WO2004050593A1 - Procede d'elaboration de bisphenol a - Google Patents

Procede d'elaboration de bisphenol a Download PDF

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Publication number
WO2004050593A1
WO2004050593A1 PCT/JP2003/015334 JP0315334W WO2004050593A1 WO 2004050593 A1 WO2004050593 A1 WO 2004050593A1 JP 0315334 W JP0315334 W JP 0315334W WO 2004050593 A1 WO2004050593 A1 WO 2004050593A1
Authority
WO
WIPO (PCT)
Prior art keywords
phenol
acid
bisphenol
exchange resin
washing
Prior art date
Application number
PCT/JP2003/015334
Other languages
English (en)
Japanese (ja)
Inventor
Masahiro Iwahara
Jun Mase
Original Assignee
Idemitsu Kosan Co., Ltd.
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 Idemitsu Kosan Co., Ltd. filed Critical Idemitsu Kosan Co., Ltd.
Publication of WO2004050593A1 publication Critical patent/WO2004050593A1/fr

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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
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones

Definitions

  • the present invention relates to a method for producing bisphenol A [2,2-bis (4-hydroxyphenyl) pulp bread], and more particularly to a method for producing high-quality and high-purity bisphenol A with little coloring.
  • Bisphenol A is known to be an important compound as a raw material for engineering plastics such as polycarbonate resin and polyarylate resin or epoxy resin, and its demand has been increasing in recent years. You.
  • bisphenol A is produced by condensing excess phenol and acetone in the presence of an acidic catalyst and optionally a cocatalyst such as a sulfur compound.
  • mercaptans having or not having a substituent, such as methyl mercaptan, ethyl mercaptan, and thiodaricholic acid, are known to be effective.
  • the mercaptans have the effect of increasing the reaction rate and increasing the selectivity.
  • 2- (2-hydroxyphenyl) -12- (4-hydroxyphenyl) propane (o, p-form) is mainly produced as a reaction by-product, and trisphenol, Polyfunor and the like are produced.
  • an acid-type ion-exchange resin partially modified with an iodiamine-containing compound is known (for example, Japanese Patent Application Laid-Open No. 57-35533, Kaihei 1 1 1 2 4 6 4 5 8 Reference).
  • the acid-type ion-exchange resin partially modified with the iodiamine-containing compound has a problem that the quality of the product is degraded when impurities containing iodine or nitrogen flow out of the resin. Disclosure of the invention
  • the present invention has been made in view of the above situation, and uses an acid-type ion exchange resin partially modified with an iodamine-containing compound as a catalyst to react phenol and acetone to produce high-quality, high-purity with less coloring. It is an object of the present invention to provide a method for producing bisphenol A.
  • the gist of the present invention is as follows.
  • Nitrogen content in phenol used for cleaning is in the range of 0.01 to 5 ppm 2.
  • Phenol washing of the acid-type ion exchange resin is performed at the liquid hourly space velocity (L H SV).
  • the method of the present invention is a method for producing bisphenol A by using an acid-type ion-exchange resin partially modified with an iodiamine-containing compound as a catalyst to cause a condensation reaction between phenol and acetone to produce bisphenol A.
  • the base acid-type ion exchange resin used for the type ion-exchange resin is not particularly limited, and those conventionally used as a catalyst for bisphenol A can be used. Sulfonic acid ion exchange resins which are strongly acidic are preferred.
  • the sulfonic acid type ion exchange resin is not particularly limited as long as it is a strongly acidic ion exchange resin having a sulfonic acid group.
  • examples thereof include a sulfonated styrene divinyl benzene copolymer, a snolephonated cross-linked styrene polymer, and a phenol phenol resin.
  • Mualdehyde sulfonic acid resin, benzeneformaldehyde sulfonic acid resin and the like can be mentioned.
  • the iodiamin-containing compound used for the partial modification of the above-mentioned acid-type ion exchange resin is not particularly limited, and any one of conventionally known compounds which can be used for the modification of the acid-type ion exchange resin is appropriately selected. Can be used.
  • the Examples of iodiamine-containing compounds include 3-mercaptomethylpyridine,
  • Mercaptoalkylpyridines such as (2-mercaptoethyl) pyridine and 4- (2-mercaptoethyl) pyridine, 2-mercaptoethylamine, 3-mercaptopropylamine, 4-mercaptobutylamine, etc.
  • Thiazolidines such as mercaptoalkylamines, thiazolidine, 2,2-dimethylthiazolidine, 2-methyl-2-phenylthiazolidine, and 3-methylthiazolidine; and aminothiophenols such as 4-aminothiophenol.
  • 2-mercaptoethylamine, 2,2-dimethylthiazolidin, and 4- (2-mercaptoethyl) pyridine are preferred.
  • These diamine-containing compounds may be in a free form, an addition salt of an acidic substance such as hydrochloric acid, and a quaternary ammonium salt.
  • denaturation is performed by reacting an acid-type ion exchange resin with an iodamine compound in a suitable solvent, preferably an aqueous solvent such as water, so as to obtain a desired modification ratio (10 to 65%). be able to.
  • a suitable solvent preferably an aqueous solvent such as water
  • the reaction may be carried out at room temperature or, if necessary, with heating.
  • the sulfonic acid group, which is an ion exchange group, and the amino group in the ioamine compound react with each other, and an io group is introduced into a part of the ion exchange group to be modified.
