EP0450009A1 - Procede pour la fabrication de bisphenols - Google Patents

Procede pour la fabrication de bisphenols

Info

Publication number
EP0450009A1
EP0450009A1 EP90914671A EP90914671A EP0450009A1 EP 0450009 A1 EP0450009 A1 EP 0450009A1 EP 90914671 A EP90914671 A EP 90914671A EP 90914671 A EP90914671 A EP 90914671A EP 0450009 A1 EP0450009 A1 EP 0450009A1
Authority
EP
European Patent Office
Prior art keywords
crystallization
bisphenol
bisphenols
solvents
hsl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP90914671A
Other languages
German (de)
English (en)
Inventor
Efim Biller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
OWAFIN AG
Original Assignee
OWAFIN AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by OWAFIN AG filed Critical OWAFIN AG
Publication of EP0450009A1 publication Critical patent/EP0450009A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/685—Processes comprising at least two steps in series
    • 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
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
    • C07C37/74—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • 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
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
    • C07C37/84—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the invention relates to a process for the production or purification of bisphenols by crystallization from high-boiling aromatic hydrocarbons.
  • Bisphenols are important intermediates for the production of epoxy, polycarbonate, phenyloxy, polysulfones and other polyester resins.
  • Bisphenol A, 2-2-bis (4-dihydroxyphenyl) propane is an important commercial intermediate.
  • Bisphenol A can be prepared by condensing phenol with acetone in a molar ratio of 2: 1 in the presence of acidic catalysts. The condensation is usually carried out with excess phenol in the presence of strongly acidic cation exchangers or strong acids, if appropriate in the presence of accelerators. In general, cation exchangers carrying sulfonic acid groups, sulfuric acid or hydrogen chloride are used as strong acids, while mercaptans or marcaptic acids serve as accelerators.
  • the reaction gives a crude product which, in addition to Bi ⁇ phenol A, unreacted phenol and acetone, the acidic catalyst, any accelerator used and the water of reaction, also contains undesired by-products. These by-products consist e.g.
  • the bisphenol A is separated off by crystallization of its addition product with phenol. A part of the desired products remains in the mother liquor of the condensation process and another part in the mother liquor obtained after recrystallization.
  • DE-OS 17 S3 431 and 20 61 531 teach cleaning processes which are based on the formation of adducts from phenol and bisphenol, followed by a crystallization stage.
  • DE-AS 12 38 038 and DE-OS 17 93 324 describe washing-extraction processes with organic solvents or water.
  • DE-AS 12 59 346 finally teaches a crystallization process.
  • Solvents, the same solvents as in DE-AS 12 38 038 are used, but the temperatures are higher than the boiling points of the solvents.
  • the invention has for its object to provide a simple and economical method for the production or purification of bisphenols.
  • the invention relates to a process for the recovery and / or purification of bisphenols, in particular bisphenol A, from crude products produced according to the prior art, characterized in that they are crystallized, if appropriate after separation of low-boiling compounds and excess phenol from high-boiling aromatic hydrocarbons (HSL) from solvents.
  • HSL high-boiling aromatic hydrocarbons
  • Suitable hydrocarbons of the type mentioned are preferred which contain 2 or 3 benzene rings which are linked to one another directly, via methylene or oxygen and which can carry alkyl radicals and / or halogens both in the nucleus and in methylene bridges, mono- and Polyalkylbenzenes, alkyl and polyalkylindanes, tetralines, hexahydronaphthalene, alkyl and polyalkylnaphthalene and others
  • HSL e.g. are used industrially as organic heat transfer media, called: mixture isomers, benzyltoluenes (MARLOTHERM L, Huls AG), mixture isomers dibenzyltoluenes (MARLOTHERM S, Huls AG) and mixtures of dimethyl diphenyl ether (DIPHENYL DT, Bayer AG); Solvents used for carbonless carbonless papers: alkyl diphenyls, mixture isomers monoalkyl and polyalkyl naphthalenes, mixture isomers methylbutyl naphthalene, mixture isomers nonyl naphthalene, tert-butyl alkyl and polyalkylbenzenes and others.
  • the solubility of bisphenols in HSL depends on the chemical structure of the high-boiling aromatic hydrocarbons.
  • the following table shows the solubility of crude bisphenol with about 95-96% bisphenol A content in different HSL:
  • DIPN mixture isomer diisopropylnaphthalene
  • the melting point of isomers 2,4-bisphenol is 108 ° C, it is expedient to carry out the crystallization at a temperature of 100-120 ° C, preferably 105-115 ° C.
  • the solubility of the bisphenols in HSL can also be increased or reduced by adding similarly boiling compounds:
  • the mother liquor obtained during the crystallization can be concentrated and crystallized again. This crystals can e.g. be placed in the initial crystallization.
  • the mother liquor from the first crystallization contains practically all of the isomers, tri- and higher-condensed compounds, codimers and resinification in addition to dissolved bisphenol A.
  • the processing of the last mother liquor can e.g. by distilling off HSL and distillatively separating the volatile compounds from the residue.
  • the volatile compounds can be converted to the desired bisphenols according to the prior art.
  • the HSL can also be used for e.g. the following procedural steps may be of interest and advantage:
