CN115010718A - Method for preparing isosorbide by dehydrating sorbitol under catalysis of polymeric ionic liquid - Google Patents
Method for preparing isosorbide by dehydrating sorbitol under catalysis of polymeric ionic liquid Download PDFInfo
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Abstract
The invention discloses a method for preparing isosorbide by catalyzing sorbitol through polymerizing ionic liquid, and belongs to the field of catalytic chemistry and chemical engineering. The method comprises the following steps: heating solid sorbitol to be molten, adding polymeric ionic liquid serving as a catalyst into the molten sorbitol, and performing dehydration reaction to prepare the isosorbide. The method provided by the invention uses the polymeric ionic liquid as the catalyst, has the advantages of high yield of the isosorbide, good selectivity, simple and convenient operation and little pollution, and the yield of the isosorbide can reach 94%.
Description
Technical Field
The invention belongs to the field of catalytic chemistry and chemical engineering, and particularly relates to a method for preparing isosorbide by catalyzing sorbitol through polymeric ionic liquid.
Background
Sorbitol is a platform compound derived from carbohydrates and is widely found in many berries and fruits as a sweetener. Sorbitol can be prepared into a series of bio-based chemicals or materials with high added values through hydrogenolysis, polymerization, dehydration and other reactions. Among them, isosorbide is a product of secondary dehydration and cyclization of sorbitol, is an important novel bio-based chemical, and can be widely applied to the fields of food, cosmetics, medicines and the like.
At present, the domestic isosorbide production process mostly adopts processes such as liquid acid catalysis, reduced pressure distillation, organic solvent extraction crystallization and the like, the process is complex, the corrosion resistance requirement on reaction equipment is high, serious problems such as resource waste and environmental pollution are caused, and the production cost of isosorbide is high.
With the idea of green chemistry being in depth, an environment-friendly green high-efficiency reaction system is a development trend in the future. The solid acid overcomes the series defects of liquid acid, the surface of the solid acid can not only contain Bronsted acid but also contain Lewis acid, the acid has wide intensity distribution, and the solid acid has the characteristics of easy separation from a liquid phase reaction system, no corrosion to equipment, simple post-treatment, little environmental pollution, high selectivity and the like, can be used in a higher temperature range, and expands the application range of acid catalytic reaction which can be possibly carried out thermodynamically. Patent CN110092795B discloses the use of SO 4 2- /ZrO 2 -Al 2 O 3 The highest yield of the isosorbide is 80 percent by the process of catalyzing sorbitol dehydration by type immobilized acid. Patent CN111253413B discloses that the yield of isosorbide obtained by dehydration of sorbitol catalyzed by acidic niobium pentoxide can reach more than 85%. The further improvement of the yield of the isosorbide can effectively reduce side reactions, simplify the separation and purification process and reduce the production cost, so the development of the high-efficiency catalyst is always a research hotspot.
The polymerized ionic liquid is a novel renewable ionic liquid, combines the characteristics of the ionic liquid and a polymer, has high thermal stability, adjustable form, corrosion resistance and the like, can be used as a catalyst or a catalyst carrier, and is an attractive catalytic material suitable for biomass resource utilization. The invention discloses a strong acid activated polymerization ionic liquid catalytic system aiming at the problem of low yield of isosorbide, and the catalyst is environment-friendly, does not corrode production equipment, and has higher catalytic efficiency for producing isosorbide by dehydrating sorbitol.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the invention aims to provide a method for preparing isosorbide by polymerizing ionic liquid catalytic sorbitol.
In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows:
a method for preparing isosorbide by dehydrating sorbitol under the catalysis of polymeric ionic liquid comprises the following specific steps: heating solid sorbitol to be molten, adding polymerization ionic liquid serving as a catalyst into the molten sorbitol, and performing dehydration reaction to prepare the isosorbide.
According to the above method, preferably, the addition amount of the polymeric ionic liquid is 0.1wt% to 20wt% of the mass of the solid sorbitol.
According to the method, the dehydration reaction temperature is preferably 110-160 ℃, the reaction pressure is-0.09 MPa, and the reaction time is preferably 2-10 h.
According to the above process, preferably, the polymeric ionic liquid is prepared by the following process:
(1) dissolving a C = C double-bond substituted imidazole monomer, 2-bromoethylamine hydrobromic acid and an initiator in a solvent, and reacting to obtain an aminated polymeric ionic liquid;
(2) weighing a proper amount of the polymeric ionic liquid obtained in the step (1), adding a metal salt solution into the polymeric ionic liquid, and stirring and reacting at the temperature of 20-80 ℃ for 1-4 hours to obtain a metal modified polymeric ionic liquid;
(3) and (3) adding an acid solution into the metal modified polymeric ionic liquid obtained in the step (2) for acidification, and removing the solvent to obtain the target polymeric ionic liquid.
