CN1321744C - Macroporous cationic exchanging resin, preparing method and use in synthetic bisphenol A catalyst - Google Patents
Macroporous cationic exchanging resin, preparing method and use in synthetic bisphenol A catalyst Download PDFInfo
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- CN1321744C CN1321744C CNB2004100449623A CN200410044962A CN1321744C CN 1321744 C CN1321744 C CN 1321744C CN B2004100449623 A CNB2004100449623 A CN B2004100449623A CN 200410044962 A CN200410044962 A CN 200410044962A CN 1321744 C CN1321744 C CN 1321744C
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- bisphenol
- resin
- cation exchanger
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Abstract
The present invention relates to basic resin of a catalyst for synthesizing bisphenol A by an ion exchange resin method and a preparation method thereof. A macroporous copolymer white ball is synthesized from styrene or substituted styrene as monomers, divinyl benzene, etc. as crosslinking agents and liquid paraffin, etc. as pore-foaming agents; after being sulfonated, the copolymer white ball is used for preparing basic resin of a bisphenol A catalyst; the basic resin is modified by an ion exchange method according to the conventional technology of mercaptoalkyl quaternary ammonium salt as a mercapto-reagent to acquire a bisphenol A synthetic catalyst. The catalyst of the present invention has the characteristics of high catalytic activity, good selectivity and long service life.
Description
Purposes in the synthesis of bisphenol A catalyst
Technical field
The present invention relates to the catalyst of ion-exchange-resin process synthesis of bisphenol A, refer in particular to a kind of large hole cation exchanger resin and preparation method and the purposes in the synthesis of bisphenol A catalyst.
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 the gel or the macroporous type sulfonic acid ion exchange resin of exchange capacity 2.0-5.5 mM/gram dried resin.As the styrene diethylene benzene copoly mer of sulfonation, the phenolic resins of sulfonation etc., the trade names that are suitable for as: Amberlite-118 ,-200 ,-IR ,-XE307; Amberlyst-15; Dowex-50 ,-MSC-1; Purolite 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, for the structure of base resin to catalyst activity with optionally influence research is not enough.The present macroreticular resin of commodity, the degree of cross linking is higher, with its catalyst that makes as base resin, catalysis initial activity height, selectivity is good, but the catalyst duct easily stops up, and makes that catalysqt deactivation speed is fast, influenced the service life of catalyst; The catalyst that the gel-type base resin of low crosslinking degree makes, the catalytic activity height, long service life, but selectivity is relatively low, and the catalyst mechanical strength is relatively poor, and easily broken.
Catalyst has very high selectivity, can reduce the growing amount of accessory substance, reduces the load that the accessory substance cracking is reset, the investment of fundamentally cutting down the consumption of raw materials and installing.
Summary of the invention
The purpose of this invention is to provide a kind of macropore sulfonic acid ion exchange resin, the catalyst that it can be used for by phenol and condensation of acetone synthesis of bisphenol A has the catalytic activity height, and selectivity is good, and deactivation rate is slow, the characteristics that mechanical strength is good.
Another object of the present invention provides above-mentioned macropore sulfonic acid ion exchange resin preparation method.
Described sulfonic acid ion exchange resin has following general structure:
Wherein
Can be by oneself
Or
Preparation method of the present invention is:
With styrene is monomer, and the divinyl substituted arene is a crosslinking agent, and atoleine, fatty alcohol etc. is a perforating agent, and synthesizing cross-linked EVA is used as preparation bisphenol A catalyst base resin after the EVA sulfonation,
Described divinyl substituted arene crosslinking agent is divinylbenzene, divinyl phenylmethane.
With sulfonic acid ion exchange resin of the present invention, be the sulfhydrylation agent according to routine techniques with the mercaptoalkyl quaternary ammonium salt, by ion-exchange base resin is carried out modification, can obtain the bisphenol-A synthetic catalyst.
