CN104525252A - Immobilized ionic liquid solid acid catalyst and preparation method thereof - Google Patents
Immobilized ionic liquid solid acid catalyst and preparation method thereof Download PDFInfo
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- CN104525252A CN104525252A CN201410704312.0A CN201410704312A CN104525252A CN 104525252 A CN104525252 A CN 104525252A CN 201410704312 A CN201410704312 A CN 201410704312A CN 104525252 A CN104525252 A CN 104525252A
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Abstract
The invention provides an immobilized ionic liquid solid acid catalyst and a preparation method thereof. The preparation method comprises the following steps: reacting aminoalkyltrialkoxy silane with propanesultone or butanesultone to obtain trialkoxysilicon-containing ylid, acidifying by using an acid, adding a hydroxy group-containing carrier, and reacting to obtain the immobilized ionic liquid solid acid catalyst. The catalyst material has the advantages of high heat stability, high acid value of above 2.5mmol/g, large surface area, good catalysis effect, and repeated use.
Description
Technical field
The present invention relates to organic chemical synthesis technical field, particularly a kind of immobilized ionic liquid solid acid catalyst and preparation method thereof.
Background technology
Occur that crisis now in energy problem, environmental problem, do not produce unnecessary accessory substance with a small amount of energy and only effectively generate the target that object product becomes modern chemical industry pursuit.In modern chemistry industry, acid catalyst is absolutely necessary, and is widely used in the manufacture of various products such as medicine, petro chemical industry product, macromolecule product, but the liquid acid catalyst being mostly hydrochloric acid, sulfuric acid and so on used at present.The liquid catalyst used in process of production needs to be neutralized by alkali, the operations such as the salt generated by neutralization by removing, is separated, reclaims from product.But, in the removal step of above-mentioned neutralization and salt, consume quite a few energy.In addition, the salt excess supply commercially reclaimed, it is mostly the little accessory substance of availability, is therefore usually difficult to process.
Relative to above-mentioned situation, due to solid acid catalyst being separated, reclaim time do not need above-mentioned in and or the removal step of salt, unnecessary accessory substance can not be generated, and energy-conservation ground manufacturing purpose product, therefore the research of this respect has been subject to concern (Ishihara, the K of scientific worker; Hasegawa, A; Yamamoto, H.Angew.Chem.Int.Ed.2001,40,4077.).In the research and development of solid acid catalyst, the solid acid catalysts such as zeolite, silica-alumina, moisture niobium have become the huge achievement of chemical industry, bring very large contribution to society.In addition, as strong acid polymer, can think that by the material that polystyrene sulfonation obtains be solid acid, in the past always as having acid cationic ion-exchange resin.In addition, the known Nafion (registration mark of E.I.Du Pont Company) in polytetrafluoroethylene (PTFE) skeleton with sulfo group has hydrophilic extremely strong solid acid (solid super-strong acid), known they work as the super acids with the acid strength being greater than liquid acid.But, have the problem to selling at exorbitant prices when thermally labile, industrial use.Accordingly, from the viewpoint of performance and cost etc., use solid acid catalyst than using aforesaid liquid acid and be more difficult to the favourable industrial processes of design, Chemical Industries nearly all now all depends on liquid acid catalyst.Ionic liquid is subject to the attention of Chinese scholars as a kind of environmental protection catalyst and reaction dissolvent always.
But ionic liquid recovery in use, particularly after the alcohols larger with polarity, carboxylic-acid substance react, cannot reclaim owing to can be dissolved in delamination in organic matter.
Summary of the invention
For solving the problem, the present invention considers to prepare a kind of immobilized ionic liquid solid acid catalyst, on the basis keeping ionic liquid high catalytic activity, simplifies the removal process of material.In conventional ion liquid, introducing hydrolyzable alkoxyl silicone, by reacting with the carrier of hydroxyl, being grafted on carrier, obtain immobilized ionic liquid solid acid catalyst.
One object of the present invention is to provide a kind of immobilized ionic liquid solid acid catalyst, and this catalyst recovery utilizes easy; Heat endurance is high; Moisture-stable; Acid number is high; Excellent catalytic effect.
