| PATENT ASSIGNEE'S COUNTRY | USA |
| UPDATE | 01.01 |
| PATENT NUMBER | This data is not available for free |
| PATENT GRANT DATE | 09.01.01 |
| PATENT TITLE |
Hydrocyanation processes and multidentate phosphite ligand and nickel catalyst compositions therefor |
| PATENT ABSTRACT |
A process for hydrocyanation of an aliphatic monoethylenically unsaturated compound, in which the ethylenic double bond is not conjugated to any other unsaturated group in the molecule, or a monoethylenically unsaturated compound in which the ethylenic double bond is conjugated to an ester group, which process uses a catalyst composition comprising a zero-valent nickel and a multidentate phosphite ligand in the presence of a Lewis acid promoter. |
| PATENT INVENTORS | This data is not available for free |
| PATENT ASSIGNEE | This data is not available for free |
| PATENT FILE DATE | 13.07.99 |
| PATENT REFERENCES CITED |
Tolman et al., Advances in Catalysis, 33, No. 1, 1985. M.J. Baker et al., J. Chem. Soc., Chem. Commun., 1292, 1991. Baker et al., J. Chem. Soc., Chem. Commun., 803, 1991. Cuny et al., J. Am. Chem. Soc., 115, 2066, 1993. |
| PATENT PARENT CASE TEXT | This data is not available for free |
| PATENT CLAIMS |
What is claimed is: 1. A multidentate phosphite ligand selected from the group represented by the following Formula I, II, III, IV, V, VI, VII, VIII and IX: ##STR33## ##STR34## wherein each R.sup.1 is independently a primary, secondary, or tertiary hydrocarbyl of 1 to 12 carbon atoms; with the proviso that at least one of R.sup.1 must be a primary hydrocarbyl; each R.sup.2 is independently H, halogen, primary or secondary hydrocarbyl of 1 to 12 carbon atoms, OR.sup.3 wherein R.sup.3 is a C.sub.1 to C.sub.12 alkyl, or CO.sub.2 R.sup.3 ' wherein R.sup.3 ' is an aryl or a C.sub.1 to C.sub.12 alkyl; each R.sup.2 ' is independently H, halogen, CHO, primary, secondary or tertiary hydrocarbyl of 1 to 12 carbon atoms, OR.sup.3 wherein R.sup.3 is a C.sub.1 to C.sub.12 alkyl, CO.sub.2 R.sup.3 ' wherein R.sup.3 ' is an aryl or a C.sub.1 to C.sub.12 alkyl, or C(R.sup.3)(O) wherein R.sup.3 is a C.sub.1 to C.sub.12 alkyl; each R.sup.4 is independently H, a primary or secondary hydrocarbyl of 1 to 12 carbon atoms or CO.sub.2 R.sup.3 wherein R.sup.3 is a C.sub.1 to C.sub.12 alkyl; and each R.sup.4 ' is independently H, a primary or secondary hydrocarbyl of 1 to 12 carbon atoms or aryl. 2. A catalyst precursor composition comprising zero-valent nickel and a multidentate phosphite ligand according to claim 1. 3. The catalyst precursor composition of claim 2 wherein a Lewis acid is also present. 4. The catalyst composition of claim 3 wherein the Lewis acid is selected from the group consisting of ZnBr.sub.2, ZnI.sub.2, ZnCl.sub.2, ZnSO.sub.4, CuCl.sub.2, CuCl, Cu(O.sub.3 SCF.sub.3).sub.2, CoCl.sub.2, CoI.sub.2, FeI.sub.2, FeCl.sub.3, FeCl.sub.2 (tetrahydrofuran).sub.2, FeCl.sub.2, TiCl.sub.4 (tetrahydrofuran).sub.2, TiCl.sub.4, TiCl.sub.3, ClTi(OiPr).sub.3, MnCl.sub.2, ScCl.sub.3, AlCl.sub.3, (C.sub.8 H.sub.17)AlCl.sub.2, (C.sub.8 H.sub.17).sub.2 AlCl, (iso-C.sub.4 H.sub.9).sub.2 AlCl, (phenyl).sub.2 AlCl, phenylAlCl.sub.2, ReCl.sub.5, ZrCl.sub.4, NbCl.sub.5, VCl.sub.3, CrCl.sub.2, MoCl.sub.5, YCl.sub.3, CdCl.sub.2, LaCl.sub.3, Er(O.sub.3 SCF.sub.3).sub.3, Yb(O.sub.2 CCF.sub.3).sub.3, SmCl.sub.3, TaCl.sub.5, CdCl.sub.2, B(C.sub.6 H.sub.5).sub.3, and (C.sub.6 H.sub.5).sub.3 SnX, where X=CF.sub.3 SO.sub.3, CH.sub.3 C.sub.6 H.sub.5 SO.sub.3, or (C.sub.6 H.sub.5).sub.3 BCN. 5. The catalyst precursor composition of claim 2 wherein the zero-valent nickel and the multidentate phosphite ligand are supported on the same solid support. -------------------------------------------------------------------------------- |
| PATENT DESCRIPTION |
