Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
  • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/06—Phosphorus compounds without P—C bonds
  • C07F9/08—Esters of oxyacids of phosphorus
  • C07F9/141—Esters of phosphorous acids
  • C07F9/145—Esters of phosphorous acids with hydroxyaryl compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
  • B01J2231/32—Addition reactions to C=C or C-C triple bonds
  • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/84—Metals of the iron group
  • B01J2531/847—Nickel

Definitions

• This invention relates to a process for the preparation of a catalyst which is a complex of nickel and a bidentate phosphorous compound.
• U.S. Patent 3,903,120 discloses a process for preparing zerovalent nickel complexes by reacting elemental nickel with a monodentate phosphorous ligand of the formula PZ 3 where Z is an alkyl or alkoxy group, preferably an aryloxy group.
• the process uses finely divided elemental nickel and is preferably carried out in the presence of a nitrile solvent.
• the reaction is taught to be carried out in the presence of excess ligand.
• U.S. Patent 3,846,461 discloses a process for preparing zerovalent nickel complexes of triorganophosphites by reacting triorganophosphite compounds with nickel chloride in the presence of a finely divided reducing metal which is more electropositive than nickel, and in the presence of a promoter selected from the group consisting of NH 3 , NH X, Zn(NH 3 ) 2 X 2 , and mixtures of NH 4 X and ZnX 2 , where X is a halide.
• Reducing metals include Na, Li, Mg, Ca, Ba, Sr, Ti, V, Fe, Co, Cu, Zn, Cd, Al, Ga, In, Sn, Pb, and Th, with Zn being preferred.
• U.S. Patent 5,523,453 discloses a method of preparing nickel hydrocyanation catalysts containing bidentate phosphorous ligands.
• Zero- valent nickel compounds that contain ligands that can be displaced by the bidentate phosphorous ligand are a preferred source of nickel.
• Two such compounds are Ni(COD) 2 , where COD is 1 ,5-cyclooctadiene, and (oTTP) 2 Ni(C 2 H 4 ), where oTTP is P(O-ortho-C 6 H 4 CH 3 )3.
• divalent nickel compounds may be combined with reducing agents to produce a suitable nickel source. In the latter method of preparing catalyst, as the temperature of the catalyst preparation increases, the catalyst formation rate increases, but the amount of degradation product also increases.
• US Patent 6,069,267 describes a method for preparing a crude bidentate phosphorus-containing ligand suitable for use in the catalyst preparation.
• the resulting product is, however, not pure ligand, but rather a crude ligand mixture that contains byproducts of the reaction which may affect the rate of formation of the nickel-containing catalyst. That process does not provide for isolation and purification of the bidentate ligand.
• the present inventors observed that, compared to the use of purified ligand, such crude ligand mixtures do inhibit catalyst preparation reactions wherein divalent nickel compounds are contacted with reducing agents to produce the nickel catalyst.
• the present invention is a process for preparing a nickel/ligand catalyst, said process comprising:
• step (b) contacting the first reaction product at a temperature between about -25 deg C and about 35 deg C with about one half molar equivalent of HO-Z- OH, wherein Z is a substituted or unsubstituted aryl group different from R1 , to produce a second reaction product comprising a solids content, provided that if less than three molar equivalents of organic base are used in step (a), then sufficient organic base is used in step (b) to bring the total amount of organic base used in steps (a) and (b) combined to at least three molar equivalents of organic base relative to the PCI 3 ;
• step (c) separating the solids content from the second reaction product by filtration or extraction with water to produce a crude ligand mixture, said solids content comprising a salt formed from the organic base used in step (a) and optionally in step (b);
• step (e) recovering from the product of step (d) a solution containing a ligand of the formula
• step (f) contacting the solution of step (e) with nickel chloride in the presence of a nitrile solvent and a reducing metal which is more electropositive than nickel to produce the nickel/ligand catalyst.
