CN107876089B - 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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- 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
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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
- B01J31/0285—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
Abstract
The invention relates to an ionic liquid catalyst system for bisphenol A synthesis and a preparation method thereof. The ionic liquid catalyst system comprises the following raw materials in a molar ratio of 1: (20-80) a sulfydryl functional ionic liquid and a sulfonated acidic ionic liquid. The synthesis method of bisphenol A comprises the following steps: uniformly mixing phenol and acetone according to a preset molar ratio to obtain a reaction mixed solution; and then adding an ionic liquid catalyst system for reaction, separating the reaction product, and then dehydrating, crystallizing, washing, filtering, melting and crystallizing to obtain the target product bisphenol A. According to the ionic liquid catalyst system provided by the invention, the condensation reaction speed in the bisphenol A synthesis process is remarkably accelerated and the acetone conversion rate and the selectivity of bisphenol A are improved through the synergistic effect of the main sulfonated acidic ionic liquid catalyst and the auxiliary mercapto functional ionic liquid catalyst; the whole synthesis process is green and environment-friendly, does not corrode equipment, and avoids the use of other volatile organic solvents.
Description
Technical Field
The invention relates to the technical field of bisphenol A synthesis, in particular to an ionic liquid catalyst system for bisphenol A synthesis and a preparation method thereof.
Background
Bisphenol A belongs to phenol derivatives, also called BPA, and is prepared by condensing two molecules of phenol and one molecule of acetone through sulfuric acid, hydrogen chloride and acidic catalysts such as ion exchange resin. The compound is one of the most widely used industrial compounds in the world, the demand is rapidly increased at present, and the compound is mainly used for producing various high polymer materials such as polycarbonate, epoxy resin, polysulfone resin, polyphenyl ether resin, unsaturated polyester resin and the like; in addition, the method can also be used for producing fine chemical products such as plasticizers, flame retardants, antioxidants, heat stabilizers, rubber antioxidants, pesticides, coatings and the like.
In the conventional industry, bisphenol A is produced mainly by using a strong inorganic acid such as sulfuric acid, hydrochloric acid, etc. as a catalyst. However, the sulfuric acid method has poor product quality, high material consumption rate, high labor intensity, more three wastes, difficult treatment and serious environmental pollution. Compared with the sulfuric acid method, the product quality obtained by the hydrogen chloride method process is better, but the device needs to adopt expensive corrosion-resistant materials due to strong corrosivity of hydrochloric acid, so that the investment is increased; and the process requires large wastewater treatment facilities.
One alternative catalyst that is widely used in the current bisphenol a production process is the cation exchange resin catalyst: the catalyst reduces the corrosion to equipment, ensures that reaction substances are easy to separate, improves the reliability of a system, and can obtain a bisphenol A product with higher quality. However, the ion exchange resins have the disadvantages of poor thermal stability, poor swelling property and the like when used as catalysts for synthesizing bisphenol A.
Based on this, a new catalyst system is studied, so that the production process of bisphenol A is very important.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an ionic liquid catalyst system for bisphenol A synthesis and a preparation method thereof. The ionic liquid catalyst system provided by the invention has the advantages that the condensation reaction speed in the bisphenol A synthesis process is remarkably accelerated and the acetone conversion rate and the selectivity of bisphenol A are improved through the synergistic effect of the main sulfonated acidic ionic liquid catalyst and the auxiliary mercapto functional ionic liquid catalyst. In addition, the catalytic system is applied to the bisphenol A synthesis process, the whole synthesis process is green and environment-friendly, a corrosion reaction system cannot be caused to equipment, and the use of any other volatile organic solvent and other catalysts is avoided.
Therefore, the invention provides the following technical scheme:
in a first aspect, the present invention provides an ionic liquid catalyst system for use in the synthesis of bisphenol a; and the raw material components of the ionic liquid catalyst system comprise: sulfonated acidic ionic liquid and sulfydryl functional ionic liquid.
In a further embodiment of the invention, the sulphonated acidic ionic liquid is selected from [ BmimSO no ]3H][HSO4]、[BPySO3H][HSO4]、[EPySO3H][HSO4]、[PpimSO3H]CF3SO3、[BmimSO3H]CF3SO3、[EPySO3H][H2PO4]And [ CnmimSO3H][HSO4]One or more of; wherein n is 2, 4 or 6.
