CN1243818A - Process for preparing polycarbonate-class biphenol A by heteropoly acid method - Google Patents

Process for preparing polycarbonate-class biphenol A by heteropoly acid method Download PDF

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CN1243818A
CN1243818A CN99109957A CN99109957A CN1243818A CN 1243818 A CN1243818 A CN 1243818A CN 99109957 A CN99109957 A CN 99109957A CN 99109957 A CN99109957 A CN 99109957A CN 1243818 A CN1243818 A CN 1243818A
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phenol
toluene
polycarbonate
dihydroxyphenyl propane
bisphenol
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CN1079092C (en
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金昌范
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HELONG CHEMICAL PLANT
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HELONG CHEMICAL PLANT
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P20/582—Recycling of unreacted starting or intermediate materials

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Abstract

A process for preparing polycarbonate-class biphenol A by heteropoly acid method features that under the action of phosphotungstic acid as primary catalyst and mercaptoacetic acid as secondary catalyst, phenol and ketone take part in condensating reaction to obtain diphenol A required by polycarbonate. In the process, "cyclic nest synthesis" and "closed-loop circulation of phenol-contained non-ionic water" are used for non-pollution drainage.

Description

The heteropolyacid method is produced the novel process of polycarbonate-grade bis phenol A
The present invention relates to the novel process of a kind of production 2,2 '-two (4-hydroxy phenyl) propane (trade name dihydroxyphenyl propane).
Dihydroxyphenyl propane has sulfuric acid process synthesis of bisphenol A, hydrogenchloride or salt acid system synthesis of bisphenol A, ion-exchange-resin process synthesis of bisphenol A by industrial preparative method.As in CN 103796 A being that the dihydroxyphenyl propane of Preparation of Catalyst is called heteropolyacid method synthesis of bisphenol A with the heteropolyacid.External sulfuric acid process bisphenol-a-production process was eliminated the sixties.The hydrogen chloride synthesis of bisphenol A has the acetone conversion height, O, the advantage that P '-the isomer by product is low, yet dianin by-product object height, shortcoming such as strong and environmental pollution is serious to equipment corrosion.Advantages such as though the ion-exchange-resin process dihydroxyphenyl propane has not etching apparatus, and the dianin by product is low, and environmental pollution is low, yet acetone conversion is low, O, P '-shortcomings (for example CN 1034360 A) such as isomer by product height.Although hydrogen chloride and amberlite method have their own characteristics each, its weak point is all arranged, thereby bring a lot of troubles to aftertreatment.Heteropolyacid method synthesis of bisphenol A had both had acetone conversion height (＞95%), the dihydroxyphenyl propane selectivity is up to 98%, O, the low advantage that waits hydrogen chloride of P '-isomer by product, not etching apparatus is arranged again, the dianin by product is low, the advantage of the low plasma exchange resin method of environmental pollution, and realized not having the bisphenol-a-production process that discharges phenolic wastewater.
The object of the present invention is to provide a kind of heteropolyacid method to produce the novel process of the desired high-purity and ultrapure dihydroxyphenyl propane of polycarbonate.This technology in condensation reaction because acetone conversion and dihydroxyphenyl propane selectivity height, so just can obtain polycarbonate-grade bis phenol A by better simply aftertreatment.The product purity height, the catalyzer consumption is low, and especially aftertreatment technology is simple, and no phenol-containing wastewater discharging is free from environmental pollution.
Purpose of the present invention is achieved through the following technical solutions:
According to the present invention, at the special-purpose H of industry 3PW 12O 40NH 2Under the effect of O Primary Catalysts and Thiovanic acid promotor, by phenol condensation with acetone reaction, synthesis of bisphenol A, in condensation reaction, take off generation water with the continuous azeotropic steaming of toluene, the mol ratio of phenol and acetone is 6-10: 1, and setting-up point 40-80 ℃, reaction times 6-10 hour.The content of dihydroxyphenyl propane is about 25% (per-cent among the present invention all is weight percentage) in synthesis mother liquid.This synthesis mother liquid directly changes bisphenol a/phenol adducts Crystallization Procedure over to, carry out the crystallization of bisphenol a/phenol adducts, temperature is controlled at 25-40 ℃ of scope, this crystalline adduct is through crystalline adduct strainer, cold wash operation vacuum, suction filtration, excessive phenol and catalyzer and toluene are returned in the synthesis reactor, add required starting material, carry out recycled resynthesis dihydroxyphenyl propane, the synthetic number of times of synthesis mother liquid recycled is 8-16 time;
