CN104492494B - Magnetic iron oxide-immobilized ionic liquid solid acid material catalyst and preparation method thereof - Google Patents
Magnetic iron oxide-immobilized ionic liquid solid acid material catalyst and preparation method thereof Download PDFInfo
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- CN104492494B CN104492494B CN201410696483.3A CN201410696483A CN104492494B CN 104492494 B CN104492494 B CN 104492494B CN 201410696483 A CN201410696483 A CN 201410696483A CN 104492494 B CN104492494 B CN 104492494B
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Abstract
The invention provides a magnetic iron oxide-immobilized ionic liquid solid acid material catalyst and a preparation method thereof. The preparation method comprises the steps: carrying out a reaction of an olefinic bond-containing imidazole, pyridine and tertiary amine compound with propane sultone or butane sultone, to obtain olefinic bond-containing ylide; then acidifying with an acid, to obtain sulfonyl functionalized ionic liquid monomers with anions as acid radicals; followed by, synthesizing magnetic iron oxide through coprecipitation, adding mercaptoalkyl trialkoxysilane, carrying out hydrolytic condensation, and thus forming a magnetic iron oxide core having the surface with sulfydryl; and finally, carrying out mixed copolymerization of the ionic liquid monomers with the magnetic iron oxide core having the surface sulfydryl, and thus forming the magnetic iron oxide-immobilized ionic liquid solid acid material catalyst. The catalyst material has the advantages of high thermal stability, stability to water, easy contact with acidic centers, high acid value, good catalytic effect, and simple and convenient recycling, and can be recycled by magnetic absorption.
Description
Technical field
The present invention relates to organic chemical synthesis technical field, particularly a kind of magnetic iron oxide solid-loaded ionic-liquid solid acid
Material catalyst and preparation method thereof.
Background technology
There is crisis now in energy problem, environmental problem, unnecessary by-product is not produced only with a small amount of energy
Efficiently generating purpose product becomes the target of modern chemical industry pursuit.Acid catalyst is essential in modern chemistry industry
, it is widely used in the manufacture of the various productss such as medicine, petro chemical industry product, macromolecule product, but use at present
The liquid acid catalyst for being mostly hydrochloric acid, sulphuric acid etc.The liquid catalyst for using in process of production needs to be neutralized by alkali,
By removing the operations such as the salt generated by neutralization, separate from product, reclaim.But, in the removal step of above-mentioned neutralization and salt
Consume quite a few energy.In addition, the salt excess supply for commercially reclaiming, it is mostly the little by-product of availability, because
This is typically difficult to process.
Relative to above-mentioned situation, due to solid acid catalyst do not need when separating, reclaiming it is above-mentioned in and/or salt removing
Operation, can not generate unnecessary by-product, and energy-conservation ground manufacturing purpose product, therefore the research of this respect has been subject to science
Concern (Ishihara, the K of worker；Hasegawa,A；Yamamoto,H.Angew.Chem.Int.Ed.2001,40,
4077.).In terms of the research and development of solid acid catalyst, the solid acid catalysis such as zeolite, silica-alumina, aqueous niobium
Agent has become the huge achievement of chemical industry, and to society very big contribution is brought.In addition, as strong acid polymer, it is believed that will be poly-
The material that styrene sulfonation is obtained is solid acid, has been used as having acid cation exchange resin in the past.Additionally, it is known that
The Nafion (registered trade mark of E.I.Du Pont Company) with sulfo group is also to consolidate with hydrophilic extremely strong in politef skeleton
Body acid (solid super-strong acid), it is known that they work as the super acids with the acid strength more than liquid acid.But, it is above-mentioned solid
Body acid catalyst there are to thermally labile, be difficult to reclaim, industrially use when selling at exorbitant prices problem.
