CN1460552A - Bisphenol A synthesis catalyst and its preparation method - Google Patents
Bisphenol A synthesis catalyst and its preparation method Download PDFInfo
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- CN1460552A CN1460552A CN 03113425 CN03113425A CN1460552A CN 1460552 A CN1460552 A CN 1460552A CN 03113425 CN03113425 CN 03113425 CN 03113425 A CN03113425 A CN 03113425A CN 1460552 A CN1460552 A CN 1460552A
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Abstract
The present invention relates to a catalyst for synthesizing bisphenal A by using ion exchange resin method and its preparation method. Said preparation includes the following steps: using styrene or substituted styrene as monomer, using diving phenylmethane, etc. as cross-linking agent, synthesizing relatively-uniform cross-linked copolymer, solfonating the copolymer, after it is modified in heat-resisting property, using it as basic resin of catalyst for preparing bisphenol A, according to conventional method using mercaptoallkylamine as sulfhydrylation agent, and utilizing partial neutralizing method to modify the basic resin so as to obtain the catalyst for synthesizing bisphenol A. Its catalytic activity, selectivity and service life can meet the requirements for production of bisphenol A.
Description
Affiliated technical field
The present invention relates to the Catalysts and its preparation method of ion-exchange-resin process synthesis of bisphenol A.
Background technology
The ion-exchange-resin process synthesis of bisphenol A, technology is simple, equipment corrosion is little, the three wastes are few, obtain very big development in recent years, particularly, made it become the vanguard technology method of the raw material bisphenol-A of high-quality engineering plastics and high insulation level epoxy resin along with the updating of ion-exchange resin catalyst performance.
The present ion-exchange resin catalyst that adopts, base resin is an exchange capacity 2, the gel of 0-5.5 mM/gram dried resin or macroporous type sulfonic acid ion exchange resin.Cohabit the phenolic resins of thing, sulfonation etc. as the styrene-divinylbenzene of sulfonation, the trade names that are suitable for as: Amberlite-118 ,-200 ,-IR ,-XE307; Amberlyst-15; Dowex-50 ,-MSC-1; Duolite C-20; Permutit QH; Chempro C-20; CT151; CT124 etc.
Aforesaid base resin is modified as the catalyst that synthesis of bisphenol A is used, and the method that adopts is with helping catalytic group usually, as sulfydryl, introduces the ion exchange resin matrix, thereby improves its reaction rate and selectivity.The research work of this respect never has been interrupted since the ion-exchange-resin process synthesis of bisphenol A comes out.With regard to introducing sulfydryl (sulfhydrylation), bibliographical information has a lot of methods, as partial reduction method (USP3,172,916), partial esterification method (USP3,153,001; BP937,072), introduce sulfydryl method (USP4,294,995 through the sulfonamide covalent bond; USP4,346,247; USP4,396,728) and the part neutralisation.
Because have better catalytic performance by the catalyst that other method obtained by the part neutralisation, this method has caused people's attention, worked out the multiple compound that contains sulfydryl in succession and carried out the part neutralization.These compounds (sulfhydrylation agent) that contain sulfydryl have: tetrahydro-thiazoles or thiazolidine (USP3,634,341; USP3,760,006), aryl mercapto-amine or its salt (USP4,045,379), pyridyl alkyl mercaptan (USP4,478,956), N-(2-mercaptoalkyl) acid amides (USP4,595,704; CN85106111), many alkyl mercaptoamines (EP268,318; USP4,820,740), alkyl thiol amine (USP3,394,089; BP1,183,564), N-alkyl thiol amine (EP144,735), N, N-dialkyl group mercapto-amine (CN1,119,129) waits other compounds (JP10,314,595; JP10,211,433; JP10,328573).