After the crystalline adduct water that is obtained by the crystalline adduct operation, the toluene biphasic solvent cold wash, change hot water wash and water distillation process over to the dissolving crystallized adducts of toluene, carry out the hot water wash adducts, the temperature of hot water wash is controlled to be 60-80 ℃ of scope.After this washing thing standing demix water phase separated, change the adducts recrystallization over to, filter operation, carry out bisphenol a/phenol adducts recrystallization, temperature is controlled at 20-40 ℃ of scope, is filtered to make crystalline adduct colourity＜No. 10, is preferably＜No. 5;
With changing thin film evaporation, dissolution process over to behind the dissolving crystallized adducts of toluene.By two tandem thin-film evaporator Separation and Recovery toluene and phenol, and obtain containing the crude bisphenol that phenol is 3-6%; The toluene evaporates actuator temperature is controlled to be 120-140 ℃, and pressure is 200-300mmHg, and the phenol evaporator temperature is controlled to be 160-180 ℃, and pressure is＜30mmHg.The toluene that reclaims is directly used in bisphenol a/phenol adducts Crystallization Procedure, and the phenol of recovery is delivered to rectification process;
Crude bisphenol dissolves with toluene, changes dihydroxyphenyl propane recrystallization operation over to, carries out the dihydroxyphenyl propane recrystallization, and Tc is 30-60 ℃.Obtaining water capacity by the centrifuging operation is the dihydroxyphenyl propane of 10-15%, obtains the high-purity dihydroxyphenyl propane of polycarbonate-class that purity is 99.5-99.9% through the vacuum-drying operation again, and drying temperature is 40-100 ℃, and the time is 4h, and vacuum tightness is below the 300mmHg.High-purity dihydroxyphenyl propane underpressure distillation or thin film evaporation and toluene recrystallization are obtained purity and be＞99.99% the ultrapure dihydroxyphenyl propane of polycarbonate-class.
In the condensation reaction of phenol and acetone, take off generation water with the continuous azeotropic steaming of toluene in addition, toluene returns synthesis reactor through condenser and water-and-oil separator.In thin film evaporation, adopt nitrogen protection and add the measure of dihydroxyphenyl propane thermo-stabilizer.Thermo-stabilizer comprises tartrate, oxalic acid, citric acid or reaches other salt.The waste water that contains heteropolyacid and phenol after washing reclaims " containing the phenol deionized water " through distillation, and the closed cycle utilization, accomplishes not have discharging phenolic wastewater production technique.
The enforcement of process technology scheme of the present invention has solved following technology knotty problem:
1, in condensation reaction, takes off generation water, thereby accelerated reaction process, guarantee and improved the transformation efficiency of acetone reaction with the continuous azeotropic steaming of toluene;
2, the method with " recycled synthetic " has not only reduced catalyst consumption, and has significantly improved the high-purity dihydroxyphenyl propane once through yield of polycarbonate-class and reach (in acetone) more than 70%;
3, the washing by crystalline adduct and the method for adducts recrystallization and underpressure distillation or thin film evaporation, elimination may be brought in the dihydroxyphenyl propane product and influence the various impurity and the side components of colourity;
4, because the purifying process water treatment capacity had both been saved in " containing the phenol deionized water " closed cycle utilization, can accomplish not have the production technique of discharging phenolic wastewater again, free from environmental pollution;
5, owing to the vacuum-drying dihydroxyphenyl propane, not only got rid of the possibility of external environmental dihydroxyphenyl propane product, and helped reducing free phenol content.
In a word, adopt technical scheme of the present invention can improve product yield, product purity and catalyst utilization, and accomplish that aftertreatment technology is simple, free from environmental pollution.
Adopt method of the present invention, the products obtained therefrom detected result is as follows:
