CN107876089A - Ionic liquid catalyst system for bisphenol-A synthesis and preparation method thereof - Google Patents
Ionic liquid catalyst system for bisphenol-A synthesis and preparation method thereof Download PDFInfo
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- CN107876089A CN107876089A CN201711193935.6A CN201711193935A CN107876089A CN 107876089 A CN107876089 A CN 107876089A CN 201711193935 A CN201711193935 A CN 201711193935A CN 107876089 A CN107876089 A CN 107876089A
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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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0298—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature the ionic liquids being characterised by the counter-anions
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Abstract
The present invention relates to a kind of ionic liquid catalyst system for bisphenol-A synthesis and preparation method thereof.It is 1 that the raw material of ionic liquid catalyst system, which includes mol ratio,：The thiol-functionalized ionic liquid of (20~80) and sulfonated acidic ion liquid.The synthetic method of bisphenol-A：Phenol is uniform by default mixed in molar ratio with acetone, obtain reaction mixture；Ionic liquid catalyst system is added afterwards to be reacted, above-mentioned reaction product is separated, and is dehydrated, is crystallized afterwards, washing, filtering fusion-crystallization processing, obtaining target product bisphenol-A.Ionic liquid catalyst system provided by the invention, pass through the synergy of sulfonated acidic ion liquid major catalyst and thiol-functionalized ionic liquid co-catalyst, the speed of condensation reaction in bisphenol-A building-up process is dramatically speeded up, improves the selectivity of acetone conversion and bisphenol-A；Whole building-up process is green, equipment will not be caused to corrode, while avoid the use of other volatile organic solvents.
Description
Technical field
The present invention relates to the synthesis technical field of bisphenol-A, and in particular to a kind of for the ionic liquid-catalyzed of bisphenol-A synthesis
Agent system and preparation method thereof.
Background technology
Bisphenol-A belongs to phenol derivatives, also referred to as BPA, be by two molecule phenol and a molecule acetone through sulfuric acid, hydrogen chloride and
The condensation of the acidic catalysts such as ion exchange resin forms.It is used as one of most popular industrial compound in the world, at present
Demand rapid development, and mainly for the production of makrolon, epoxy resin, polysulfone resin, polyphenylene oxide resin and unsaturation
A variety of high polymer materials such as polyester resin；In addition, it can also be used for producing plasticizer, fire retardant, antioxidant, heat stabilizer, rubber
The fine chemical products such as glue age resistor, agricultural chemicals and coating.
In traditional industry, the production of bisphenol-A mainly makees catalyst using strong inorganic acid such as sulfuric acid, hydrochloric acid etc..However, sulfuric acid
Method products obtained therefrom is second-rate, and supplies consumption quota is high, and labor intensity is high, and the three wastes are more, and processing is especially difficult, dirty to environment
Contaminate extremely serious.Compared with sulfuric acid process, the product quality that hydrogen chloride technique obtains is preferable, but because hydrochloric acid corrosion resistance is strong,
Device is needed using expensive corrosion resistant material, so as to add investment；And the technique needs large-scale waste water disposal facility.
At present in bisphenol A production process, a kind of widely used alternative catalyst is cation exchange resin catalyst：Should
The catalyst degradation corrosion to equipment, reactive material easily separate, and system reliability increases, can obtain higher quality
Bisphenol-A product.However, there is heat endurance difference and swellability in catalyst of such ion exchange resin as synthesis of bisphenol A
The deficiencies of poor.
Based on this, a kind of new catalyst system is studied, is particularly important so as to the production process of notable bisphenol-A.
The content of the invention
For in the prior art the defects of, the present invention is intended to provide it is a kind of for bisphenol-A synthesis ionic-liquid catalyst
System and preparation method thereof.Ionic liquid catalyst system provided by the invention, pass through sulfonated acidic ion liquid main catalytic
Agent and the synergy of thiol-functionalized ionic liquid co-catalyst, dramatically speed up the speed of condensation reaction in bisphenol-A building-up process
Degree, improve the selectivity of acetone conversion and bisphenol-A.In addition, the catalyst system and catalyzing is applied in bisphenol-A building-up process, it is whole to close
It is green into process, corrosion reaction system will not be caused to equipment, while avoid other any volatile organic solvents and
The use of other catalyst.