Though above-mentioned technology has been developed the co-catalyst of various molecular structures, and they are incorporated into method on the base resin, these technology have brought raising to a certain degree for activity of such catalysts and selectivity, but the shortcoming of sulfonic acid ion exchange resin ubiquity temperature tolerance difference, sulfonic group can come off gradually under the situation of being heated, catalytic activity reduces gradually, the sulfonic group that comes off simultaneously will etching reactor and pipeloop, easily caused the catalyst poisoning inactivation by the metal ion under molten, reduce the service life of catalyst, and bring impurity and color into for the bisphenol-A product, influence product quality.The part catalyst also exists the activated centre utilization rate low, the susceptible to plugging shortcoming in catalyst duct.And these technology only limit to the kind of co-catalyst and the change of introducing method, and do not relate to base resin itself, can not address the above problem effectively.
Summary of the invention
The objective of the invention is to overcome above-mentioned defective, a kind of sulfonic acid type cation exchange resin catalyst that can be used for by phenol and condensation of acetone synthesis of bisphenol A is provided.
Another object of the present invention provides a kind of sulfonic acid type cation exchange resin catalyst preparation method by phenol and condensation of acetone synthesis of bisphenol A.
The compounds of this invention is the sulfonic acid ion exchange resin with particular chemical and physical arrangement, forms by thiolated modified.Wherein sulfonic acid ion exchange resin has following general structure:
Wherein X can be electron withdraw groups such as halogen (comprising fluorine, chlorine, bromine), nitro, acyl group, carboxyl, sulfonic group by oneself.
Preparation method of the present invention is:
With styrene is monomer, divinyl phenylmethane etc. is a crosslinking agent, synthesizing cross-linked more uniform EVA, be used as preparation bisphenol A catalyst base resin after EVA sulfonation, the temperature tolerance modification, according to routine techniques is the sulfhydrylation agent with the alkyl mercaptoamine, by the part neutralisation base resin is carried out modification, obtain the bisphenol-A synthetic catalyst.
Above-mentioned temperature tolerance modification or for being monomer with the substituted phenylethylene, divinyl phenylmethane etc. is a crosslinking agent, synthesizing cross-linked more uniform EVA.
Above-mentioned temperature tolerance modification also can be at some group of introducing after styrene and the polymerization of divinyl phenylmethane on the resin phenyl ring.
The consumption of divinyl phenylmethane is the 2-10% of total monomer weight in the above-mentioned base resin, preferably 2-6%.
The exchange capacity of resin is a 2.0-5.0mmol/g butt resin, and it can be gel-type or macroporous type, and the sulfonic acid group of 10-30% combines with the mode of mercaptoalkyl amine with ionic bond on the resin.
Above-mentioned catalyst is prepared from by following concrete steps:
(1) styrene or substituted phenylethylene and divinyl phenylmethane are carried out suspension polymerisation, the divinyl phenylmethane
Account for the 2-10% of total monomer weight, preferably 2-6%.
(2) the white bead that will obtain routinely the preparation method of sulfonic acid ion exchange resin carry out sulfonation, must prepare
The base resin of bisphenol A catalyst.
(3) some group on the resin phenyl ring also can be introduced after styrene and the polymerization of divinyl phenylmethane.
(4) be the sulfhydrylation agent with the alkyl mercaptoamine according to disclosed technology, by the part neutralisation base resin carried out modification, the sulfonic acid group of 10-30% combines with the mode of mercaptoalkyl amine with ionic bond on the resin.
The present invention introduces electron withdraw groups such as halogen (comprising fluorine, chlorine, bromine), nitro or carbonyl on crosslinked polystyrene type cationic ion-exchange resin, the heat resistance of resin obviously improves, under the bisphenol-A synthesis condition, sulfonic group does not come off, the sulfonic group degradation rate is low, and has activated centre utilization rate height.With divinyl phenylmethane etc. is crosslinking agent, synthetic cationic ion-exchange resin, exchange with the quaternary ammonium salt close with phenol-acetone condensation product molecular dimension, exchange rate is higher by 80% than commodity cationic ion-exchange resin, illustrate that molecule is little at the resistance of resin inside, the activated centre can effectively be utilized.The catalyst of making uses after 4 months continuously, and the tar content that accumulates in the catalyst is lower by 40% than commodity cationic ion-exchange resin, shows that the catalyst duct is difficult for stopping up, and catalytic activity, selectivity and life-span can be satisfied the needs that bisphenol-A is produced.