Above-mentioned catalyst is prepared from by following concrete steps:
(1) according to a conventional method styrene, crosslinking agent and pore-foaming agent are carried out suspension polymerisation, crosslinking agent accounts for the 2-6% of total monomer weight, and preferably 2-4% gets white EVA bead.
(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) be the sulfhydrylation agent according to disclosed technology with the mercaptoalkyl quaternary ammonium salt, by ion-exchange base resin carried out modification, the sulfonic acid group of 10-30% combines with the mode of alkyl mercaptoamine with ionic bond on the resin.
With the synthetic cationic ion-exchange resin of this method, specific surface is: 20-25m
2/ g, pore volume is: 0.78-1.1cm
3/ g, pore-size distribution: greater than 40nm,＞30%; 1～40nm, 50%～70%; Less than 1nm,＜1%.Resin exchanges with triethyl benzyl ammonia chloride, and exchange rate illustrates that greater than 99% reactant molecule is little at the resistance of resin inside, and the activated centre can effectively be utilized.Catalytic performance is intermittently estimated and shown: acetone conversion is greater than 98%, and selectivity is greater than 97%, and after catalyst used 3 months continuously, acetone conversion was greater than 96%, and selectivity 96% obviously is better than common macroreticular resin and gel resin.
Description of drawings
Fig. 1 acetone conversion is with the catalyst variation of service time
Fig. 2 BPA selectivity is with the catalyst variation of service time
The specific embodiment
The following examples will be further specified the present invention, but therefore not limit the present invention.
The acetone conversion computational methods are as follows:
Acetone conversion C=(C
Ace 0-C
Ace)/C
Ace 0* 100
C in the formula
Ace 0Content for acetone in the raw mix; C
AceContent for acetone in the reaction solution.
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.The scape that contains of each component all is to adopt high-pressure liquid phase chromatogram therapy determining in the product.
Specific surface and pore structure adopt the BET method to measure, and calculate.
Quaternary ammonium salt exchange rate=(sodium exchange capacity-quaternary ammonium salt exchange capacity)/sodium exchange capacity
In 500 milliliters of four-hole boiling flasks that agitator, thermometer, condenser pipe are housed, add 1.2 gram gelatin, 0.2 gram dispersion aids, 200 ml waters, 28 gram sodium chloride after stirring makes the dispersant dissolving, add 62.2 gram styrene respectively again, 2.44 gram divinylbenzene (content 52.1%), 60 gram atoleine pore-foaming agents and 0.65 gram benzoyl peroxide initator are warming up to 70 ℃ under stirring, and are incubated 1 hour, be warming up to 80 ℃ of insulations 6 hours again, steam pore-foaming agent, cooling discharge, washing, qualified EVA Archon is sieved out in oven dry.
In 1000 milliliters of four-hole boiling flasks that agitator, thermometer, condenser pipe are housed, add the EVA Archon that 60 grams make as stated above, 200 milliliters of dichloroethanes after stirring makes resin swelling, add 1000 milliliters of concentrated sulfuric acids again, heat up and steam behind the dichloroethanes to 100 ℃, be incubated 12 hours, cooling is filtered, dilute with dilute sulfuric acid carefully, and wash neutrality with water.Drain, the water content of sulfate resin (a), exchange capacity, the pore structure measurement result sees Table 1.
In the sulfhydrylation device, add 300 ml deionized water, the above-mentioned sulfate resin of 100 grams, the N of sulfonic 20% (mole percent) in the suitable resin, N-dimethyl-N-ethyl-3-sulfydryl propylamin hydrochloride, stirred 5 hours, take out resin, spend deionised water, get bisphenol-A synthetic catalyst (A).The sulfhydrylation rate sees Table 2.
Embodiment 2
As embodiment 1, change the consumption of divinylbenzene into 4.88 grams, atoleine changes tert-pentyl alcohol into, and other condition is constant, makes sulfate resin (b) and catalyst (B) performance sees Table 1,2.
