Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D11/00—Solvent extraction
  • B01D11/04—Solvent extraction of solutions which are liquid
  • B01D11/0492—Applications, solvents used
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D11/00—Solvent extraction
• • 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
  • C07F9/025—Purification; Separation; Stabilisation; Desodorisation of organo-phosphorus compounds
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/50—Organo-phosphines

Definitions

• the present invention relates to a process for the purification of phosphorus-containing chelate ligands by extraction with polar extractants.
• US-A-6,069,167, US-A-6,031,120, WO-A-03/44029 and WO-A-03/62171 disclose the selective synthesis of certain chelating ligands by reaction with amine auxiliary bases.
• the ligands fall in these syntheses after separation of the Aminbasenhydrochlo- ride (phase separation or filtration), as a crude solution in a nonpolar Amsterdamsmit ⁇ tel, such as. Toluene, on.
• a nonpolar Amsterdam-catalyzed hydrocyanation of 3-pentenenitrile to ADN may be mentioned, where the polar solvent is the same as the reactant.
• Our own investigations have shown that these chelate ligands are stable in non-polar media, whereas they irreversibly decompose or rearrange in polar media due to amine and amine hydrochloride traces from ligand synthesis.
• the present invention can be carried out as follows:
• Phosphorus-containing chelate ligands from syntheses such as are known from US Pat. No. 6,069,267, US Pat. No. 6,031,120, WO-A-03/44029 and DE-A-102 30 222 can be prepared according to the purifications described there, preferably there described reaction effluents directly with a polar extractant at temperatures of (-20) to 150 0 C, preferably (-10) to 12O 0 C, more preferably 0 to 60 0 C and a pressure of 1 to 5000 kPa, preferably 10 to 1000 kPa, more preferably 50 to 500 kPa, in particular 75 to 250 kPa are purified.
• Suitable polar extractants are all aprotic polar solvents which form two phases with aliphatics and cycloaliphatic compounds, preferably nitriles, dinitriles and dialkylamines, more preferably dinitriles such as, for example, adiponitrile or methylglutaronitrile.
• the extraction can be carried out in batch, semibatch or continuous mode in any suitable device known to the person skilled in the art. Preference can be given to working in countercurrent extraction columns, mixer-settler cascades or combinations of mixer-settler cascades with columns, particularly preferably in countercurrent extraction columns, which are equipped in particular with sheet metal packings as dispersing elements. In a further particularly preferred embodiment, the extraction can be carried out in countercurrent in a compartmented, stirred extraction column.
• the phase separation can be carried out in one or more devices which are generally known per se for such phase separations. In an advantageous embodiment, the phase separation can be carried out, for example, in the extraction apparatus with one or more mixer-settler combinations or by equipping an extraction column with a settling zone.
• the phase separation can be considered spatially and temporally depending on the apparatus design as the last part of the extraction.
• the phase separation can be carried out in one or more devices known to the person skilled in the art for such phase separations.
• the phase separation can be carried out in the extraction apparatus, for example in one or more mixer-settler combinations or by equipping an extraction column with a settling zone.
• the reaction product is used as the continuous phase and the polar phase as the disperse phase.
• the reverse direction of dispersion, ie reaction discharge as continuous and hydrocarbon as disperse phase is also possible.
• the extractant is used as the disperse phase and the reaction effluent of the hydrocyanation as the continuous phase.
• Mulm means an area of incomplete phase separation between the upper and lower phases, usually a liquid / liquid mixture in which solids can also be dispersed. Excessive mulching is undesirable since it prevents the extraction and possibly the extraction device can be flooded by the muck, whereby it can no longer fulfill its separation task.
• reaction discharge or the prepurified phosphorus-containing chelate ligands ovin ⁇ nen with an aliphatic or cycloaliphatic hydrocarbon or mixtures thereof such as.
• aliphatic or cycloaliphatic hydrocarbon or mixtures thereof such as.
• hexane-isomer mixture, n-hexane, heptane isomer mixture, n-heptane, octane Isomeriengemisch, n-octane, cyclohexane, methylcyclohexane or mixtures thereof, preferably n-heptane, n-octane, cyclohexane, methylcyclohexane or mixtures thereof before or diluted during extraction or phase separation were ⁇ the.
• the volume ratio of the phases in the extraction can vary within wide ranges and is generally between 0.01: 1 to 10: 1, preferably 0.04: 1 to 2.5: 1, more preferably 0.07 : 1 to 1.5: 1.
• Suitable phosphorus-containing chelating ligands are ligands of the formula (I)
• R 11 , R 12 are independently identical or different, single or bridged organic radicals
• R 21 , R 22 independently of one another are identical or different, individual or bridged organic radicals,
• compound (II) is a single compound or a mixture of different compounds of the abovementioned formula.
• X 11 , X 12 , X 13 , X 21 , X 22 , X 23 may be oxygen.
• the bridging group Y is linked with phosphite groups.
• X 11 and X 12 can be oxygen and X 13 is a single bond or X 11 and X 13 is oxygen and X 12 is a single bond such that the phosphorus atom surrounded by X 11 , X 12 and X 13 is the central atom of a phosphonite.
