Quaternary ammonium salt ionic liquid catalyst for biether fluorene synthesis and preparation method thereof
The quaternary ammonium salt ionic liquid catalyst addresses the challenges of existing catalysts by providing a stable, low-corrosion, and recyclable solution for synthesizing bisether fluorene with improved efficiency and reduced environmental footprint.
Patent Information
- Application Number
- CN202411165420.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-08-23
- Publication Date
- 2024-12-31
AI Technical Summary
Existing catalysts for synthesizing bisether fluorene face issues such as high corrosion, environmental pollution, low yield, and difficulty in recycling, particularly with inorganic acids, organic acids, heteropolyacids, and strong acid cation exchange resins.
A quaternary ammonium salt ionic liquid catalyst is developed with a preparation method involving the reaction of a quaternary ammonium base compound with 1,3-propane sultone, followed by dissolution in an inorganic acid and deionized water, resulting in a catalyst with good fluidity, low volatility, and high acid site density, suitable for synthesizing bisether fluorene.
The catalyst exhibits good stability, low reaction temperature, and small dosage, improving conversion efficiency and yield while minimizing environmental impact and facilitating easy separation and recycling.
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of catalysts for synthesizing bisether fluorene, and in particular to a quaternary ammonium salt ionic liquid catalyst for synthesizing bisether fluorene and a preparation method thereof. Background Art
[0002] Bis(2-(4-phenylene)fluorene (BPEF) is a monomer raw material with good heat resistance and optical properties. It is mainly used in terminal fields such as mobile phone touch screens, high-end optical resin lenses, liquid crystal displays, camera lenses, drone lenses, and automotive lenses, and has good development prospects.
[0003] Synthesis mechanism of bisether fluorene: Using 9-fluorenone and phenoxyethanol as starting materials, crude bisether fluorene is synthesized under the catalysis of catalyst and co-catalyst, and then high-purity bisether fluorene is prepared by recrystallization.
[0004] The catalysts used in the traditional synthesis of bis(ether)fluorene can be divided into four categories: inorganic acids, organic acids, heteropolyacids and strong acid cation exchange resins; however, inorganic acid catalysts are highly corrosive to metal reactors, require large amounts of acid, are difficult to recycle, contain large amounts of methanol and sulfuric acid (hydrochloric acid) in the wastewater, are difficult to handle, and cause serious environmental pollution; among organic acids, mercaptosulfonic acid catalysts are expensive; heteropolyacid catalysts have low product yields and high catalyst prices; thermal stability and swelling are the main problems faced by strong acid cation exchange resin catalysts, and the large amount of catalyst required is also a disadvantage of the catalyst.
[0005] In view of this, the present invention is proposed. Summary of the invention
[0006] The purpose of the present invention is to provide a quaternary ammonium salt ionic liquid catalyst for bisether fluorene synthesis and a preparation method thereof. The catalyst of the present invention has the advantages of good fluidity, low volatility, and low corrosion to containers. In the process of catalyzing the synthesis of bisether fluorene, the catalyst has the characteristics of good stability, low reaction temperature, and small dosage. The catalyst can improve the conversion efficiency of bisether fluorene and has broad application prospects.
[0007] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are particularly adopted:
[0008] The first aspect of the present invention provides a method for preparing a quaternary ammonium salt ionic liquid catalyst for the synthesis of bisetherfluorene, the preparation method comprising the following steps:
[0009] (a) reacting a quaternary ammonium base compound with 1,3-propane sultone to obtain a precursor;
[0010] (b) dissolving the precursor in an inorganic acid and adding deionized water, and then heating and refluxing the mixture. After the reflux reaction is completed, the mixture is cooled and the water is removed by rotary evaporation, and then washed and dried to obtain the quaternary ammonium salt ionic liquid catalyst for the synthesis of bisetherfluorene.
[0011] Preferably, in step (a), the quaternary ammonium base compound is selected from at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, dodecyltrimethylammonium hydroxide, trioctylmethylammonium hydroxide, choline, acetylcholine, butyrylcholine, benzoylcholine and phosphatidylcholine.