Therefore, the present invention provides following technical scheme：
In a first aspect, the present invention provides a kind of ionic liquid catalyst system, ionic liquid catalyst system is used for bisphenol-A
Building-up process in；And the raw material components of ionic liquid catalyst system include：Sulfonated acidic ion liquid and sulfydryl function
Change ionic liquid.
In the further embodiment of the present invention, sulfonated acidic ion liquid is selected from [BmimSO3H][HSO4]、
[BPySO3H][HSO4]、[EPySO3H][HSO4]、[PpimSO3H]CF3SO3、[BmimSO3H]CF3SO3、[EPySO3H]
[H2PO4] and [CnmimSO3H][HSO4] in one or more；Wherein, n=2,4 or 6.
In the further embodiment of the present invention, thiol-functionalized ionic liquid co-catalyst is selected from [HS-Cn1mim]
NO3、[HS-Pbim][HSO4] and [Et-SH] NO3In one or more；Wherein, n1=2,4 or 10.
In the further embodiment of the present invention, thiol-functionalized ionic liquid rubs with sulfonated acidic ion liquid
You are than being 1：(20~80).Wherein, thiol-functionalized ionic liquid can ensure that proton passes in course of reaction as co-catalyst
That passs is smoothed out, and assists to accelerate reaction speed.
Second aspect, the present invention provide a kind of preparation method of ionic liquid catalyst system, comprised the following steps：By sulphur
Acidifying acidic ion liquid is well mixed with thiol-functionalized ionic liquid, obtained catalyst system.
The third aspect, the present invention provide a kind of method of synthesis of bisphenol A, comprised the following steps：S101：By phenol and acetone
It is uniform by default mixed in molar ratio, obtain reaction mixture；Ionic liquid catalyst system provided by the invention is added afterwards,
Preset time is stirred under preset temperature；S102：The product that S101 is obtained is separated, and is dehydrated, is crystallized afterwards, washing, filtering
Fusion-crystallization processing, obtains target product bisphenol-A.
In the further embodiment of the present invention, in S102, product that S101 is obtained also includes before being separated
Step：The product stratification that S101 is obtained, obtains ionic liquid and bisphenol-A head product；Ionic liquid can with direct reuse,
Ionic liquid is used as to the raw material of the ionic liquid catalyst system in S101, using bisphenol-A head product as the original in S102
Material is separated.
In the further embodiment of the present invention, in S101, the mol ratio of phenol and acetone is (8~1)：1；Phenol with
The mol ratio of sulfonated acidic ion liquid is 1 in ionic liquid catalyst system：(0.15~3).
In the further embodiment of the present invention, in S101, preset temperature is 30 DEG C~100 DEG C, and preferably 60 DEG C
~80 DEG C；Preset time is 2h~8h, and preferably 3h~5h.
Above-mentioned technical proposal provided by the invention has advantages below：
(1) applicant has found by numerous studies：The present invention is provided to the ionic-liquid catalyst body of bisphenol-A synthesis
System from sulfonated acidic ion liquid is major catalyst, thiol-functionalized ionic liquid is co-catalyst；The first step so that
Raw material phenol and acetone are condensed under catalyst system and catalyzing catalysis, and then synthesis of bisphenol A.Based on the stronger acid of major catalyst
Property, make the carbon in acetone that there is fabulous electrophilicity, activity significantly improves, and then makes phenol and acetone dehydrating condensation speed notable
Improve, generate isopropenyl phenol carbocation；Second step, to isopropenyl phenol carbocation and another molecule phenol with reference to and obtain
Product bisphenol A, whole reaction depend on the most slow first step and reacted.In addition, had based on divalent sulfur in sulfydryl in co-catalyst
Very strong nucleophilicity, the proton transfer being adapted between organic reagent, and then the H that ionic liquid can be discharged+Smoothly transmit.
