WO2002085830A1 - Procede de production de bisphenol a - Google Patents

Procede de production de bisphenol a Download PDF

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Publication number
WO2002085830A1
WO2002085830A1 PCT/JP2002/003540 JP0203540W WO02085830A1 WO 2002085830 A1 WO2002085830 A1 WO 2002085830A1 JP 0203540 W JP0203540 W JP 0203540W WO 02085830 A1 WO02085830 A1 WO 02085830A1
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WO
WIPO (PCT)
Prior art keywords
acetone
bisphenol
exchange resin
acid
mercaptan
Prior art date
Application number
PCT/JP2002/003540
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English (en)
Japanese (ja)
Inventor
Masahiro Iwahara
Original Assignee
Idemitsu Petrochemical Co., Ltd.
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Filing date
Publication date
Application filed by Idemitsu Petrochemical Co., Ltd. filed Critical Idemitsu Petrochemical Co., Ltd.
Publication of WO2002085830A1 publication Critical patent/WO2002085830A1/fr

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    • 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 bisphenol A [2,2-bis (4-hydroxyphenol)]. More specifically, in the production of bisphenol A by condensing phenol and acetone using an acid-type ion-exchange resin catalyst partially modified with an iodamine compound, the mercaptan compound
  • the present invention relates to a method for stably producing bisphenol A at a high conversion by suppressing a decrease in catalytic activity due to methanol, which is an impurity in acetone, by adding the compound.
  • Bisphenol A is known to be an important compound as a raw material for engineering plastics such as polycarbonate resin and polyarylate resin, or as a raw material for epoxy resins, and the demand for bisphenol A has been increasing in recent years.
  • This 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.
  • an acidic catalyst used in this reaction, inorganic mineral acids such as sulfuric acid and hydrogen chloride have been used in the past, but cation exchange resins have recently attracted attention (UK Patent No. 842209). No. 8,495,655 and No. 8,339,91), which have been used industrially.
  • alkyl mercaptans having or not having a substituent such as methyl mercaptan, ethyl mercaptan, and thiodaricholic acid are known to be effective (US Patent No. 235 No. 242, specification No. 2,775,620). These mercaptans have the effect of increasing the reaction rate and increasing the selectivity.
  • 2- (2-hydroxyphenyl) -12- (4-hydroxyphenyl) propane (o, ⁇ '-isomer) is mainly produced as a reaction by-product, and other trisphenols are produced. And polyphenols are generated.
  • raw materials such as polycarbonate resin and polyarylate resin
  • bisphenol / A with high purity and low content of these by-products is required.
  • mercaptans are used as a co-catalyst to increase the reaction rate, suppress the generation of the by-products, and increase the selectivity.
  • an acid-type ion exchange resin partially modified with an iodiamine-containing compound is known.
  • bisphenol A is produced by condensing phenol and acetone with this modified acid-type ion-exchange resin as a catalyst
  • methanol which is an impurity in acetone. Occurs. Therefore, in order to solve such a problem, a method has been proposed in which a small amount of water is present in the reaction raw material to suppress the decrease in the catalyst activity (Japanese Patent Application Laid-Open No. HEI 6-172722).
  • the reaction raw material is purified in advance, and the impurities in the raw material, R—X (R is an alkyl group, a ⁇ enyl group, a cycloalkyl group or a cycloalkenyl group, and X is ⁇ , a halogen atom,
  • R—X R is an alkyl group, a ⁇ enyl group, a cycloalkyl group or a cycloalkenyl group, and X is ⁇ , a halogen atom
  • the present invention provides a method for producing bisphenol by condensing phenol and acetone using an acid-type ion-exchange resin catalyst partially modified with an iodiamine-containing compound. It is an object of the present invention to provide a method for stably producing bisphenol A at a high conversion rate while suppressing a decrease in catalytic activity due to methanol, Things.
  • the present inventor has conducted intensive studies to achieve the above object, and as a result, using a catalyst in which the modification rate of an acid-type ion exchange resin partially modified with an iodiamin compound is in a specific range, a mercaptan compound is prepared. It has been found that the purpose can be achieved by the addition. The present invention has been completed based on such findings.