• X 21 , X 22 and X 23 may be oxygen or X 21 and X 22 oxygen and X 23 a single bond or X 21 and X 23 oxygen and X 22 a single bond or X 23 oxygen and X 21 and X 22 a single bond or X 21 oxygen and X 22 and X 23 is a single bond, so that the phosphorus atom surrounded by X 21 , X 22 and X 23 can be the central atom of a phosphite, phosphonite or phosphinite, preferably a phosphonite.
• X is a single bond
• X 11 is oxygen and X 12 and X 13 represent a single bond
• X 11, X 12 and X 13 phosphorus atom surrounded central atom ei ⁇ nes Phosphonite
• X 21 , X 22 and X 23 can be oxygen or X 23 oxygen and X 21 and X 22 a single bond or X 21 oxygen and X 22 and X 23 a single bond such that X 21 , X 22 and X 23 surrounded phosphorus atom may be central atom of a phosphite, or phosphinite, preferably a phosphinite.
• bridging group Y are preferably substituted, for example with C 1 -C 4 - alkyl, halogen, such as fluorine, chlorine, bromine, halogenated alkyl, such as trifluoromethyl, aryl, such as phenyl, or unsubstituted aryl groups, preferably those having 6 to 20 carbon atoms in the aromatic system, in particular pyrocatechol, bis (phenol) or bis (naphthol).
• halogen such as fluorine, chlorine, bromine
• halogenated alkyl such as trifluoromethyl
• aryl such as phenyl
• unsubstituted aryl groups preferably those having 6 to 20 carbon atoms in the aromatic system, in particular pyrocatechol, bis (phenol) or bis (naphthol).
• radicals R 11 and R 12 may independently of one another represent identical or different organic radicals.
• Suitable radicals R 11 and R 12 are preferably aryl radicals, in particular those having 6 to 10 carbon atoms, which may be unsubstituted or monosubstituted or polysubstituted, in particular by C 1 -C 4 -alkyl, halogen, such as fluorine, chlorine, bromine , halogenated alkyl, such as trifluoromethyl, aryl, such as phenyl, or unsubstituted aryl groups.
• radicals R 21 and R 22 may independently represent identical or different organic radicals.
• radicals R 21 and R 22 are aryl radicals, preferably those having 6 to 10 carbon atoms, are suitable, which may be unsubstituted or mono- or polysubstituted, in particular by C r C 4 alkyl, halogen, such as fluorine, chlorine, bromine, halogenated alkyl, such as trifluoromethyl, aryl such as phenyl, or unsubstituted aryl groups.
• the radicals R 11 and R 12 may be singly or bridged.
• the radicals R 21 and R 22 may be singly or bridged.
• radicals R 11 , R 12 , R 21 and R 22 may all be individually bridged and two individually or all four bridged in the manner described.
• the compounds of the formula I, II, III, IV, V and VI mentioned in US Pat. No. 5,512,695, in particular the compounds used there in Examples 1 to 6, are suitable.
• the compounds of the formula I, II, III, IV, V, VI, VII, VIII, IX and X mentioned in US Pat. No. 6,020,516, in particular the compounds used there in Examples 1 to 33, are suitable .
• the compounds mentioned in US Pat. No. 5,959,135 and compounds used there in Examples 1 to 13 are suitable.
• the compounds mentioned in WO 01/14392 preferably those mentioned in formula V, VI, VII, VIII, IX, X, XI, XII, XIII, 1 XIV, XV, XVI, XVII, XXI, XXII, XXIII compounds, into consideration.
• the compounds mentioned in WO 98/27054 are suitable.
• the compounds mentioned in WO 99/64155 are suitable.
• German patent application DE 100 380 37 come into consideration.
• German patent application DE 100 460 25 come into consideration.
• German patent application DE 101 502 85 come into consideration.
• German Patent Application DE 101 502 86 come into consideration.
• German patent application DE 102 071 65 come into consideration.
• the phosphorus-containing chelate ligands mentioned in US 2003/0100442 A1 come into consideration.
• the phosphorus-containing chelate ligands mentioned in US 2004/062765 A1 come into consideration.
• phosphorus-containing chelate ligands can be obtained which have a content of amine base, amine hydrochloride or mixtures thereof of less than 100 ppm, preferably less than 80 ppm, more preferably less than 60 ppm.
• amine bases are, for example, tralkylamines, pydidine bases, dialkylamines, monoalkylamines, preferably methylimidazole, and the amine hydrochlorides formed therefrom, for example triethylamine hydrochloride and methylimidazole hydrochloride, preferably methylimidazole hydrochloride.
• Suitable ligands for the hydrocyanation of butadiene to pentenenitriles, the isomerization of 2-methyl-3-butenenitrile to 3-pentenenitrile and the hydrocyanation of 3-pentenenitrile to adiponitrile.
• the phospho-containing chelating ligands eg chelate phosphites known from US Pat. No. 5,981,772 and US Pat. No.
• chelate phosphonites are known from WO-A-99/64155, WO-A-99/13983, DE-A-101 50 285 and DE-A-102 07 165, chelate phosphinites are known from US-A-5,523,453, US-A-5,693,843 and DE-A-101 50 286 and chelate phosphite phosphinites
• DE-A-103 50 999 may e.g. be converted into the catalysts with the aid of nickel (O).
• the upper phase was each mixed with 3-pentenenitrile and 48 getem- pert h at 100 C c. After annealing, the content of intact ligand 1 was determined by 31 P-NMR.

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• 2004
  • 2004-10-08 DE DE102004049339A patent/DE102004049339A1/de not_active Withdrawn
• 2005
  • 2005-09-30 US US11/576,575 patent/US20080076944A1/en not_active Abandoned
  • 2005-09-30 AT AT05796041T patent/ATE549344T1/de active
  • 2005-09-30 JP JP2007535066A patent/JP2008515831A/ja active Pending
  • 2005-09-30 WO PCT/EP2005/010561 patent/WO2006040023A1/de not_active Ceased
  • 2005-09-30 EP EP05796041A patent/EP1799697B1/de not_active Revoked
  • 2005-09-30 CN CN2005800341236A patent/CN101035799B/zh not_active Expired - Fee Related
  • 2005-09-30 KR KR1020077010332A patent/KR20070060157A/ko not_active Ceased

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