Accordingly, from from the aspect of performance and cost etc., using solid acid catalyst ratio aforesaid liquid acid is used
It is more difficult to design favourable industrial processes, now almost all of Chemical Industries all rely on liquid acid catalyst.Ionic liquid
The attention of Chinese scholars is constantly subjected to as a kind of environmental protection catalyst and reaction dissolvent.
But ionic liquid recovery in use, particularly reacts in the alcohols larger with polarity, carboxylic-acid substance
Afterwards, cannot be reclaimed due to delamination in Organic substance can be dissolved in.
The content of the invention
For drawbacks described above, the present invention provides a kind of immobilized ionic liquid solid-acid material catalyst and its preparation side
Method, on the basis of ionic liquid high catalytic activity is kept, simplifies the removal process of material.Introduce in conventional ion liquid double
Key, by the magnetic iron oxide core with surface sulfhydrylation hybrid reaction is carried out, and obtains magnetic iron oxide solid-loaded ionic-liquid solid
Sour material.
It is an object of the present invention to provide a kind of magnetic iron oxide solid-loaded ionic-liquid solid-acid material catalyst, should
Catalyst heat stability is high；Moisture-stable；Acid number is high；Excellent catalytic effect；Can be absorbed by magnetic and be reclaimed, be recycled easy.
For achieving the above object, the present invention is employed the following technical solutions：
A kind of magnetic iron oxide solid-loaded ionic-liquid solid-acid material catalyst and preparation method thereof, using the miaow containing ethylene linkage
Azoles, pyridine and tertiary amine compounds and propane sultone or butane sultone reaction, obtain the inner salt containing ethylene linkage, then are entered with acid
Row acidifying, obtains the sulfonic functional ion liquid monomer that anion is acid group, then, by Co deposited synthesis magnetic oxygen
Change ferrum, add mercapto alkyltrialkoxysilaneand to be hydrolyzed condensation, form the magnetic iron oxide core that surface has sulfydryl, finally general
Ionic liquid monomer carries out mixing copolymerization with the magnetic iron oxide core containing surface sulfydryl, forms magnetic iron oxide solid-loaded ionic-liquid
Solid-acid material catalyst.
Further, the described compound containing ethylene linkage be vinyl imidazole, allyl imidazole, 2- vinylpyridines, 4- ethylene
One kind in pyridine, triallylamine etc., preferably vinyl imidazole.
Further, described acid is sulphuric acid, hydrochloric acid, phosphoric acid, the one kind in p-methyl benzenesulfonic acid etc., preferably sulphuric acid.
Further, described mercapto alkyltrialkoxysilaneand be mercapto ethyl trimethoxy silane, mercapto propyl trimethoxy silicon
One kind in alkane, mercaptoethyltriethoxysilane, mercaptopropyltriethoxysilane etc., preferably mercaptopropyltriethoxysilane.
Further object is that providing a kind of preparation of magnetic iron oxide solid-loaded ionic-liquid solid-acid material
Method.
For achieving the above object, the present invention is employed the following technical solutions：
A kind of preparation method of magnetic iron oxide solid-loaded ionic-liquid solid-acid material, comprises the following steps:
Step a, the preparation of inner salt, with the imidazoles containing ethylene linkage, pyridine and tertiary amine compounds as raw material, adds propane sulphur
After lactone or butane sultone mixing, it is stirred at room temperature and obtains inner salt, wherein the imidazoles containing ethylene linkage, pyridine and tertiary amine compounds
It is 1 with the mol ratio of propane sultone or butane sultone:1；
Step b, acidifying, the acid of the amount of substance such as addition in inner salt, mixing revolving forms homogeneous ionic liquid monomer；
Step c, ferric chloride and ferrous chloride are in molar ratio 2 by the preparation of magnetic iron oxide core：1 is dissolved in distilled water
In, after stirring and dissolving, 25% strong aqua ammonia is added, reaction is stirred at room temperature, after Magnet absorption and separation, washing is dried；
By ferrum oxide, ethanol, water, ammonia and mercapto alkyltrialkoxysilaneand are in molar ratio 1：30～150：1～10：2
～5：0.5～4 carries out mechanical agitation dispersion, in room temperature reaction, with Magnet absorption and separation after, respectively washing and ethanol wash, be dried
The magnetic iron oxide core that surface has sulfydryl is obtained afterwards；
Step d, ionic liquid monomer obtained in step b is dissolved in ethanol and water mixed solvent, obtained in step c
Magnetic iron oxide core is added in above-mentioned ionic liquid solution, and magnetic core consumption is 0.1～5.0 times of ionic liquid weight, plus
Enter azodiisobutyronitrile initiator, heated and stirred after hydrolytic condensation, carries out Magnet absorption, and reusable heat water washing is obtained final product after being dried
Magnetic iron oxide solid-loaded ionic-liquid solid-acid material catalyst.
