CN113101979B - Lewis acid promoted compound protonic acid and catalytic application thereof - Google Patents
Lewis acid promoted compound protonic acid and catalytic application thereof Download PDFInfo
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Abstract
The invention discloses a Lewis acid promoted compound protonic acid and catalytic application thereof, belonging to the fields of chemical materials and industry. Aiming at the defects of the traditional bisphenol F synthesis method, the invention provides a method for synthesizing bisphenol F by using phosphoric acid/lithium fluoride/perchloric acid/potassium trifluoromethanesulfonate as a compound catalyst, wherein the mass ratio of the phosphoric acid/lithium fluoride/perchloric acid/potassium trifluoromethanesulfonate is 30-60: 1-5: 1-3: 1. the catalyst is used in the reaction for synthesizing bisphenol F, has good catalytic effect, higher conversion rate and selectivity and higher selectivity to 4, 4-dihydroxy diphenylmethane. Meanwhile, the catalytic system can also be used for synthesizing bisphenol A, and is particularly effective for synthesizing an industrially important industrial product, namely n-butyl acetate.
Description
Technical Field
The invention relates to a Lewis acid promoted compound protonic acid and catalytic application thereof, belonging to the fields of chemical materials and industry.
Background
Bisphenol F is chemically named dihydroxy diphenylmethane, and currently, the industrial production of bisphenol F generally adopts phenol and formaldehyde as raw materials and is obtained by condensation reaction in the presence of an acid catalyst. It is mainly composed of three isomers of dihydroxy diphenyl methane, and is mainly used as low-viscosity epoxy resin, special polyester raw material and information recording paper additive, etc. Among them, 4-dihydroxydiphenylmethane, which is the most excellent in performance, is used as a raw material for Polycarbonate (PC) resins, but a process for separately synthesizing 4, 4-dihydroxydiphenylmethane has not been studied so far.
The selection of the catalyst is one of the important process conditions in the bisphenol F synthesis process. The traditional catalyst uses Lewis acid (AlCl)3，FeCl3，TiCl4，BF3Etc.) and protonic acids (HF, H)2SO4HCl). However, these catalysts have some disadvantages such as poor selectivity and side effectsThe method has the advantages of more reactions, low yield, strong corrosivity, difficult product separation, serious environmental pollution and the like, so that the development of green and environment-friendly catalysts is concerned by many researchers. In order to solve these problems, many studies have been reported in recent years at home and abroad, and the research has been focused on catalysts, and different kinds of catalysts have been tried to improve selectivity, yield, recoverability and service life of the acylation reaction.
The phenol and formaldehyde are catalyzed by inorganic acids including phosphoric acid, sulfuric acid, hydrochloric acid and the like to synthesize the bisphenol F, the reaction has stronger acidity, rapid reaction, obvious conversion trend towards the direction of generating the phenolic resin, and higher conversion rate and selectivity. The reaction is controlled by adjusting the ratio of the raw material phenolic aldehyde, and the catalyst shows better catalytic performance. The trifluoromethanesulfonate is a Lewis solid super acid, and high acid strength and large acid amount are determinants for catalyzing the benzene and toluylation reaction; furthermore, the introduction of-CF into the compound3The group has strong electronegativity, high stability and lipophilicity, so that the catalyst has high activity, high stability and good moisture resistance, and is an efficient, stable and environment-friendly catalyst.
However, the problems of low catalytic activity and relatively low selectivity of bisphenol F and 4, 4-dihydroxydiphenylmethane still exist in the current bisphenol F synthesis process.
Disclosure of Invention
Aiming at the defects of the traditional bisphenol F synthesis method, the invention provides a very convenient and simple method for synthesizing bisphenol F, and phosphoric acid/perchloric acid/potassium trifluoromethanesulfonate/lithium fluoride is used as a compound catalyst. Experiments show that the proportion of the compound catalyst (Lewis acid-promoted compound protonic acid) has great influence on the reaction. Two strategies are mainly adopted: 1) the trifluoromethanesulfonate is a Lewis strong acid and is beneficial to the reaction; 2) lithium fluoride is a Lewis acid with strong coordination capacity, and the coordination capacity of the catalyst is further enhanced by introducing the trifluoromethanesulfonate and the lithium fluoride, so that the reaction effect is enhanced. And the catalyst has good catalytic effect when being used in the reaction for synthesizing the bisphenol F. Meanwhile, the catalytic system can also be used for the synthesis of bisphenol A. Further research shows that the catalyst is especially effective for the synthesis of industrially important industrial products of the n-butyl acetate, and particularly for the mass synthesis of the n-butyl acetate, higher yield and chemical selectivity as high as 99 percent can be still obtained under the condition that the catalyst is less used.