FIELD OF THE INVENTION The invention generally relates to a process and catalyst precursor composition for the hydrocyanation of monoethylenically unsaturated compounds wherein zero-valent nickel and a multidentate phosphite ligand are used in the presence of a Lewis acid promoter. BACKGROUND OF THE INVENTION Hydrocyanation catalyst systems, particularly pertaining to the hydrocyanation of ethylenically unsaturated compounds, are known in the art. For example, systems useful for the hydrocyanation of butadiene to form pentenenitrile (PN) and in the subsequent hydrocyanation of pentenenitrile to form adiponitrile (ADN), are known in the commercially important nylon synthesis field. The hydrocyanation of ethylenically unsaturated compounds using transition metal complexes with monodentate phosphite ligands is documented in the prior art. See, for example, U.S. Pat. Nos. 3,496,215; 3,631,191; 3,655,723; and 3,766,237, and Tolman et al., Advances in Catalysis, 1985, 33, 1. The hydrocyanation of activated ethylenically unsaturated compounds, such as with conjugated ethylenically unsaturated compounds (e.g., butadiene and styrene), and strained ethylenically unsaturated compounds (e.g., norbomene) proceeds without the use of a Lewis acid promoter, while hydrocyanation of unactivated ethylenically unsaturated compounds, such as 1-octene and 3-pentenenitrile, requires the use of a Lewis acid promoter. Teachings regarding the use of a promoter in the hydrocyanation reaction appear, for example, in U.S. Pat. No. 3,496,217. This patent discloses an improvement in hydrocyanation using a promoter selected from a large number of metal cation compounds with a variety of anions as catalyst promoters. U.S. Pat. No. 3,496,218 discloses a nickel hydrocyanation catalyst promoted with various boron-containing compounds, including triphenylboron and alkali metal borohydrides. U.S. Pat. No. 4,774,353 discloses a process for the preparation of dinitriles, including ADN, from unsaturated nitrites, including PN, in the presence of a zero-valent nickel catalyst and a triorganotin catalyst promoter. Moreover, U.S. Pat. No. 4,874,884 discloses a process for producing ADN by the zero-valent nickel-catalyzed hydrocyanation of pentenenitriles in the presence of a synergistic combination of promoters selected in accordance with the reaction kinetics of the ADN synthesis. Phosphite ligands have been shown to be useful ligands in the hydrocyanation of activated ethylenically unsaturated compounds. See, for example, Baker, M. J., and Pringle, P. G., J Chem. Soc. Chem. Commun., 1991, 1292; Baker et al., J Chem. Soc., Chem. Commun., 1991, 803; Union Carbide, WO 93,03839. Also, phosphite ligands have been disclosed with rhodium in the hydroformylation of functionalized ethylenically unsaturated compounds: see, Cuny et al., J. Am. Chem. Soc., 1993, 115, 2066. U.S. Pat. No. 5,512,696, which issued Apr. 30, 1996, discloses processes and catalyst compositions for the hydrocyanation of monoethyleneically unsaturated compounds using zero-valent nickel and certain multidentate phosphite ligands, and Lewis acid promoters, which are similar to those encompassed by the present invention, except for the choice of the ortho substituent for the group or the phosphite phenyl termin. Like U.S. Pat. No. 5,512,696, the present invention provides processes and catalyst precursor compositions which are more rapid, selective, efficient and stable than prior processes and catalyst complexes employed in the hydrocyanation of monoethylenically unsaturated compounds. Other objects and advantages of the present invention will become apparent to those skilled in the art upon reference to the detailed description of the invention which hereinafter follows. SUMMARY OF THE INVENTION The present invention provides for a hydrocyanation process, comprising reacting an acyclic, aliphatic, monoethylenically unsaturated compound in which the ethylenic double bond is not conjugated to any other olefinic group in the molecule, or a monoethylenically unsaturated compound in which the ethylenic double bond is conjugated to an organic ester group, with a source of HCN in the presence of a catalyst precursor composition comprising a Lewis acid, a zero-valent nickel, and at least one multidentate phosphite ligand selected from the group represented by the following Formulas I, II, III, IV, V, VI, VII, VIII, and IX, in which all like reference characters have the same meaning, except as further explicitly limited. ##STR1## ##STR2## wherein each