CN108465487A - It is a kind of for the poly ion liquid base heteropolyacid catalyst of epoxidation reaction of olefines, preparation method and applications - Google Patents
It is a kind of for the poly ion liquid base heteropolyacid catalyst of epoxidation reaction of olefines, preparation method and applications Download PDFInfo
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- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F126/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F126/06—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/72—Epoxidation
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Abstract
The present invention relates to a kind of for the poly ion liquid base heteropolyacid catalyst of epoxidation reaction of olefines, preparation method and applications, belongs to chemical catalysis field.The preparation method of catalyst provided by the invention includes the following steps：Using ion-exchange reactions, by H3PW12O40Heteropoly acid is added in the poly ion liquid solution of piperidines functionalization, is obtained white solid particle, is obtained after filtration washing drying.Gained catalyst is used in epoxidation reaction of olefines, reaction result is detected with GC, and conversion ratio is selective up to 97% up to 100%.After the catalyst advantage of the present invention is that the ionic liquid cation of piperidines functionalization is combined with heteropolyanion, electric charge transfer in catalyst molecule can be effectively improved, reaction is accelerated to carry out, not only increase the yield of epoxide, and catalyst does not dissolve in system in the reaction, by simple filtration with regard to reusable, catalytic activity is high, long lifespan.
Description
Technical field
The invention belongs to chemical catalysis fields, and in particular to a kind of poly ion liquid base for epoxidation reaction of olefines is miscellaneous
Polyacid catalyst；The invention further relates to the preparation method and application of the catalyst.
Background technology
Epoxide is a kind of important organic intermediate, prepares epoxy coating, pesticide, rubber accelerator, medicine, combustion
Material etc., also be used to prepare in surfactant and polymer modulator.Epoxidation reaction of olefines is that prepare epoxides most straight
The approach connect, by academia and industrial circle great attention and conduct extensive research.Hydrogen peroxide is due to active
Oxygen and the water for generating environmental sound after the reaction are a kind of ideal environmental-friendly oxygen sources.In recent years, it is with hydrogen peroxide
The catalyzing expoxidation of olefines system of oxygen source is developed into the leading of epoxidation research field and makes great progress.
The catalyst of epoxidation reaction is mainly with the catalyst for containing metallic element (Al, Mn, W, Ti, Fe, Mo etc.) at present
Main, heteropoly acid (also known as polyoxometallate) is a kind of metal oxygen that position bridging is usually total to by the metal ions such as vanadium, molybdenum, tungsten and oxygen
Cluster compound has very strong oxidisability, wherein the phosphorus tungsten of Keggin-type since metallic atom is generally in highest valence state
Heteropoly acid has been demonstrated to be very effective olefin epoxidation catalysts.But during EPOXIDATION OF ALKENES CATALYZED BY, by
It is often degraded to PW step by step in the Keggin-type structure of the addition of hydrogen peroxide, heteropoly acid4, PW3, PW2Equal peroxides polyacid active matter
Kind, the behavior that catalyst is dissolved in reaction system is showed, difficulty is brought to the utilization and recycle of catalyst.Recent years, reaction control
System phase separation catalyst system and catalyzing and biphasic catalytic system system occur in succession, are provided newly for the utilization and recycle of heteropolyacid catalyst
Method, but still there are active groups to be easy to run off, reaction terminates the problems such as catalyst recovery step is complicated.
Currently, Keggin-type anion such as [XM12O40]3-5(X=P5+Or Si4+And M=W6+, Mo6+) and ionic liquid at room temperature
The novel organic-inorganic hybrid material being bonded has caused the concern of researcher.In terms of catalysis, it has been reported that some
The catalyst that imidazoles ionic liquid presoma is combined with heteropoly acid is used for the report of epoxidation reaction of olefines.Chinese patent
The preparation and its application on catalyzing expoxidation of olefines that CN106975522A discloses a kind of heteropoly phosphorus molybdenum tungstic acid, in the invention
Epoxides yield is obtained up to 99% with the catalyst, but catalyst terminates catalysis recycling difficulty, utilization rate is low.
Therefore, activity height is obtained, easily recycling, the repeatable ion liquid type heteropolyacid catalyst used of stablizing is still one
A urgent need to solve the problem.
Invention content
The purpose of the present invention is on the basis of existing technology, provide a kind of polyion liquid for epoxidation reaction of olefines
Body base heteropolyacid catalyst.
Another mesh of the present invention is to provide a kind of preparation method of above-mentioned catalyst.
Third object of the present invention is to provide a kind of applications of above-mentioned catalyst.
