CN113275036A - Preparation and application of SBA-15 supported phase transfer catalyst - Google Patents
Preparation and application of SBA-15 supported phase transfer catalyst Download PDFInfo
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- CN113275036A CN113275036A CN202110516193.6A CN202110516193A CN113275036A CN 113275036 A CN113275036 A CN 113275036A CN 202110516193 A CN202110516193 A CN 202110516193A CN 113275036 A CN113275036 A CN 113275036A
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- phase transfer
- transfer catalyst
- sba
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- supported phase
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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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
- B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
Abstract
The invention discloses preparation and application of an SBA-15 loaded phase transfer catalyst, and relates to the field of phase transfer catalysts and application thereof. The catalyst is used in fluorine-halogen exchange reactions, especially fluorine-chlorine exchange reactions. The preparation method of the SBA-15 load phase transfer catalyst is simple and convenient to operate, good in application effect and reusable.
Description
Technical Field
The invention relates to the field of phase transfer catalysts and application thereof, in particular to preparation of a recyclable SBA-15 loaded phase transfer catalyst and application thereof in fluorine-chlorine exchange reaction.
Background
The phase transfer catalyst is applied to heterogeneous chemical reactions and mainly classified into three types, namely onium salts, inclusion and open-chain polyethers.
Fluorine-chlorine substitution is a typical nucleophilic substitution reaction and has been widely applied to the preparation and production of organofluorine compounds. The fluorine-chlorine substitution usually adopts anhydrous KF as a fluorination reagent, adopts an aprotic solvent, such as dimethyl sulfoxide, dimethylformamide, sulfolane, acetonitrile and the like as a reaction solvent, and needs to add a phase transfer catalyst in the reaction process.
After the traditional fluorine-chlorine substitution reaction is finished, the added phase transfer catalyst is difficult to separate and difficult to recycle, so that the invention has the advantages of simple preparation process, high stability and excellent catalytic performance and has important significance.
Disclosure of Invention
The invention aims to solve the problem of providing a preparation method and application of an SBA-15 loaded phase transfer catalyst, so as to overcome the problem that the traditional phase transfer catalyst is difficult to separate in fluorine-chlorine substitution reaction and achieve the purpose of recycling the phase transfer catalyst.
The preparation method of the SBA-15 supported phase transfer catalyst comprises the following steps:
dissolving the SBA-15 ordered mesoporous material in an organic solvent, stirring at normal temperature, adding a phase transfer catalyst, heating to reflux temperature, refluxing for a required time, distilling under reduced pressure to remove the solvent, and drying to obtain the SBA-15 supported phase transfer catalyst.
In a further technical scheme, the organic solvent is benzene solvent, wherein the benzene solvent comprises one or a mixture of a plurality of solvents of toluene, xylene, ethylbenzene and diethylbenzene.
According to a further technical scheme, the selected catalyst is an onium salt phase transfer catalyst, wherein the onium salt phase transfer catalyst comprises one of tetrapropylphosphonium chloride, tetrapropylphosphonium bromide, tetraethylphosphonium chloride, tetraethylphosphonium bromide, tetraphenylphosphonium chloride and tetraphenylphosphonium bromide.
According to a further technical scheme, the mass ratio of the SBA-15 ordered mesoporous material to the solvent is 1: 2-6 g/g.
According to a further technical scheme, the mass ratio of the SBA-15 ordered mesoporous material to the phase transfer catalyst is 1: 1-5 g/g.
According to a further technical scheme, the stirring temperature is 100-180 ℃, and the preferable reflux temperature is 100-120 ℃.
According to the further technical scheme, the stirring time is 1-10 hours, and the preferable time is 2-5 hours.
In a further technical scheme, the prepared SBA-15 load phase transfer catalyst is applied to fluorine-halogen exchange, and is preferably applied to fluorine-chlorine exchange reaction.
The invention has the advantages of
The preparation method has the advantages of simple process, high stability and excellent catalytic performance, and the phase transfer catalyst has important significance, overcomes the problem that the traditional phase transfer catalyst is difficult to separate in fluorine-chlorine substitution reaction, and achieves the purpose of recycling the phase transfer catalyst.