According to the above method, preferably, in the step (1), the molar ratio of the C = C double bond substituted imidazole monomer to the 2-bromoethylamine hydrobromic acid is 1 to 10: 1.
according to the above method, preferably, the amount of the initiator used in step (1) is 2.7wt% of the C = C double bond substituted imidazole monomer.
According to the method, in the step (1), the reaction time is preferably 1-10 h, and the reaction temperature is preferably 60-100 ℃.
According to the above method, preferably, the C = C double bond substituted imidazole monomer in step (1) is 1-vinylimidazole or N-allylimidazole, and the initiator is azobisisobutyronitrile AIBN.
According to the above method, more preferably, the C = C double bond substituted imidazole monomer in step (1) is 1-vinylimidazole.
According to the above method, preferably, the metal salt solution in the step (2) is KNbO 3 Solutions or KTaO 3 Any one of the solutions.
According to the above process, more preferably, the metal salt solution in the step (2) is KNbO 3 And (3) solution.
According to the above method, preferably, the specific operation of acidification in step (3) is: and (3) adding an acid solution with the concentration of 1-10 mol/L into the metal modified polymeric ionic liquid obtained in the step (2), and stirring and acidifying at 40 ℃ for 4-8 h.
According to the above method, more preferably, the volume ratio of the metal-modified polymeric ionic liquid to the acid solution is 2: 1.
according to the above method, preferably, the acid solution is any one of sulfuric acid, phosphoric acid, nitric acid or hydrochloric acid.
According to the above method, more preferably, the acid solution is any one of sulfuric acid and phosphoric acid.
Compared with the prior art, the invention has the following beneficial effects:
1. the method adopts the polymerization ionic liquid activated by strong acid as a catalyst, adopts sorbitol as a raw material, directly prepares the isosorbide through dehydration reaction under the conditions of no solvent and vacuum, and has the advantages of high yield of the isosorbide, good selectivity, simple and convenient operation and little pollution, and the yield of the isosorbide can reach 94%. The adopted catalyst is a long-chain polymer, has larger anion and cation molecular weight than the conventional ionic liquid, is easier to separate from a product, and can be repeatedly used.
2. The addition amount of the polymeric ionic liquid in the method provided by the invention is 0.1-20 wt% of the mass of the solid sorbitol, compared with the existing preparation method, the dosage of the catalyst is greatly reduced, and the cost is saved.
3. The catalyst adopted by the invention is a modified ionic liquid polymer, a chain monomer is firstly subjected to amino modification to form chemical combination with carbonyl and hydroxyl in reactant molecules, and then is mixed with a metal salt solution, and the metal center is taken as an active site to adjust the surface acid property, so that the aim of improving the catalytic performance of the catalyst is fulfilled. Therefore, the catalyst prepared by the invention can more effectively grab reactant molecules, improve the diffusion rate and the reaction rate of the sorbitol and improve the economic benefit of the process for preparing the isosorbide.
Drawings
FIG. 1 is a graph of sorbitol conversion over time for the reaction;
FIG. 2 is a graph showing the change in yield of 1, 4-sorbitan as an intermediate of the reaction with time;
FIG. 3 is a graph showing the change of isosorbide yield with time in the reaction.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the scope of the invention.
Example 1:
a method for preparing isosorbide by dehydrating sorbitol under the catalysis of polymeric ionic liquid comprises the following specific steps:
(1) 3.0336 g of 1-vinyl imidazole, 0.0808 g of initiator AIBN and 4.3600 g of 2-bromoethylamine hydrobromide are dissolved in 40 mL of absolute ethyl alcohol, the mixture is stirred and condensed and refluxed for 4 hours at 80 ℃ under the protection of nitrogen, the solution becomes orange yellow and yellow solid appears at the bottom, and the orange yellow solid, namely the aminated polyvinyl imidazole [ VIM ], is obtained after the reaction liquid is dried]NH 2 ；
(2) Weighing 1.4 g of aminated polyvinyl imidazole [ VIM ] obtained in step (1)]NH 2 Adding 100 mL KNbO into the three-necked bottle 3 Completely dissolving the solution, and stirring and reacting at 40 ℃ for 4 hours to obtain the metal modified polymeric ionic liquid Nb/[ VIM]NH 2 ；
(3) Adding 3 mol/L sulfuric acid solution (volume ratio is 2: 1) into the metal modified polymeric ionic liquid obtained in the step (2), stirring and acidifying for 4 hours at 40 ℃, and evaporating excessive water to obtain the acidic polymeric ionic liquid catalyst 3H-Nb/[ VIM ]]NH 2 ；
(4) Weighing 5g solid sorbitol in a reactor, heating to liquid state at 120 deg.C, adding 0.5 g 3H-Nb/[ VIM ]]NH 2 And (3) stirring the catalyst under the condition that the pressure is-0.09 MPa for reacting for 6 hours, and continuously measuring the materials in the reaction system at certain time intervals in the reaction process, wherein the result is shown in a figure 1-3.