(2) ionic liquid catalyst system synthesis of bisphenol A provided by the invention is used, passes through sulfonated acidic ion liquid
The synergy of major catalyst and thiol-functionalized ionic liquid co-catalyst, dramatically speed up in bisphenol-A building-up process and be condensed instead
The speed answered, while improve the selectivity of acetone conversion and bisphenol-A.In addition, the catalyst system and catalyzing is applied to bisphenol-A building-up process
In, the use of any volatile organic solvent of other in reaction system and other catalyst is not only avoid, and entirely synthesize
Process is stable, selectivity is high, acetone conversion is high, product yield is high, quality is good；And ionic-liquid catalyst body of the present invention
System is stable to water and air, to equipment non-corrosiveness, equipment requirement is reduced, so as to significantly reduce production cost.In addition, should
Ionic liquid catalyst system may be reused, green.
The additional aspect and advantage of the present invention will be set forth in part in the description, and will partly become from the following description
Obtain substantially, or recognized by the practice of the present invention.
Embodiment
The embodiment of technical solution of the present invention will be described in detail below.Following examples are only used for clearer
Explanation technical scheme, therefore be only used as example, and can not be limited the scope of the invention with this.
Experimental method in following embodiments, it is conventional method unless otherwise specified.
Test material used, is to be commercially available from conventional reagent shop unless otherwise specified in following embodiments.
Quantitative test in following examples, it is respectively provided with and repeats to test three times, data is to repeat the average value of experiment three times
Or mean+SD.
The present invention provides a kind of ionic liquid catalyst system, and ionic liquid catalyst system is used for the synthesis of bisphenol-A
Cheng Zhong；And the raw material components of ionic liquid catalyst system include：Sulfonated acidic ion liquid and mercapto-functionalized ionic liquid
Body.Wherein, the mol ratio of thiol-functionalized ionic liquid and sulfonated acidic ion liquid is 1：(20~80).
Preferably, sulfonated acidic ion liquid is selected from [BmimSO3H][HSO4]、[BPySO3H][HSO4]、[EPySO3H]
[HSO4]、[PpimSO3H]CF3SO3、[BmimSO3H]CF3SO3、[EPySO3H][H2PO4] and [CnmimSO3H][HSO4] in
It is one or more；Wherein, n=2,4 or 6.Thiol-functionalized ionic liquid co-catalyst is selected from [HS-Cn1mim]NO3、[HS-
Pbim][HSO4] and [Et-SH] NO3In one or more；Wherein, n1=2,4 or 10.
In addition, being directed to ionic liquid catalyst system provided by the invention, the present invention specially provides preparation method, including
Following steps：Sulfonated acidic ion liquid is well mixed with thiol-functionalized ionic liquid, obtained catalyst system.
In addition, the invention provides the application process of ionic liquid catalyst system, it is applied to the synthesis of bisphenol-A
Cheng Zhong.Specifically, the present invention provides a kind of method of synthesis of bisphenol A, comprises the following steps：
S101：Phenol is uniform by default mixed in molar ratio with acetone, obtain reaction mixture；Claim is added afterwards
Ionic liquid catalyst system in 1~4, preset time is stirred under preset temperature.Wherein, in S101, phenol and acetone
Mol ratio is (8~1)：1；The mol ratio of phenol and sulfonated acidic ion liquid in ionic liquid catalyst system is 1：
(0.15~3)；In S101, preset temperature is 30 DEG C~100 DEG C, and preferably 60 DEG C~80 DEG C；Preset time is 2h~8h, and
Preferably 3h~5h.The reaction equation of synthesis of bisphenol A is as follows：
S102：The product that S101 is obtained is separated, and is dehydrated, is crystallized afterwards, washing, filtering fusion-crystallization processing, obtaining
To target product bisphenol-A.Wherein, in S102, product that S101 is obtained also includes step before being separated：S101 is obtained
Product stratification, obtain ionic liquid and bisphenol-A head product；Ionic liquid is used as the ionic-liquid catalyst in S101
The raw material of system, separated bisphenol-A head product as the raw material in S102.
Illustrated with reference to embodiment：
Embodiment one
(1) preparation of ionic liquid catalyst system
Sulfonated acidic ionic liquid catalysts and mercapto-functionalized ionic liquid are compounded with certain proportion, obtain from
Sub- Liquid catalyst systems.