The specific embodiment
The following examples will be further specified the present invention, but therefore not limit the present invention.
Yield and selectivity computational methods that phenol and acetone reaction generate bisphenol-A are as follows:
Yield C=C
BP(M
PXR+M
A)/M
BPC in the X100 formula
BPMiddle content of bisphenol A; M
PBe the phenol molecular weight; R is the mol ratio of raw material phenol and acetone; M
ABe the acetone molecules amount; M
BPBe the bisphenol-A molecular weight.
Selectivity S=C
BP/ (C
BP+ C
2+ C
3+ C
4+ C
5) C in the formula
BP, C
2, C
3, C
4, C
5Be respectively bisphenol-A in the product, 2, the content of 4-bisphenol-A, triphenol, chroman, other impurity.Each components contents all is to adopt high-pressure liquid phase chromatogram therapy determining in the product.
Quaternary ammonium salt exchange rate=(sodium exchange capacity-quaternary ammonium salt exchange capacity)/sodium exchange capacity
Embodiment 1
In 1000 milliliters of four-hole boiling flasks that agitator, thermometer, condenser pipe are housed, add 2.4 gram gelatin, 400 ml waters are after stirring makes the gelatin dissolving, add 191 grams more respectively to chlorostyrene, 11 gram divinyl phenylmethanes and 1.3 gram benzoyl peroxides are warming up to 70 ℃ under stirring, and are incubated 1 hour, be warming up to 80 ℃ of insulations 6 hours again, take out material, washing, oven dry make water white transparency EVA Archon.
In 1000 milliliters of four-hole boiling flasks that agitator, thermometer, condenser pipe are housed, add the EVA Archon that 200 grams make as stated above, 200 milliliters of dichloroethanes, after stirring makes resin swelling, add 600 milliliters of concentrated sulfuric acids again, heat up and steam behind the dichloroethanes to 90 ℃, be incubated 12 hours, cooling, dilute with water carefully, and wash neutrality with water.Drain, the water content of sulfate resin (a), the exchange capacity measurement result sees Table 1
In the sulfhydrylation device, add 300 ml deionized water, the above-mentioned sulfate resin of 100 grams, stir drip down sulfonic 20% (mole percent) in the suitable resin 2,2-dimethylthiazole alkane, dripping off the back continues to stir 1 hour, take out resin, spend deionised water, get bisphenol-A synthetic catalyst (A).The sulfhydrylation rate sees Table 1
Embodiment 2
As example 1, will change into fluorobenzene ethene chlorostyrene, the consumption of divinyl phenylmethane changes 6 grams into, and other condition is constant, makes sulfate resin (b) and catalyst (B) performance sees Table 1
Embodiment 3
In 1000 milliliters of four-hole boiling flasks that agitator, thermometer, condenser pipe are housed, add 2.4 gram gelatin, 400 ml waters are after stirring makes the gelatin dissolving, add 180 gram styrene more respectively, 20 gram divinyl phenylmethanes and 1.3 gram benzoyl peroxides are warming up to 70 ℃ under stirring, and are incubated 1 hour, be warming up to 80 ℃ of insulations 6 hours again, take out material, washing, oven dry make water white transparency EVA Archon.
In 1000 milliliters of four-hole boiling flasks that agitator, drying tube, condenser pipe are housed, add the EVA Archon that 52 grams make as stated above, 400 milliliters of carbon disulfide; after stirring makes resin swelling, add 140 gram aluminum trichloride (anhydrous)s again, at 10-30 ℃ of very long Dropwise 50 gram acetic anhydride; refluxed 4 hours; cooling boils off carbon disulfide, and resin is used 10% hydrochloric acid successively; water; methanol wash, oven dry gets acetylation EVA Archon.