R.sup.1 is independently a primary, secondary, or tertiary hydrocarbyl of 1 to 12 carbon atoms; with the proviso that at least one of R.sup.1 must be a primary hydrocarbyl; each R.sup.2 is independently H, halogen, primary or secondary hydrocarbyl of 1 to 12 carbon atoms, OR.sup.3 wherein R.sup.3 is a C.sub.1 to C.sub.12 alkyl, or CO.sub.2 R.sup.3 ' wherein R.sup.3 ' is an aryl or a C.sub.1 to C.sub.12 alkyl; each R.sup.2 ' is independently H, halogen, CHO, primary, secondary or tertiary hydrocarbyl of 1 to 12 carbon atoms, OR.sup.3 wherein R.sup.3 is a C.sub.1 to C.sub.12 alkyl, CO.sub.2 R.sup.3 ' wherein R.sup.3 ' is an aryl or a C.sub.1 to C.sub.12 alkyl, or C(R.sup.3)(O) wherein R.sup.3 is a C.sub.1 to C.sub.12 alkyl; each R.sup.4 is independently H, a primary or secondary hydrocarbyl of 1 to 12 carbon atoms or CO.sub.2 R.sup.3 wherein R.sup.3 is a C.sub.1 to C.sub.12 alkyl; and each R.sup.4 ' is independently H, a primary or secondary hydrocarbyl of 1 to 12 carbon atoms or aryl. In the above catalyst precursor compositions, the Lewis acid is considered to be a promoter. The term "hydrocarbyl" is well known in the art and designates a hydrocarbon molecule from which one hydrogen atom has been removed. Such molecules can contain single, double or triple bonds. The present invention further provides for novel multidentate phosphite ligands selected from one of Formulas I-IX, as defined above and catalyst precursor compositions made therefrom with zero-valent nickel. Preferably, the catalyst precursor compositions also have a Lewis acid present. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Representative ethylenically unsaturated compounds which are useful in the process of this invention are shown in Formulas X or XII, and the corresponding terminal nitrile compounds produced are illustrated by Formulas XI or XII, respectively, wherein like reference characters have same meaning. ##STR3## wherein R.sup.5 is H, CN, CO.sub.2 R.sup.3 ', or perfluoroalkyl; y is an integer of 0 to 12; x is an integer of 0 to 12 when R.sup.5 is H, CO.sub.2 R.sup.3 ' or perfluoroalkyl; x is an integer of 1 to 12 when R.sup.5 is CN; and R.sup.3 ' is aryl or a C.sub.1 to C.sub.12 alkyl. One of the ligands useful in the catalyst compositions of the present invention is illustrated above by Formula I, as defined above. At least one of R.sup.1 is a primary alkyl, examples of which include methyl, ethyl and n-propyl. In the preferred Formula I ligand, each R.sup.1 is methyl, each R.sup.2 is methyl except R.sup.2 para to oxygen. R.sup.2 para to oxygen is hydrogen and R.sup.2 ' is hydrogen. The catalyst composition of the invention may be considered a "precursor" composition in that the zero-valent nickel at some point becomes complexed to the multidentate phosphite ligand, and, further in all likelihood, additional reactions occur during hydrocyanation, such as, for example, complexing of the initial catalyst composition to an ethylenically unsaturated compound. These ligands can be prepared by a variety of methods known in the art, for example, see descriptions in European Patent Application 92109599.8 of Mitsubishi Kasei Corporation and the corresponding U.S. Pat. No. 5,235,113 to Sato et al. The reaction of o-cresol with phosphorus trichloride gives the phosphorochloridite. The reaction of this phosphorochloridite with 3,3',4,4',6,6'-hexamethyl-2,2'-biphenol in the presence of triethylamine gives the above-identified preferred ligand of Formula I. The phosphorochloridite may be prepared by a variety of methods known in the art, for example, see descriptions in Polymer, 1992, 33, 161; Inorganic Synthesis, 1966, 8, 68;.U.S. Pat. No. 5,210,260; Z. Anorg. Allg. Chem., 1986, 535, 221. With bulky ortho-substituted phenols (e.g., 2-t-butylphenol), phosphorochloridites can be prepared in situ from PCl.sub.3 and the phenol. With less bulky groups, purification by high vacuum distillation is typically necessary. High vacuum distillation is difficult for large scale operations. An improved process for preparing the phosphochlorodite comprises treatment of N,N-dialkyl diarylphosphoramidite with HCl. ClP(OMe).sub.2 has