  • the methanol concentration in acetone is 4%.
  • the modified acid-type ion exchange resin having a modification ratio of 15 to 50 mol% is used, and a mercaptan compound is added.
  • the modification rate in the present invention means a molar modification rate of an acid-type ion-exchange resin with a sulfonic acid group-containing diamine compound.
  • the method of the present invention is a method for producing bisphenol A by condensing phenol and acetone with an acid-type ion-exchange resin partially modified with an iodiamine-containing compound as a catalyst
  • the base acid-type ion exchange resin used in the modified acid-type ion-exchange resin is not particularly limited, and those conventionally used as a catalyst for bisphenol A can be used. Accordingly, a strongly acidic sulfonic acid type ion exchange resin is 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-dibutylbenzene copolymer, a sulfonated crosslinked styrene polymer, and phenol formaldehyde sulfone.
  • Acid resins, benzene formaldehyde sulfonic acid resins and the like can be mentioned.
  • the iodiamine-containing compound used for the partial modification of the acid-type ion-exchange resin is not particularly limited, and any one of conventionally known compounds that can be used for the modification of the acid-type ion-exchange resin is used. Can be appropriately selected and used.
  • diamine compound examples include 3-mercaptomethyl pyridine, 3- (2 Mercaptoalkylpyridines such as 1-mercaptoethyl) pyridine, 4- (2-mercaptoethyl) pyridine, and mercaptoalkylamines such as 2-mercaptoethylamine, 3-mercaptopropylamine, and 4-mercaptobutylamine Thiazolidine, 2,2-dimethylthiazolidine, thiazolidines such as 2-methyl-2-phenylthiazolidine, 3-methylthiazolidine, and aminothiophenols such as 4-aminothiophenol, and the like.
  • 4- (2-mercaptoethyl) pyridine, 2-mercaptoethylamine and 2,2-dimethylthiazolidine are preferred.
  • iodiamine-containing compounds may be in a free form, or may be in the form of an addition salt of an acidic substance such as hydrochloric acid or a quaternary ammonium salt.
  • the method for partially modifying the above-mentioned base acid-type ion-exchange resin using these iodiamine-containing compounds can be modified 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 rate.
  • a suitable solvent preferably an aqueous solvent such as water
  • the reaction may be carried out at room temperature or, if necessary, with heating.
  • a sulfonic acid group as an ion exchange group reacts with an amino group in the ioamine compound, and an io group is introduced into a part of the ion exchange group to be modified.
  • a modified acid-type ion exchange resin having a modification ratio of 15 to 50 mol% is used when the methanol concentration in the raw material acetone is 400 to 700,000 weight ppin. .
  • the present inventors have used an acid-type ion-exchange resin partially modified with an iodamine-containing compound as a catalyst for condensation of phenol and acetone!
  • the sulfonic acid group acts as a catalyst
  • methanol which is an impurity in acetone, reacts with the mercapto group of the iodiamine-containing compound in the modified acid-type ion-exchange resin to form methyl sulfide.
  • methanol which is an impurity in acetone
  • a small amount of a mercaptan compound is added to the reaction system, and the mercaptan compound is reacted with methanol, which is an impurity in acetone, to react the mercapto group of the thiopamine-containing compound in the modified acid-type ion exchange resin with methanol. By suppressing it, the catalyst life can be prolonged.
  • Examples of the mercaptan compound include methyl mercaptan, ethyl mercaptan, n-cap pinolemercaptan, i-propinolemenolecaptan, n-ptinolemenorecaptan, sec-butyl mercaptan, t-butyltinolemenorecaptan, Alkyl mercaptans having 1 to 10 carbon atoms, such as pentinoremercaptan, hexyl menolecaptan, heptylmercaptan, octylmenolecaptan, nonolemenolecaptan, and decylmercaptan, are among these. Alkyl mercaptans having 1 to 3 carbon atoms are preferred.
  • the amount of the mercaptan compound to be added is preferably 1/20 to 1Z500 (molar ratio), preferably 1 to 50 to 1/400 (molar ratio) based on acetone.
  • the addition amount can be arbitrarily changed according to the methanol concentration in the raw material acetone, the reaction state of acetone and phenol, and the degree of deterioration of the modified acid-type ion exchange resin catalyst.
  • the methanol concentration is high or the degree of deterioration of the catalyst is severe, the added amount of the mercaptan compound increases.