In 1000 milliliters of four-hole boiling flasks that agitator, thermometer, condenser pipe are housed, add the EVA Archon that 200 grams make as stated above, 200 milliliters of dichloroethanes, after stirring makes resin swelling, add 600 milliliters of concentrated sulfuric acids again, heat up and steam behind the dichloroethanes to 90 ℃, be incubated 12 hours, cooling, dilute with water carefully, and wash neutrality with water.Drain, the water content of sulfate resin (c), the exchange capacity measurement result sees Table 1
In the sulfhydrylation device, add 300 ml deionized water, the above-mentioned sulfate resin of 100 grams, stir drip down sulfonic 20% (mole percent) in the suitable resin 2,2-dimethylthiazole alkane, dripping off the back continues to stir 1 hour, take out resin, spend deionised water, get bisphenol-A synthetic catalyst (C).The sulfhydrylation rate sees Table 1
Embodiment 4
Accurately take by weighing 1 gram dried sulfate resin (a), or (b), or (c) be loaded in the ion exchange column, after washing with 20 ml deionized water, the triethyl benzyl ammonia chloride aqueous solution with 30 milliliters of 0.1mol/L exchanges with the 10/h air speed again, mensuration exchanges out the content of hydrochloric acid of solution, calculates the exchange rate of triethyl benzyl ammonia chloride to this resin, the results are shown in Table 1
Embodiment 5
In the four-hole boiling flask that agitator, thermometer are housed, add dried sulfate resin (a), or (b), or (c) 28.5 grams, 130 gram phenol and 10 gram acetone are heated to 80 ℃, and stirring reaction 1248 hours does not detect sulfate radical in the reactant liquor.
Embodiment 6
In the four-hole boiling flask that agitator, thermometer are housed, be added in 12 hours dry catalyst of 105 ℃ of dryings (A), or (B), or (C) 2 8.5 the gram, 130 gram phenol are heated to 70 ℃ under stirring, and constant temperature is after 3 hours, add 10 gram acetone rapidly, reacted 60 minutes, and stopped reaction, the yield and the selectivity of high-pressure liquid chromatography bisphenol-A the results are shown in Table 1
Table 1
Embodiment 7
| Sulfate resin or catalyst | Water content % | Exchange capacity mmol/g | Sulfhydrylation rate % | Quaternary ammonium salt exchange rate % | Bisphenol-A yield % | Bisphenol-A selectivity % |
| ??a | ??65.5 | ??3.52 | ??19.6 | |||
| ??b | ??66.3 | ??3.48 | ??20.1 | |||
| ??c | ??64.2 | ??3.49 | ??19.8 | |||
| ??A | ??98.6 | ??84.5 | ??95.3 | |||
| ??B | ??98.9 | ??86.4 | ??95.1 | |||
| ??C | ??91.3 | ??77.9 | ??95.5 |
2.5 centimetres of the internal diameters that has chuck and thermometer, in long 70 centimetres the fixed bed glass reactor, the 280 milliliters of catalyst (A) of packing into, 70 ℃ of constant temperature, with the air speed of 1/h, adding the phenolic ketone ratio is the phenol-acetone solution of 10: 1 (mol ratio), reaction result sees Table 2
Table 2
Embodiment 8
| Running time (my god) | 3 | ?30 | ?60 | ?90 | ?120 | ?150 | ?180 |
| Bisphenol-A yield (%) | 85.2 | ?84.3 | ?82.5 | ?80.8 | ?80.3 | ?79.6 | ?78.5 |
| Bisphenol-A selectivity (%) | 95.3 | ?95.5 | ?95.1 | ?95.2 | ?95.0 | ?95.2 | ?95.1 |
The catalyst of operation after 180 days in the example 7 taken out, after water, methyl alcohol are washed, again with the washing of 5% NaOH, NaOH washing liquid is neutralized to pH=3 with 5% hydrochloric acid, there is brown solid to separate out, filters, oven dry, infrared spectrum analysis is the big molecule mixture of phenolic hydroxy group, and this big molecule mixture accounts for 0.2% (mass percent) of catalyst.