• Suitable treatment methods include contacting the crude ligand mixture with the one or more of the following:
• a weakly acidic organic resin including organic polymers with carboxylic acid functional groups, such as Amberlyst CG-50 (Rohm & Haas),
• a weakly basic organic resin including organic polymers with alkylamine functional groups, such as Amberlyst® 21 (Rohm & Haas),
• a high-surface-area neutral organic resin including polystyrene adsorbent, such as Amberlite® XAD-4, and polyacrylate adsorbent, such as Amberlite® XAD-7 (Rohm & Haas),
• an aluminosilicate zeolite commonly referred to in the art as molecular sieves, such as 3A or 13X molecular sieves,
• (6) a two phase solvent system for liquid-liquid extraction where one phase is a non-polar aliphatic hydrocarbon such as hexane or cyclohexane and the other phase is a polar organic species such as adiponitrile, methylglutaronitrile, ethylsuccinonitrile, acetonitrile, ethyleneglycol or propyleneglycol, and (7) a Lewis acid.
• a non-polar aliphatic hydrocarbon such as hexane or cyclohexane
• a polar organic species such as adiponitrile, methylglutaronitrile, ethylsuccinonitrile, acetonitrile, ethyleneglycol or propyleneglycol
• Lewis acid a Lewis acid
• a solvent may be employed during the treatment to improve flowability and contact between the crude ligand and the treating agent.
• Suitable solvents include aliphatic hydrocarbons and nitriles. 3-Pentenenitrile is a preferred solvent.
• the material used for treatment is then separated from the crude ligand mixture to recover a treated ligand mixture that is then reacted with nickel chloride in the presence of a nitrile solvent and a reducing metal, to form a nickel/ligand catalyst at a higher reaction rate than that obtained by using a untreated crude ligand mixture.
• the reducing metal hereafter referred to as MET, can be any metal which is more electropositive than nickel.
• Such metals include Na, Li, K, Mg, Ca, Ba, Sr, Ti, V, Fe, Co, Cu, Zn, Cd, Al, Ga, In, Sn, Pb, and Th. Most preferred are Fe and Zn.
• the source of nickel for this invention is preferably nickel (II) chloride, NiCI 2 .
• NiCI 2 Either hydrated or anhydrous forms of NiCI 2 may be used.
• Anhydrous NiCI 2 is preferred in order to minimize the hydrolytic degradation of the ligand.
• the expression “anhydrous” means that the nickel chloride contains less than
• Nickel chloride containing 1 % or less water is preferred. Processes for producing anhydrous nickel chloride have been described in co-pending application no. 09/994,102.
• the expression "hydrated NiCI 2 " means NiCI 2 containing 2% or more water by weight. Examples of hydrated NiCb include the dihydrate, the hexahydrate and aqueous solutions of NiCb. Preferred sources for producing anhydrous NiCI 2 are the hexahydrate product and an aqueous solution. NiCl2 as an aqueous solution is particularly preferred. The aqueous solution is available commercially as an approximately 29 weight percent NiCI 2 aqueous solution.
• the catalyst formation reaction is carried out in the presence of a nitrile solvent, preferably 3-pentenenitrile or 2-methyl-butenenitrile.
• concentration of ligand may range from about 1 % to 90% by weight. For practical reasons the preferred range of ligand concentration is 5% to 50%.
• the amount of reducing metal (MET) will generally fall in the range of 0.1% to 5% of the reaction mass.
• the molar ratio of NiCb to MET ranges from 0.1:1 to 100:1.
• the preferred ratio of NiCI 2 :MET ranges from 2:1 to 50:1.
• the reaction temperature may range from 0°C to 120°C. The preferred temperature range is dependent on the NiCI 2 form. Hydrated forms of NiCb react rapidly at lower temperatures than anhydrous NiCI 2 .
• the preferred temperature range is 0°C to 60°C, and the most preferred range is 25°C to 50°C.
• the preferred temperature range is 30°C to 110°C, and the most preferred range is 50°C to 100°C.