  • Distillative separation of phenol optionally takes place with recovery of evaporation energy by e.g. Generation of steam or heat exchange to practically any residual phenol content by using the HSL as a fractionation buffer.
  • the phenol is separated from bisphenol A / phenol adducts and the bisphenol A e.g. by crystallization from HSL in practically any purity.
  • bisphenol A is separated from the residue by co-distillation with HSL in, for example, falling stream or tube evaporators at temperatures of 180-220 C and 0.5-25 Tor. Evaporation with HSL increases the thermal stability of bisphenol A and the condensation takes place without sublimation. Bisphenol A can be obtained from the liquefied condensate in virtually any purity by one or more crystallizations. 3.
  • the vacuum can be generated by using HSL as a barrier liquid for liquid ring pumps. The used or contaminated HSL can, if necessary, be worked up together with other HSL streams.
  • the process of the invention enables the production of bisphenols in virtually any purity.
  • An ultra-pure product can be obtained by recrystallization from HSL and / or washing with pure HSL or in countercurrent with wash liquor.
  • the reprocessing costs of the mother liquors and / or wash liquors of the recrystallization cause minimal costs.
  • the crystallization can be carried out at temperatures above 100 C under vacuum.
  • the cooling or condensation of the vapors can be carried out using air, water, evaporation, heat exchange, etc. respectively. No cooling systems and other complex cooling devices are required, as is necessary for crystallization from low-boiling solvents.
  • the present process allows bisphenols to be obtained from any raw product.
  • Processes that work with HC1 or sulfuric acid as catalysts provide products with a high content of by-products, resins and traces of metal. These impurities cause discoloration of the bisphenols and impair the use in the production of polymers. In such cases, it may be expedient to carry out the preliminary purification by co-distillation of the bisphenols with HSL and then to obtain the product by crystallization from the condensed HSL.
  • the bisphenols can be crystallized from HSL solution in various ways.
  • the solution is conveniently obtained with stirring and then cooled.
  • most of the bisphenol crystallizes out as crystal slurry and can be extracted from it by e.g. Filtration or centrifugation can be obtained.
  • Cooling by evaporation or vapor condensation under vacuum, with controlled or uncontrolled supersaturation, with or without a crystal bed, and / or circulation crystallization is preferred.
  • bisphenols can be purified according to the process of the invention: bisphenol A 2,2-bis (4 hydroxyphenyl) -propa j bisphenol F 4,4-bis-hydroxyphenyl-methane; Bisphenol Z 2,2-bis (hydroxyphenyl) cyclohexane; Bisphenol S 4-4 dihydroxydiphenyl sulfone; Bisphenol E 4-4 dihydroxydiphenylethane and others
  • the crystal masses obtained by the process according to the invention can be mixed with low-boiling solvents such as toluene, benzene, cyclohexane, heptane, methanol, ethanol, acetic acid and others. freed from adhering mother liquor residues and e.g. be dried in vacuum. Water can also be used as a detergent.
  • low-boiling solvents such as toluene, benzene, cyclohexane, heptane, methanol, ethanol, acetic acid and others. freed from adhering mother liquor residues and e.g. be dried in vacuum. Water can also be used as a detergent.
  • the method according to the invention can be operated continuously or discontinuously.
  • the method is particularly suitable for continuous implementation, which can be implemented in various embodiments.
  • Figure 3 shows the co-distillation of bisphenol A with HSL in a falling film evaporator.
  • the vapors from HSL and bisphenol A are condensed together and worked up in a crystallizer.
  • the residues containing resins and non-volatile impurities are already removed here. If appropriate, the residues of the volatile products can be removed using a thin-film evaporator (Luwa).
  • the mother liquor from the crystallization is e.g. concentrated by evaporation, crystallized in the post-crystallizer and the crystals led to the crystallization.
  • the mother liquor from the post-concentration is freed of HSL in an evaporator and the products are returned to the isomerization.
  • the crystal mass can be melted with water above 85 ° C. and freed from HSL residues by steam distillation, displacement of the HSL residues with water (subsequently decanting) or by extraction with, for example paraffinic hydrocarbons with C c -C 0 • An HSL-free product is then obtained by crystallization from water.
  • the crystals are washed three times with adhering mother liquor with cyclohexane and dried in vacuo.
  • Example 2 The procedure is as in Example 1, but is cooled to about 28-30 ° C., filtered and the crystals are washed three times with cyclohexane and dried in vacuo.
  • the vapors are condensed (no sublimation) and the crystal slurry obtained is then filtered through glass frit.
  • the crystal mass is separated with a pre-heated to about 110 ° C centrifuge and the crystals washed with a little toluene ⁇ . 210 g of crystals with a purity of 99.85% purity are obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Des bisphénols de pratiquement n'importe quelle pureté sont obtenus par cristallisation à partir d'hydrocarbures aromatiques à point d'ébullition de plus de 200 °C, le cas échéant après que le phénol ait été éliminé par distillation en présence des solvants susmentionnés.
EP90914671A 1989-10-17 1990-10-15 Procede pour la fabrication de bisphenols Withdrawn EP0450009A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH3769/89 1989-10-17
CH376989 1989-10-17