been prepared in this manner, see Z. Naturforsch, 1972, 27B, 1429. Phosphorochloridites derived from substituted phenols have been prepared using this procedure as described in copending commonly assigned application Ser. No. 08/563,718, filed Nov. 28, 1995. It has also been found that phosphorochloridite of o-cresol can be prepared in situ from PCl.sub.3 and o-cresol. The zero-valent nickel compounds can be prepared or generated according to techniques well known in the art, as described, for example, in U.S. Pat. Nos. 3,496,217; 3,631,191; 3,846,461; 3,847,959; and 3,903,120, which are incorporated herein by reference. Zero-valent nickel compounds that contain ligands which can be displaced by the organophosphorus ligand are a preferred source of zero-valent nickel. Two such preferred zero-valent nickel compounds are Ni(COD).sub.2 (COD is 1,5-cyclooctadiene) and Ni{P(O-o-C.sub.6 H.sub.4 CH.sub.3).sub.3 }.sub.2 (C.sub.2 H.sub.4), both of which are known in the art. Alternatively, divalent nickel compounds may be combined with a reducing agent, to serve as a source of zero-valent nickel in the reaction. Suitable divalent nickel compounds include compounds of the formula NiY.sub.2 where Y is halide, carboxylate, or acetylacetonate. Suitable reducing agents include metal borohydrides, metal aluminum hydrides, metal alkyls, Zn, Fe, Al, Na, or H.sub.2. Elemental nickel, preferably nickel powder, when combined with a halogenated cataylst, as described in U.S. Pat. No. 3,903,120, is also a suitable source of zero-valent nickel. The nonconjugated acyclic, aliphatic, monoethylenically unsaturated starting materials useful in this invention include unsaturated organic compounds containing from 2 to approximately 30 carbon atoms. 3-Pentenenitrile and 4-pentenenitrile are especially preferred. As a practical matter, when the nonconjugated acyclic aliphatic monoethylenically unsaturated compounds are used in accordance with this invention, up to about 10% by weight of the mono-ethylenically unsaturated compound may be present in the form of a conjugated isomer, which itself may undergo hydrocyanation. For example, when 3-pentene-nitrile is used, as much as 10% by weight thereof may be 2-pentenenitrile. (As used herein, the term "pentenenitrile" is intended to be identical with "cyanobutene"). Suitable unsaturated compounds include unsubstituted hydrocarbons as well as hydrocarbons substituted with groups which do not attack the catalyst, such as cyano. These unsaturated compounds include monoethylenically unsaturated compounds containing from 2 to 30 carbons such as ethylene, propylene, butene-1, pentene-2, hexene-2, etc., nonconjugated diethylenically unsaturated compounds such as allene, substituted compounds such as 3-pentenenitrile, 4-pentenenitrile, methyl pent-3-enoate, and ethylenically unsaturated compounds having perfluoroalkyl substituents such as, for example, C.sub.z F.sub.2z+1, where z is an integer of up to 20. The monoethylenically unsaturated compounds may also be conjugated to an ester group such as methyl pent-2-enoate. The starting ethylenically unsaturated compounds useful in this invention and the hydrocyanation products thereof are those shown above in Formulas X through XII. Those of Formula X yield terminal nitrites of Formula XI, while those of Formula XII yield terminal nitriles of Formula XIII. Preferred are nonconjugated linear alkenes, nonconjugated linear alkene-nitriles, nonconjugated linear alkenoates, linear alk-2-enoates and perfluoroalkyl ethylenes. Most preferred substrates include 3- and 4-pentenenitrile, alkyl 2-, 3-, and 4-pentenoates, and C.sub.z F.sub.2z+1 CH=CH.sub.2 (where z is 1 to 12). The preferred products are terminal alkanenitriles, linear dicyanoalkylenes, linear aliphatic cyanoesters, and 3-(perfluoroalkyl)propionitrile. Most preferred products are adiponitrile, alkyl 5-cyanovalerate and C.sub.z F.sub.2z+1 CH.sub.2 CH.sub.2 CN, where z is 1 to 12. The present hydrocyanation process may be carried out, for example, by charging a reactor with the reactants, catalyst composition, and solvent, if any; but preferably, the hydrogen cyanide is added