Firstly, the first purpose of the invention is to provide a Lewis acid promoted compound protonic acid catalyst, which comprises phosphoric acid, lithium fluoride, perchloric acid and potassium trifluoromethanesulfonate, wherein the mass ratio of the four is 30-60: 1-5: 1-3: 1.
the second purpose of the invention is to provide a preparation method of the Lewis acid promoted compound protonic acid catalyst, which comprises the following steps: mixing phosphoric acid, lithium fluoride, perchloric acid and potassium trifluoromethanesulfonate together according to a certain mass ratio, stirring for 10min-2h, and finally mixing to obtain the catalyst.
The third purpose of the invention is to provide a method for catalyzing the reaction for synthesizing bisphenol F, wherein the Lewis acid promoted compound protonic acid catalyst is used as a catalyst.
In one embodiment of the present invention, the method for the catalytic synthesis of bisphenol F specifically comprises: firstly, adding phenol into a reaction container, taking methylbenzene as a solvent, heating until the phenol is completely dissolved, adding the Lewis acid promoted compound protonic acid catalyst into the reaction container under the condition of stirring, and then mixing the Lewis acid promoted compound protonic acid catalyst with the phenol according to the ratio of 1: adding formaldehyde into a reaction container according to the mass ratio of 6-10, reacting for 2-12 h at 40-90 ℃, adding the reaction solution after the reaction is finished, adjusting the pH value of the reaction solution to 5-6, collecting an organic phase, and recrystallizing to obtain the bisphenol F.
In one embodiment of the present invention, the reaction vessel is a four-neck flask.
In one embodiment of the present invention, it was found experimentally that the mixed solution gradually became cloudy as formaldehyde was added dropwise.
In one embodiment of the present invention, after the reaction is completed, the aqueous-oily layer is separated from the reaction mixture liquid while it is hot.
In one embodiment of the invention, sodium bicarbonate is added to adjust the pH after the reaction is complete.
In one embodiment of the present invention, the solvent is recovered by rotary evaporation, the residual phenol that has not reacted is recovered by reduced pressure distillation, and after the distillation is completed, the residual product is recovered and the solvent is recrystallized to obtain pure white leafy crystal bisphenol F.
The fourth purpose of the invention is to provide a method for catalytically synthesizing bisphenol A, which takes the Lewis acid promoted compound protonic acid catalyst as a catalyst.
In one embodiment of the present invention, the method for catalytically synthesizing bisphenol a specifically comprises: firstly, adding phenol into a reaction container, adding toluene as a solvent, heating until the phenol is completely dissolved, adding the Lewis acid promoted compound protonic acid catalyst into the reaction container under the condition of stirring, and then mixing the Lewis acid promoted compound protonic acid catalyst with the phenol according to the ratio of 1: adding acetone into a reaction container according to the mass ratio of 6-10, reacting for 15-30 h at 60-80 ℃, adding the mixture after the reaction is finished, adjusting the pH of the reaction solution to 5-6, collecting an organic phase, and recrystallizing to obtain the bisphenol F.
The fifth purpose of the invention is to provide a method for catalytically synthesizing n-butyl acetate, which takes the Lewis acid-promoted compound protonic acid catalyst as a catalyst.
In one embodiment of the present invention, the method for catalytically synthesizing n-butyl acetate specifically comprises: adding the Lewis acid promoted compound protonic acid catalyst into a reaction container, adding glacial acetic acid and n-butyl alcohol into the reaction container according to the mass ratio of 1: 1-1.5, keeping the temperature of a reaction mixture at 60-70 ℃, reacting for 0.5-1.5 h after the dropwise adding is finished, cooling and separating liquid after the reaction is finished, collecting an organic phase, distilling and purifying to obtain a product, and collecting a product with the temperature of 124-.
Finally, the invention provides the application of the Lewis acid promoted compound protonic acid catalyst in the reaction of synthesizing bisphenol F, bisphenol A and n-butyl acetate.
Compared with the prior art, the invention has the following advantages and effects:
(1) the invention synthesizes the Lewis acid promoted complex protonic acid catalyst consisting of phosphoric acid/lithium fluoride/perchloric acid/potassium trifluoromethanesulfonate, and compared with the prior method, the catalyst has stronger catalytic efficiency and better selectivity.
(2) The Lewis acid promoted compound protonic acid catalyst synthesized by the method can be used for synthesizing bisphenol F, the condition for generating the bisphenol F by using the catalyst is mild, the yield of the catalytically synthesized bisphenol F is high, and the selectivity of the 4, 4-dihydroxy diphenylmethane is high.