[0012] Preferably, in step (a), the molar ratio of the quaternary ammonium base compound to 1,3-propane sultone is (1-1.2):1.
[0013] Preferably, in step (a), the reaction temperature is room temperature and the reaction time is 10 to 15 hours.
[0014] Preferably, in step (b), the inorganic acid consists of H2SO4, H3PO4 and HBF4;
[0015] The molar ratio of H2SO4, H3PO4 and HBF4 is (0.1~0.3):1:(2~3).
[0016] Preferably, in step (b), the mass volume ratio of the precursor to the inorganic acid is 1:(10-20);
[0017] The amount of deionized water added is 8% to 15% of the volume of the inorganic acid.
[0018] Preferably, in step (b), the reflux reaction temperature is 70-85° C. and the time is 6-8 h.
[0019] The second aspect of the present invention provides a quaternary ammonium salt ionic liquid catalyst for the synthesis of bisetherfluorene prepared by the above preparation method.
[0020] The third aspect of the present invention provides a method for synthesizing bisether fluorene, which comprises the following steps:
[0021] 9-fluorenone, phenoxyethanol, a solvent, thioglycolic acid and a quaternary ammonium salt ionic liquid catalyst for the synthesis of bisether fluorene prepared by any one of the preparation methods described in claims 1 to 7 are mixed, and heated under reflux reaction under stirring conditions. After the reaction is completed, the solvent is removed by rotary evaporation, vacuum drying is performed, and then filtering and low-temperature washing are performed to obtain bisether fluorene.
[0022] Preferably, the molar ratio of the quaternary ammonium salt ionic liquid catalyst, thioglycolic acid, 9-fluorenone, and phenoxyethanol used for the synthesis of bisetherfluorene is (0.02-0.10):0.002:(0.9-1.1):(2-3);
[0023] The reflux reaction temperature is 60-100°C and the time is 1-8h;
[0024] The solvent used for washing is acetone-toluene.
[0025] Compared with the prior art, the beneficial effects of the present invention include at least:
[0026] The quaternary ammonium salt ionic liquid catalyst for bisether fluorene synthesis of the present invention has a strong acid functional group in its structure and is in liquid state, so it has good fluidity, uniform acid strength distribution and high acid site density. In addition, the catalyst is easy to separate, has low volatility, does not corrode equipment, does not generate harmful gas, has little environmental pollution, has good recyclability, can be recycled for more than 5 times after simple treatment, and has no obvious decrease in activity. In addition, in the process of catalyzing the synthesis of bisether fluorene, the catalyst has the characteristics of good stability, low reaction temperature and small dosage, and can improve the conversion efficiency of bisether fluorene and improve the yield. DETAILED DESCRIPTION
[0027] The following embodiments of the technical solution of the present invention are described in detail in conjunction with the embodiments. The following embodiments are only used to more clearly illustrate the technical solution of the present invention, and are therefore only used as examples, and cannot be used to limit the protection scope of the present invention.
[0028] It should be noted that, unless otherwise specified, the technical terms or scientific terms used in this application should have the common meanings understood by those skilled in the art to which the present invention belongs.
[0029] The embodiment of the present invention provides a method for preparing a quaternary ammonium salt ionic liquid catalyst for the synthesis of bisetherfluorene, the preparation method comprising the following steps:
[0030] (a) reacting a quaternary ammonium base compound with 1,3-propane sultone to obtain a precursor;
[0031] (b) dissolving the precursor in an inorganic acid and adding deionized water, and then heating and refluxing the mixture. After the reflux reaction is completed, the mixture is cooled and the water is removed by rotary evaporation, and then washed and dried to obtain the quaternary ammonium salt ionic liquid catalyst for the synthesis of bisetherfluorene.