slowly to the mixture of the other components of the reaction. Hydrogen cyanide may be delivered as a liquid or as a vapor to the reaction. Another suitable technique is to charge the reactor with the catalyst and the solvent to be used, and feed both the unsaturated compound and the HCN slowly to the reaction mixture. The molar ratio of unsaturated compound to catalyst can be varied from about 10:1 to about 2000:1. Preferably, the reaction medium is agitated, for example, by stirring or shaking. The reaction product can be recovered by conventional techniques such as, for example, by distillation. The reaction may be run either batchwise or in a continuous manner. The hydrocyanation reaction can be carried out with or without a solvent. The solvent, if used, should be liquid at the reaction temperature and pressure and inert towards the unsaturated compound and the catalyst. Suitable solvents include hydrocarbons, such as benzene or xylene, and nitriles, such as acetonitrile or benzonitrile. In some cases, the unsaturated compound to be hydrocyanated may itself serve as the solvent. The exact temperature is dependent to a certain extent on the particular catalyst being used, the particular unsaturated compound being used and the desired rate. Normally, temperatures of from -25.degree. C. to 200.degree. C. can be used, the range of 0.degree. C. to 150.degree. C. being preferred. Atmospheric pressure is satisfactory for carrying out the present invention and hence pressures of from about 0.05 to 10 atmospheres (50.6 to 1013 kPa) are preferred. Higher pressures, up to 10,000 kPa or more, can be used, if desired, but any benefit that may be obtained thereby would probably not justify the increased cost of such operations. HCN can be introduced to the reaction as a vapor or liquid. As an alternative, a cyanohydrin can be used as the source of HCN. See, for example, U.S. Pat. No. 3,655,723. The process of this invention is carried out in the presence of one or more Lewis acid promoters which affect both the activity and the selectivity of the catalyst system. The promoter may be an inorganic or organometallic compound in which the cation is selected from scandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, boron, aluminum, yttrium, zirconium, niobium, molybdenum, cadmium, rhenium and tin. Examples include ZnBr.sub.2, ZnI.sub.2, ZnCl.sub.2, ZnSO.sub.4, CuCl.sub.2, CuCl, Cu(O.sub.3 SCF.sub.3).sub.2, CoCl.sub.2 CoI.sub.2, FeI.sub.2, FeCl.sub.3, FeCl.sub.2, FeCl.sub.2 (THF).sub.2, TiCl.sub.4 (THF).sub.2, TiCl.sub.4, TiCl.sub.3, ClTi(OiPr).sub.3, MnCl.sub.2, ScCl.sub.3, AlCl.sub.3, (C.sub.8 H.sub.17)AlCl.sub.2, (C.sub.8 H.sub.17).sub.2 AlCl, (iso-C.sub.4 H.sub.9).sub.2 AlCl, Ph.sub.2 AlCl, PhAlCl.sub.2, ReCl.sub.5, ZrCl.sub.4, NbCl.sub.5, VCl.sub.3, CrCl.sub.2, MoCl.sub.5, YCl.sub.3, CdCl.sub.2, LaCl.sub.3, Er(O.sub.3 SCF.sub.3).sub.3, Yb(O.sub.2 CCF.sub.3).sub.3, SmCl.sub.3, B(C.sub.6 H.sub.5).sub.3, TaCl.sub.5. Suitable promoters are further described in U.S. Pat. Nos. 3,496,217; 3,496,218; and 4,774,353. These include metal salts (such as ZnCl.sub.2, Col.sub.2, and SnCl.sub.2), and organometallic compounds (such as RAlCl.sub.2, R.sub.3 SnO.sub.3 SCF.sub.3, and R.sub.3 B, where R is an alkyl or aryl group). U.S. Pat. No. 4,874,884 describes how synergistic combinations of promoters can be chosen to increase the catalytic activity of the catalyst system. Preferred promoters include CdCl.sub.2, FeCl.sub.2, ZnCl.sub.2, B(C.sub.6 H.sub.5).sub.3, and (C.sub.6 H.sub.5).sub.3 SnX, where X=CF.sub.3 SO.sub.3, CH.sub.3 C.sub.6 H.sub.5 SO.sub.3, or (C.sub.6 H.sub.5).sub.3 BCN. The mole ratio of promoter to nickel present in the reaction can be within the range of about 1:16 to about 50: 1. One embodiment of the invention is a catalyst precursor composition comprising zero valent nickel and a multidentate phosphite ligand select from the group represented by the following Formula I, II, III, IV, V, VI, VII, VIII and IX, as described above, wherein the zero-valent nickel and the multidentate phosphite ligand are supported on the same solid support. |
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