CZ2008547A3 (en) | 2009-06-10 |
| CN101405292A (en) | 2009-04-08 |
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