Further, water consumption is distilled in step c for 30～50 times of ferric chloride quality.
Further, the consumption of 25% strong aqua ammonia is 3～10 times of ferric chloride quality in step c.
Further, the volume ratio of second alcohol and water is 1 in ethanol and water mixed solvent in step d:1.
Further, the amount of ethanol and water mixed solvent is 10～50 times of ionic liquid monomer quality in step b.
Further, the consumption of initiator is the 1% of ionic liquid monomer quality in step b.
Preferably, reaction temperature, wash temperature and baking temperature are 80 DEG C in step b.
Compared with prior art, it is an advantage of the invention that：The magnetic iron oxide solid-loaded ionic-liquid solid of present invention synthesis
Sour material catalyst heat stability is high, and heat decomposition temperature is more than 180 DEG C；Acid number is high, in more than 2.6mmol/g；Active center
Material surface is covered in, is easily acted on reactant；Excellent catalytic effect, to general acid catalyzed reaction such as：Esterification, condensation, alkyl
Change, etherificate etc. have very high catalysis activity；Reclaim easy, can be repeated several times and use by magnetic absorption and separation, catalyst.This
The magnetic iron oxide solid-loaded ionic-liquid solid-acid material catalyst of invention synthesis is with a wide range of applications.
Further, the preparation method operation letter of magnetic iron oxide solid-loaded ionic-liquid solid-acid material catalyst of the present invention
Single, reaction is gentle, environmentally friendly, and yield is high.
Specific embodiment
Below will the present invention is further elaborated by specific embodiment：
Embodiment 1
The preparation of the immobilized vinyl imidazol sulfate ion liquid solid acid material of magnetic iron oxide
The preparation of the 1st step inner salt
The vinyl imidazol of amount of substance and the raw material of Isosorbide-5-Nitrae-butane sultone such as weigh, be stirred at room temperature after 72h and obtain white
The solid salt of color, then sucking filtration, after washing 3 times for 99% ether with concentration, 60 DEG C carry out vacuum drying, obtain final product inner salt；
2nd step is acidified
Inner salt and sulphuric acid, phosphoric acid, hydrochloric acid or p-methyl benzenesulfonic acid are carried out to mix revolving, the consumption of acid and the thing of inner salt
Quality is equal, and revolving 4h is carried out at 80 DEG C, obtains homogeneous ionic liquid monomer；
It is prepared by the 3rd step sulfhydrylation magnetic iron oxide core
It is in molar ratio 2 by ferric chloride and ferrous chloride：1 is dissolved in distilled water, and distillation water consumption is tri-chlorination irony
35 times of amount, after stirring and dissolving, add 25% strong aqua ammonia, are 4 times of ferric chloride quality during consumption, are stirred at room temperature after adding
Reaction 2h, after Magnet absorption and separation, washes 3 times, is dried after 4h in 80 DEG C of baking ovens, by ferrum oxide, ethanol, water, ammonia and mercapto
Propyl-triethoxysilicane is in molar ratio 1：100：8：3：1 carries out mechanical agitation dispersion, in room temperature reaction 48h, is inhaled with Magnet
Contracture is washed and ethanol is washed each 3 times from rear, is dried in 80 DEG C of baking ovens after 4h and is obtained the magnetic iron oxide core that surface has sulfydryl；
4th step magnetic iron oxide solid-loaded ionic-liquid solid-acid material
Ionic liquid monomer is dissolved in into volume ratio 1:In 1 ethanol and water mixed solvent, quantity of solvent is ionic liquid list
20 times of weight, add azodiisobutyronitrile initiator, consumption to be the 0.5% of ionic liquid monomer quality, add after dissolving
Sulfhydrylation magnetic iron oxide core, magnetic core consumption is 1g ionic liquid 1.0g, and heated and stirred hydrolysis contracting is proceeded at 80 DEG C
After closing 12h, Magnet absorption is carried out, then with 80 DEG C of hot washes 3 times, solid is dried into 12h in 80 DEG C of baking ovens and obtains final product ionic liquid
The immobilized magnetic solid acid material of body, acid number 3.8mmol/g, 213 DEG C of pyrolysis temperature.