Wherein, thiol-functionalized ionic liquid is [HS-Pbim] [HSO4], sulfonated acidic ion liquid is
[PpimSO3H]CF3SO3；The mol ratio of thiol-functionalized ionic liquid and sulfonated acidic ion liquid is 1：20.
(2) synthesis of bisphenol-A
S101：Phenol is uniform by default mixed in molar ratio with acetone, obtain reaction mixture；The present embodiment is added afterwards
Ionic catalyst systems, stir preset time under preset temperature.Wherein, the mol ratio of phenol and acetone is 7：1, phenol with
[PpimSO3H]CF3SO3Mol ratio be 1：0.5, reaction temperature is 55 DEG C, reaction time 3h.
S102：The product that S102 is obtained is separated, and is dehydrated, is crystallized afterwards, washing, filtering fusion-crystallization, obtaining pure
Net target product bisphenol-A.
Comparative example one
The preparation method of bisphenol-A is identical with embodiment one in the comparative example, but does not have the mercapto-functionalized ion of co-catalyst
Liquid.
Specifically, the synthesis of bisphenol-A comprises the following steps：
S101：Phenol is uniform by default mixed in molar ratio with acetone, obtain reaction mixture；Ionic catalysis is added afterwards
Agent [PpimSO3H]CF3SO3, preset time is stirred under preset temperature.Wherein, the mol ratio of phenol and acetone is 7：1, phenol
With [PpimSO3H]CF3SO3Mol ratio be 1：0.5, reaction temperature is 55 DEG C, reaction time 3h.
S102：The product that S102 is obtained is separated, and is dehydrated, is crystallized afterwards, washing, filtering fusion-crystallization, obtaining pure
Net target product bisphenol-A.
Embodiment two
(1) preparation of ionic liquid catalyst system
Sulfonated acidic ionic liquid catalysts and mercapto-functionalized ionic liquid are compounded with certain proportion, obtain from
Sub- Liquid catalyst systems.
Wherein, thiol-functionalized ionic liquid is [Et-SH] NO3, sulfonated acidic ion liquid is [EPySO3H]
[H2PO4]；The mol ratio of thiol-functionalized ionic liquid and sulfonated acidic ion liquid is 1：60.
(2) synthesis of bisphenol-A
S101：Phenol is uniform by default mixed in molar ratio with acetone, obtain reaction mixture；The present embodiment is added afterwards
Ionic catalyst systems, stir preset time under preset temperature.Wherein, the mol ratio of phenol and acetone is 7.5：1, phenol
With [EPySO3H][H2PO4] mol ratio be 1：1.1, reaction temperature is 50 DEG C, reaction time 4h.
S102：The product that S102 is obtained is separated, and is dehydrated, is crystallized afterwards, washing, filtering fusion-crystallization, obtaining pure
Net target product bisphenol-A.
Embodiment three
(1) preparation of ionic liquid catalyst system
Sulfonated acidic ionic liquid catalysts and mercapto-functionalized ionic liquid are compounded with certain proportion, obtain from
Sub- Liquid catalyst systems.
Wherein, thiol-functionalized ionic liquid is [Et-SH] NO3, sulfonated acidic ion liquid is [EPySO3H]
[H2PO4]；The mol ratio of thiol-functionalized ionic liquid and sulfonated acidic ion liquid is 1：70.
(2) synthesis of bisphenol-A
S101：Phenol is uniform by default mixed in molar ratio with acetone, obtain reaction mixture；The present embodiment is added afterwards
Ionic catalyst systems, stir preset time under preset temperature.Wherein, the mol ratio of phenol and acetone is 6：1, phenol with
[EPySO3H][H2PO4] mol ratio be 1：3, reaction temperature is 60 DEG C, reaction time 3h.
S102：The product that S102 is obtained is separated, and is dehydrated, is crystallized afterwards, washing, filtering fusion-crystallization, obtaining pure
Net target product bisphenol-A.
Example IV
(1) preparation of ionic liquid catalyst system
Sulfonated acidic ionic liquid catalysts and mercapto-functionalized ionic liquid are compounded with certain proportion, obtain from
Sub- Liquid catalyst systems.
Wherein, thiol-functionalized ionic liquid is [Et-SH] NO3, sulfonated acidic ion liquid is [BmimSO3H]
[HSO4]；The mol ratio of thiol-functionalized ionic liquid and sulfonated acidic ion liquid is 1：40.