(3) The Lewis acid promoted compound protonic acid catalyst synthesized by the method can be used for synthesizing bisphenol A, and has high selectivity which is up to 98 percent.
(4) The catalyst is especially effective for the synthesis of industrially important industrial products of n-butyl acetate, and particularly for the mass synthesis of the n-butyl acetate, under the condition that the catalyst is less used, higher yield and chemical selectivity as high as 99 percent can be still obtained.
Detailed Description
The calculation formula of the yield is as follows: yield-the actual mass of the target product obtained/theoretically 100% of the target product obtained.
The present invention is further described below with reference to examples, but the embodiments of the present invention are not limited thereto.
In the following, the applicant has made some specific experiments on the present invention, which show the synthesis steps of a phosphoric acid/lithium fluoride/perchloric acid/potassium trifluoromethanesulfonate compound catalyst, and also show the specific steps of using the catalyst to catalyze and synthesize bisphenol F. These are merely intended to be exhaustive of the invention and do not limit the scope of the invention in any way.
Example 1: catalytic reaction of phenol and formaldehyde to synthesize bisphenol F
Adding 10g of phenol into a four-neck flask, adding 50mL of toluene as a solvent, heating until the phenol is completely dissolved, mixing 20mL of 85% phosphoric acid, 1.5g of lithium fluoride, 1mL of perchloric acid and 0.8g of potassium trifluoromethane sulfonate together under constant stirring, stirring for 0.3h, adding the mixture into the four-neck flask, and adding 1.5g of formaldehyde into the four-neck flask dropwise. Keeping the temperature of the reaction mixture at 55 ℃, reacting for 6h, adding sodium bicarbonate after the reaction is finished until the pH of the reaction solution is 5-6, collecting an organic phase, performing rotary evaporation on the obtained crude product to recover the solvent, performing reduced pressure distillation to recover the residual phenol which is not reacted, and after the distillation is finished, recovering the solvent from the residual product to perform recrystallization, thus obtaining pure white leaf-shaped crystal bisphenol F.
As a result of calculation, the yield was 87%, and the selectivity for bisphenol F was 99%, wherein the selectivity for 4, 4-dihydroxydiphenylmethane was 72%.
Example 2: catalytic reaction of phenol and formaldehyde to synthesize bisphenol F
Adding 10g of phenol into a four-neck flask, adding 50mL of toluene as a solvent, heating until the phenol is completely dissolved, mixing 25mL of 85% phosphoric acid, 2g of lithium fluoride, 1mL of perchloric acid and 0.8g of potassium trifluoromethane sulfonate together under the condition of keeping uniform stirring, adding the mixture into the four-neck flask for 0.5h under stirring, and adding 1.5g of formaldehyde into the four-neck flask dropwise. And (3) keeping the temperature of the reaction mixture at 60 ℃, reacting for 6h, adding sodium bicarbonate until the pH of the reaction solution is 5-6 after the reaction is finished, collecting an organic phase, carrying out rotary evaporation on the obtained crude product to recover the solvent, carrying out reduced pressure distillation to recover the unreacted residual phenol, and after the distillation is finished, carrying out recrystallization on the residual product to recover the solvent, thus obtaining the pure white leafy crystal bisphenol F.
As a result of calculation, the yield was 89%, and the selectivity for bisphenol F was 99%, wherein the selectivity for 4, 4-dihydroxydiphenylmethane was 75%.
Example 3: catalytic reaction of phenol and formaldehyde to synthesize bisphenol F
Adding 10g of phenol into a four-neck flask, adding 50mL of toluene serving as a solvent, heating until the phenol is completely dissolved, mixing 30mL of 85% phosphoric acid, 2g of lithium fluoride, 1.5mL of perchloric acid and 1g of potassium trifluoromethane sulfonate together under constant stirring for 0.5h, adding the mixture into the four-neck flask, and adding 1g of formaldehyde into the four-neck flask dropwise. Keeping the temperature of the reaction mixture at 60 ℃, reacting for 6h, adding sodium bicarbonate after the reaction is finished until the pH of the reaction solution is 5-6, collecting an organic phase, performing rotary evaporation on the obtained crude product to recover the solvent, performing reduced pressure distillation to recover the residual phenol which is not reacted, and after the distillation is finished, recovering the solvent from the residual product to perform recrystallization, thus obtaining pure white leaf-shaped crystal bisphenol F.