The ultrapure dihydroxyphenyl propane of the high-purity dihydroxyphenyl propane of specification title
Purity (%) 99.8 99.95～99.99
Colourity (MeOH 50%APHA)＜20＜5
Freezing point (℃) 156.5 156.5
Ashes (%) 0.0016 0.001
Iron-holder (PPM) 0.3 0.01
24-isomer (%) 0.0016 does not detect
Chroman (%) does not detect
Triphenol (%) does not detect
Free phenol (%) 0.0021 does not detect
Moisture content (%) 0.06 0.05
Below in conjunction with accompanying drawing embodiments of the invention are further specified:
Fig. 1 is a process flow sheet of the present invention.
1-1 phenol 1-2 acetone 1-3 Primary Catalysts
1-4 promotor 1-5 toluene
2-(1,2) condensation reaction operation
3 phenol A/ phenol adducts Crystallization Procedure
4 crystalline adduct strainers, cold wash operation
5-(1,2) hot water wash, water distillation process
6 adducts recrystallizations, filtration operation
7-(1,2) thin film evaporation, dissolution process
8 dihydroxyphenyl propane recrystallization operations
9 centrifuging operations
10 vacuum-drying operations
Embodiment 1
With phenol (1-1) 752Kg, toluene (1-5) 140Kg, promotor Thiovanic acid (1-4) 6Kg, Primary Catalysts heteropolyacid HPWOnHO (1-3) 2Kg, acetone (1-2) 58Kg join the 2M synthesis reactor successively---operation 2.In condensation reaction, take off generation water with the continuous azeotropic steaming of toluene, 60 ℃ of setting-up point, in 8 hours reaction times, the content that obtains dihydroxyphenyl propane in synthesis mother liquid is about 25%.The toluene steam returns synthesis reactor through condenser and water-and-oil separator.This synthesis mother liquid directly changes operation 3 over to, carries out the crystallization of bisphenol a/phenol adducts, and temperature is controlled at 30 ℃.This crystalline adduct is carried out vacuum filtration through operation 4.The crystalline adduct that is obtained by operation 4 changes operation 5 with after toluene-water biphasic solvent cold wash over to the dissolving crystallized adducts of toluene, carries out the hot water wash adducts, and the temperature of hot water wash is controlled to be 70 ℃.Water phase separated behind this washing thing standing demix changes operation 6 over to.The waste water that contains heteropolyacid and phenol after the washing is reclaimed " containing the phenol deionized water " through distillation, and the closed cycle utilization, accomplish not have discharging phenolic wastewater production technique.Carry out bisphenol a/phenol adducts recrystallization, temperature is controlled at 30 ℃, is filtered to make crystalline adduct colourity＜No. 5.With changing operation 7 over to behind the dissolving crystallized adducts of toluene, by two tandem thin-film evaporator Separation and Recovery toluene and phenol.In thin film evaporation, adopt nitrogen protection and add the measure of dihydroxyphenyl propane thermo-stabilizer.Thermo-stabilizer is tartrate, oxalic acid, citric acid or its salt.And obtain containing phenol and be 4% crude bisphenol.The toluene evaporates actuator temperature is controlled to be 130 ℃, and pressure is 200mmHg; The phenol evaporator temperature is controlled to be 170 ℃, and pressure is＜30mmHg.The toluene that reclaims is directly used in bisphenol a/phenol adducts Crystallization Procedure 3, and the phenol of recovery is delivered to rectification process.Crude bisphenol dissolves with toluene, changes operation 8 over to, carries out the dihydroxyphenyl propane recrystallization, and Tc is 50 ℃.Obtaining water capacities by operation 9 is 12% dihydroxyphenyl propane, obtains the high-purity dihydroxyphenyl propane 136.8Kg of polycarbonate-class of purity＞99.5% again through operation 10.
Embodiment 2
The synthesis mother liquid 536Kg that gets among the embodiment 1 carries out recycled, adds phenol 172Kg, toluene 16Kg, heteropolyacid H 3PW 12O 40NH 2O 0.4Kg, Thiovanic acid 1.2Kg, acetone 48Kg join in the synthesis reaction vessel successively, press embodiment 1 operation sequence and handle, and finally can get the high-purity dihydroxyphenyl propane of 135.4Kg polycarbonate-class.
Each synthesis mother liquid recycled successively synthesizes 8-16 time, all obtains high-purity dihydroxyphenyl propane product.
Embodiment 3
High-purity dihydroxyphenyl propane is steamed dihydroxyphenyl propane through underpressure distillation or thin film evaporation, and residue is the band colour cell branch in the dihydroxyphenyl propane at the bottom of the still, the dihydroxyphenyl propane that steams with the toluene recrystallization and to obtain colourity be＜5, and purity is 99.95～99.99% extra-pure grade dihydroxyphenyl propane.The yield of extra-pure grade dihydroxyphenyl propane can reach 80-85%, and the loss of dihydroxyphenyl propane is less than 0.5% in the whole technological process.