For achieving the above object, the present invention is by the following technical solutions:
A kind of immobilized ionic liquid solid-acid material catalyst, aminoalkyl trialkoxy silane and sultone is adopted to react, obtain the inner salt containing tri-alkoxy silicon, acidifying is carried out again with acid, obtain the sulfonic functional ion liquid monomer that anion is acid group, finally the carrier of ionic liquid and hydroxyl being carried out hybrid reaction is grafted on carrier by ionic liquid, forms immobilized ionic liquid solid acid catalyst.
Further, described aminoalkyl trialkoxy silane is the one in 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminoethyl triethoxysilane, 2-aminoethyl trimethoxy silane etc., preferably 3-aminopropyl trimethoxysilane.
Further, described acid is sulfuric acid, hydrochloric acid, phosphoric acid, the one in p-methyl benzenesulfonic acid etc., preferably sulfuric acid.
Further, the carrier of described hydroxyl is chromatographic silica gel, diatomite, imvite, molecular sieve, kaolin, the one in carclazyte.
Another object of the present invention is the preparation method providing a kind of immobilized ionic liquid solid acid catalyst, and this preparation method is simple to operate, and productive rate is high.
For achieving the above object, the present invention is by the following technical solutions:
A preparation method for immobilized ionic liquid solid-acid material, comprises the following steps:
Step a, the preparation of inner salt, with aminoalkyl trialkoxy silane for raw material, oxolane is solvent, after adding propane sultone or butane sultone mixing, adds thermal agitation and obtains inner salt; Wherein the mol ratio of aminoalkyl trialkoxy silane and propane sultone or butane sultone is 1:1;
Step b, acidifying, after inner salt being dissolved in ethanol water mixed solvent, the acid amount of substance such as adding is stirred in room temperature, and the anion obtaining homogeneous phase is the ionic liquid solution of acid group;
Step c, immobilized ionic liquid, the carrier of hydroxyl is added in above-mentioned ionic liquid solution, carrier consumption is 0.5 ~ 5.0 times of ionic liquid weight, after proceeding to add thermal agitation hydrolytic condensation 12h, filter, reusable heat water washing 3 times, namely 12h dry in solid baking oven is obtained immobilized ionic liquid solid-acid material.
Preferably, the consumption of tetrahydrofuran solvent described in step a is 4 ~ 10 times of aminoalkyl trialkoxy silane quality.
Preferably, in step a, heating-up temperature is 70 DEG C.
Further, the inner salt obtained in step a is white solid, after suction filtration, is greater than the ether of 99% or after ethyl acetate washs 3 times, 60 DEG C are carried out vacuum drying, obtain inner salt by concentration;
Preferably, the volume ratio 1:1 of second alcohol and water in ethanol water mixed solvent in step b.
Preferably, in step c during hydrolysis-condensation reaction, heating-up temperature is 80 DEG C.
Preferably, in step c, bake out temperature and wash temperature are 80 DEG C.
Compared with prior art, advantage of the present invention is: catalyst heat endurance prepared by the present invention is high, and heat decomposition temperature is more than 190 DEG C; Acid number is high, at more than 2.5mmol/g; There is larger surface area; Excellent catalytic effect, to general acid catalyzed reaction as: esterification, condensation, alkylation, etherificate etc. have very high catalytic activity; Catalyst recovery is easy, is separated, can repeatedly uses by simple filtration.The immobilized ionic liquid solid-acid material of the present invention's synthesis is with a wide range of applications.
Further, the preparation method of catalyst of the present invention is simple to operate, and productive rate is high.