In a further embodiment of the invention, the thiol functionThe ionic liquid cocatalyst is selected from [ HS-C ]n1mim]NO3、[HS-Pbim][HSO4]And [ Et-SH ]]NO3One or more of; wherein n1 is 2, 4 or 10.
In a further embodiment of the present invention, the molar ratio of thiol-functionalized ionic liquid to sulfonated acidic ionic liquid is 1: (20-80). The sulfydryl functionalized ionic liquid is used as a cocatalyst, so that the smooth progress of proton transfer in the reaction process can be ensured, and the reaction speed is assisted to be accelerated.
In a second aspect, the present invention provides a method for preparing an ionic liquid catalyst system, comprising the steps of: and uniformly mixing the sulfonated acidic ionic liquid and the mercapto functional ionic liquid to obtain the catalyst system.
In a third aspect, the present invention provides a method for synthesizing bisphenol a, comprising the steps of: s101: uniformly mixing phenol and acetone according to a preset molar ratio to obtain a reaction mixed solution; then adding the ionic liquid catalyst system provided by the invention, and stirring for a preset time at a preset temperature; s102: and (3) separating the product obtained in the step (S101), and then dehydrating, crystallizing, washing, filtering, melting and crystallizing to obtain the target product bisphenol A.
In a further embodiment of the present invention, before the separation of the product obtained in S101 in S102, the method further comprises the steps of: standing and layering the product obtained in the step S101 to obtain ionic liquid and a bisphenol A primary product; the ionic liquid can be directly recycled, namely the ionic liquid is used as a raw material of an ionic liquid catalyst system in S101, and a bisphenol A primary product is used as a raw material in S102 for separation.
In a further embodiment of the present invention, in S101, the molar ratio of phenol to acetone is (8-1): 1; the molar ratio of phenol to sulfonated acidic ionic liquid in the ionic liquid catalyst system is 1: (0.15-3).
In a further embodiment of the present invention, in S101, the preset temperature is 30 to 100 ℃, and preferably 60 to 80 ℃; the preset time is 2 to 8 hours, and preferably 3 to 5 hours.
The technical scheme provided by the invention has the following advantages:
(1) the applicant has found through a great deal of research that: the invention provides an ionic liquid catalyst system for bisphenol A synthesis, which selects sulfonated acidic ionic liquid as a main catalyst and sulfydryl functionalized ionic liquid as a cocatalyst; in the first step, raw materials of phenol and acetone are condensed under the catalysis of the catalytic system, and then bisphenol A is synthesized. Based on the strong acidity of the main catalyst, the carbon in the acetone has excellent electrophilicity, the activity is obviously improved, and further the dehydration condensation rate of the phenol and the acetone is obviously improved to generate isopropenylphenol carbocation; in the second step, the isopropenylphenol carbocation is combined with another molecule of phenol to produce a bisphenol A product, and the whole reaction depends on the slowest reaction in the first step. In addition, based on strong nucleophilicity of divalent sulfur in sulfydryl in the cocatalyst, the catalyst is suitable for proton transfer between organic reagents, and further can release H of ionic liquid+The transfer is smooth.
(2) The ionic liquid catalyst system provided by the invention is adopted to synthesize bisphenol A, and the condensation reaction speed in the bisphenol A synthesis process is remarkably accelerated and the acetone conversion rate and the bisphenol A selectivity are improved through the synergistic effect of the sulfonated acidic ionic liquid main catalyst and the mercapto functional ionic liquid cocatalyst. In addition, the catalytic system is applied to the bisphenol A synthesis process, so that the use of any other volatile organic solvent and other catalysts in a reaction system is avoided, and the whole synthesis process has the advantages of stable process, high selectivity, high acetone conversion rate, high product yield and good quality; the ionic liquid catalyst system is stable to water and air, has no corrosion to equipment, and reduces the equipment requirement, thereby obviously reducing the production cost. In addition, the ionic liquid catalyst system can be repeatedly used, and is green and environment-friendly.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby.
The experimental procedures in the following examples are conventional unless otherwise specified.
The test materials used in the following examples were purchased from a conventional reagent store unless otherwise specified.
In the quantitative tests in the following examples, three replicates were set, and the data are the mean or the mean ± standard deviation of the three replicates.
The invention provides an ionic liquid catalyst system, which is used in the process of synthesizing bisphenol A; and the raw material components of the ionic liquid catalyst system comprise: sulfonated acidic ionic liquid and sulfydryl functional ionic liquid. Wherein the molar ratio of the sulfydryl functional ionic liquid to the sulfonated acidic ionic liquid is 1: (20-80).