As a result of calculation, the yield was 92%, and the selectivity for bisphenol F was 99%, with the selectivity for 4, 4-dihydroxydiphenylmethane being 74%.
Example 4: catalytic reaction of phenol and formaldehyde to synthesize bisphenol F
Adding 20g of phenol into a four-neck flask, adding 100mL of toluene as a solvent, heating until the phenol is completely dissolved, mixing 40mL of 85% phosphoric acid, 3g of lithium fluoride, 2mL of perchloric acid and 1.5g of potassium trifluoromethane sulfonate together under the condition of keeping uniform stirring, adding the mixture into the four-neck flask under stirring for 0.5h, and adding 2.5g of formaldehyde into the four-neck flask drop by drop. Keeping the temperature of the reaction mixture at 60 ℃, reacting for 6h, adding sodium bicarbonate after the reaction is finished until the pH of the reaction solution is 5-6, collecting an organic phase, performing rotary evaporation on the obtained crude product to recover the solvent, performing reduced pressure distillation to recover the residual phenol which is not reacted, and after the distillation is finished, recovering the solvent from the residual product to perform recrystallization, thus obtaining pure white leaf-shaped crystal bisphenol F.
As a result of calculation, the yield was 83%, and the selectivity for bisphenol F was 99%, wherein the selectivity for 4, 4-dihydroxydiphenylmethane was 70%.
Example 5: catalytic reaction of phenol and formaldehyde to synthesize bisphenol F
Adding 20g of phenol into a four-neck flask, adding 100mL of toluene as a solvent, heating until the phenol is completely dissolved, mixing 45mL of 85% phosphoric acid, 4g of lithium fluoride, 2mL of perchloric acid and 1.5g of potassium trifluoromethane sulfonate together under the condition of keeping uniform stirring, stirring for 1h, adding the mixture into the four-neck flask, and adding 2.5g of formaldehyde into the four-neck flask dropwise. Keeping the temperature of the reaction mixture at 65 ℃, reacting for 8h, adding sodium bicarbonate after the reaction is finished until the pH of the reaction solution is 5-6, collecting an organic phase, performing rotary evaporation on the obtained crude product to recover the solvent, performing reduced pressure distillation to recover the residual phenol which is not reacted, and after the distillation is finished, recovering the solvent from the residual product to perform recrystallization to obtain pure white phylliform crystals, namely bisphenol F.
As a result of calculation, the yield was 85%, and the selectivity for bisphenol F was 99%, with the selectivity for 4, 4-dihydroxydiphenylmethane being 74%.
Example 6: catalytic reaction of phenol and formaldehyde to synthesize bisphenol F
Adding 20g of phenol into a four-neck flask, adding 100mL of toluene as a solvent, heating until the phenol is completely dissolved, mixing 50mL of 85% phosphoric acid, 4.5g of lithium fluoride, 2.5mL of perchloric acid and 1.8g of potassium trifluoromethane sulfonate together under constant stirring for 1 hour, adding the mixture into the four-neck flask, and adding 2g of formaldehyde into the four-neck flask dropwise. And (3) keeping the temperature of the reaction mixture at 60 ℃, reacting for 12h, adding sodium bicarbonate until the pH of the reaction solution is 5-6 after the reaction is finished, collecting an organic phase, carrying out rotary evaporation on the obtained crude product to recover the solvent, carrying out reduced pressure distillation to recover the unreacted residual phenol, and after the distillation is finished, carrying out recrystallization on the residual product to recover the solvent, thus obtaining the pure white phylliform crystal bisphenol F.
As a result of calculation, the yield was 88%, and the selectivity for bisphenol F was 99%, with the selectivity for 4, 4-dihydroxydiphenylmethane being 72%.
Example 7: catalytic reaction of phenol and formaldehyde to synthesize bisphenol F
Adding 60g of phenol into a four-neck flask, adding 150mL of toluene as a solvent, heating until the phenol is completely dissolved, mixing 60mL of 85% phosphoric acid, 6g of lithium fluoride, 3mL of perchloric acid and 2.5g of potassium trifluoromethane sulfonate together under the condition of keeping uniform stirring, stirring for 1h, adding into the four-neck flask, and then dropwise adding 8g of formaldehyde into the four-neck flask. Keeping the temperature of the reaction mixture at 60 ℃, reacting for 6h, adding sodium bicarbonate after the reaction is finished until the pH of the reaction solution is 5-6, collecting an organic phase, performing rotary evaporation on the obtained crude product to recover the solvent, performing reduced pressure distillation to recover the residual phenol which is not reacted, and after the distillation is finished, recovering the solvent from the residual product to perform recrystallization, thus obtaining pure white leaf-shaped crystal bisphenol F.