  • the addition of the mercaptan compound of the present invention not only has the effect of extending the catalyst life, but also promotes the reaction of forming bisphenol A by the cocatalytic effect of the mercaptan compound, thereby improving the overall catalytic activity.
  • the water content of phenol as a raw material is generally 500 to 100 ppm in a reagent or an industrial product.
  • the water content of the raw material acetone is also included in the range of 100 to 300 ppm.
  • the use ratio of phenol and acetone is not particularly limited, but the amount of unreacted acetone is reduced from the viewpoint of easy purification and economical efficiency of the produced bisphenol A. It is desirable to have as little as possible, and it is therefore advantageous to use the phenol in excess of the stoichiometric amount.
  • the reaction solvent is generally not required, except that the reaction liquid is reacted at a low temperature at which the viscosity of the reaction liquid is too high or the solidification hardens the operation.
  • the condensation reaction between phenol and acetone in the present invention is carried out by continuously supplying phenol and acetone to a reactor filled with an acid-type ion-exchange resin partially modified with the above-described iodamine-containing compound.
  • a fixed bed continuous reaction system can be used. In this case, one reactor may be used, or two or more reactors may be arranged in series or in parallel.
  • the acetone / phenol molar ratio is usually selected in the range of 1/30 to 1Z3, preferably 1/20 to 1/5. If the molar ratio is less than 1/30, the reaction rate may be too slow. If the molar ratio is more than 1 Z3, the generation of impurities may increase, and the selectivity of bisphenol A tends to decrease.
  • the method of supplying the phenol, acetone and mercaptan compound to the reactor is not particularly limited, but it is preferable to separately supply the acetone and mercaptan compound to each reactor.
  • the reaction temperature is selected in the range of usually 40 to 150 ° C, preferably 55 to 100 ° C. If the temperature is lower than 40 ° C, the reaction rate is low, and the viscosity of the reaction solution is extremely high. In some cases, the reaction solution may be solidified. If the temperature exceeds 150 ° C, the reaction control becomes difficult, and bisphenol The selectivity of A ( ⁇ , 'one) decreases, and the modified acid-type ion-exchange The fat may decompose or deteriorate.
  • the LHSV (liquid hourly space velocity) of the raw material mixture is usually selected in the range of 0.2 to 30 hr—preferably 0.5 to 20 hr— 1 .
  • the reaction mixture coming out of the reactor is subjected to a post-treatment by a known method, and bisphenol A is taken out.
  • 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 1 ⁇ 0 ° C, impurities may increase or coloring may occur.
  • the concentration of bisphenol A in the concentrated residual liquid is advantageously in the range of 25 to 40 weight 0/0. If the concentration is less than 25% by weight, the recovery of bisphenol A is low, and if it exceeds 40% by weight, 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 utilizes the latent heat of water evaporation under reduced pressure.
  • vacuum cooling crystallization method about 3 to 20% by weight of water is added to the concentrated residue, and crystallization is performed 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 weight, the heat removal ability is not sufficient, and the weight is 20%. If the ratio exceeds / 0 , the dissolution opening of bisphenol A becomes large, which is not preferable. If the crystallization temperature is lower than 40 ° C, the viscosity of the crystallized liquid may increase or solidify. If it exceeds 70 ° C, the dissolution loss of bisphenol A increases, which is not preferable.
  • the thus-crystallized adduct of bisphenol A and phenol is separated by a known method, and is usually washed with phenol.
  • the washed adduct is separated into bisphenol A and phenol.
  • the temperature is usually selected in the range of 130 to 200 ° C, preferably in the range of 150 to 180 ° C.
  • Orientation pressure is usually selected in the range of 3 to 20 kPa.
  • Bisphenol A obtained by this separation treatment is substantially completely removed by a method such as steam stripping to remove residual phenol therein, thereby obtaining high-quality bisphenol A.
  • a sulfonic acid type ion-exchange resin denatured with 20 mol% of 2-mercaptoethylamine as a catalyst [Mitsubishi Chemical Corporation Product name: DIAION SK-104H] 69.3 Milliliter (swelled with water) was filled. The two reactors were connected in series.