Preferably, the sulfonated acidic ionic liquid is selected from [ BmimSO3H][HSO4]、[BPySO3H][HSO4]、[EPySO3H][HSO4]、[PpimSO3H]CF3SO3、[BmimSO3H]CF3SO3、[EPySO3H][H2PO4]And [ CnmimSO3H][HSO4]One or more of; wherein n is 2, 4 or 6. The mercapto-functionalized ionic liquid cocatalyst is selected from [ HS-C ]n1mim]NO3、[HS-Pbim][HSO4]And [ Et-SH ]]NO3One or more of; wherein n1 is 2, 4 or 10.
In addition, aiming at the ionic liquid catalyst system provided by the invention, the invention specially provides a preparation method, which comprises the following steps: and uniformly mixing the sulfonated acidic ionic liquid and the mercapto functional ionic liquid to obtain the catalyst system.
In addition, the invention provides an application method of the ionic liquid catalyst system, which is applied to the synthesis process of bisphenol A. Specifically, the invention provides a method for synthesizing bisphenol A, which comprises the following steps:
s101: uniformly mixing phenol and acetone according to a preset molar ratio to obtain a reaction mixed solution; then adding the ionic liquid catalyst system of claims 1-4, and stirring at a predetermined temperature for a predetermined time. Wherein in S101, the molar ratio of phenol to acetone is (8-1): 1; the molar ratio of phenol to sulfonated acidic ionic liquid in the ionic liquid catalyst system is 1: (0.15 to 3); in S101, the preset temperature is 30-100 ℃, and preferably 60-80 ℃; the preset time is 2 to 8 hours, and preferably 3 to 5 hours. The reaction equation for the synthesis of bisphenol A is as follows:
s102: and (3) separating the product obtained in the step (S101), and then dehydrating, crystallizing, washing, filtering, melting and crystallizing to obtain the target product bisphenol A. Wherein, in S102, before separating the product obtained in S101, the method further comprises the following steps: standing and layering the product obtained in the step S101 to obtain ionic liquid and a bisphenol A primary product; the ionic liquid was used as a raw material for the ionic liquid catalyst system in S101, and the bisphenol a primary product was isolated as a raw material in S102.
The following description is made with reference to specific embodiments:
example one
(1) Preparation of ionic liquid catalyst systems
The sulfonated acidic ionic liquid catalyst and the sulfydryl functionalized ionic liquid are compounded according to a certain proportion to obtain an ionic liquid catalyst system.
Wherein, the sulfydryl functionalized ionic liquid is [ HS-Pbim ]][HSO4]The sulfonated acidic ionic liquid is [ PlimSO [)3H]CF3SO3(ii) a The molar ratio of the sulfydryl functional ionic liquid to the sulfonated acidic ionic liquid is 1: 20.
(2) synthesis of bisphenol A
S101: uniformly mixing phenol and acetone according to a preset molar ratio to obtain a reaction mixed solution; the ionic catalyst system of this example was then added and stirred at the preset temperature for the preset time. Wherein, benzeneThe molar ratio of phenol to acetone was 7: 1, phenol with [ PlimSO ]3H]CF3SO3In a molar ratio of 1: 0.5, the reaction temperature is 55 ℃, and the reaction time is 3 h.
S102: and (3) separating the product obtained in the step (S102), and then dehydrating, crystallizing, washing, filtering, melting and crystallizing to obtain a pure target product bisphenol A.
Comparative example 1
In this comparative example, bisphenol A was prepared in the same manner as in example one, but without the co-catalyst mercapto-functionalized ionic liquid.
Specifically, the synthesis of bisphenol A comprises the following steps:
s101: uniformly mixing phenol and acetone according to a preset molar ratio to obtain a reaction mixed solution; then adding an ionic catalyst [ PpiMSO3H]CF3SO3Stirring at a predetermined temperature for a predetermined time. Wherein the molar ratio of phenol to acetone is 7: 1, phenol with [ PlimSO ]3H]CF3SO3In a molar ratio of 1: 0.5, the reaction temperature is 55 ℃, and the reaction time is 3 h.
S102: and (3) separating the product obtained in the step (S102), and then dehydrating, crystallizing, washing, filtering, melting and crystallizing to obtain a pure target product bisphenol A.