Embodiment 2-6
Except for the following differences, remaining with embodiment 1, alkenyl compound as shown in table 1, obtains following result respectively.
Alkenyl compound used by embodiment 2-6 of table 1 and the catalyst parameters for obtaining
Embodiment 7-9
Except for the following differences, remaining with embodiment 1, different acid the results are shown in Table 2.
Acid used by embodiment 7-9 of table 2 and the catalyst parameters for obtaining
Embodiment 10
Catalytic esterification:Electromagnetic agitation is being had, thermometer, reflux condensing tube adds in the 100mL three-necked bottles of water knockout drum
Entering 0.1mol citric acids, 0.45mol n-butyl alcohol carries out heated and stirred, and acidity is measured by sampling after citric acid is entirely molten, is subsequently adding
Catalyst obtained in 0.15g embodiments 1, carries out being heated to reflux stirring, the water that reaction is produced is separated from water knockout drum, reacts 4h,
Calculated yield is 99.4%.
Embodiment 11-15
Except for the following differences, remaining is reacted after terminating with embodiment 8, and catalyst is recovered by filtration, and uses washing with acetone
Afterwards, it is placed in after being dried in 100 DEG C of baking ovens, continues to react, the results are shown in Table 3.
The yield of the catalyst of table 3 difference recovered frequency
Embodiment 16
Catalyzing and condensing reacts:Electromagnetic agitation is being had, reflux condensing tube is added in the 100mL three-necked bottles of water knockout drum
0.1mol Ketohexamethylene, 0.15mol ethylene glycol, 10ml hexamethylene and catalyst obtained in 0.1g embodiments 1, carry out being heated to reflux stirring
The water that mixing produces reaction is steamed with entrainer azeotropic, reaction 1.5h or so, and yield is that 99.3%. catalyst is reused 5 times, catalysis
Activity is without change.
Embodiment 17
Catalytic alkylation reaction:Electromagnetic agitation is being had, reflux condensing tube is added in the 100mL three-necked bottles of water knockout drum
0.1mol catechols, the 0.15mol tert-butyl alcohols and catalyst obtained in 0.1g embodiments 1, carry out being heated to reflux stirring, react 4h
Left and right, yield is that 95%. catalyst are reused 5 times, and catalysis activity does not change.
Embodiment 18
Catalyst etherifying reacts:Electromagnetic agitation is being had, reflux condensing tube is added in the 100mL three-necked bottles of water knockout drum
0.1mol2- naphthols, 0.15mol methanol and catalyst obtained in 0.1g embodiments 1, carry out being heated to reflux stirring, and 6h is left for reaction
The right side, yield is that 93%. catalyst are reused 5 times, and catalysis activity does not change.