[0032] The quaternary ammonium salt ionic liquid catalyst for bisether fluorene synthesis of the present invention has a strong acid functional group in its structure and is in liquid state, so it has good fluidity, uniform acid strength distribution and high acid site density. In addition, the catalyst is easy to separate, has low volatility, does not corrode equipment, does not generate harmful gas, has little environmental pollution, has good recyclability, can be recycled for more than 5 times after simple treatment, and has no obvious decrease in activity. In addition, in the process of catalyzing the synthesis of bisether fluorene, the catalyst has the characteristics of good stability, low reaction temperature and small dosage, and can improve the conversion efficiency of bisether fluorene and improve the yield.
[0033] In one embodiment, in step (a), the quaternary ammonium base compound is selected from at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, dodecyltrimethylammonium hydroxide, trioctylmethylammonium hydroxide, choline, acetylcholine, butyrylcholine, benzoylcholine and phosphatidylcholine.
[0034] In one embodiment, in step (a), the molar ratio of the quaternary ammonium base compound to 1,3-propane sultone is (1-1.2):1.
[0035] In one embodiment, in step (a), the reaction temperature is room temperature and the reaction time is 10 to 15 hours.
[0036] In one embodiment, in step (b), the inorganic acid consists of H2SO4, H3PO4 and HBF4;
[0037] The molar ratio of H2SO4, H3PO4 and HBF4 is (0.1~0.3):1:(2~3).
[0038] In one embodiment, in step (b), the mass volume ratio of the precursor to the inorganic acid is 1:(10-20);
[0039] The amount of deionized water added is 8% to 15% of the volume of the inorganic acid.
[0040] In one embodiment, in the step (b), the reflux reaction temperature is 70-85° C. and the time is 6-8 hours.
[0041] Another embodiment of the present invention provides a quaternary ammonium salt ionic liquid catalyst for the synthesis of bisetherfluorene prepared by the above preparation method.
[0042] Another embodiment of the present invention provides a method for synthesizing bisether fluorene, the method comprising the following steps:
[0043] 9-fluorenone, phenoxyethanol, a solvent, thioglycolic acid and a quaternary ammonium salt ionic liquid catalyst for the synthesis of bisether fluorene prepared by any one of the preparation methods described in claims 1 to 7 are mixed, and heated under reflux reaction under stirring conditions. After the reaction is completed, the solvent is removed by rotary evaporation, vacuum drying is performed, and then filtering and low-temperature washing are performed to obtain bisether fluorene.
[0044] In one embodiment, the molar ratio of the quaternary ammonium salt ionic liquid catalyst, thioglycolic acid, 9-fluorenone, and phenoxyethanol used for the synthesis of bisetherfluorene is (0.02-0.10): 0.002: (0.9-1.1): (2-3);
[0045] The reflux reaction temperature is 60-100°C and the time is 1-8h;
[0046] The solvent used for washing is acetone-toluene.
[0047] The technical solution of the present invention is further described in detail below through specific embodiments.
[0048] Example 1
[0049] This embodiment is a method for preparing a quaternary ammonium salt ionic liquid catalyst for the synthesis of bisetherfluorene, and the preparation method comprises the following steps:
[0050] (a) First, 20 ml of methanol solution was added to a 100 ml round-bottom flask and marked as solution a. Then, 9 g of tetramethylammonium hydroxide and 10 g of 1,3-propane sultone were dissolved in 10 ml of methanol solution under stirring conditions and marked as solution b. The completely dissolved solution b was poured into solution a, refluxed at room temperature for 12 h and then filtered. The filter cake was washed three times with ether and vacuum dried to obtain the target white powder precursor with a yield of 52%;
[0051] (b) Prepare an inorganic acid with a molar ratio of H2SO4, H3PO4 and HBF4 of 0.2:1:2.5 for use; 3 g of the catalyst precursor is dissolved in 45 ml of the inorganic acid, 5 ml of deionized water is added, refluxed at 80°C for 7 h, naturally cooled to room temperature, the aqueous solution is removed by rotary evaporation, washed with ether and filtered three times, and vacuum dried at 120°C for 5 h to obtain a quaternary ammonium salt ionic liquid catalyst for the synthesis of bisetherfluorene.