• the reaction may be run within a wide pressure range. For practical reasons, the preferred pressure ranges from about 5 psia to 50 psia (34 to 340 kPa). The reaction may be run in batch or continuous mode.
• Suitable ligands for the present invention are bidentate phosphorous- containing ligands selected from the group consisting of bidentate phosphites and bidentate phosphinites.
• Preferred ligands are bidentate phosphite ligands.
• the preferred bidentate phosphite ligands are of the following structural formulae:
• R 1 is phenyl, unsubstituted or substituted with one or more Ci to C 12 alkyl or C 1 to C 12 alkoxy groups; or naphthyl, unsubstituted or substituted with one or more C 1 to C 12 alkyl or C 1 to C 12 alkoxy groups; and Z is independently selected from the group consisting of structural formulae II, III, IV, V, and VI:
• R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are independently selected from the group consisting of H, Ci to C12 alkyl, and Ci to C 12 alkoxy;
• X is O, S, or CH(R 10 );
• R 10 is H or d to C 12 alkyl
• R 11 and R 2 are independently selected from the group consisting of H, Ci to C12 alkyl, and Ci to C12 alkoxy; and CO 2 R 13 , R 13 is Ci to C 12 alkyl or C 6 to C 10 aryl, unsubstituted or substituted, with C to C 4 alkyl ; Y is O, S, or CH(R 14 ); R 14 is H or Ci to C 12 alkyl;
• R 15 is selected from the group consisting of H, Ci to C 12 alkyl, and Ci to
• R 16 is Ci to C 12 alkyl or C 6 to C 10 aryl, unsubstituted or substituted with
• Ci to C 4 alkyl In the structural formulae I through VIII, the Ci to C 12 alkyl, and Ci to C 12 alkoxy groups may be straight chains or branched.
• bidentate phosphite ligands that are useful in the present process include those having the formulae VII to XXIV, shown below wherein for each formula, R 17 is selected from the group consisting of methyl, ethyl or isopropyl, and R 18 and R 19 are independently selected from H or methyl:
• bidentate phosphites are of the type disclosed in atents 5,512,695; 5,512,696; 5,663,369; 5,688,986; 5,723,641; 5,847,101 ; 5,959,135; 6,120,700; 6,171 ,996; 6,171 ,997 and 6,399,534; the disclosures of which are incorporated herein by reference.
• Suitable bidentate phosphinites are of the type disclosed in U. S. Patents 5,523,453 and 5,693,843, the disclosures of which are incorporated herein by reference.
• the reaction may be carried out in a manner such that unreacted NiCb and MET may be separated from the reaction product by filtration or centrifugation. The collected excess nickel chloride can then be recycled back to a catalyst preparation reactor.
• the reducing metal is the limiting reagent in each reaction, and therefore the extent of reaction (conversion) is expressed as the percentage of the reducing metal reacted.
• the extent of reaction (conversion) is determined by analyzing for the amount of active nickel produced by the catalyst synthesis reaction. The analysis is carried out by treating a solids- free aliquot of the reaction solution with dimethyl acetylenedicarboxylate (DMAD), which forms a stable nickel complex, (Ligand)Ni(DMAD), and analyzing quantitatively for this complex by High Pressure Liquid Chromatography (HPLC).
• DMAD dimethyl acetylenedicarboxylate
• HPLC High Pressure Liquid Chromatography
• the Comparative Example illustrates typical reaction behavior when the crude ligand mixture is not treated according to this invention.
• Examples 2, 3, and 5 illustrate that treating the crude ligand with various resins results in higher rates of reaction compared with reaction using no treatment of the ligand (Comparative Example).
• Example 6 illustrates the effect of treating the crude ligand with activated carbon.
• Examples 4 and 7 illustrate the positive effect of treatment with alumino silicate zeolites (molecular sieves).
• Examples 1 , 8, and 10 illustrate the benefits of utilizing liquid-liquid extraction to treat the crude ligand. mixture.
• Example 9 illustrates the benefits of treating the crude ligand mixture with small amount of a Lewis acid prior to the catalyst preparation.