Detailed description of the invention
Below will the present invention is further elaborated by specific embodiment:
Embodiment 1
The preparation of immobilized 3-aminopropyl trimethoxysilane ionic liquid solid acid catalyst
The preparation of the 1st step inner salt
Get 3-aminopropyl trimethoxysilane and 1, the raw material that the material amount of 4-butane sultone is equal, add tetrahydrofuran solvent, consumption is 6 times of 3-aminopropyl trimethoxysilane quality, white solid is obtained, then suction filtration, after being 99% washed with diethylether 3 times by concentration after carrying out adding thermal agitation 2h in 70 DEG C, 60 DEG C are carried out vacuum drying, obtain inner salt;
2nd step acidifying
In the ethanol that 1g inner salt is dissolved in 5g volume ratio 1:1 and water mixed solvent, add the sulfuric acid equal with the material amount of inner salt, at room temperature carry out being uniformly mixed 4h, obtain the ionic liquid solution that corresponding anion is bisulfate ion;
The immobilized ionic liquid solid acid catalyst synthesis of 3rd step
Chromatographic silica gel is added in above-mentioned ionic liquid solution, chromatographic silica gel consumption is 1g ionic liquid 2.0g, proceed to add thermal agitation hydrolytic condensation 12h at 80 DEG C after, filter, use 80 DEG C of hot washes 3 times again, namely solid dry 12h in 80 DEG C of baking ovens is obtained immobilized ionic liquid solid acid catalyst, the acid number 3.2mmol/g of obtained catalyst, pyrolysis temperature 198 DEG C;
Embodiment 2-4
Except for the following differences, all the other are with embodiment 1, and aminoalkyl trialkoxy silane is pressed shown in table 1 respectively, obtain following immobilized ionic liquid solid-acid material catalyst.
Table 1 embodiment 2-4 aminoalkyl trialkoxy silane used and the catalyst parameters obtained
Embodiment 5-6
Except for the following differences, all the other are with embodiment 1, and acid is pressed shown in table 2 respectively, and the catalyst result that different acid obtains is as table 2.
Table 2 embodiment 5-6 acid used and the catalyst parameters obtained
Embodiment 7
Catalytic esterification: having electromagnetic agitation, thermometer, reflux condensing tube, add 0.1mol citric acid in the 100mL three-necked bottle of water knockout drum, 0.45mol n-butanol carries out adding thermal agitation, sampling and measuring acidity after citric acid is entirely molten, then add the catalyst that 0.15g embodiment 6 is obtained, carry out heating return stirring, the water that reaction is produced separates from water knockout drum, and reaction 4h, calculated yield is 99.3%.
Embodiment 8-12
Except for the following differences, all the other and embodiment 7, after reaction terminates, catalyst carries out filtered and recycled, after acetone washing, after being placed in 100 DEG C of baking oven dryings, continuing reaction, the results are shown in Table 3
The productive rate of the different recovered frequency of table 3 catalyst
Embodiment 13
Catalyzing and condensing reacts: having electromagnetic agitation, reflux condensing tube, the catalyst that 0.1mol cyclohexanone, 0.15mol ethylene glycol, 10ml cyclohexane and 0.1g embodiment 6 is obtained is added in the 100mL three-necked bottle of water knockout drum, carry out heating return stirring water that reaction is produced and entrainer azeotropic steams, reaction about 1.5h, yield is that 99.6%. catalyst reuses 5 times, and catalytic activity does not change.
Embodiment 14
Catalytic alkylation reaction: having electromagnetic agitation, reflux condensing tube, the catalyst that 0.1mol catechol, the 0.15mol tert-butyl alcohol and 0.1g embodiment 6 is obtained is added in the 100mL three-necked bottle of water knockout drum, carry out heating return stirring, reaction about 4h, yield is that 94%. catalyst reuse 5 times, and catalytic activity does not change.
Embodiment 15
Catalyst etherifying reacts: having electromagnetic agitation, reflux condensing tube, the catalyst that 0.1mol2-naphthols, 0.15mol methyl alcohol and 0.1g embodiment 6 is obtained is added in the 100mL three-necked bottle of water knockout drum, carry out heating return stirring, reaction about 6h, yield is that 91%. catalyst reuse 5 times, and catalytic activity does not change.
Claims (10)
1. an immobilized ionic liquid solid acid catalyst, it is characterized in that: described catalyst adopts aminoalkyl trialkoxy silane and sultone to react, obtain the inner salt containing tri-alkoxy silicon, acidifying is carried out again with acid, obtain the sulfonic functional ion liquid monomer that anion is acid group, finally the carrier of ionic liquid and hydroxyl being carried out hybrid reaction is grafted on carrier by ionic liquid, forms immobilized ionic liquid solid acid catalyst.
2. catalyst according to claim 1, is characterized in that: described aminoalkyl trialkoxy silane is the one in 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminoethyl triethoxysilane, 2-aminoethyl trimethoxy silane.