The yield was 77% and the selectivity to bisphenol F was 99%, with a selectivity to 4, 4-dihydroxydiphenylmethane of 71%.
Example 8: catalytic reaction of phenol and formaldehyde to synthesize bisphenol F
Adding 60g of phenol into a four-neck flask, adding 150mL of toluene as a solvent, heating until the phenol is completely dissolved, mixing 60mL of 85% phosphoric acid, 6g of lithium fluoride, 4mL of perchloric acid and 3g of potassium trifluoromethanesulfonate together under the condition of keeping uniform stirring, stirring for 2 hours, adding into the four-neck flask, and then dropwise adding 8g of formaldehyde into the four-neck flask. Keeping the temperature of the reaction mixture at 60 ℃, reacting for 9 hours, adding sodium bicarbonate after the reaction is finished until the pH of the reaction solution is 5-6, collecting an organic phase, performing rotary evaporation on the obtained crude product to recover the solvent, performing reduced pressure distillation to recover the residual phenol which is not reacted, and after the distillation is finished, recovering the solvent from the residual product to perform recrystallization to obtain pure white phylliform crystals, namely bisphenol F.
As a result of calculation, the yield was 80%, and the selectivity for bisphenol F was 99%, with the selectivity for 4, 4-dihydroxydiphenylmethane being 69%.
Example 9: catalytic reaction of phenol and formaldehyde to synthesize bisphenol F
Adding 60g of phenol into a four-neck flask, adding 150mL of toluene as a solvent, heating until the phenol is completely dissolved, mixing 70mL of 85% phosphoric acid, 7g of lithium fluoride, 4mL of perchloric acid and 2.5g of potassium trifluoromethane sulfonate together under the condition of keeping uniform stirring, stirring for 2 hours, adding the mixture into the four-neck flask, and then dropwise adding 7g of formaldehyde into the four-neck flask. Keeping the temperature of the reaction mixture at 65 ℃, reacting for 9 hours, adding sodium bicarbonate after the reaction is finished until the pH of the reaction solution is 5-6, collecting an organic phase, performing rotary evaporation on the obtained crude product to recover the solvent, performing reduced pressure distillation to recover the residual phenol which is not reacted, and after the distillation is finished, recovering the solvent from the residual product to perform recrystallization to obtain pure white phylliform crystals, namely bisphenol F.
As a result of calculation, the yield was 84%, and the selectivity for bisphenol F was 99%, with the selectivity for 4, 4-dihydroxydiphenylmethane being 72%.
Example 10: catalytic reaction of phenol and acetone to synthesize bisphenol A
Adding 60g of phenol into a four-neck flask, adding 150mL of toluene as a solvent, heating until the phenol is completely dissolved, mixing 40mL of 85% phosphoric acid, 3g of lithium fluoride, 3mL of perchloric acid and 2g of potassium trifluoromethanesulfonate together under the condition of keeping uniform stirring, stirring for 2 hours, adding the mixture into the four-neck flask, and adding 10g of acetone into the four-neck flask dropwise. And (3) keeping the temperature of the reaction mixture at 80 ℃, reacting for 24h, adding sodium bicarbonate after the reaction is finished until the pH of the reaction solution is 5-6, collecting an organic phase, carrying out rotary evaporation on the obtained crude product to recover the solvent, carrying out reduced pressure distillation to recover the residual phenol which is not reacted, and after the distillation is finished, recovering the solvent from the residual product to recrystallize, thus obtaining the pure bisphenol A.
As a result of calculation, the yield was 64% and the selectivity to bisphenol A was 98%.
Example 11: catalytic reaction of phenol and acetone to synthesize bisphenol A
60g of phenol is placed in warm water at 65 ℃, 50mL of toluene is added and heated until the phenol is completely dissolved, 30mL of 85% phosphoric acid, 3g of lithium fluoride, 2mL of perchloric acid and 1.5g of potassium trifluoromethane sulfonate are mixed together and stirred for 2h while keeping uniform stirring, the mixture is added into a four-neck flask, and 10g of acetone is added into the four-neck flask dropwise. Keeping the temperature of the reaction mixture at 70 ℃, reacting for 18h, adding sodium bicarbonate after the reaction is finished until the pH of the reaction solution is 5-6, collecting an organic phase, performing rotary evaporation on the obtained crude product to recover the solvent, performing reduced pressure distillation to recover the residual phenol which is not reacted, and after the distillation is finished, recovering the solvent from the residual product to perform recrystallization to obtain the pure bisphenol A.