Example 2:
a method for preparing isosorbide by dehydrating sorbitol under the catalysis of polymeric ionic liquid comprises the following specific steps:
(1) 3.0336 g of 1-vinyl imidazole, 0.0808 g of initiator AIBN and 4.3600 g of 2-bromoethylamine hydrobromide are dissolved in 40 mL of absolute ethyl alcohol, the mixture is stirred and condensed and refluxed for 4 hours at 80 ℃ under the protection of nitrogen, the solution becomes orange yellow and yellow solid appears at the bottom, and the orange yellow solid, namely the aminated polyvinyl imidazole [ VIM ], is obtained after the reaction liquid is dried]NH 2 ；
(2) Weighing 1.4 g of aminated polyvinyl imidazole [ VIM ] obtained in step (1)]NH 2 Adding 100 mL KNbO into the three-necked bottle 3 Completely dissolving the solution, and stirring and reacting at 40 ℃ for 4 hours to obtain the metal modified polymeric ionic liquid Nb/[ VIM]NH 2 ；
(3) Adding 3 mol/L sulfuric acid solution (volume ratio is 2: 1) into the metal modified polymeric ionic liquid obtained in the step (2), stirring and acidifying for 4 hours at 40 ℃, and evaporating excessive water to obtain the acidic polymeric ionic liquid catalyst 3H-Nb/[ VIM ]]NH 2 ；
(4) Weighing 5g solid sorbitol in a reactor, heating to liquid state at 130 deg.C, adding 0.5 g 3H-Nb/[ VIM ]]NH 2 The catalyst is stirred and reacts for 2 hours under the condition that the pressure is-0.09 MPa, and materials in a reaction system are continuously reacted at certain time intervals in the reaction processThe results of the measurements are shown in FIGS. 1 to 3.
Example 3:
a method for preparing isosorbide by dehydrating sorbitol under the catalysis of polymeric ionic liquid comprises the following specific steps:
(1) 3.0336 g of 1-vinyl imidazole, 0.0808 g of initiator AIBN and 4.3600 g of 2-bromoethylamine hydrobromide are dissolved in 40 mL of absolute ethyl alcohol, the mixture is stirred and condensed and refluxed for 4 hours at 80 ℃ under the protection of nitrogen, the solution becomes orange yellow and yellow solid appears at the bottom, and the orange yellow solid, namely the aminated polyvinyl imidazole [ VIM ], is obtained after the reaction liquid is dried]NH 2 ；
(2) Weighing 1.4 g of aminated polyvinyl imidazole [ VIM ] obtained in step (1)]NH 2 Adding 100 mL KNbO into the three-necked bottle 3 Completely dissolving the solution, and stirring and reacting at 40 ℃ for 4 hours to obtain the metal modified polymeric ionic liquid Nb/[ VIM]NH 2 ；
(3) Adding 3 mol/L sulfuric acid solution (volume ratio is 2: 1) into the metal modified polymeric ionic liquid obtained in the step (2), stirring and acidifying for 4 hours at 40 ℃, and evaporating excessive water to obtain the acidic polymeric ionic liquid catalyst 3H-Nb/[ VIM ]]NH 2 ；
(4) Weighing 5g solid sorbitol in a reactor, heating to liquid state at 140 deg.C, adding 0.5 g 3H-Nb/[ VIM ]]NH 2 And (3) stirring the catalyst under the pressure of-0.09 MPa for reacting for 1.25 h, and continuously measuring the materials in the reaction system at certain intervals in the reaction process, wherein the results are shown in the figure 1-3.
And (3) gas chromatography detection:
the reaction processes of examples 1 to 3 were subjected to gas chromatography, and the sorbitol conversion rate and the yield of intermediate 1, 4-sorbitan and isosorbide as changes with time are shown in fig. 1 to 3.