  • the first-stage reactor was charged with 277 milliliters of phenol and the first and second stages were charged with 500 ppm by weight of methanol and 1/400 ppm of ethyl mercaptan (vs. The reaction was carried out while maintaining the reaction temperature at 75 ° C. by dividing and passing acetonitrile containing 15.6 tons / mole ratio (15.6 torr / mol).
  • Example 1 a sulfonic acid type ion-exchange resin (described above) modified with 2,2-dimethylthiazolidine at 25 mol% was used as a catalyst, and methanol (1000 ppm by weight) and ethyl mercaptan (1/20) were used. The procedure was performed in the same manner as in Example 1 except that the acetone was changed to 0 (molar ratio to acetone).
  • Example 1 a sulfonic acid-type ion-exchange resin (described above) modified with 2,2-dimethylthiazolidine at 25 mol% was used as a catalyst, and methanol 5,000 weight 111 and ethyl mercaptan 1/1 were used. The procedure was performed in the same manner as in Example 1 except that the acetone was changed to include acetone (molar ratio to acetone).
  • Example 1 a sulfonic acid type ion-exchange resin (described above) modified with 45 mol% of 2,2-dimethylthiazolidine was used as a catalyst, and methanol 5,000 weight 111 and ethyl mercaptan 1/50 were used. (Mole ratio to acetone) The procedure was performed in the same manner as in Example 1 except that the acetone was changed to include acetone.
  • Example 1 a sulfonic acid type ion-exchange resin (described above) denatured by 30 mol% with 4 _ (2-mercaptoethyl) pyridine was used as a catalyst. The procedure was carried out in the same manner as in Example 1 except that the acetone was changed to contain ethyl mercaptan 1/200 (molar ratio to acetone).
  • Example 1 a sulfonic acid-type ion-exchange resin (described above) modified with 2-mercaptoethylamine by 10 mol% was used as a catalyst, and was changed to acetone containing 1,000,000 ppm by weight of methanol. Except for the above, the procedure was the same as in Example 1.
  • Example 1 was carried out in the same manner as in Example 1 except that acetone containing 5,000 weight ppm of methanol was used.
  • Example 1 a sulfonic acid-type ion-exchange resin (described above) modified with 2,2-dimethylthiazolidine at 25 mol% was used as the catalyst, and the catalyst was changed to acetone containing 100,000 weight-methanol.
  • a sulfonic acid-type ion-exchange resin (described above) modified with 2,2-dimethylthiazolidine at 25 mol% was used as the catalyst, and the catalyst was changed to acetone containing 100,000 weight-methanol.
  • Example 1 using 4 i (2 Merukaputechiru) pyridine 7 mole 0/0 denatured sulphonic acid type ion-exchange resin (supra) as a catalyst, the Aseton containing methanol 4, 0 0 0 weight m Except having changed, it carried out similarly to Example 1.
  • Example 1 As the catalyst, 1 6 mole at 2-dimethyl-thiazolidine 0/0 denatured Example 2 except that the sulfonic acid type ion-exchange resin (described above) was used, and the acetone was changed to contain 200,000 wt.% Methanol and ethyl mercaptan 1Z400 (molar ratio to acetone). This was performed in the same manner as in 1.
  • Bisphenol A when bisphenol A is produced by condensing phenol and acetone using an acid-type ion exchange resin catalyst partially modified with an iodiamine-containing compound, by adding a mercaptan compound, Bisphenol A can be stably produced at a high conversion rate by suppressing a decrease in catalytic activity due to methanol, which is an impurity of phenol.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé de production de bisphénol A qui consiste à condenser du phénol avec de l'acétone, par utilisation, en tant que catalyseur, d'une résine échangeuse d'ions sous forme acide en partie modifiée à l'aide d'un composé d'amine sulfurisé. Ledit procédé est caractérisé en ce que lorsque l'acétone présente une concentration en méthanol comprise entre 400 et 7000 ppm en poids, alors la résine échangeuse d'ions sous forme acide modifiée est une résine présentant un degré de modification de 15 à 50 % en mole et un composé de mercaptan (de préférence de l'éthylmercaptan) est ajouté. Du fait de l'addition du composé de mercaptan, l'activité catalytique ne peut être réduite par le méthanol contenu en tant qu'impureté dans l'acétone. Ainsi, du bisphénol A présentant une conversion et une sélectivité élevées peut être produit.
PCT/JP2002/003540 2001-04-17 2002-04-09 Procede de production de bisphenol a WO2002085830A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001118012A JP2002316962A (ja) 2001-04-17 2001-04-17 ビスフェノールａの製造方法
JP2001/118012 2001-04-17