Example two
(1) Preparation of ionic liquid catalyst systems
The sulfonated acidic ionic liquid catalyst and the sulfydryl functionalized ionic liquid are compounded according to a certain proportion to obtain an ionic liquid catalyst system.
Wherein the sulfhydryl functional ionic liquid is [ Et-SH ]]NO3The sulfonated acidic ionic liquid is [ EPySO3H][H2PO4](ii) a The molar ratio of the sulfydryl functional ionic liquid to the sulfonated acidic ionic liquid is 1: 60.
(2) synthesis of bisphenol A
S101: uniformly mixing phenol and acetone according to a preset molar ratio to obtain a reaction mixed solution; the ionic catalyst system of this example was then added and stirred at the preset temperature for the preset time. Wherein the molar ratio of phenol to acetone is7.5: 1, phenol with [ EPySO3H][H2PO4]In a molar ratio of 1: 1.1, the reaction temperature is 50 ℃, and the reaction time is 4 h.
S102: and (3) separating the product obtained in the step (S102), and then dehydrating, crystallizing, washing, filtering, melting and crystallizing to obtain a pure target product bisphenol A.
EXAMPLE III
(1) Preparation of ionic liquid catalyst systems
The sulfonated acidic ionic liquid catalyst and the sulfydryl functionalized ionic liquid are compounded according to a certain proportion to obtain an ionic liquid catalyst system.
Wherein the sulfhydryl functional ionic liquid is [ Et-SH ]]NO3The sulfonated acidic ionic liquid is [ EPySO3H][H2PO4](ii) a The molar ratio of the sulfydryl functional ionic liquid to the sulfonated acidic ionic liquid is 1: 70.
(2) synthesis of bisphenol A
S101: uniformly mixing phenol and acetone according to a preset molar ratio to obtain a reaction mixed solution; the ionic catalyst system of this example was then added and stirred at the preset temperature for the preset time. Wherein the molar ratio of phenol to acetone is 6: 1, phenol with [ EPySO3H][H2PO4]In a molar ratio of 1: 3, the reaction temperature is 60 ℃, and the reaction time is 3 h.
S102: and (3) separating the product obtained in the step (S102), and then dehydrating, crystallizing, washing, filtering, melting and crystallizing to obtain a pure target product bisphenol A.
Example four
(1) Preparation of ionic liquid catalyst systems
The sulfonated acidic ionic liquid catalyst and the sulfydryl functionalized ionic liquid are compounded according to a certain proportion to obtain an ionic liquid catalyst system.
Wherein the sulfhydryl functional ionic liquid is [ Et-SH ]]NO3The sulfonated acidic ionic liquid is [ BmimSO3H][HSO4](ii) a The molar ratio of the sulfydryl functional ionic liquid to the sulfonated acidic ionic liquid is 1: 40.
(2) synthesis of bisphenol A
S101: uniformly mixing phenol and acetone according to a preset molar ratio to obtain a reaction mixed solution; the ionic catalyst system of this example was then added and stirred at the preset temperature for the preset time. Wherein the molar ratio of phenol to acetone is 5: 1, phenol with [ BmimSO ]3H][HSO4]In a molar ratio of 1: 1, the reaction temperature is 40 ℃, and the reaction time is 5 hours.
S102: and (3) separating the product obtained in the step (S102), and then dehydrating, crystallizing, washing, filtering, melting and crystallizing to obtain a pure target product bisphenol A.
EXAMPLE five
(1) Preparation of ionic liquid catalyst systems
The sulfonated acidic ionic liquid catalyst and the sulfydryl functionalized ionic liquid are compounded according to a certain proportion to obtain an ionic liquid catalyst system.
Wherein, the sulfhydryl functional ionic liquid is [ HS-C ]4mim]NO3The sulfonated acidic ionic liquid is [ C ]2mimSO3H][HSO4](ii) a The molar ratio of the sulfydryl functional ionic liquid to the sulfonated acidic ionic liquid is 1: 40.
(2) synthesis of bisphenol A
S101: uniformly mixing phenol and acetone according to a preset molar ratio to obtain a reaction mixed solution; the ionic catalyst system of this example was then added and stirred at the preset temperature for the preset time. Wherein the molar ratio of phenol to acetone is 6: 1, phenol with [ BmimSO ]3H][HSO4]In a molar ratio of 1: 0.8, the reaction temperature is 55 ℃, and the reaction time is 4 h.