As can be seen from FIG. 1, the sorbitol conversion rate can reach 100% within the temperature range of 120-140 ℃, and the sorbitol conversion rate can reach 100% after the reaction is carried out for 1.25 h at the temperature of 140 ℃.
As can be seen from FIG. 2, at 120 ℃ the yield of 1, 4-sorbitan as an intermediate increases and then decreases, because sorbitol rapidly undergoes a dehydration reaction, the intermediate rapidly accumulates in a short time, and the yield increases. The intermediate is then converted to isosorbide with a consequent reduction in yield. While at temperatures of 130 ℃ and 140 ℃, the yield of the intermediate product 1, 4-sorbitan gradually decreases.
As can be seen from FIG. 3, the yield of isosorbide increases gradually with time at a temperature of 120 ℃ with a maximum yield of 39%. The highest yield of isosorbide is 78% at a temperature of 130 ℃. At a temperature of 140 ℃, the yield of isosorbide increases and then decreases with time, because in a high-temperature, strongly acidic catalytic system, side reactions are severe and the resulting isosorbide undergoes further dehydration and polymerization reactions. The highest yield of isosorbide is 94% at a temperature of 140 ℃.
Example 4:
a method for preparing isosorbide by dehydrating sorbitol under the catalysis of polymeric ionic liquid comprises the following specific steps:
(1) 3.0336 g of 1-vinyl imidazole, 0.0808 g of initiator AIBN and 4.3600 g of 2-bromoethylamine hydrobromide are dissolved in 40 mL of absolute ethyl alcohol, the mixture is stirred and condensed and refluxed for 4 hours at 80 ℃ under the protection of nitrogen, the solution becomes orange yellow and yellow solid appears at the bottom, and the orange yellow solid, namely the aminated polyvinyl imidazole [ VIM ], is obtained after the reaction liquid is dried]NH 2 ；
(2) Weighing 1.4 g of aminated polyvinyl imidazole [ VIM ] obtained in step (1)]NH 2 Adding 100 mL KNbO into the three-necked bottle 3 Completely dissolving the solution, and stirring and reacting at 40 ℃ for 4 hours to obtain the metal modified polymeric ionic liquid Nb/[ VIM]NH 2 ；
(3) Adding 2 mol/L sulfuric acid solution (volume ratio is 2: 1) into the metal modified polymeric ionic liquid obtained in the step (2), stirring and acidifying for 4 hours at 40 ℃, and evaporating excessive water to obtain an acidic polymeric ionic liquid catalyst 2H-Nb/[ VIM ]]NH 2 ；
(4) Weighing 5g solid sorbitol in a reactor, heating to liquid state at 140 deg.C, adding 0.5 g 2H-Nb/[ VIM ]]NH 2 The catalyst is stirred and reacts for 2 hours under the condition that the pressure is-0.09 MPa, and materials in a reaction system are continuously reacted at certain time intervals in the reaction processAccording to gas chromatography test, the highest yield of the isosorbide is 74 percent according to the detection result of the gas chromatography.
Example 5:
a method for preparing isosorbide by catalyzing sorbitol to dehydrate through polymeric ionic liquid comprises the following specific steps:
(1) 3.0336 g of 1-vinyl imidazole, 0.0808 g of initiator AIBN and 4.3600 g of 2-bromoethylamine hydrobromide are dissolved in 40 mL of absolute ethyl alcohol, the mixture is stirred and condensed and refluxed for 4 hours at 80 ℃ under the protection of nitrogen, the solution becomes orange yellow and yellow solid appears at the bottom, and the orange yellow solid, namely the aminated polyvinyl imidazole [ VIM ], is obtained after the reaction liquid is dried]NH 2 ；
(2) Weighing 1.4 g of aminated polyvinyl imidazole [ VIM ] obtained in step (1)]NH 2 Adding 100 mL KNbO into the three-necked bottle 3 Completely dissolving the solution, and stirring and reacting at 40 ℃ for 4 hours to obtain the metal modified polymeric ionic liquid Nb/[ VIM]NH 2 ；
(3) Adding 1 mol/L sulfuric acid solution (volume ratio is 2: 1) into the metal modified polymeric ionic liquid obtained in the step (2), stirring and acidifying at 40 ℃ for 4 hours, and evaporating excess water to obtain an acidic polymeric ionic liquid catalyst 1H-Nb/[ VIM ]]NH 2 ；
(4) Weighing 5g solid sorbitol in a reactor, heating to liquid state at 140 deg.C, adding 0.5 g 1H-Nb/[ VIM ]]NH 2 And (3) stirring the catalyst under the pressure of-0.09 MPa for reacting for 2 hours, and continuously reacting the materials in the reaction system at certain time intervals in the reaction process, wherein the gas chromatography detection result shows that the highest yield of the isosorbide is 61%.