Technical scheme is as follows：
A kind of poly ion liquid base heteropolyacid catalyst for epoxidation reaction of olefines, the structural formula of the catalyst are as follows
It is shown：
The ratio that the catalyst of the present invention is named as IMPD-IMDO-PW, wherein x and y is 1:0.9~1.1, by cation
Ion exchange is made in aqueous solution for presoma and anion presoma.In the present invention, cationic presoma is by piperidyl work(
The ionic liquid of energyization and the ion liquid polymerization of dodecyl functionalization obtain, and anion presoma is H3PW12O40。
Preferably, in the present invention, the molar ratio of cationic presoma and anion presoma is 1.5:1~2.0:1.
A kind of preparation method of poly ion liquid base heteropolyacid catalyst for epoxidation reaction of olefines, it includes following
Step：
(1) prepared by piperidines functionalized ion liquid：By 1- vinyl imidazoles, N- (2- chloroethyls) piperidine hydrochlorates and anhydrous
After ethyl alcohol mixing, return stirring, then wash, obtain the ionic liquid of piperidyl functionalization；
(2) prepared by dodecane functionalized ion liquid：1- vinyl imidazoles, bromododecane and absolute ethyl alcohol are mixed
Afterwards, return stirring obtains the ionic liquid of dodecyl functionalization except being washed after solvent；
(3) prepared by cationic presoma：Product, azodiisobutyronitrile and the solvent that step (1) and step (2) are obtained are mixed
After conjunction, return stirring is added KOH and removes HCl, obtain cationic presoma except being washed after solvent；
(4) preparation of poly ion liquid base heteropolyacid catalyst：The product and H that step (3) is obtained3PW12O40Water-soluble
It stirs, filter in liquid to obtain the final product.
In a kind of preferred embodiment, in step (1), dichloromethane is used after 24~60h of return stirring under nitrogen protection
Washing.
In another preferred embodiment, in step (2), under nitrogen protection after 12~48h of return stirring, revolving is except molten
Agent, then washed with ether.
In a kind of more preferable scheme, in step (3), azodiisobutyronitrile is as initiator, and absolute ethyl alcohol is as molten
Agent, under nitrogen protection 12~48h of return stirring.The product and H that step (3) is obtained again3PW12O40Room temperature stirs in aqueous solution
Mix, filter, wash again it is dry to get.
It is original that a kind of application of poly ion liquid base heteropolyacid catalyst for epoxidation reaction of olefines, which is with alkene,
Material, hydrogen peroxide is oxidant, and acetonitrile is solvent, and the poly ion liquid base heteropoly acid is catalyst, carries out back flow reaction, filtering
Afterwards, poly ion liquid base heteropolyacid catalyst, recycling are recycled.
Preferably, alkene is cyclo-octene or cyclohexene.Solvent dosage is 10ml, reaction time 2-6h, hydrogen peroxide
Dosage is 2-12mmol, catalyst amount 0.1g.Catalyst recovery yield is 82-89%.
After completion of the reaction, it catalyst can be realized is detached with product by filtering or centrifuging.Reaction solution gas-chromatography into
Row analysis.
Technical solution using the present invention, advantage are as follows:
Provided by the present invention for the poly ion liquid base heteropolyacid catalyst of epoxidation reaction of olefines, done with acetonitrile molten
Agent, for hydrogen peroxide as oxidant, reaction process is heterogeneous catalytic oxidation, and reaction, which terminates catalyst, can pass through simple filtration
Utilization and recycle.Entire reaction system green high-efficient, reaction condition is mild, and dioxygen water use efficiency is high, is advantageously implemented industrialization and answers
With.
Description of the drawings
Fig. 1 is the infrared spectrum of poly ion liquid base heteropolyacid catalyst of the present invention；
Fig. 2 is that poly ion liquid base heteropolyacid catalyst reaction of the present invention terminates, the infrared spectrum after recycling；
Fig. 3 is the thermogravimetric spectrogram of poly ion liquid base heteropolyacid catalyst of the present invention.
Specific implementation mode
By following embodiment and in conjunction with attached drawing to a kind of poly ion liquid for epoxidation reaction of olefines of the present invention
Base heteropolyacid catalyst, preparation method and applications are further described, but these embodiments are not any to present invention composition
Limitation.
Embodiment 1
1, the preparation of poly ion liquid base heteropolyacid catalyst
(1) prepared by piperidines functionalized ion liquid
1- vinyl imidazoles 9.89g, N- (2- chloroethyls) piperidine hydrochlorate 18.40g is weighed respectively, and 150ml flasks are added
In, 40mL absolute ethyl alcohols are added, return stirring 48h is cooled to room temperature after reaction under nitrogen protection after mixing,
White solid is precipitated, filters, is dissolved and washed away and washed 2-3 times with dichloromethane, 80 DEG C of dryings 2 hours obtain white powdery solids particle
IMPD。
(2) prepared by dodecane functionalized ion liquid
1- vinyl imidazoles 4.7592g (0.05mol), bromododecane 12.5529g (0.05mol) mixing are weighed respectively
It is added in 100ml round-bottomed flasks, 40mL absolute ethyl alcohols is added, return stirring for 24 hours, rotates under nitrogen protection after mixing
It goes out solvent, obtains weak yellow liquid, 3 times are washed with ether, then 80 DEG C of dryings 2 hours, obtain pale yellow oily liquid
IMDO becomes white solid when temperature is relatively low.