[0052] Example 2
[0053] This embodiment is a method for preparing a quaternary ammonium salt ionic liquid catalyst for the synthesis of bisetherfluorene, and the preparation method comprises the following steps:
[0054] (a) First, 20 ml of methanol solution was added to a 100 ml round-bottom flask and marked as solution a. Then, 9 g of tetramethylammonium hydroxide and 10 g of 1,3-propane sultone were dissolved in 10 ml of methanol solution under stirring conditions and marked as solution b. The completely dissolved solution b was poured into solution a, refluxed at room temperature for 12 h and then filtered. The filter cake was washed three times with ether and vacuum dried to obtain the target white powder precursor with a yield of 52%;
[0055] (b) Prepare an inorganic acid with a molar ratio of H2SO4, H3PO4 and HBF4 of 0.2:1:2.5 for use; 3 g of the catalyst precursor is dissolved in 45 ml of the inorganic acid solution, 5 ml of deionized water is added, refluxed at 80°C for 3 h, naturally cooled to room temperature, and the aqueous solution is removed by rotary evaporation. The mixture is washed and filtered three times with ether, and vacuum dried at 120°C for 5 h to obtain a quaternary ammonium salt ionic liquid catalyst for the synthesis of bisetherfluorene.
[0056] Example 3
[0057] This embodiment is a method for synthesizing bisether fluorene, and the method for synthesizing bisether fluorene comprises the following steps:
[0058] In a 100mL reaction kettle, 30ml of solvent methanol, the quaternary ammonium salt ionic liquid catalyst for the synthesis of bisether fluorene in Example 1, mercaptoacetic acid, 9-fluorenone, and phenoxyethanol were added in sequence, wherein the molar ratio of the quaternary ammonium salt ionic liquid catalyst for the synthesis of bisether fluorene, mercaptoethanol, 9-fluorenone, and phenoxyethanol was 0.10:0.002:1:2.8; then, under stirring, slowly heated to 80°C for reflux reaction for 5h. After the reaction was completed, the solvent was removed by rotary evaporation, and the crude product bisether fluorene and catalyst were obtained after vacuum drying. The crude product was filtered and washed at low temperature with an acetone-toluene solution to obtain pure bisether fluorene with a yield of 96%.
[0059] Example 4
[0060] This embodiment is a method for synthesizing bisether fluorene, and the method for synthesizing bisether fluorene comprises the following steps:
[0061] In a 100mL reaction kettle, 30ml of solvent methanol, the quaternary ammonium salt ionic liquid catalyst for the synthesis of bisether fluorene in Example 2, mercaptoacetic acid, 9-fluorenone, and phenoxyethanol were added in sequence, wherein the molar ratio of the quaternary ammonium salt ionic liquid catalyst for the synthesis of bisether fluorene, mercaptoethanol, 9-fluorenone, and phenoxyethanol was 0.10:0.002:1:2.8; then, under stirring conditions, slowly heated to 80°C for reflux reaction for 5h. After the reaction was completed, the solvent was removed by rotary evaporation, and the crude product bisether fluorene and catalyst were obtained after vacuum drying. The crude product was filtered and washed at low temperature with an acetone-toluene solution to obtain pure bisether fluorene with a yield of 83%.
[0062] Example 5
[0063] This embodiment is a method for synthesizing bisether fluorene, and the method for synthesizing bisether fluorene comprises the following steps:
[0064] In a 100mL reaction kettle, 30ml of solvent methanol, a quaternary ammonium salt ionic liquid catalyst for bisether fluorene synthesis, thioglycolic acid, 9-fluorenone, and phenoxyethanol are added in sequence, wherein the molar ratio of the quaternary ammonium salt ionic liquid catalyst for bisether fluorene synthesis, thioglycolic acid, 9-fluorenone, and phenoxyethanol is 0.10:0.002:1:2.8; then, under stirring conditions, slowly heated to 80°C for reflux reaction for 5h, after the reaction is completed, the solvent is removed by rotary evaporation, and after vacuum drying, a crude product of bisether fluorene and a catalyst is obtained, which is then filtered and washed at low temperature with an acetone-toluene solution to obtain pure bisether fluorene with a yield of 75%;
[0065] The quaternary ammonium salt ionic liquid catalyst used for the synthesis of bisetherfluorene is the catalyst in Example 3 after the reaction is completed, and the solvent is removed by rotary evaporation to recover the catalyst, and the catalyst is reused after the second time.