Publications (1)

Publication Number Publication Date
EP0450009A1 true EP0450009A1 (fr) 1991-10-09

Family

ID=4263093

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90914671A Withdrawn EP0450009A1 (fr) 1989-10-17 1990-10-15 Procede pour la fabrication de bisphenols

Country Status (6)

Country Link
EP (1) EP0450009A1 (fr)
JP (1) JPH04503817A (fr)
AU (1) AU6500590A (fr)
BR (1) BR9006953A (fr)
CA (1) CA2044247A1 (fr)
WO (1) WO1991005755A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5723689A (en) * 1996-01-16 1998-03-03 General Electric Company Process for recovering bisphenols
WO2000056693A1 (fr) * 1999-03-22 2000-09-28 Purac Biochem B.V. Procede de purification d'acide lactique a l'echelle industrielle
JP4419492B2 (ja) * 2002-10-28 2010-02-24 三菱化学株式会社 改善された連続晶析方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB739907A (en) * 1952-09-10 1955-11-02 Distillers Co Yeast Ltd Recovery of phenols
GB743740A (en) * 1953-07-04 1956-01-25 Distillers Co Yeast Ltd Recovery of phenols
US4167456A (en) * 1978-10-06 1979-09-11 Phillips Petroleum Co. Extractive distillation to separate cyclohexylbenzene from phenol-cyclohexanone mixture containing the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9105755A1 *

Also Published As

Publication number Publication date
AU6500590A (en) 1991-05-16
WO1991005755A1 (fr) 1991-05-02
JPH04503817A (ja) 1992-07-09
CA2044247A1 (fr) 1991-04-18
BR9006953A (pt) 1991-11-12

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