Detailed Description
The essential features and advantages of the invention will be further explained below with reference to examples, but the invention is not limited to the examples listed.
Example 1
Step 1: in a 1000ml four-mouth round-bottom flask, with a stirring pipe, a condenser pipe and a thermometer, 200g of SBA-15 ordered mesoporous material is dissolved in 700g of toluene solvent, 200g of phase transfer catalyst tetraphenyl phosphonium bromide is slowly added at room temperature, the temperature is raised to the reflux temperature of 110 ℃, the reflux temperature is kept and stirring is continued for 3h, the stirring is stopped, the toluene is distilled under reduced pressure, and 396.7g of SBA-15 supported phase transfer catalyst is obtained after vacuum drying and drying.
Step 2: in a 250 ml four-mouth round bottom flask, with a stirring, a condenser and a thermometer, 20g of the prepared SBA-15 supported phase transfer catalyst, 150ml of acetonitrile, 25g of chloroethylene carbonate and 14.2g of potassium fluoride are taken, stirring is started, heating is carried out to the reflux temperature, and the reaction progress is tracked by adopting GC chromatography. After 4h, GC analysis, GC content of chloroethylene carbonate: 0.1% (area normalization method). And distilling and recovering the acetonitrile solvent to obtain crude fluoroethylene carbonate. And (3) soaking the residual solid in ice water, filtering, recovering the SBA-15 supported phase transfer catalyst, and drying in vacuum to remove water to obtain 19.7g of the SBA-15 supported phase transfer catalyst.
Example 2
Taking 19.7g of the recovered BA-15 supported phase transfer catalyst, repeating the operation of the step 2 in the step 1, after 4h, carrying out GC analysis, wherein the content of the chloroethylene carbonate GC is as follows: 0.4% (area normalization method). And distilling and recovering the acetonitrile solvent to obtain crude fluoroethylene carbonate. And (3) soaking the residual solid in ice water, filtering, recovering the SBA-15 supported phase transfer catalyst, and drying in vacuum to remove water to obtain 18.3g of the SBA-15 supported phase transfer catalyst.
Example 3
Taking 18.3g of the recovered BA-15 supported phase transfer catalyst, repeating the operation of the step 2 in the step 1, after 4h, carrying out GC analysis, wherein the content of the chloroethylene carbonate is as follows: 1.2% (area normalization method). And distilling and recovering the acetonitrile solvent to obtain crude fluoroethylene carbonate. And (3) soaking the residual solid in ice water, filtering, recovering the SBA-15 supported phase transfer catalyst, and drying in vacuum to remove water to obtain 16.9g of the SBA-15 supported phase transfer catalyst.
Example 4
Taking 16.9g of the recovered BA-15 supported phase transfer catalyst, repeating the operation of the step 2 in the step 1, after 4h, carrying out GC analysis, wherein the content of the chloroethylene carbonate GC is as follows: 3.9% (area normalization method). And distilling and recovering the acetonitrile solvent to obtain crude fluoroethylene carbonate. And (3) soaking the residual solid in ice water, filtering, recovering the SBA-15 supported phase transfer catalyst, and drying in vacuum to remove water to obtain 15.2g of the SBA-15 supported phase transfer catalyst.
Example 5
Taking 15.2g of the recovered BA-15 supported phase transfer catalyst, repeating the operation of the step 2 in the step 1, after 4h, carrying out GC analysis, wherein the content of the chloroethylene carbonate GC is as follows: 10.2% (area normalization method). And distilling and recovering the acetonitrile solvent to obtain crude fluoroethylene carbonate. And (3) soaking the residual solid in ice water, filtering, recovering the SBA-15 supported phase transfer catalyst, and drying in vacuum to remove water to obtain 14.0g of the SBA-15 supported phase transfer catalyst. The effect of the SBA-15 load phase transfer catalyst is obviously reduced.