(3) prepared by cationic presoma
Products therefrom IMPD (1g) is weighed, absolute ethyl alcohol 50mL is added in 100ml flasks in IMDO (1.23g), and mixing is equal
After even, it is slowly added into azodiisobutyronitrile 0.05g, return stirring for 24 hours, rotates away solvent under nitrogen protection, obtains yellowish
Distillation water dissolution appropriate is added in color thick liquid, is slowly added into KOH, adjusts PH to 10, after persistently stirring 2h, revolving
Water removal is added ethyl alcohol appropriate and removes KCl, obtains cationic presoma IMPD-IMDO.
(4) preparation of poly ion liquid base heteropolyacid catalyst
Such as preceding gained IMPD-IMDO, 30ml distilled water is added, by 2g H3PW12O40It is dissolved in another 30ml distilled water, mole
Than being 1.5:1~2.0:1, mixing generates solid precipitation immediately, and for 24 hours, filtering is washed with deionized 2-3 times stirring at normal temperature,
80 DEG C of dryings 2 hours, obtain white powdery solids IMPD-IMDO-PW.
2, the application IMPD-IMDO-PW of poly ion liquid base heteropolyacid catalyst
10mmol cyclohexene 0.82g, 10ml acetonitrile is weighed, 0.1g catalyst IMPD-IMDO-PW is added to 25ml round bottoms burning
In bottle, it is placed in 75 DEG C of water-baths of temperature controller, is stirred using magnetic stirring apparatus, hydrogen peroxide is slowly added dropwise into reaction system
5h is reacted in 6mmol, completion of dropwise addition.After reaction, mixture is centrifuged, takes its group of upper solution gas chromatographic analysis
At lower layer's solid can be used for lower secondary response after recycling.Catalyst recovery yield 83%, cyclohexene conversion rate 100%, selectivity
91.8%.
Embodiment 2
According to the application of poly ion liquid base heteropolyacid catalyst in embodiment 1, change reactant, the specific method is as follows：
10mmol cyclo-octene 1.08g, 10ml acetonitrile is weighed, 0.1g catalyst IMPD-IMDO-PW is added to 25ml round bottoms burning
In bottle, it is placed in 75 DEG C of water-baths of temperature controller, is stirred using magnetic stirring apparatus, hydrogen peroxide is slowly added dropwise into reaction system
5h is reacted in 8mmol, completion of dropwise addition.After reaction, mixture is centrifuged, takes its group of upper solution gas chromatographic analysis
At lower layer's solid can be used for lower secondary response after recycling.Catalyst recovery yield 86%, cyclohexene conversion rate 100%, selectivity
97.4%.
Comparative example 1
According to the method that embodiment 1 prepares poly ion liquid base heteropolyacid catalyst, IMDO is replaced with acrylamide, is prepared
Catalyst IMPD-ACAM-PW.The specific method is as follows：
(1) preparation of IMPD-ACAM
Products therefrom IMPD (0.01mol) is weighed, absolute ethyl alcohol is added in 100ml flasks in acrylamide (0.01mol)
50mL is slowly added into azodiisobutyronitrile 0.05g after mixing, and return stirring for 24 hours, rotates away molten under nitrogen protection
Agent obtains light yellow viscous liquid, and distillation water dissolution appropriate is added, and is slowly added into KOH, adjusts PH to 10, persistently stirs
After mixing 2h, revolving water removal is added ethyl alcohol appropriate and removes KCl, obtains cationic presoma IMPD-ACAM.
(2)IMPD-ACAM-PW
Such as preceding gained IMPD-ACAM, 30ml distilled water is added, by 2g H3PW12O40It is dissolved in another 30ml distilled water, mole
Than being 1.5:1~2.0:1, mixing generates solid precipitation immediately, and for 24 hours, filtering is washed with deionized 2-3 times stirring at normal temperature,
80 DEG C of dryings 2 hours, obtain white powdery solids IMPD-ACAM-PW.
(3) applications of the catalysis IMPD-ACAM-PW in epoxidation reaction of olefines
10mmol cyclohexene 0.82g, 10ml acetonitrile is weighed, 0.1g catalyst IMPD-ACAM-PW is added to 25ml round bottoms burning
In bottle, it is placed in 75 DEG C of water-baths of temperature controller, is stirred using magnetic stirring apparatus, hydrogen peroxide is slowly added dropwise into reaction system
5h is reacted in 6mmol, completion of dropwise addition.After reaction, mixture is centrifuged, takes its group of upper solution gas chromatographic analysis
At lower layer's solid can be used for lower secondary response after recycling.Catalyst recovery yield 82%, cyclohexene conversion rate 89.9%, selectivity
57.6%.