S102: and (3) separating the product obtained in the step (S102), and then dehydrating, crystallizing, washing, filtering, melting and crystallizing to obtain a pure target product bisphenol A.
EXAMPLE six
The preparation method of the embodiment is the same as that of the embodiment I, but [ C ] is selected as the sulfonated acidic ionic liquid4mimSO3H][HSO4]Selecting sulfydryl functionalized ionic liquid [ HS-C ]10mim]NO3。
EXAMPLE seven
The preparation method of the embodiment is the same as that of the embodiment, but the sulfonated acidic ionic liquid is BPySO3H][HSO4]The sulfydryl functionalized ionic liquid is selected from [ HS-Pbim ]][HSO4]。
Example eight
The preparation method of the embodiment is the same as that of the embodiment, but the sulfonated acidic ionic liquid is prepared by using the following components in a molar ratio of 1: 1 of [ C2mimSO3H][HSO4]And [ C6mimSO3H][HSO4]The thiol-functionalized ionic liquid is prepared from the following components in a molar ratio of 1: 0.3 of [ HS-Pbim [ ]][HSO4]And [ Et-SH ]]NO3。
Example nine
The preparation method of the example is the same as that of the example four, but the sulfonated acidic ionic liquid is selected from [ C ]2mimSO3H][HSO4]、[C4mimSO3H][HSO4]And [ C6mimSO3H][HSO4]The mol ratio of the three components is 2: 2: 1; the thiol-functionalized ionic liquid is prepared from the following components in a molar ratio of 5: 1 of [ HS-Pbim ]][HSO4]And [ Et-SH ]]NO3。
Example ten
The preparation method of the embodiment is the same as that of the fifth embodiment, but the sulfonated acidic ionic liquid is [ BmimSO ]3H]CF3SO3The mercapto-functionalized ionic liquid is selected from [ HS-C ]10mim]NO3、[HS-C4mim]NO3And [ HS-C ]2mim]NO3The molar ratio of the three components is 1: 3: 1.
EXAMPLE eleven
(1) Preparation of ionic liquid catalyst systems
The sulfonated acidic ionic liquid catalyst and the sulfydryl functionalized ionic liquid are compounded according to a certain proportion to obtain an ionic liquid catalyst system.
Wherein, the sulfhydryl functional ionic liquid is [ HS-C ]10mim]NO3The sulfonated acidic ionic liquid is [ C ]6mimSO3H][HSO4](ii) a Sulfydryl functionalized ionic liquid and sulfurThe molar ratio of the acidified acidic ionic liquid is 1: 20.
(2) synthesis of bisphenol A
S101: uniformly mixing phenol and acetone according to a preset molar ratio to obtain a reaction mixed solution; the ionic catalyst system of this example was then added and stirred at the preset temperature for the preset time. Wherein the molar ratio of phenol to acetone is 8: 1, phenol and [ C ]6mimSO3H][HSO4]In a molar ratio of 1: 3, the reaction temperature is 70 ℃, and the reaction time is 2 h.
S102: and (3) separating the product obtained in the step (S102), and then dehydrating, crystallizing, washing, filtering, melting and crystallizing to obtain a pure target product bisphenol A.
Example twelve
(1) Preparation of ionic liquid catalyst systems
The sulfonated acidic ionic liquid catalyst and the sulfydryl functionalized ionic liquid are compounded according to a certain proportion to obtain an ionic liquid catalyst system.
Wherein, the sulfhydryl functional ionic liquid is [ HS-C ]4mim]NO3The sulfonated acidic ionic liquid is [ EPySO3H][HSO4](ii) a The molar ratio of the sulfydryl functional ionic liquid to the sulfonated acidic ionic liquid is 1: 80.
(2) synthesis of bisphenol A
S101: uniformly mixing phenol and acetone according to a preset molar ratio to obtain a reaction mixed solution; the ionic catalyst system of this example was then added and stirred at the preset temperature for the preset time. Wherein the molar ratio of phenol to acetone is 1: 1, phenol with [ EPySO3H][HSO4]In a molar ratio of 1: 0.15, the reaction temperature is 40 ℃, and the reaction time is 6 h.
S102: and (3) separating the product obtained in the step (S102), and then dehydrating, crystallizing, washing, filtering, melting and crystallizing to obtain a pure target product bisphenol A.
In addition, in order to better highlight the technical solution of the present invention, the acetone conversion and BPA selectivity during the bisphenol A synthesis process of each example were determined, and the test results and the reaction conditions of each example are shown in tables 1 and 2.