Claims (9)
1. a kind of magnetic iron oxide solid-loaded ionic-liquid solid-acid material catalyst, it is characterised in that：The catalyst is adopted and contained
The imidazoles of ethylene linkage, pyridine or tertiary amine compounds and propane sultone or butane sultone reaction, obtain the inner salt containing ethylene linkage,
It is acidified with acid again, is obtained the sulfonic functional ion liquid monomer that anion is acid group, then, is closed by coprecipitation
Into magnetic iron oxide, mercapto alkyltrialkoxysilaneand is added to be hydrolyzed condensation, formation surface has the magnetic iron oxide of sulfydryl
Core, ionic liquid monomer and the magnetic iron oxide core containing surface sulfydryl finally carried out mixing copolymerization, is formed magnetic iron oxide and is consolidated
Borne ionic liquid solid-acid material catalyst；The described compound containing ethylene linkage be vinyl imidazole, 2- vinylpyridines, three allyls
One kind in amine.
2. catalyst according to claim 1, it is characterised in that：Described acid be sulphuric acid, hydrochloric acid, phosphoric acid, to toluene sulphur
One kind in acid.
3. catalyst according to claim 1, it is characterised in that：Described mercapto alkyltrialkoxysilaneand is mercapto ethyl three
Methoxy silane, mercaptopropyl trimethoxysilane, mercaptoethyltriethoxysilane, the one kind in mercaptopropyltriethoxysilane.
4. a kind of preparation method of magnetic iron oxide solid-loaded ionic-liquid solid-acid material catalyst as claimed in claim 1,
It is characterized in that：
Comprise the following steps：
Step a, the preparation of inner salt, with the imidazoles containing ethylene linkage, pyridine or tertiary amine compounds as raw material, adds propane sultone
Or after butane sultone mixing, be stirred at room temperature and obtain inner salt, wherein the imidazoles containing ethylene linkage, pyridine or tertiary amine compounds and third
The mol ratio of alkane sultone or butane sultone is 1:1；
Step b, acidifying, the acid of the amount of substance such as addition in inner salt, mixing revolving forms homogeneous ionic liquid monomer；
Step c, ferric chloride and ferrous chloride are in molar ratio 2 by the preparation of magnetic iron oxide core：1 is dissolved in distilled water, stirs
After mixing dissolving, 25% strong aqua ammonia is added, reaction is stirred at room temperature, after Magnet absorption and separation, washing is dried；
By ferrum oxide, ethanol, water, ammonia and mercapto alkyltrialkoxysilaneand are in molar ratio 1：30～150：1～10：2～5：
0.5～4 carries out mechanical agitation dispersion, in room temperature reaction, with Magnet absorption and separation after, respectively washing and ethanol wash, be dried after
Surface has the magnetic iron oxide core of sulfydryl；
Step d, ionic liquid monomer obtained in step b is dissolved in ethanol and water mixed solvent, obtained magnetic in step c
Ferrum oxide core is added in above-mentioned ionic liquid solution, and magnetic core consumption is 0.1～5.0 times of ionic liquid weight, adds even
Nitrogen bis-isobutyronitrile initiator, heated and stirred after hydrolytic condensation, carries out Magnet absorption, and reusable heat water washing obtains final product magnetic after being dried
Ferrum oxide solid-loaded ionic-liquid solid-acid material catalyst.
5. method according to claim 4, it is characterised in that：Water consumption is distilled in step c for the 30 of ferric chloride quality
～50 times.
6. method according to claim 4, it is characterised in that：The consumption of 25% strong aqua ammonia is tri-chlorination irony in step c
3～10 times of amount.
7. method according to claim 4, it is characterised in that：Second alcohol and water in ethanol and water mixed solvent in step d
Volume ratio is 1:1.
8. method according to claim 4, it is characterised in that：The amount of ethanol and water mixed solvent is ionic liquid in step d
10～50 times of body monomer mass.
9. method according to claim 4, it is characterised in that：The consumption of initiator is ionic liquid monomer matter in step d
The 1% of amount.
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