Embodiment 3
Comparative example 1
With CT-151 large hole cation exchanger resin (production of Purolite company) is base resin (d), as the sulfhydrylation method of embodiment 1, gets bisphenol-A synthetic catalyst (D).Performance sees Table 1,2.
Comparative example 2
With CT-124 gel cation exchange resin (production of Purolite company) is base resin (e), as the sulfhydrylation method of embodiment 1, gets bisphenol-A synthetic catalyst (E).Performance sees Table 1,2.
Embodiment 4
Accurately take by weighing 1 gram dried sulfate resin (a), or (b), or (c), or (d), or (e) be loaded in the ion exchange column, after washing with 20 ml deionized water, the triethyl benzyl ammonia chloride aqueous solution of using 30 milliliters of 0.1mol/L again is with 10h
-1The content of hydrochloric acid that exchanges out solution is measured in the air speed exchange, 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, be added in 12 hours dry catalyst of 105 ℃ of dryings (A), or (B), or (C), or (D), or (E) 20 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 2.
Table 1
| Sulfate resin | Water content % | Exchange capacity mmol/g | Specific surface m 2/g | Pore volume cm 3/g | Pore size distribution % | Quaternary ammonium salt exchange rate % | ||
| ＞ |
1～40nm | ＜1nm | ||||||
| a | 83.6 | 4.86 | 22.5 | 1.08 | 45.61 | 53.52 | 0.87 | 99.6 |
| b | 68.9 | 5.02 | 24.8 | 0.95 | 38.44 | 60.62 | 0.94 | 99.0 |
| c | 73.2 | 4.95 | 20.9 | 0.87 | 42.23 | 56.88 | 0.89 | 99.3 |
| d | 55.8 | 5.17 | 41.7 | 0.43 | 14.26 | 83.21 | 2.53 | 49.2 |
| e | 65.2 | 5.03 | 99.0 | |||||
Table 2
| Catalyst | Sulfhydrylation rate % | Acetone conversion % | Bisphenol-A selectivity % |
| A | 19.6 | 99.17 | 97.2 |
| B | 20.1 | 99.05 | 97.1 |
| C | 19.8 | 98.50 | 97.0 |
| D | 19.7 | 90.51 | 97.4 |
| E | 20.2 | 98.2 | 95.1 |
Embodiment 7
In the adiabatic tubular reactor that has the vacuum heat-preserving cover, 110 catalyst (A) that restrain of giving money as a gift of packing into, or catalyst (D), or catalyst (E), 70 ℃ of constant temperature are with 1h
1Air speed, adding the phenolic ketone ratio is the phenol-acetone solution of 14: 1 (mol ratio), reaction result is seen Fig. 1, Fig. 2.
Claims (5)
1. a large hole cation exchanger resin is characterized in that
(1) have following general structure:
Wherein
Or
(2) its specific surface is: 20-25m
2/ g, pore volume is: 0.78-1.1cm
3/ g, pore-size distribution: greater than 40nm,＞30%; 1～40nm, 50%～70%; Less than 1nm,＜1%.
2. the preparation method of the described large hole cation exchanger resin of claim 1 is characterized in that with styrene being monomer, and divinylbenzene or divinyl phenylmethane are crosslinking agent, adds pore-foaming agent, synthetic macropore EVA Archon; As preparation bisphenol A catalyst base resin, wherein crosslinking agent accounts for the 2-6% of total monomer weight after the sulfonation of EVA Archon.
3. the preparation method of large hole cation exchanger resin according to claim 2 is characterized in that it is 2-4% that described crosslinking agent accounts for total monomer weight.
4. the preparation method of large hole cation exchanger resin according to claim 2 is characterized in that pore-foaming agent is atoleine or tert-pentyl alcohol.
5. realize the purposes of the described large hole cation exchanger resin of claim 1 in the synthesis of bisphenol A catalyst, it is characterized in that with described large hole cation exchanger resin be base resin, with the mercaptoalkyl quaternary ammonium salt is the sulfhydrylation agent, by ion-exchange it is carried out modification, obtain the bisphenol-A synthetic catalyst.