(2) synthesis of bisphenol-A
S101：Phenol is uniform by default mixed in molar ratio with acetone, obtain reaction mixture；The present embodiment is added afterwards
Ionic catalyst systems, stir preset time under preset temperature.Wherein, the mol ratio of phenol and acetone is 5：1, phenol with
[BmimSO3H][HSO4] mol ratio be 1：1, reaction temperature is 40 DEG C, reaction time 5h.
S102：The product that S102 is obtained is separated, and is dehydrated, is crystallized afterwards, washing, filtering fusion-crystallization, obtaining pure
Net target product bisphenol-A.
Embodiment five
(1) preparation of ionic liquid catalyst system
Sulfonated acidic ionic liquid catalysts and mercapto-functionalized ionic liquid are compounded with certain proportion, obtain from
Sub- Liquid catalyst systems.
Wherein, thiol-functionalized ionic liquid is [HS-C4mim]NO3, sulfonated acidic ion liquid is [C2mimSO3H]
[HSO4]；The mol ratio of thiol-functionalized ionic liquid and sulfonated acidic ion liquid is 1：40.
(2) synthesis of bisphenol-A
S101：Phenol is uniform by default mixed in molar ratio with acetone, obtain reaction mixture；The present embodiment is added afterwards
Ionic catalyst systems, stir preset time under preset temperature.Wherein, the mol ratio of phenol and acetone is 6：1, phenol with
[BmimSO3H][HSO4] mol ratio be 1：0.8, reaction temperature is 55 DEG C, reaction time 4h.
S102：The product that S102 is obtained is separated, and is dehydrated, is crystallized afterwards, washing, filtering fusion-crystallization, obtaining pure
Net target product bisphenol-A.
Embodiment six
The preparation method of the embodiment is identical with embodiment one, but sulfonated acidic ion liquid selects [C4mimSO3H]
[HSO4], thiol-functionalized ionic liquid select [HS-C10mim]NO3。
Embodiment seven
The preparation method of the embodiment is identical with embodiment two, but sulfonated acidic ion liquid selects [BPySO3H]
[HSO4], thiol-functionalized ionic liquid select [HS-Pbim] [HSO4]。
Embodiment eight
The preparation method of the embodiment is identical with embodiment three, but sulfonated acidic ion liquid is 1 from mol ratio：1
[C2mimSO3H][HSO4] and [C6mimSO3H][HSO4], thiol-functionalized ionic liquid is 1 from mol ratio：0.3
[HS-Pbim][HSO4] and [Et-SH] NO3。
Embodiment nine
The preparation method of the embodiment is identical with example IV, but sulfonated acidic ion liquid selects [C2mimSO3H]
[HSO4]、[C4mimSO3H][HSO4] and [C6mimSO3H][HSO4], the mol ratio of three is followed successively by 2：2：1；It is mercapto-functionalized
Ionic liquid is 5 from mol ratio：1 [HS-Pbim] [HSO4] and [Et-SH] NO3。
Embodiment ten
The preparation method of the embodiment is identical with embodiment five, but sulfonated acidic ion liquid selects [BmimSO3H]
CF3SO3, thiol-functionalized ionic liquid is from [HS-C10mim]NO3、[HS-C4mim]NO3[HS-C2mim]NO3, three rubs
You are followed successively by 1 by ratio：3：1.
Embodiment 11
(1) preparation of ionic liquid catalyst system
Sulfonated acidic ionic liquid catalysts and mercapto-functionalized ionic liquid are compounded with certain proportion, obtain from
Sub- Liquid catalyst systems.
Wherein, thiol-functionalized ionic liquid is [HS-C10mim]NO3, sulfonated acidic ion liquid is [C6mimSO3H]
[HSO4]；The mol ratio of thiol-functionalized ionic liquid and sulfonated acidic ion liquid is 1：20.
(2) synthesis of bisphenol-A
S101：Phenol is uniform by default mixed in molar ratio with acetone, obtain reaction mixture；The present embodiment is added afterwards
Ionic catalyst systems, stir preset time under preset temperature.Wherein, the mol ratio of phenol and acetone is 8：1, phenol with
[C6mimSO3H][HSO4] mol ratio be 1：3, reaction temperature is 70 DEG C, reaction time 2h.