Example 6
Step 1: in a 1000ml four-neck round-bottom flask, with a stirring pipe, a condenser pipe and a thermometer, 200g of SBA-15 ordered mesoporous material is dissolved in 700g of ethylbenzene solvent, 300g of tetraphenylphosphonium chloride serving as a phase transfer catalyst is slowly added at room temperature, the temperature is raised to 120 ℃, the temperature is kept, stirring is continued for 4h, the stirring is stopped, ethylbenzene is distilled out through reduced pressure distillation, and the SBA-15 supported phase transfer catalyst 497.5g is obtained through vacuum drying and drying.
Step 2: in a 250 ml four-mouth round bottom flask, with a stirring, a condenser and a thermometer, 20g of the prepared SBA-15 supported phase transfer catalyst, 150ml of dimethylformamide, 25g of chloroethylene carbonate and 14.2g of potassium fluoride are taken, stirring is started, heating is carried out to the reflux temperature, and the reaction progress is tracked by adopting GC chromatography. After 4h, GC analysis, GC content of chloroethylene carbonate: 0.3% (area normalization method). And distilling and recovering the solvent dimethylformamide to obtain crude fluoroethylene carbonate. And (3) soaking the residual solid in ice water, filtering, recovering the SBA-15 supported phase transfer catalyst, and drying in vacuum to remove water to obtain 19.5g of the SBA-15 supported phase transfer catalyst.
Example 7
Taking 19.5g of the recovered BA-15 supported phase transfer catalyst, repeating the operation of the step 2 in the step 6, after 4h, carrying out GC analysis, wherein the content of the chloroethylene carbonate is as follows: 0.7% (area normalization method). And distilling and recovering the solvent dimethylformamide to obtain crude fluoroethylene carbonate. And (3) soaking the residual solid in ice water, filtering, recovering the SBA-15 supported phase transfer catalyst, and drying in vacuum to remove water to obtain 18.5g of the SBA-15 supported phase transfer catalyst.
Example 8
Taking 18.5g of the recovered BA-15 supported phase transfer catalyst, repeating the operation of the step 2 in the step 6, after 4h, carrying out GC analysis, wherein the content of the chloroethylene carbonate is as follows: 1.2% (area normalization method). And distilling and recovering the solvent dimethylformamide to obtain crude fluoroethylene carbonate. And (3) soaking the residual solid in ice water, filtering, recovering the SBA-15 supported phase transfer catalyst, and drying in vacuum to remove water to obtain 17.2g of the SBA-15 supported phase transfer catalyst.
Example 9
Taking 17.2g of the recovered BA-15 supported phase transfer catalyst, repeating the operation of the step 2 in the step 6, after 4h, carrying out GC analysis, wherein the content of the chloroethylene carbonate GC is as follows: 5.7% (area normalization method). And distilling and recovering the solvent dimethylformamide to obtain crude fluoroethylene carbonate. And (3) soaking the residual solid in ice water, filtering, recovering the SBA-15 supported phase transfer catalyst, and drying in vacuum to remove water to obtain 15.8g of the SBA-15 supported phase transfer catalyst.
Example 10
Taking 15.8g of the recovered BA-15 supported phase transfer catalyst, repeating the operation of the step 2 in the step 6, after 4h, carrying out GC analysis, wherein the content of the chloroethylene carbonate GC is as follows: 12.7% (area normalization method). And distilling and recovering the solvent dimethylformamide to obtain crude fluoroethylene carbonate. And (3) soaking the residual solid in ice water, filtering, recovering the SBA-15 supported phase transfer catalyst, and drying in vacuum to remove water to obtain 14.3g of the SBA-15 supported phase transfer catalyst. The effect of the SBA-15 load phase transfer catalyst is obviously reduced.
It should be noted that the above-mentioned preferred embodiments are merely illustrative of the technical concepts and features of the present invention, and are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (8)
1. A preparation method of an SBA-15 supported phase transfer catalyst is characterized by comprising the following steps:
dissolving the SBA-15 ordered mesoporous material in an organic solvent, stirring at normal temperature, adding a phase transfer catalyst, heating to reflux temperature, refluxing for a required time, distilling under reduced pressure to remove the solvent, and drying to obtain the SBA-15 supported phase transfer catalyst.
