Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
  • C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
  • C07C37/66—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring by conversion of hydroxy groups to O-metal groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/20—General preparatory processes
  • C08G64/30—General preparatory processes using carbonates
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
• • 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
  • C07F9/54—Quaternary phosphonium compounds

Definitions

• the application relates to a process for the preparation of phosphonium phenolates.
• the object of the present application is therefore to find a process in which the temperature load and the amounts of solvent obtained remain as low as possible, but the purity of the phosphonium phenolate is as high as possible.
• the application relates to a process for the preparation of phosphonium phenolates by reacting phosphonium halides and phenols in aqueous alkaline solution, characterized in that the phosphonium phenolate produced is separated from the synthesis mixture by crystallization.
• the reaction is preferably carried out at temperatures from 0 to 55 ° C., in particular 15 to 50 ° C.
• the reaction is preferably carried out at molar ratios of phenol to phosphonium halide from 2: 1 to 10: 1, preferably from 4.5: 1 to 6: 1 and in particular 5: 1.
• the reaction is preferably carried out at pH values from 9.5 to 11, preferably from 9.5 to 10.5 and in particular from 10 to 10.5.
• the reaction is optionally carried out in the presence of alcohols in amounts of from 50% by weight to 200% by weight, preferably from 66% by weight to 125% by weight, based on the amount by weight of the aqueous phase, the alcohols preferably being soluble in pure water of a maximum of 15% by weight.
• the phosphonium phenolates produced in this way contain no more than 0.1% by weight of halide.
• R j to R4 are the same or different, each for one C5-C6 cycloalkyl, C7-C 1 2-aralkyl or Cö-C ⁇ aryl radical, and
• ⁇ (-) represents a halogen ion, preferably F ( ⁇ ) , C " ) or Br ( ⁇ ) , and
• n the number 1 or 2
• R 4 represents a C 2 -Ci 2 alkylene radical.
• the radicals R j to R 4 are each a Cg-C ⁇ aryl radical or the radicals Rj to R 3 are each a -C1 4 - aryl radical and R is a C2-Ci2 alkylene.
• Such phosphonium halides and their preparation are known or can be obtained by known methods (see, for example, "Houben-Weyl, Methods of Organic Chemistry” Volume XII / 1, pages 79 ff. And Worrall, J. Amer. Chem. Soc. 52 (1930), Pages 293 ff.).
• These compounds (I) are formed in the reaction of trialkyl- or triarylphosphines, for example triphenylphosphine with haloarylene or halogenoalkylene, e.g. Benzyl bromide in the presence of metal salts (Friedel-Crafts alkylation) or in the presence of Grignard compounds and cobalt (II) chloride.
• trialkyl- or triarylphosphines for example triphenylphosphine with haloarylene or halogenoalkylene, e.g. Benzyl bromide in the presence of metal salts (Friedel-Crafts alkylation) or in the presence of Grignard compounds and cobalt (II) chloride.
• Preferred phenols for the reaction are phenol or substituted phenols and bisphenols.
• Particularly preferred phenols are those of the formula (II)
• R5 to R7 independently of one another are H, Ci-Ci2-alkyl, Cs-Cg-cycloalkyl, 7-Ci2-rylalkyl and Cg-C ⁇ aryl; R5 to R7 are preferably hydrogen. Such phenols are known from the literature.
• Phosphonium phenolates of the formula (III) are preferably prepared
• Deionized water or distilled water is preferably used to produce the aqueous alkaline phase.
• the pH from 9.5 to 11.0 preferably from 9.5 to 10.5, particularly preferably from 10.0 to 10.5, is preferably set using an alkali metal hydroxide solution, preferably sodium hydroxide solution or potassium hydroxide solution, taking into account the buffering effect of phenol / Na phenolate.
• an alkali metal hydroxide solution preferably sodium hydroxide solution or potassium hydroxide solution
• the process according to the invention can be carried out continuously or batchwise, a batchwise procedure being preferred.
• the pH is adjusted to from 9.5 to 11.0, preferably from 9.5 to 10.5, particularly preferably from 10.0 to 10.5, with the addition of alkali metal hydroxide solution.
• the temperature is preferably maintained at 0 to 55 ° C., preferably 15 to 50 ° C., with intensive mixing of the reaction components.
• the reaction time should be less than 2 hours, preferably less than 1 hour.
• the phosphonium phenolate produced according to the invention is isolated, preferably by separating the aqueous phase from the organic phase using an alcohol which is sparingly soluble in water (the solubility of the alcohols in water is known from the literature) and the latter is separated at least once, preferably three times with demineralized water or extracted distilled water.
• the solution is then cooled to 26 to 0 ° C., preferably to 23 to 10 ° C.
• the precipitated phenolate is then filtered off and cleaned by washing. If necessary, the product obtained is recrystallized and dried.
• Alcohols suitable for the reaction solution according to the invention are aliphatic
• n H2 n +] -OH where n is an integer from 4 to 10 inclusive, such as.
• Alcohols suitable according to the invention for the reaction solution are also cycloaliphatic of the formula C n H2 n- ⁇ -OH, where n is an integer from 5 to 10 inclusive, such as.
• alcohols can also be used to wash out the phenolate.
• water-soluble alcohols can also be used here, such as. As ethanol, n-propanol or isopropanol.
• Propanols in particular isopropanol, are preferred here.
• polyhydric aliphatic or cycloaliphatic alcohols can also be used.
• Preferred aliphatic alcohols are propanols, (iso) butanols, pentanols and hexanols, in particular isobutanol and isopropanol.
• Preferred cycloaliphatic alcohols are cyclopentanol, cycloheptanol and cyclooctanol, particularly preferably cyclohexanol.
• the weight ratio of water to alcohol is between 2: 1 and 1: 2, preferably between 1: 1 and 1: 2.
• the alcohols to be used according to the invention are added for better processing, since the phenol / alcohol mixture has a lower density than the aqueous solution and is therefore the organic over the aqueous phase.
• the aqueous phase can thus be drained off at the bottom, the organic phase which contains the phenolate can then be washed with demineralized water in the same separation vessel and the wash water can again be drained off at the bottom.
• Quaternary phosphonium phenolates produced according to the invention are in particular the compounds of the formulas
• the process according to the invention makes it possible to produce phosphonium phenolates in high yields and high purity.
• the phosphonium phenolates prepared in this way are particularly suitable as catalysts for esterification and for transesterification, in particular for the production of polycarbonates by the melt transesterification process (see US Pat. No. 3,442,854).
• melt transesterification process is based, for example, on aromatic diphenols, carbonic acid diaryl esters and optionally branching agents and / or monophenols.
• the phosphonium phenolates obtainable according to the invention are used as catalysts in amounts of 10 ⁇ 1 mol to 10 " 8 mol, preferably in amounts of 10 ⁇ 3 mol to 10 " ⁇ mol, per mole of diphenol.
• thermoplastic polycarbonates produced with the phosphonium phenolates obtainable according to the invention are solvent-free, have a light inherent color and are largely free of undesirable defects in the polycarbonate.
• thermoplastic polycarbonates for example in electrical engineering, as lamp covers, as safety disks or as optical data storage media, such as CD material.
• the lower aqueous phase is drained off and the organic phase is washed three times with deionized water, and the wash water as the heavier phase is drained off at the bottom.
• the organic phase is then cooled to room temperature with stirring.
• the product crystallizes out. After at least 4 h crystallization time, the product is suctioned off.
• the filtrate is returned to the reaction after NMR analysis for the content of phenol, isobutanol and tetraphenylphosphonium phenolate.
• the crystalline residue is washed with 2-propanol, then dried at 100 ° C. in a water jet vacuum.
• the content of branching of formula (VII) in the polycarbonate produced is 25 ppm.
• the phenolic OH value of the polycarbonate is 70 ppm.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Biochemistry (AREA)
• General Health & Medical Sciences (AREA)
• Molecular Biology (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Polyesters Or Polycarbonates (AREA)