  • the modification ratio means a molar modification ratio of the sulfonic acid group of the acid-type ion-exchange resin with the diol amine compound.
  • an acid-type ion exchange resin partially modified with a diamine compound containing a catalyst (hereinafter, simply referred to as an ion exchange resin) is charged into a fixed-bed reactor, before the reaction is started, the ion-exchange resin is used. Must be washed with phenol.
  • the temperature in the washing conditions of the ion exchange resin is preferably in the range of 45 to 110 ° C, more preferably in the range of 55 to 90 ° C. 4 5. If the temperature is lower than C, the phenol may solidify.If the temperature exceeds 110 ° C, the ion exchange resin is decomposed. May advance.
  • the liquid hourly space velocity (LHSV) is preferably in the range of 0.02 to 5 hr—more preferably 0.05 to 2 hr. If it is less than 0.02 hr 1 , it may take a long time and the efficiency may be poor. If it exceeds 5 hr- 1 , a large amount of phenol may be required.
  • the above washing is performed until the nitrogen content in the phenol used for washing is preferably in the range of 0.01 to 5 ppm, more preferably 0.05 to 3 ppm. If it is less than 0.1 ppm, the time required for cleaning and the amount of phenol used may increase, which may be economically disadvantageous. If it exceeds 5 ppm, the quality of the product may deteriorate.
  • the condensation reaction between phenol and acetone in the present invention can be carried out by a fixed bed continuous reaction system in which phenol and acetone are continuously supplied to a reaction tower filled with the above-mentioned phenol-washed ion exchange resin and reacted.
  • the number of reaction towers may be one, or two or more may be arranged in series or in parallel.
  • the acetone / phenol molar ratio is usually selected in the range of 1 to 30 to 1/3, preferably 1/20 to 1Z5. If the molar ratio is less than 1/30, the reaction rate may be too slow. If the molar ratio is more than 1Z3, the generation of impurities increases, and the selectivity of bisphenol A tends to decrease.
  • the reaction temperature is usually selected in the range of 40 to 150 ° (preferably 55 to 100 ° C.) When the temperature is lower than 40 ° C., the reaction speed is slow and the viscosity of the reaction solution is extremely high. If the temperature exceeds 150 ° C., reaction control becomes difficult, the selectivity of bisphenol A decreases, and the ion exchange resin of the catalyst may decompose or deteriorate.
  • LHSV liquid space-time velocity
  • LHSV liquid space-time velocity of the raw material mixture is usually 0. 2 to 30 hr, preferably chosen in the range of 0. 5 to 20 hr 1.
  • the reaction mixture coming out of the reaction tower is subjected to a known method. Further post-treatment is performed to extract bisphenol A. Next, an example of the post-treatment will be described.
  • concentration is performed prior to crystallization.
  • the concentration conditions are not particularly limited, but the concentration is usually performed at a temperature of 130 to 170 ° C and a pressure of 13 to 53 kPa. If the temperature is lower than 130 ° C, a high vacuum is required. If the temperature is higher than 170 ° C, impurities may increase or coloring may occur.
  • the concentration of Bisufu Wenoru A concentrated residual liquid is in the range of 2 5-4 0 weight 0/0 are preferred. If the concentration is less than 25% by mass, the recovery of bisphenol A is low, and if it exceeds 40% by mass, it becomes difficult to transfer the slurry after crystallization.
  • Crystallization of the adduct of bisphenol A and phenol from the concentrated residue is usually carried out by vacuum cooling crystallization, which uses the latent heat of vaporization of water under reduced pressure.
  • vacuum cooling crystallization method about 3 to 20% by mass of water is added to the concentrated residue, and crystallization is carried out at a normal temperature of 40 to 70 ° C and a pressure of 3 to 13 kPa. Processing is performed. If the amount of water added is less than 3% by mass, the heat removal ability is not sufficient, and the mass is 20%. /. If it exceeds 2,000, the dissolution loss of bisphenol A increases, which is not preferable.
  • the crystallization temperature is less than 40 ° C, the viscosity of the crystallization liquid may increase or solidify. If the crystallization temperature exceeds 70 ° C, the dissolution loss of bisphenol A increases, which is not preferable.
  • the adduct of bisphenol A and phenol thus crystallized is separated by a known method, and is usually subjected to a washing treatment with phenol.
  • the washed adduct is separated into bisphenol A and phenol, in which case the temperature is usually from 130 to 200 ° C, preferably from 150 to 180 ° C.
  • the pressure is usually selected in the range of 3 to 20 kPa.
  • Bisphenol A obtained by this separation treatment is substantially completely removed of the residual phenol therein by a method such as steam stripping, so that high-quality bisphenol A can be obtained.
  • Cation exchange resin (Sumitomo Chemical Co., Ltd.) in a 1,000 milliliter flask 200 Duolite SC 400) (water swelling) and 400 ml of ion-exchanged water were suspended and stirred.
  • a modified catalyst was prepared in the same manner as in Example 1 using 2,2-dimethylthiazolidine. This catalyst had 23% of the acid sites modified.
  • the reaction was carried out at 5 ° C and LHS V4 hr- 1 .
  • the reaction results were as follows: acetone conversion: 60%, bisphenol A selectivity: 96.2%, o, p-isomer: 2.8%.