2. The method of claim 1, wherein the organic solvent is benzene solvent, wherein the benzene solvent comprises one or more of toluene, xylene, ethylbenzene, and diethylbenzene.
3. The method for preparing an SBA-15 supported phase transfer catalyst according to claim 1, wherein the selected catalyst is an onium salt type phase transfer catalyst, wherein the onium salt type phase transfer catalyst comprises one of tetrapropylphosphonium chloride, tetrapropylphosphonium bromide, tetraethylphosphonium chloride, tetraethylphosphonium bromide, tetraphenylphosphonium chloride and tetraphenylphosphonium bromide.
4. The preparation method of the SBA-15 supported phase transfer catalyst according to claim 1, wherein the mass ratio of the SBA-15 ordered mesoporous material to the solvent is 1: 2-6 g/g.
5. The preparation method of the SBA-15 supported phase transfer catalyst according to claim 1, wherein the mass ratio of the SBA-15 ordered mesoporous material to the phase transfer catalyst is 1: 1-5 g/g.
6. The preparation method of the SBA-15 supported phase transfer catalyst according to claim 1, wherein the stirring temperature is 100-180 ℃, preferably the reflux temperature is 100-120 ℃.
7. The preparation method of the SBA-15 supported phase transfer catalyst according to claim 1, wherein the stirring time is 1-10 h, preferably 2-5 h.
8. Use of a SBA-15 supported phase transfer catalyst, characterized in that the SBA-15 supported phase transfer catalyst prepared according to the process of any one of claims 1 to 7 is used in a fluorine-halogen exchange, preferably in a fluorine-chlorine exchange reaction.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114539055A (en) * | 2022-03-15 | 2022-05-27 | 西安近代化学研究所 | Method for realizing phase transfer catalysis beta-dicarbonyl compound alkylation reaction by using microchannel reactor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774923A (en) * | 2010-01-26 | 2010-07-14 | 中化国际（苏州）新材料研发有限公司 | Method of preparing fluoroethylene carbonate |
| CN104987292A (en) * | 2015-06-04 | 2015-10-21 | 上海化学试剂研究所有限公司 | Method for preparing aromatic fluoride by using supported phase-transfer catalyst |
| CN106902869A (en) * | 2017-02-09 | 2017-06-30 | 鄂尔多斯市瀚博科技有限公司 | A kind of immobilized phase transfer catalyst and its application in the new certain herbaceous plants with big flowers acid isopropyl phenyl ester of peroxidating is prepared |
| CN110981849A (en) * | 2019-12-16 | 2020-04-10 | 苏州华一新能源科技有限公司 | Preparation method and application of fluoroethylene carbonate |
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- 2021-05-12 CN CN202110516193.6A patent/CN113275036A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774923A (en) * | 2010-01-26 | 2010-07-14 | 中化国际（苏州）新材料研发有限公司 | Method of preparing fluoroethylene carbonate |
| CN104987292A (en) * | 2015-06-04 | 2015-10-21 | 上海化学试剂研究所有限公司 | Method for preparing aromatic fluoride by using supported phase-transfer catalyst |
| CN106902869A (en) * | 2017-02-09 | 2017-06-30 | 鄂尔多斯市瀚博科技有限公司 | A kind of immobilized phase transfer catalyst and its application in the new certain herbaceous plants with big flowers acid isopropyl phenyl ester of peroxidating is prepared |
| CN110981849A (en) * | 2019-12-16 | 2020-04-10 | 苏州华一新能源科技有限公司 | Preparation method and application of fluoroethylene carbonate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114539055A (en) * | 2022-03-15 | 2022-05-27 | 西安近代化学研究所 | Method for realizing phase transfer catalysis beta-dicarbonyl compound alkylation reaction by using microchannel reactor |
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Application publication date: 20210820 |