Claims (6)

1, a kind of heteropolyacid method is produced the novel process of polycarbonate-grade bis phenol A, it is characterized in that:
(a), with H 3PW 12O 40NH 2O is a Primary Catalysts, is promotor with the Thiovanic acid, is solvent with toluene, the mol ratio of phenol and acetone is 6～10: 1, carries out condensation reaction in synthesis reactor, and temperature of reaction is controlled between 40-80 ℃, reaction times 6-10 hour, obtain content and be about 25% dihydroxyphenyl propane;
(b), with the synthesis mother liquid in (a) operation through crystallization of bisphenol a/phenol adducts and crystalline adduct strainer, excessive phenol and catalyzer and toluene are returned in the synthesis reactor, it is synthetic to carry out recycled, the synthetic number of times of recycled is 8-16 time;
(c), crystalline adduct water, toluene biphasic solvent cold wash, heat are washed, carry out bisphenol a/phenol adducts recrystallization again, be filtered to and make crystalline adduct colourity＜No. 10;
(d), the toluene solution of crystalline adduct is by thin-film evaporator Separation and Recovery toluene and phenol, and obtains containing the crude bisphenol that phenol is 3-6% (weight percent, as follows);
(e), with crude bisphenol with toluene recrystallization, filtration, vacuum-drying and obtain the high-purity dihydroxyphenyl propane of polycarbonate-class that purity is 99.5-99.9%;
(f), high-purity dihydroxyphenyl propane is obtained purity through underpressure distillation or thin film evaporation and toluene recrystallization and be＞99.99% the ultrapure dihydroxyphenyl propane of polycarbonate-class.
2, heteropolyacid method according to claim 1 is produced the novel process of polycarbonate-grade bis phenol A, it is characterized in that in the condensation reaction of phenol and acetone, steams with the continuous azeotropic of toluene and takes off generation water, and toluene returns synthesis reactor through condenser and water-and-oil separator.
3, heteropolyacid method according to claim 1 is produced the novel process of polycarbonate-grade bis phenol A, it is characterized in that directly cover is used for cold wash, heat is washed operation from the toluene that contains phenol of thin-film evaporator Separation and Recovery, recovery toluene behind cold wash and the adducts recrystallization becomes smart toluene through the rectifying purifying, is used for crude bisphenol recrystallization operation.
4, heteropolyacid method according to claim 1 is produced the novel process of polycarbonate-grade bis phenol A, it is characterized in that adopting nitrogen protection and add the measure of dihydroxyphenyl propane thermo-stabilizer in thin film evaporation.
5, heteropolyacid method according to claim 1 is produced the novel process of polycarbonate-grade bis phenol A, it is characterized in that the waste water that contains heteropolyacid and phenol after the washing is reclaimed " containing the phenol deionized water " through distillation, and the closed cycle utilization accomplishes not have discharging phenolic wastewater production technique.
6, heteropolyacid method according to claim 1 is produced the novel process of polycarbonate-grade bis phenol A, it is characterized in that bisphenol a/phenol adducts recrystallization be filtered to make crystalline adduct colourity be preferably＜No. 5.
CN99109957A 1999-07-12 1999-07-12 Process for preparing polycarbonate-class biphenol A by heteropoly acid method Expired - Fee Related CN1079092C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104140361A (en) * 2014-06-30 2014-11-12 湘潭大学 Method for synthesizing bisphenol F under catalysis of phosphotungstic acid imidazolium salt
CN104496761A (en) * 2014-11-29 2015-04-08 南京威安新材料科技有限公司 Bisphenol A preparation method
CN108658987A (en) * 2018-06-20 2018-10-16 德州绿霸精细化工有限公司 A kind of synthesis of diquat dibromide and process for refining

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5032576A (en) * 1973-07-26 1975-03-29
CN1039796A (en) * 1988-07-27 1990-02-21 东北师范大学 With the heteropolyacid is the method for Preparation of Catalyst bisphenol-A
US5368827A (en) * 1991-07-10 1994-11-29 Chiyoda Corporation Process for the production of crystalline adduct of bisphenol A and phenol and apparatus therefor
DE69227849T2 (en) * 1991-07-10 1999-04-29 Chiyoda Chem Eng Construct Co Process and preparation of a crystalline adduct of bisphenol A with phenol and device therefor

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104140361A (en) * 2014-06-30 2014-11-12 湘潭大学 Method for synthesizing bisphenol F under catalysis of phosphotungstic acid imidazolium salt
CN104140361B (en) * 2014-06-30 2015-09-23 湘潭大学 A kind of phospho-wolframic acid imidazole salts catalyzes and synthesizes the method for Bisphenol F
CN104496761A (en) * 2014-11-29 2015-04-08 南京威安新材料科技有限公司 Bisphenol A preparation method
CN108658987A (en) * 2018-06-20 2018-10-16 德州绿霸精细化工有限公司 A kind of synthesis of diquat dibromide and process for refining

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