The yield was found to be 58% and the selectivity to bisphenol A was found to be 96%.
Example 12: catalytic synthesis of n-butyl acetate
2mL of 85% phosphoric acid, 0.2g of lithium fluoride, 0.15mL of perchloric acid, 0.1g of potassium trifluoromethanesulfonate were added to a round-bottomed flask, mixed together and stirred for 10 minutes, and 14mL of glacial acetic acid was added to the flask. And then, beginning to dropwise add 23mL of n-butanol to keep the temperature of the reaction mixture at 60 ℃, reacting for 0.5h after dropwise adding, cooling and separating liquid after the reaction is finished, collecting an organic phase, distilling and purifying to obtain a product, and collecting the product at the temperature of 124-126 ℃, namely n-butyl acetate.
The yield was calculated to be 74% and the selectivity of the product, n-butyl acetate, was 98% by gas chromatography.
Example 13: catalytic synthesis of n-butyl acetate
3mL of 85% phosphoric acid, 0.45g of lithium fluoride, 0.15mL of perchloric acid, 0.1g of potassium trifluoromethanesulfonate were added to a round-bottomed flask, mixed together and stirred for 10 minutes, and 72mL of glacial acetic acid were added to the flask. And then, dropwise adding 115mL of n-butanol to keep the temperature of the reaction mixture at 60 ℃, reacting for 1h after the dropwise adding is finished, cooling and separating the solution after the reaction is finished, collecting an organic phase, distilling and purifying to obtain a product, and collecting the product at 124-126 ℃, namely n-butyl acetate.
The yield was calculated to be 72% and the selectivity of the product, n-butyl acetate, as analyzed by gas chromatography, was 99%.
Example 14: catalytic synthesis of n-butyl acetate
5mL of 85% phosphoric acid, 1g of lithium fluoride, 0.3mL of perchloric acid, 0.2g of potassium trifluoromethanesulfonate were added to a round-bottom flask, mixed together and stirred for 20 minutes, and 360mL of glacial acetic acid were added to the flask. Then, 575mL of n-butanol is added dropwise to keep the temperature of the reaction mixture at 60 ℃, the reaction is carried out for 1h after the dropwise addition is finished, cooling and liquid separation are carried out after the reaction is finished, an organic phase is collected, a product is obtained by distillation and purification, and a product with the temperature of 124-126 ℃ is collected, namely n-butyl acetate.
The yield was calculated to be 86% and the selectivity of the product, n-butyl acetate, was 99% by gas chromatography.
Comparative example 1
10g of phenol is firstly added into a four-neck flask, 50mL of toluene is added as a solvent, the mixture is heated to 40 ℃ until the phenol is completely dissolved, 20mL of 85 percent phosphoric acid and 1.5g of lithium fluoride are mixed together and stirred for 0.3h under the condition of keeping uniform stirring, then the mixture is added into the four-neck flask, and 1.5g of formaldehyde is added into the four-neck flask drop by drop. Keeping the temperature of the reaction mixture at 55 ℃, reacting for 6h, adding sodium bicarbonate after the reaction is finished until the pH of the reaction solution is 5-6, collecting an organic phase, performing rotary evaporation on the obtained crude product to recover the solvent, performing reduced pressure distillation to recover the residual phenol which is not reacted, and after the distillation is finished, recovering the solvent from the residual product to perform recrystallization.
As a result of calculation, the yield was 41%, and the selectivity for bisphenol F was 61%, whereas the selectivity for 4, 4-dihydroxydiphenylmethane was 42%.
Comparative example 2
10g of phenol is added into a four-neck flask, 50mL of toluene is added as a solvent, the mixture is heated to 40 ℃ until the phenol is completely dissolved, 20mL of 85% phosphoric acid, 1.5g of lithium fluoride and 1mL of perchloric acid are mixed together and stirred for 0.3h under the condition of keeping uniform stirring, then the mixture is added into the four-neck flask, and 1.5g of formaldehyde is added into the four-neck flask dropwise. Keeping the temperature of the reaction mixture at 55 ℃, reacting for 6h, adding sodium bicarbonate after the reaction is finished until the pH of the reaction solution is 5-6, collecting an organic phase, performing rotary evaporation on the obtained crude product to recover the solvent, performing reduced pressure distillation to recover the residual phenol which is not reacted, and after the distillation is finished, recovering the solvent from the residual product to perform recrystallization, thus obtaining pure white leaf-shaped crystal bisphenol F.
The yield was calculated to be 61% and the selectivity to bisphenol F was 72%, with a selectivity to 4, 4-dihydroxydiphenylmethane of 56%.