Claims (5)
1. the synthetic catalyst of bisphenol-A, it is by the sulfonic acid ion exchange resin with particular chemical and physical arrangement, forms through thiolated modified, it is characterized in that sulfonic acid ion exchange resin has following general structure:
Wherein X can be electron withdraw groups such as halogen (comprising fluorine, chlorine, bromine), nitro, acyl group, carboxyl, sulfonic group by oneself.
2. realize the preparation method of the described bisphenol-A synthetic catalyst of claim 1, it is characterized in that with styrene being monomer, divinyl phenylmethane etc. is a crosslinking agent, synthetic EVA, be used as preparation bisphenol A catalyst base resin after EVA sulfonation, the temperature tolerance modification, according to routine techniques is the sulfhydrylation agent with the alkyl mercaptoamine, by the part neutralisation base resin is carried out modification, obtains the bisphenol-A synthetic catalyst.
3. the catalyst that bisphenol-A according to claim 1 is synthetic is characterized in that it is monomer that temperature tolerance is modified as with the substituted phenylethylene, and divinyl phenylmethane etc. is a crosslinking agent, synthesizing cross-linked more uniform EVA.
4. the catalyst that bisphenol-A according to claim 1 is synthetic is characterized in that some group that temperature tolerance is modified as on the resin phenyl ring can introduce after styrene and the polymerization of divinyl phenylmethane.
5. the catalyst that bisphenol-A according to claim 1 is synthetic, the consumption that it is characterized in that divinyl phenylmethane in the base resin is the 2-10% of total monomer weight, preferably 2-6%.
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| CN 03113425 CN1202914C (en) | 2003-05-09 | 2003-05-09 | Bisphenol A synthesis catalyst and its preparation method |
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| CN1202914C CN1202914C (en) | 2005-05-25 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321744C (en) * | 2004-06-07 | 2007-06-20 | 中国石油化工股份有限公司 | Macroporous cationic exchanging resin, preparing method and use in synthetic bisphenol A catalyst |
| CN106563502A (en) * | 2016-11-04 | 2017-04-19 | 凯瑞环保科技股份有限公司 | Bisphenol A synthetic resin catalyst and preparation method thereof |
| CN113333026A (en) * | 2021-06-08 | 2021-09-03 | 中石化南京化工研究院有限公司 | Solid acid catalyst for synthesizing bis-OPP-A and preparation method and application thereof |
| WO2022110559A1 (en) * | 2020-11-26 | 2022-06-02 | 西安蓝晓科技新材料股份有限公司 | Solid-phase synthesis carrier, preparation method therefor and use thereof |
| CN115888825A (en) * | 2022-10-11 | 2023-04-04 | 江苏全邦材料科技有限公司 | Bisphenol A synthetic composite resin catalyst and preparation method thereof |
-
2003
- 2003-05-09 CN CN 03113425 patent/CN1202914C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321744C (en) * | 2004-06-07 | 2007-06-20 | 中国石油化工股份有限公司 | Macroporous cationic exchanging resin, preparing method and use in synthetic bisphenol A catalyst |
| CN106563502A (en) * | 2016-11-04 | 2017-04-19 | 凯瑞环保科技股份有限公司 | Bisphenol A synthetic resin catalyst and preparation method thereof |
| WO2022110559A1 (en) * | 2020-11-26 | 2022-06-02 | 西安蓝晓科技新材料股份有限公司 | Solid-phase synthesis carrier, preparation method therefor and use thereof |
| CN113333026A (en) * | 2021-06-08 | 2021-09-03 | 中石化南京化工研究院有限公司 | Solid acid catalyst for synthesizing bis-OPP-A and preparation method and application thereof |
| CN115888825A (en) * | 2022-10-11 | 2023-04-04 | 江苏全邦材料科技有限公司 | Bisphenol A synthetic composite resin catalyst and preparation method thereof |
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| CN1202914C (en) | 2005-05-25 |
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