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• 1999
  • 1999-12-20 DE DE19961520A patent/DE19961520A1/de not_active Withdrawn
• 2000
  • 2000-12-07 AT AT00983239T patent/ATE279385T1/de not_active IP Right Cessation
  • 2000-12-07 CN CNB00817427XA patent/CN1211389C/zh not_active Expired - Fee Related
  • 2000-12-07 KR KR1020027007869A patent/KR20020062354A/ko not_active Withdrawn
  • 2000-12-07 AU AU20059/01A patent/AU2005901A/en not_active Abandoned
  • 2000-12-07 WO PCT/EP2000/012325 patent/WO2001046100A1/de not_active Ceased
  • 2000-12-07 EP EP00983239A patent/EP1242347B1/de not_active Expired - Lifetime
  • 2000-12-07 US US10/168,166 patent/US6710153B2/en not_active Expired - Fee Related
  • 2000-12-07 ES ES00983239T patent/ES2231294T3/es not_active Expired - Lifetime
  • 2000-12-07 BR BR0016559-0A patent/BR0016559A/pt not_active Application Discontinuation
  • 2000-12-07 JP JP2001546614A patent/JP4856340B2/ja not_active Expired - Fee Related
  • 2000-12-07 DE DE2000508270 patent/DE50008270D1/de not_active Expired - Lifetime
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