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WO2002085830A1 true WO2002085830A1 (fr) 2002-10-31

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MY (1) MY139605A (fr)
TW (1) TWI238818B (fr)
WO (1) WO2002085830A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8143456B2 (en) 2007-08-29 2012-03-27 Dow Global Technologies Llc Method of reducing methanol in recycle streams in bisphenol-A production process
US8436055B2 (en) 2003-09-30 2013-05-07 Mitsui Chemicals, Inc. Modified acidic ion-exchange resin and method for preparing bisphenol
CN112739676A (zh) * 2018-07-06 2021-04-30 巴杰许可有限责任公司 来自双酚制造的残余料流的处理

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7491855B2 (en) * 2003-06-04 2009-02-17 Sabic Innovative Plastics Ip B.V. Integrated process for the production of bisphenol A from cumene hydroperoxide
US7154010B2 (en) * 2003-06-04 2006-12-26 General Electric Company Integrated process for the production of bisphenol A from cumene hydroperoxide
US20120283485A1 (en) * 2011-05-02 2012-11-08 Umesh Krishna Hasyagar Robust promoter catalyst system

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0625042A (ja) * 1992-07-08 1994-02-01 Idemitsu Petrochem Co Ltd ２，２−ビス（４−ヒドロキシフェニル）プロパンの製造方法
JPH0692889A (ja) * 1992-09-11 1994-04-05 Idemitsu Petrochem Co Ltd ２，２−ビス（４−ヒドロキシフェニル）プロパンの製造方法
JPH08325185A (ja) * 1995-06-01 1996-12-10 Chiyoda Corp ビスフェノールａ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
WO2000053315A1 (fr) * 1999-03-09 2000-09-14 Idemitsu Petrochemical Co., Ltd. Procede de preparation d'un catalyseur destine a etre utilise pour produire du bisphenol

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0625042A (ja) * 1992-07-08 1994-02-01 Idemitsu Petrochem Co Ltd ２，２−ビス（４−ヒドロキシフェニル）プロパンの製造方法
JPH0692889A (ja) * 1992-09-11 1994-04-05 Idemitsu Petrochem Co Ltd ２，２−ビス（４−ヒドロキシフェニル）プロパンの製造方法
JPH08325185A (ja) * 1995-06-01 1996-12-10 Chiyoda Corp ビスフェノールａ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
WO2000053315A1 (fr) * 1999-03-09 2000-09-14 Idemitsu Petrochemical Co., Ltd. Procede de preparation d'un catalyseur destine a etre utilise pour produire du bisphenol

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8436055B2 (en) 2003-09-30 2013-05-07 Mitsui Chemicals, Inc. Modified acidic ion-exchange resin and method for preparing bisphenol
US8143456B2 (en) 2007-08-29 2012-03-27 Dow Global Technologies Llc Method of reducing methanol in recycle streams in bisphenol-A production process
CN112739676A (zh) * 2018-07-06 2021-04-30 巴杰许可有限责任公司 来自双酚制造的残余料流的处理

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MY139605A (en) 2009-10-30
JP2002316962A (ja) 2002-10-31

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