Comparative example 3
Adding 10g of phenol into a four-neck flask, adding 50mL of toluene as a solvent, heating to 40 ℃ until the phenol is completely dissolved, mixing 10mL of 85% phosphoric acid, 0.5g of lithium fluoride, 1mL of perchloric acid and 0.8g of potassium trifluoromethanesulfonate together under the condition of keeping uniform stirring, stirring for 0.3h, adding the mixture into the four-neck flask, and dropwise adding 1.5g of formaldehyde into the four-neck flask. Keeping the temperature of the reaction mixture at 55 ℃, reacting for 6h, adding sodium bicarbonate after the reaction is finished until the pH of the reaction solution is 5-6, collecting an organic phase, performing rotary evaporation on the obtained crude product to recover the solvent, performing reduced pressure distillation to recover the residual phenol which is not reacted, and after the distillation is finished, recovering the solvent from the residual product to perform recrystallization, thus obtaining pure white leaf-shaped crystal bisphenol F.
As a result of calculation, the yield was 68%, and the selectivity for bisphenol F was 88%, with the selectivity for 4, 4-dihydroxydiphenylmethane being 62%.
Comparative example 4
Adding 60g of phenol into a four-neck flask, adding 150mL of toluene serving as a solvent, heating to 65 ℃ until the phenol is completely dissolved, starting to mix 40mL of 85% phosphoric acid and 3g of lithium fluoride together under stirring at a constant speed for 2 hours, adding the mixture into the four-neck flask, and adding 10g of acetone dropwise into the four-neck flask. And (3) keeping the temperature of the reaction mixture at 80 ℃, reacting for 24h, adding sodium bicarbonate after the reaction is finished until the pH of the reaction solution is 5-6, collecting an organic phase, carrying out rotary evaporation on the obtained crude product to recover the solvent, carrying out reduced pressure distillation to recover the residual phenol which is not reacted, and after the distillation is finished, recovering the solvent from the residual product to recrystallize, thus obtaining the pure bisphenol A.
The yield was calculated to be 52% and the selectivity to bisphenol A was 73%.
Comparative example 5
Adding 60g of phenol into a four-neck flask, adding 150mL of toluene as a solvent, heating until the phenol is completely dissolved, mixing 20mL of 85% phosphoric acid, 1g of lithium fluoride, 3mL of perchloric acid and 2g of potassium trifluoromethanesulfonate together under the condition of keeping uniform stirring, stirring for 2 hours, adding into the four-neck flask, and adding 10g of acetone into the four-neck flask dropwise. And (3) keeping the temperature of the reaction mixture at 80 ℃, reacting for 24h, adding sodium bicarbonate after the reaction is finished until the pH of the reaction solution is 5-6, collecting an organic phase, carrying out rotary evaporation on the obtained crude product to recover the solvent, carrying out reduced pressure distillation to recover the residual phenol which is not reacted, and after the distillation is finished, recovering the solvent from the residual product to recrystallize, thus obtaining the pure bisphenol A.
The yield was calculated to be 55% and the selectivity to bisphenol A was calculated to be 94%.
Comparative example 6
2mL of 85% phosphoric acid and 0.2g of lithium fluoride were added to a round bottom flask, mixed together and stirred for 10 minutes, and 14mL of glacial acetic acid was added to the flask. And then, beginning to dropwise add 23mL of n-butanol to keep the temperature of the reaction mixture at 60 ℃, reacting for 0.5h after dropwise adding, cooling and separating liquid after the reaction is finished, collecting an organic phase, distilling and purifying to obtain a product, and collecting the product at the temperature of 124-126 ℃, namely n-butyl acetate.
The yield was calculated to be 26% and the selectivity of the product, n-butyl acetate, by gas chromatography, was 87%.
Comparative example 7
1mL of 85% phosphoric acid, 0.1g of lithium fluoride, 0.1mL of perchloric acid, 0.15g of potassium trifluoromethanesulfonate were added to a round-bottomed flask, mixed together and stirred for 10 minutes, and 14mL of glacial acetic acid was added to the flask. And then, beginning to dropwise add 23mL of n-butanol to keep the temperature of the reaction mixture at 60 ℃, reacting for 0.5h after dropwise adding, cooling and separating liquid after the reaction is finished, collecting an organic phase, distilling and purifying to obtain a product, and collecting the product at the temperature of 124-126 ℃, namely n-butyl acetate.
The yield was calculated to be 67% and the selectivity of the product, n-butyl acetate, by gas chromatography, was 95%.