S102：The product that S102 is obtained is separated, and is dehydrated, is crystallized afterwards, washing, filtering fusion-crystallization, obtaining pure
Net target product bisphenol-A.
Embodiment 12
(1) preparation of ionic liquid catalyst system
Sulfonated acidic ionic liquid catalysts and mercapto-functionalized ionic liquid are compounded with certain proportion, obtain from
Sub- Liquid catalyst systems.
Wherein, thiol-functionalized ionic liquid is [HS-C4mim]NO3, sulfonated acidic ion liquid is [EPySO3H]
[HSO4]；The mol ratio of thiol-functionalized ionic liquid and sulfonated acidic ion liquid is 1：80.
(2) synthesis of bisphenol-A
S101：Phenol is uniform by default mixed in molar ratio with acetone, obtain reaction mixture；The present embodiment is added afterwards
Ionic catalyst systems, stir preset time under preset temperature.Wherein, the mol ratio of phenol and acetone is 1：1, phenol with
[EPySO3H][HSO4] mol ratio be 1：0.15, reaction temperature is 40 DEG C, reaction time 6h.
S102：The product that S102 is obtained is separated, and is dehydrated, is crystallized afterwards, washing, filtering fusion-crystallization, obtaining pure
Net target product bisphenol-A.
In addition, in order to preferably highlight the advantage of technical solution of the present invention, determine in each embodiment bisphenol-A building-up process
Acetone conversion and BPA selectivity, and test result and each embodiment reaction condition are listed in Tables 1 and 2.
The reaction raw materials list of each embodiment ionic liquid catalyst system of table 1
Each embodiment reaction condition of table 2 and test result list
From list data as can be seen that using ionic liquid catalyst system provided by the invention and synthetic method, have
Excellent feed stock conversion and target product selectivity：Acetone conversion is up to 99.4%, bisphenol-A selectively up to 93.6%.
Certainly, except the situation that embodiment one is enumerated to embodiment 12, the percentage by weight of other raw material components, prepare
During each condition and parameter etc. it is also possible.
A kind of ionic liquid catalyst system for bisphenol-A synthesis provided by the invention, from sulfonated acid ion
Liquid is major catalyst, thiol-functionalized ionic liquid is co-catalyst, the first step so that raw material phenol and acetone are in the catalysis
It is condensed under system catalysis, and then synthesis of bisphenol A.Based on the stronger acidity of major catalyst, there is the carbon in acetone fabulous
Electrophilicity, activity significantly improves, and then phenol is significantly improved with acetone dehydrating condensation speed, generation isopropenyl phenol carbon sun
Ion；Second step, to isopropenyl phenol carbocation and another molecule phenol with reference to and product bisphenol A, whole reaction are depended on
Reacted in the most slow first step.In addition, there is very strong nucleophilicity based on divalent sulfur in sulfydryl in co-catalyst, it is adapted to organic examination
Proton transfer between agent, and then the H that ionic liquid can be discharged+Smoothly transmit, so as to greatly accelerate condensation reaction speed
Rate.In addition, the catalyst system and catalyzing is applied in bisphenol-A building-up process, it not only avoid that other in reaction system are any volatile to be had
The use of solvent and other catalyst, and whole building-up process process stabilizing, selectivity are high, acetone conversion height, product
High income, quality are good；And ionic liquid catalyst system of the present invention is stable to water and air, to equipment non-corrosiveness, reduces
Equipment requirement, so as to significantly reduce production cost.In addition, the ionic liquid catalyst system may be reused, green ring
Protect.
In the description of the invention, it is to be understood that term " first ", " second " are only used for describing purpose, and can not
It is interpreted as indicating or implies relative importance or imply the quantity of the technical characteristic indicated by indicating.Thus, define " the
One ", one or more this feature can be expressed or be implicitly included to the feature of " second ".In the description of the invention,
" multiple " are meant that two or more, unless otherwise specifically defined.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or the spy for combining the embodiment or example description
Point is contained at least one embodiment or example of the present invention.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.Moreover, specific features, structure, material or the feature of description can be with office
Combined in an appropriate manner in one or more embodiments or example.In addition, in the case of not conflicting, the skill of this area
Art personnel can be tied the different embodiments or example and the feature of different embodiments or example described in this specification
Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changed, replacing and modification.