[0066] Comparative Example 1
[0067] This comparative example is a method for synthesizing bisether fluorene, which comprises the following steps:
[0068] In a 100mL reaction kettle, 30ml of solvent methanol, thioglycolic acid, 9-fluorenone and phenoxyethanol were added in sequence. The molar ratio of thioglycolic acid, 9-fluorenone and phenoxyethanol was 0.002:1:2.8. Then, under stirring conditions, the mixture was slowly heated to 80°C for reflux reaction for 5h. After the reaction was completed, the solvent was removed by rotary evaporation. After vacuum drying, the crude product diether fluorene and catalyst were obtained. The crude product was filtered and washed at low temperature with acetone-toluene solution to obtain pure diether fluorene with a yield of 25%.
[0069] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein by equivalents. These modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention, and they should all be included in the scope of the claims and specification of the present invention.
Claims
1. A method for preparing a quaternary ammonium salt ionic liquid catalyst for the synthesis of bisetherfluorene, characterized in that: The steps include: (a) reacting a quaternary ammonium base compound with 1,3-propane sultone to obtain a precursor; (b) dissolving the precursor in an inorganic acid and adding deionized water, and then heating and refluxing the mixture. After the reflux reaction is completed, the mixture is cooled and the water is removed by rotary evaporation, and then washed and dried to obtain the quaternary ammonium salt ionic liquid catalyst for the synthesis of bisetherfluorene.
2. The preparation method according to claim 1, characterized in that: In the step (a), the quaternary ammonium base compound is selected from at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, dodecyltrimethylammonium hydroxide, trioctylmethylammonium hydroxide, choline, acetylcholine, butyrylcholine, benzoylcholine and phosphatidylcholine.
3. The preparation method according to claim 1, characterized in that: In the step (a), the molar ratio of the quaternary ammonium base compound to 1,3-propane sultone is (1-1.2):
1.
4. The preparation method according to claim 1, characterized in that: In the step (a), the reaction temperature is room temperature and the reaction time is 10 to 15 hours.
5. The preparation method according to claim 1, characterized in that: In the step (b), the inorganic acid is composed of H2SO4, H3PO4 and HBF4; The molar ratio of H2SO4, H3PO4 and HBF4 is (0.1~0.3):1:(2~3).
6. The preparation method according to claim 1, characterized in that: In the step (b), the mass volume ratio of the precursor to the inorganic acid is 1:(10-20); The amount of deionized water added is 8% to 15% of the volume of the inorganic acid.
7. The preparation method according to claim 1, characterized in that: In the step (b), the reflux reaction temperature is 70-85° C. and the time is 6-8 hours.
8. A quaternary ammonium salt ionic liquid catalyst for the synthesis of bisetherfluorene obtained by the preparation method according to any one of claims 1 to 7.
9. A method for synthesizing bisether fluorene, characterized in that: The steps include: 9-fluorenone, phenoxyethanol, a solvent, thioglycolic acid and a quaternary ammonium salt ionic liquid catalyst for the synthesis of bisether fluorene prepared by any one of the preparation methods described in claims 1 to 7 are mixed, and heated under reflux reaction under stirring conditions. After the reaction is completed, the solvent is removed by rotary evaporation, vacuum drying is performed, and then filtering and low-temperature washing are performed to obtain bisether fluorene.
10. The method for synthesizing bisether fluorene according to claim 9, characterized in that: The molar ratio of the quaternary ammonium salt ionic liquid catalyst, thioglycolic acid, 9-fluorenone and phenoxyethanol used for the synthesis of bisetherfluorene is (0.02-0.10):0.002:(0.9-1.1):(2-3); The reflux reaction temperature is 60-100°C and the time is 1-8h; The solvent used for washing is acetone-toluene.