The above comparative experiments clearly illustrate the importance of the compound catalyst, and particularly, the synergistic catalytic performance exists among four substances of the compound catalyst in which lithium is used as a Lewis acid capable of catalyzing reaction, so that the catalytic performance of the compound catalyst is greatly improved.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (9)
1. A Lewis acid promoted compound protonic acid catalyst for catalytically synthesizing bisphenol F, bisphenol A and n-butyl acetate is characterized by comprising phosphoric acid, lithium fluoride, perchloric acid and potassium trifluoromethanesulfonate, wherein the mass ratio of the four components is 30-60: 2-5: 1: 1;
the preparation method comprises the following steps: mixing phosphoric acid, lithium fluoride, perchloric acid and potassium trifluoromethanesulfonate together according to the mass ratio, and stirring for 10min-2h to obtain the catalyst.
2. A method for catalyzing the reaction for synthesizing bisphenol F, characterized in that the Lewis acid-promoted complex protonic acid catalyst of claim 1 is used as a catalyst.
3. The method of claim 2, wherein the method comprises: firstly, adding phenol into a reaction vessel, taking toluene as a solvent, heating until the phenol is completely dissolved, adding the Lewis acid promoted complex protonic acid catalyst into the reaction vessel according to the proportion of 1: adding formaldehyde into a reaction container according to the mass ratio of 6-10, reacting for 2-12 h at 40-90 ℃, adjusting the pH of a reaction solution to be 5-6 after the reaction is finished, collecting an organic phase, and recrystallizing to obtain the bisphenol F.
4. The method of claim 3, wherein the pH is adjusted by adding sodium bicarbonate after the reaction is completed.
5. A process for the catalytic synthesis of bisphenol a, characterized in that a Lewis acid promoted built-up protonic acid catalyst according to claim 1 is used as catalyst.
6. The method of claim 5, wherein the method comprises: adding phenol into a reaction vessel, adding toluene as a solvent, heating until the phenol is completely dissolved, adding the Lewis acid promoted complex protonic acid catalyst into the reaction vessel under the condition of stirring, and adding the Lewis acid promoted complex protonic acid catalyst into the reaction vessel according to the ratio of 1: adding acetone into a reaction container according to the mass ratio of 6-10, reacting for 15-30 h at 60-80 ℃, adjusting the pH of a reaction solution to be 5-6 after the reaction is finished, collecting an organic phase, and recrystallizing to obtain the bisphenol A.
7. A process for the catalytic synthesis of n-butyl acetate, characterized in that a Lewis acid-promoted built protonic acid catalyst as claimed in claim 1 is used as catalyst.
8. The method for catalytically synthesizing n-butyl acetate according to claim 7, wherein the method for catalytically synthesizing n-butyl acetate comprises: adding the Lewis acid promoted compound protonic acid catalyst into a reaction container, adding glacial acetic acid and n-butyl alcohol into the reaction container according to the mass ratio of 1: 1-1.5, keeping the temperature of a reaction mixture at 60-70 ℃, reacting for 0.5-1.5 h after the dropwise adding is finished, cooling and separating liquid after the reaction is finished, collecting an organic phase, distilling and purifying to obtain a product, and collecting a product with the temperature of 124-.
9. The use of a Lewis acid promoted complex protonic acid catalyst of claim 1 in the synthesis of bisphenol F, bisphenol A and n-butyl acetate.
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| US5169992A (en) * | 1992-04-20 | 1992-12-08 | Texaco Chemical Company | Bisphenol A production using acidic clay catalysts |
| JP3351065B2 (en) * | 1993-10-29 | 2002-11-25 | 日本メクトロン株式会社 | Method for producing 2,2-diphenylhexafluoropropanes |
| DE10353934A1 (en) * | 2003-11-18 | 2005-06-23 | Sasol Germany Gmbh | Process for the preparation of metal salts of trifluoromethanesulfonic acid and their use as esterification catalysts |
| CN103319314B (en) * | 2013-06-09 | 2015-10-28 | 陕西师范大学 | The synthetic method of Bisphenol F under salt bath system |
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| CN104447217A (en) * | 2014-12-05 | 2015-03-25 | 四川东材绝缘技术有限公司 | Synthesis method of 4,4-bisphenol F |
| CN105461522A (en) * | 2015-11-06 | 2016-04-06 | 江南大学 | Novel bisphenol F and preparation method thereof |
| KR102215078B1 (en) * | 2016-07-12 | 2021-02-15 | 사빅 글로벌 테크놀러지스 비.브이. | Preparation of bisphenol A |
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