Claims (10)
1. a kind of poly ion liquid base heteropolyacid catalyst for epoxidation reaction of olefines, it is characterised in that the knot of the catalyst
Structure formula is as follows：
2. the poly ion liquid base heteropolyacid catalyst according to claim 1 for epoxidation reaction of olefines, feature
It is, the ratio of x and y are 1:0.9~1.1.
3. the poly ion liquid base heteropolyacid catalyst according to claim 1 for epoxidation reaction of olefines, feature
It is, by cationic presoma and anion presoma, ion exchange is made the catalyst in aqueous solution；The cation
Presoma is obtained by the ionic liquid and the ion liquid polymerization of dodecyl functionalization of piperidyl functionalization；Before the anion
Drive body is H3PW12O40；The molar ratio of the cation presoma and anion presoma is 1.5:1~2.0:1.
4. a kind of preparation of the poly ion liquid base heteropolyacid catalyst as described in claim 1 for epoxidation reaction of olefines
Method, which is characterized in that it includes the following steps：
(1) prepared by piperidines functionalized ion liquid：By 1- vinyl imidazoles, N- (2- chloroethyls) piperidine hydrochlorates and absolute ethyl alcohol
After mixing, return stirring, then wash, obtain the ionic liquid of piperidyl functionalization；
(2) prepared by dodecane functionalized ion liquid：After 1- vinyl imidazoles, bromododecane and absolute ethyl alcohol are mixed, return
Stream stirring, except being washed after solvent, obtains the ionic liquid of dodecyl functionalization；
(3) prepared by cationic presoma：Product, azodiisobutyronitrile and the solvent mixing that step (1) and step (2) are obtained
Afterwards, return stirring is added KOH and removes HCl, obtain cationic presoma except being washed after solvent；
(4) preparation of poly ion liquid base heteropolyacid catalyst：The product and H that step (3) is obtained3PW12O40In aqueous solution
It stirs, filter to obtain the final product.
5. the preparation side of the poly ion liquid base heteropolyacid catalyst according to claim 4 for epoxidation reaction of olefines
Method, which is characterized in that in step (1), washed under nitrogen protection with dichloromethane after 24~60h of return stirring.
6. the preparation side of the poly ion liquid base heteropolyacid catalyst according to claim 4 for epoxidation reaction of olefines
Method, which is characterized in that in step (2), under nitrogen protection after 12~48h of return stirring, revolving removes solvent, then is washed with ether
It washs.
7. the preparation side of the poly ion liquid base heteropolyacid catalyst according to claim 4 for epoxidation reaction of olefines
Method, which is characterized in that in step (3), azodiisobutyronitrile is as initiator, and absolute ethyl alcohol is as solvent, in nitrogen protection
12~48h of lower return stirring.
8. the preparation side of the poly ion liquid base heteropolyacid catalyst according to claim 4 for epoxidation reaction of olefines
Method, which is characterized in that in step (4), product and H that step (3) is obtained3PW12O40Stirring at normal temperature, mistake in aqueous solution
Drying is washed in filter again.
9. a kind of poly ion liquid base heteropolyacid catalyst as described in claim 1 for epoxidation reaction of olefines is answered
With, which is characterized in that using alkene as raw material, hydrogen peroxide is oxidant, and acetonitrile is solvent, and the poly ion liquid base heteropoly acid is
Catalyst carries out back flow reaction, after filtering, recycles poly ion liquid base heteropolyacid catalyst, recycling.
10. the application of the poly ion liquid base heteropolyacid catalyst according to claim 9 for epoxidation reaction of olefines,
It is characterized in that, the alkene is cyclo-octene or cyclohexene.
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| CN109574851A (en) * | 2018-11-27 | 2019-04-05 | 浙江工业大学上虞研究院有限公司 | A kind of method that ionic liquid-catalyzed Chlorobenzene Nitration prepares dinitrofluorobenzene |
| CN114904576A (en) * | 2022-05-09 | 2022-08-16 | 河南大学 | Catalyst for glycerol condensation reaction and preparation method and application thereof |
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| CN114904576A (en) * | 2022-05-09 | 2022-08-16 | 河南大学 | Catalyst for glycerol condensation reaction and preparation method and application thereof |
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