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| CN1321744C true CN1321744C (en) | 2007-06-20 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107138177A (en) * | 2017-05-26 | 2017-09-08 | 丹东明珠特种树脂有限公司 | Methanol extraction water depickling resin catalyst prepared by methyl tertiary butyl ether(MTBE) and preparation method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101987879B (en) * | 2010-11-05 | 2012-05-30 | 山东鲁抗立科药物化学有限公司 | Macroporous quaternary ammonium type epoxy carrier resin and preparation method thereof |
| CN113492018B (en) * | 2020-04-01 | 2024-01-09 | 丹东明珠特种树脂有限公司 | Resin catalyst for bisphenol A synthesis and application of bisphenol A in catalytic synthesis |
| CN114539459B (en) * | 2020-11-26 | 2023-07-25 | 西安蓝晓科技新材料股份有限公司 | Solid phase synthesis carrier and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4256840A (en) * | 1958-07-18 | 1981-03-17 | Rohm And Haas Company | Macroreticular cation exchange beads and preparation of same |
| CN1076385A (en) * | 1992-03-13 | 1993-09-22 | 中国石油化工总公司抚顺石油化工研究院 | Method for preparing high-temp-resistant strong acid type cation exchange resin catalyst |
| CN1121442A (en) * | 1994-10-25 | 1996-05-01 | 中国石油化工总公司 | Ion exchange resin catalyzer for synthesising bisphenol and preparation thereof |
| CN1460552A (en) * | 2003-05-09 | 2003-12-10 | 中国石油化工股份有限公司 | Bisphenol A synthesis catalyst and its preparation method |
-
2004
- 2004-06-07 CN CNB2004100449623A patent/CN1321744C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4256840A (en) * | 1958-07-18 | 1981-03-17 | Rohm And Haas Company | Macroreticular cation exchange beads and preparation of same |
| CN1076385A (en) * | 1992-03-13 | 1993-09-22 | 中国石油化工总公司抚顺石油化工研究院 | Method for preparing high-temp-resistant strong acid type cation exchange resin catalyst |
| CN1121442A (en) * | 1994-10-25 | 1996-05-01 | 中国石油化工总公司 | Ion exchange resin catalyzer for synthesising bisphenol and preparation thereof |
| CN1460552A (en) * | 2003-05-09 | 2003-12-10 | 中国石油化工股份有限公司 | Bisphenol A synthesis catalyst and its preparation method |
Non-Patent Citations (4)
| Title |
|---|
| 以脂肪醇为致孔剂的苯乙烯－二乙烯苯共聚体的合成及其膦酰胺化反应 何炳林等，高分子通讯，第1984卷第5期 1984 * |
| 特大孔交联苯乙烯－二乙烯苯共聚物的制备和孔结构研究I 何炳林等，高分子通讯，第1982卷第04期 1982 * |
| 高交联大孔苯乙烯/二乙烯苯共聚物的合成及其孔结构的研究I 于占如等，高分子学报，第1988卷第3期 1988 * |
| 高交联大孔苯乙烯/二乙烯苯共聚物的合成及其孔结构的研究I 于占如等，高分子学报，第1988卷第3期 1988;特大孔交联苯乙烯－二乙烯苯共聚物的制备和孔结构研究I 何炳林等，高分子通讯，第1982卷第04期 1982;以脂肪醇为致孔剂的苯乙烯－二乙烯苯共聚体的合成及其膦酰胺化反应 何炳林等，高分子通讯，第1984卷第5期 1984 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107138177A (en) * | 2017-05-26 | 2017-09-08 | 丹东明珠特种树脂有限公司 | Methanol extraction water depickling resin catalyst prepared by methyl tertiary butyl ether(MTBE) and preparation method thereof |
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| CN1583269A (en) | 2005-02-23 |
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