Claims (10)
- A kind of 1. ionic liquid catalyst system, it is characterised in that：The ionic liquid catalyst system is used in the building-up process of bisphenol-A；And the original of the ionic liquid catalyst system Material component includes：Sulfonated acidic ion liquid and thiol-functionalized ionic liquid.
- 2. ionic liquid catalyst system according to claim 1, it is characterised in that：The sulfonated acidic ion liquid is selected from [BmimSO3H][HSO4]、[BPySO3H][HSO4]、[EPySO3H][HSO4]、 [PpimSO3H]CF3SO3、[BmimSO3H]CF3SO3、[EPySO3H][H2PO4] and [CnmimSO3H][HSO4] in one kind or more Kind；Wherein, the n=2,4 or 6.
- 3. ionic liquid catalyst system according to claim 1, it is characterised in that：The thiol-functionalized ionic liquid co-catalyst is selected from [HS-Cn1mim]NO3、[HS-Pbim][HSO4] and [Et-SH] NO3In one or more；Wherein, the n1=2,4 or 10.
- 4. according to the ionic liquid catalyst system described in any one of claims 1 to 3, it is characterised in that：The mol ratio of the thiol-functionalized ionic liquid and the sulfonated acidic ion liquid is 1：(20~80).
- 5. the preparation method of the ionic liquid catalyst system according to any one of Claims 1 to 4, it is characterised in that bag Include following steps：The sulfonated acidic ion liquid is well mixed with the thiol-functionalized ionic liquid, obtains the ionic liquid Catalyst system.
- A kind of 6. method of synthesis of bisphenol A, it is characterised in that comprise the following steps：S101：Phenol is uniform by default mixed in molar ratio with acetone, obtain reaction mixture；Claims 1 to 4 is added afterwards In the ionic liquid catalyst system, stir preset time under preset temperature；S102：The obtained products of the S101 are separated, is dehydrated, crystallizes afterwards, washing, filtering fusion-crystallization processing, obtaining To target product bisphenol-A.
- 7. the preparation method of ionic liquid catalyst system according to claim 6, it is characterised in that：In the S102, step is also included before the obtained products of the S101 are separated：The product stratification that the S101 is obtained, obtains ionic liquid and bisphenol-A head product；Ionic liquid is used as S101 In ionic liquid catalyst system raw material, the bisphenol-A head product is separated as the raw material in S102.
- 8. the preparation method of ionic liquid catalyst system according to claim 6, it is characterised in that：In the S101, the mol ratio of the phenol and the acetone is (8~1)：1；The phenol is urged with the ionic liquid The mol ratio of sulfonated acidic ion liquid is 1 in agent system：(0.15~3).
- 9. the preparation method of ionic liquid catalyst system according to claim 6, it is characterised in that：In the S101, the preset temperature is 30 DEG C~100 DEG C, and the preset time is 2h~8h.
- 10. the preparation method of ionic liquid catalyst system according to claim 9, it is characterised in that：In the S101, the preset temperature is 60 DEG C~80 DEG C, and the preset time is 3h~5h.
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| CN110092712A (en) * | 2019-04-10 | 2019-08-06 | 三峡大学 | A kind of preparation method of bisphenol-A |
| CN111001440A (en) * | 2019-12-26 | 2020-04-14 | 福州大学 | Polyacid site ionic liquid catalyst and preparation method and application thereof |
| CN113248441A (en) * | 2021-04-30 | 2021-08-13 | 大连理工大学 | Dual-functional ionic liquid, preparation method thereof and application thereof in catalytic synthesis of bisphenol compound |
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Denomination of invention: Ionic liquid catalyst system and preparation method for bisphenol A synthesis Effective date of registration: 20230720 Granted publication date: 20200825 Pledgee: China Petroleum Finance Co.,Ltd. Pledgor: PUYANG SHENGTONGJUYUAN ADVANCED MATERIALS Co.,Ltd. Registration number: Y2023980048997 |