• a "crude ligand VII" was prepared by a) treating a toluene solution of PCI 3 with two molar equivalents of thymol and three molar equivalents of triethylamine while maintaining a reaction temperature of about -5°C, to produce a first reaction product comprising di(2-isopropyl-5- methylphenoxy)phosphorus chloride, triethylammonium chloride (which is substantially insoluble in the mixture), unreacted triethylamine and toluene, b) adding one half molar equivalent of binaphthol (relative to PGI 3 ) to the reaction mixture while maintaining the reaction temperature at about -5°C, c) treating the product of step (b) with water to extract the triethylammonium hydrochloride and separating the resulting aqueous lower phase from the organic product solution, and subsequently distilling a portion of the toluene from the organic product solution to produce
• Ligand VII Stock Solution was prepared by: (1) dissolving 830 grams of "crude ligand VII” in 1000 grams of 3- pentenenitrile in an air-free 3 liter round bottom flask fitted with an over head stirrer, a heating mantel, a distillation head, a dip tube to draw off material out of the flask and an addition funnel,
• step (12) heating the solution from step (1 ) under vacuum to 45 to 60 deg C to distill off the toluene and then allowing the solution to cool to ambient temperature.
• Ligand VII Stock Solution (12.067 grams) was put into a dried 20 cc vial. Into this vial was also placed 0.493 grams of anhydrous NiCb and 0.096 grams of finely divided zinc metal. A small magnetic stirring bar was added to the vial. The vial was capped and placed into a heated aluminum block that had been pre-heated to 100 deg C. A stop watch was started when the vial was placed into the heated block. The contents of the vial were agitated using a rotating magnetic bar coupled to the magnetic bar inside the vial. At 1.5 hours a sample was taken of the solution. Analysis of this sample showed 425 ppm of Ni as catalyst in solution.
• This example shows the benefit of extracting crude ligand with adiponitrile.
• This example shows the benefit of treating crude ligand with Amberlyst® 21 base resin (Rohm & Haas), a weakly basic resin containing alkylamine groups.
• This example shows the benefit of treating crude ligand with Amberlite® CG-50 (Rohm & Haas), a weakly acidic resin containing carboxylic acid groups.
• This example shows the benefit of treating crude ligand with small pore zeolites.
• 5 cc of 3A Molecular Sieves (zeolite), which had been previously activated by drying overnight at 350 deg C was loaded into a 50 cc syringe body.
• 20 cc of 3-pentenenitrile was flushed through the resin and was disposed of.
• About 15 grams of "Ligand VII Stock Solution” was then allowed to drain through the sieves.
• the ligand solution was re-analyzed and found to have about 22 wt% ligand in it.
• This example shows the benefit of treating crude ligand with an adsorbent high-surface-area neutral organic resin.
• Example 6 This example shows the benefit of treating crude ligand with activated carbon.
• This example shows the benefit of treating crude ligand with a large pore zeolite.
• a small magnetic stirring bar was added to the vial.
• the vial was capped and placed into a heated aluminum block that had been pre-heated to 100 deg C.
• a stop watch was started when the vial was placed into the heated block.
• the contents of the vial were agitated using a rotating magnetic bar coupled to the magnetic bar inside the vial.
• a sample was taken of the solution. Analysis of this sample showed 2490 ppm of Ni as catalyst in solution. This is about 6 times the amount of catalyst made in the Comparative Example.
• This example shows the benefit of extracting crude ligand with methylglutaronitrile.
• the contents of the vial were agitated using a rotating magnetic bar coupled to the magnetic bar inside the vial. At 1.5 hours a sample was taken of the solution. Analysis of this sample showed 3990 ppm of Ni as catalyst in solution. This is about 9 times the amount of catalyst made in the Comparative Example.
• This example shows the benefit of adding a Lewis acid such as ZnCb to crude ligand.
• This example shows the benefit of extracting crude ligand with ethylene glycol.

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