3. catalyst according to claim 1, is characterized in that: described acid is sulfuric acid, hydrochloric acid, phosphoric acid, the one in p-methyl benzenesulfonic acid.
4. catalyst according to claim 1, is characterized in that: the carrier of described hydroxyl is chromatographic silica gel, diatomite, imvite, molecular sieve, kaolin, the one in carclazyte.
5. a preparation method for immobilized ionic liquid solid acid catalyst as claimed in claim 1, is characterized in that: described preparation method comprises the following steps:
Step a, the preparation of inner salt, with aminoalkyl trialkoxy silane for raw material, oxolane is solvent, after adding propane sultone or butane sultone mixing, adds thermal agitation and obtains inner salt; Wherein the mol ratio of aminoalkyl trialkoxy silane and propane sultone or butane sultone is 1:1;
Step b, acidifying, after inner salt being dissolved in ethanol water mixed solvent, the acid amount of substance such as adding is stirred in room temperature, and the anion obtaining homogeneous phase is the ionic liquid solution of acid group;
Step c, immobilized ionic liquid, the carrier of hydroxyl is added in above-mentioned ionic liquid solution, carrier consumption is 0.5 ~ 5.0 times of ionic liquid weight, after proceeding to add thermal agitation hydrolytic condensation, filter, reusable heat water washing, immobilized ionic liquid solid acid catalyst will be drying to obtain in solid baking oven.
6. preparation method according to claim 4, is characterized in that: the consumption of tetrahydrofuran solvent described in step a is 4 ~ 10 times of aminoalkyl trialkoxy silane quality.
7. preparation method according to claim 4, is characterized in that: in step a, heating-up temperature is 70 DEG C.
8. preparation method according to claim 4, is characterized in that: the inner salt obtained in step a is white solid, after suction filtration, with concentration be greater than 99% ether or ethyl acetate washing after, carry out vacuum drying, obtain inner salt.
9. preparation method according to claim 4, is characterized in that: the volume ratio 1:1 of second alcohol and water in ethanol water mixed solvent in step b.
10. preparation method according to claim 4, is characterized in that: hydrolysis-condensation reaction temperature in step c, bake out temperature and wash temperature are 80 DEG C.
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Cited By (3)
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| CN106268939A (en) * | 2016-08-09 | 2017-01-04 | 长安大学 | A kind of supported ionic liquids carrier, preparation method and applications |
| CN108479849A (en) * | 2018-02-09 | 2018-09-04 | 中国日用化学工业研究院有限公司 | The solid-loaded ionic-liquid catalyst and preparation method and application of synthesis of alkyl diphenyl ether |
| CN115106125A (en) * | 2022-08-08 | 2022-09-27 | 中国石油大学(华东) | Preparation method and application of solid acid catalyst loaded with ionic liquid |
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| KR101430259B1 (en) * | 2013-03-29 | 2014-08-14 | 부산대학교 산학협력단 | Method for preparation of five-membered cyclic carbonate by using immobilized ionic liquid on a biopolymer cellulose as catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102029188A (en) * | 2010-11-15 | 2011-04-27 | 西北农林科技大学 | Carbon-based solid acid catalyst with high specific surface area and preparation method thereof |
| KR101430259B1 (en) * | 2013-03-29 | 2014-08-14 | 부산대학교 산학협력단 | Method for preparation of five-membered cyclic carbonate by using immobilized ionic liquid on a biopolymer cellulose as catalyst |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268939A (en) * | 2016-08-09 | 2017-01-04 | 长安大学 | A kind of supported ionic liquids carrier, preparation method and applications |
| CN106268939B (en) * | 2016-08-09 | 2018-12-28 | 长安大学 | A kind of supported ionic liquids carrier, preparation method and applications |
| CN108479849A (en) * | 2018-02-09 | 2018-09-04 | 中国日用化学工业研究院有限公司 | The solid-loaded ionic-liquid catalyst and preparation method and application of synthesis of alkyl diphenyl ether |
| CN115106125A (en) * | 2022-08-08 | 2022-09-27 | 中国石油大学(华东) | Preparation method and application of solid acid catalyst loaded with ionic liquid |
| CN115106125B (en) * | 2022-08-08 | 2023-09-05 | 中国石油大学(华东) | Preparation method and application of ionic liquid-loaded solid acid catalyst |
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