Table 1 list of reaction raw materials for ionic liquid catalyst systems of the examples
Table 2 list of reaction conditions and test results for each example
As can be seen from the table data, the ionic liquid catalyst system and the synthesis method provided by the invention have excellent raw material conversion rate and target product selectivity: the acetone conversion rate is as high as 99.4%, and the bisphenol A selectivity is as high as 93.6%.
Of course, other than those exemplified in examples one to twelve, the weight percentages of other raw material components, the respective conditions and parameters in the production process, and the like are also possible.
The invention provides an ionic liquid catalyst system for bisphenol A synthesis, which selects sulfonated acidic ionic liquid as a main catalyst and sulfydryl functional ionic liquid as a cocatalyst, and firstly condenses raw materials of phenol and acetone under the catalysis of the catalyst system to synthesize the bisphenol A. Based on the strong acidity of the main catalyst, the carbon in the acetone has excellent electrophilicity, the activity is obviously improved, and further the dehydration condensation rate of the phenol and the acetone is obviously improved to generate isopropenylphenol carbocation; in the second step, the isopropenylphenol carbocation is combined with another molecule of phenol to produce a bisphenol A product, and the whole reaction depends on the slowest reaction in the first step. In addition, based on strong nucleophilicity of divalent sulfur in sulfydryl in the cocatalyst, the catalyst is suitable for proton transfer between organic reagents, and further can release H of ionic liquid+The transfer is smooth, thereby greatly accelerating the condensation reaction rate. In addition, the catalytic system is applied to the bisphenol A synthesis process, not only avoids the use of any other volatile organic solvent and other catalysts in the reaction system, but also has stable process, high selectivity and acetone in the whole synthesis processThe conversion rate is high, the product yield is high, and the quality is good; the ionic liquid catalyst system is stable to water and air, has no corrosion to equipment, and reduces the equipment requirement, thereby obviously reducing the production cost. In addition, the ionic liquid catalyst system can be repeatedly used, and is green and environment-friendly.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (3)
1. A method for synthesizing bisphenol A by using an ionic liquid catalyst system is characterized by comprising the following steps:
the raw material components of the ionic liquid catalyst system comprise: sulfonating acidic ionic liquid and sulfydryl functional ionic liquid;
the sulfonated acidic ionic liquid is selected from [ BmimSO [ ]3H][HSO4]、[BPySO3H][HSO4]、[EPySO3H][HSO4]、[PpimSO3H]CF3SO3、[BmimSO3H]CF3SO3、[EPySO3H][H2PO4]And [ CnmSO3H][HSO4]Wherein n is 2, 4 or 6;
the sulfydryl functionalized ionic liquid is selected from [ HS-C ]n1mim]NO3、[HS-Pbim][HSO4]And [ Et-SH ]]NO3One or more of; wherein said n1 is 2, 4 or 10;
the molar ratio of the sulfydryl functionalized ionic liquid to the sulfonated acidic ionic liquid is 1: (20-80);
the preparation method of the ionic liquid catalyst system comprises the following steps: uniformly mixing the sulfonated acidic ionic liquid and the mercapto-functionalized ionic liquid to obtain the ionic liquid catalyst system;
the method for synthesizing bisphenol A comprises the following steps: s101: uniformly mixing phenol and acetone according to a preset molar ratio to obtain a reaction mixed solution; then adding the ionic liquid catalyst system, and stirring for a preset time at a preset temperature; s102: separating the product obtained in the step S101, and then dehydrating, crystallizing, washing, filtering, melting and crystallizing to obtain a target product bisphenol A;
in S102, before separating the product obtained in S101, the method further includes: standing and layering the product obtained in the step S101 to obtain ionic liquid and a bisphenol A primary product; using an ionic liquid as a raw material of an ionic liquid catalyst system in S101, and separating a bisphenol A primary product as a raw material in S102;
in S101, the molar ratio of the phenol to the acetone is (8-1): 1; the molar ratio of the phenol to the sulfonated acidic ionic liquid in the ionic liquid catalyst system is 1: (0.15-3).
2. The process for the synthesis of bisphenol a of claim 1, wherein:
in the step S101, the preset temperature is 30-100 ℃, and the preset time is 2-8 h.
3. The process for the synthesis of bisphenol a of claim 2, wherein:
in the step S101, the preset temperature is 60-80 ℃, and the preset time is 3-5 h.
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