Abstract

L'invention concerne un procédé d'élaboration de bisphénol A qui consiste à utiliser comme catalyseur une résine échangeuse d'ions de forme acide partiellement modifiée avec un composé amine sulfuré, aux fins de réaction phénol/acétone, ladite résine étant lavée au phénol avant le lancement de la réaction. On élabore ainsi du bisphénol A très pur de haute qualité, dont la coloration est réduite.
PCT/JP2003/015334 2002-12-05 2003-12-01 Procede d'elaboration de bisphenol a WO2004050593A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002353940A JP4338966B2 (ja) 2002-12-05 2002-12-05 ビスフェノールａの製造方法
JP2002-353940 2002-12-05

Publications (1)

Publication Number Publication Date
WO2004050593A1 true WO2004050593A1 (fr) 2004-06-17

Family

ID=32463318

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2003/015334 WO2004050593A1 (fr) 2002-12-05 2003-12-01 Procede d'elaboration de bisphenol a

Country Status (4)

Country Link
JP (1) JP4338966B2 (fr)
CN (1) CN1717379A (fr)
TW (1) TWI328575B (fr)
WO (1) WO2004050593A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1927464B (zh) * 2006-09-26 2010-09-29 蓝星化工新材料股份有限公司无锡树脂厂 防止二酚基丙烷合成反应助催化剂失活的预处理方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4423252A (en) * 1980-08-07 1983-12-27 Mitsubishi Chemical Industries Limited Process for preparing bisphenols
JPH09176069A (ja) * 1995-12-26 1997-07-08 Nippon Steel Chem Co Ltd ビスフェノール類の製造方法
JPH11246458A (ja) * 1998-02-26 1999-09-14 Mitsubishi Chemical Corp ビスフェノールの製造方法
JP2000143565A (ja) * 1998-11-12 2000-05-23 Idemitsu Petrochem Co Ltd ビスフェノールａ製造用触媒の前処理方法及び色相が安定なビスフェノールａの製造方法
EP1162188A1 (fr) * 2000-01-18 2001-12-12 Idemitsu Petrochemical Co., Ltd. Procede de preparation de bisphenol a
JP2002255879A (ja) * 2001-02-28 2002-09-11 Idemitsu Petrochem Co Ltd ビスフェノールａの製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4423252A (en) * 1980-08-07 1983-12-27 Mitsubishi Chemical Industries Limited Process for preparing bisphenols
JPH09176069A (ja) * 1995-12-26 1997-07-08 Nippon Steel Chem Co Ltd ビスフェノール類の製造方法
JPH11246458A (ja) * 1998-02-26 1999-09-14 Mitsubishi Chemical Corp ビスフェノールの製造方法
JP2000143565A (ja) * 1998-11-12 2000-05-23 Idemitsu Petrochem Co Ltd ビスフェノールａ製造用触媒の前処理方法及び色相が安定なビスフェノールａの製造方法
EP1162188A1 (fr) * 2000-01-18 2001-12-12 Idemitsu Petrochemical Co., Ltd. Procede de preparation de bisphenol a
JP2002255879A (ja) * 2001-02-28 2002-09-11 Idemitsu Petrochem Co Ltd ビスフェノールａの製造方法

Also Published As

Publication number Publication date
TWI328575B (en) 2010-08-11
CN1717379A (zh) 2006-01-04
JP2004182682A (ja) 2004-07-02
TW200412338A (en) 2004-07-16
JP4338966B2 (ja) 2009-10-07

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