Example 6:
a method for preparing isosorbide by dehydrating sorbitol under the catalysis of polymeric ionic liquid comprises the following specific steps:
(1) 3.0336 g of 1-vinyl imidazole, 0.0808 g of initiator AIBN and 4.3600 g of 2-bromoethylamine hydrobromide are dissolved in 40 mL of absolute ethyl alcohol, the mixture is stirred and condensed and refluxed for 4 hours at 80 ℃ under the protection of nitrogen, the solution becomes orange yellow and yellow solid appears at the bottom, and the orange yellow solid, namely the aminated polyvinyl imidazole [ VIM ], is obtained after the reaction liquid is dried]NH 2 ；
(2) Weighing 1.4 g of aminated polyvinyl imidazole [ VIM ] obtained in step (1)]NH 2 Adding 100 mL KNbO into the three-necked bottle 3 Completely dissolving the solution, and stirring and reacting at 40 ℃ for 4 hours to obtain the metal modified polymeric ionic liquid Nb/[ VIM]NH 2 ；
(3) Adding 3 mol/L phosphoric acid solution (volume ratio is 2: 1) into the metal modified polymeric ionic liquid obtained in the step (2), stirring and acidifying for 4 hours at 40 ℃, and evaporating excessive water to obtain the acidic polymeric ionic liquid catalyst 3H-Nb/[ VIM ]]NH 2 ；
(4) Weighing 5g solid sorbitol in a reactor, heating to liquid state at 120 deg.C, adding 0.5 g 3H-Nb/[ VIM ]]NH 2 And (3) stirring the catalyst under the pressure of-0.09 MPa for reaction for 2 hours, and continuously reacting the materials in the reaction system at intervals in the reaction process, wherein the gas chromatography detection result shows that the highest yield of the isosorbide is 58%.
The above embodiments are specific embodiments of the present invention, but the embodiments of the present invention are not limited by the above embodiments, and any other combinations, changes, modifications, substitutions, and simplifications without departing from the design concept of the present invention fall within the protection scope of the present invention.
Claims (10)
1. A method for preparing isosorbide by dehydrating sorbitol under the catalysis of polymeric ionic liquid is characterized in that solid sorbitol is heated to be molten, and then polymeric ionic liquid is added into the molten sorbitol to be used as a catalyst to carry out dehydration reaction to prepare isosorbide.
2. The method according to claim 1, wherein the polymeric ionic liquid is added in an amount of 0.1 to 20wt% based on the mass of the solid sorbitol.
3. The method according to claim 1, wherein the temperature of the dehydration reaction is 110 to 160 ℃.
4. The method according to claim 1, wherein the pressure of the dehydration reaction is-0.09 MPa, and the reaction time is 2-10 h.
5. The method of claim 1, wherein the polymerized ionic liquid is prepared by:
(1) dissolving a C = C double-bond substituted imidazole monomer, 2-bromoethylamine hydrobromic acid and an initiator in a solvent, and reacting to obtain an aminated polymeric ionic liquid;
(2) adding a metal salt solution into the polymerized ionic liquid obtained in the step (1), and stirring and reacting for 1-4 h at the temperature of 20-80 ℃ to obtain a metal modified polymerized ionic liquid;
(3) and (3) adding an acid solution into the metal modified polymeric ionic liquid obtained in the step (2) for acidification, and removing the solvent to obtain the target polymeric ionic liquid.
6. The method according to claim 5, wherein the molar ratio of the C = C double bond substituted imidazole monomer to the 2-bromoethylamine hydrobromic acid in the step (1) is 1-10: 1.
7. the method according to claim 5, wherein in the step (1), the reaction time is 1-10 h, and the reaction temperature is 60-100 ℃.
8. The method according to claim 5, wherein the C = C double bond-substituted imidazole monomer in step (1) is 1-vinylimidazole or N-allylimidazole, and the initiator is Azobisisobutyronitrile (AIBN).
9. The method according to any one of claims 5 to 8, wherein the acidifying in step (3) is carried out by: and (3) adding an acid solution with the concentration of 1-10 mol/L into the metal modified polymeric ionic liquid obtained in the step (2), and stirring and acidifying at 20-80 ℃ for 4-8 h.
10. The method according to any one of claims 1 to 9, wherein the step (2)Wherein the metal salt solution is KNbO 3 Solutions or KTaO 3 And (3) solution.
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