CN104492485B - Acidic ionic liquid-coated polymeric core solid acid material catalyst and preparation method thereof - Google Patents
Acidic ionic liquid-coated polymeric core solid acid material catalyst and preparation method thereof Download PDFInfo
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- CN104492485B CN104492485B CN201410704254.1A CN201410704254A CN104492485B CN 104492485 B CN104492485 B CN 104492485B CN 201410704254 A CN201410704254 A CN 201410704254A CN 104492485 B CN104492485 B CN 104492485B
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Abstract
The invention provides an acidic ionic liquid-coated polymeric core solid acid material catalyst and a preparation method thereof. The catalyst adopts imidazole containing ethylenic bonds, pyridine or a tertiary amine compound to react with propane sultone or butane sultone to obtain a ylide containing the ethylenic bonds, acidification is performed to obtain an ionic liquid monomer, divinylbenzene is self-polymerized in acetonitrile to form a polymeric core containing surface double bonds, and the prepared ionic liquid monomer and the polydivinylbenzene core are co-polymerized to form the acidic ionic liquid-coated polymeric core solid acid material catalyst. The catalyst material has the advantages of high thermal stability, easiness in contact with an active center, high acid value of above 3.0mmol/g, relatively large surface area and good catalytic effect, and can be used repeatedly.
Description
Technical field
The present invention relates to organic chemical synthesis technical field, particularly a kind of acidic ion liquid parcel polymer core solid
Sour material catalyst and preparation method thereof.
Background technology
Crisis occurs now in energy problem, environmental problem, unnecessary by-product is not only produced with a small amount of energy
Efficiently generating purpose product becomes the target of modern chemical industry pursuit.In modern chemistry industry, acid catalyst is essential
, it is widely used in the manufacture of the various productss such as medicine, petro chemical industry product, macromolecule product, but current use
The liquid acid catalyst being mostly hydrochloric acid, sulphuric acid etc.The liquid catalyst using in process of production needs to be neutralized by alkali,
By removing the operations such as the salt being 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 commercially reclaiming, it is mostly the little by-product of availability, because
This is typically difficult to process.
With respect to above-mentioned situation, due to solid acid catalyst do not need when separating, reclaiming above-mentioned in and/or salt removing
Operation, can not generate unnecessary by-product, and energy-conservation ground manufacturing purpose product, the therefore research of this respect have 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, brings very big contribution to society.In addition, as strong acid polymer it is believed that will gather
The material that styrene sulfonation obtains is solid acid, has been used as the cation exchange resin with acidity in the past.Additionally, it is known that
The Nafion (registered trade mark of E.I.Du Pont Company) in politef skeleton with sulfo group is also to have hydrophilic extremely strong consolidating
Body acid (solid super-strong acid) is it is known that they work as the super acids of the acid strength having more than liquid acid.But, have to heat
The problem of selling at exorbitant prices during unstable, industrial use.Accordingly, from the aspect of performance and cost etc., using solid
Body acid catalyst is more difficult to design favourable industrial processes than using aforesaid liquid acid, now almost all of Chemical Industries all according to
Rely in liquid acid catalyst.Ionic liquid is constantly subjected to Chinese scholars as a kind of environmental protection catalyst and reaction dissolvent
Pay attention to.
But ionic liquid recovery in use, particularly reacts in the alcohols larger with polarity, carboxylic-acid substance
Afterwards, cannot reclaim because meeting is dissolved in delamination in Organic substance.
Content of the invention
For solving the above problems, nucleocapsid structure acidic ion liquid parcel polymeric material is prepared in consideration of the present invention, is protecting
On the basis of holding ionic liquid high catalytic activity, simplify the removal process of material.Introducing in traditional glyoxaline ion liquid can
The double bond of polymerization so as in poly- divinyl benzene nucleus surface aggregate, synthetic acidic ionic liquid wraps up polymer core solid-acid material,
The problems such as solving traditional polymerization process and easily cause active center and embed.
It is an object of the present invention to provide a kind of acidic ion liquid wraps up polymer core solid-acid material catalyst,
This catalyst recycles easy；Heat stability is high；Moisture-stable；Sour species is many；Excellent catalytic effect.
For achieving the above object, the present invention employs the following technical solutions：
A kind of acidic ion liquid wraps up polymer core solid-acid material catalyst, using the imidazoles containing ethylene linkage, pyridine and
Tertiary amine compounds are reacted with propane sultone or butane sultone, obtain containing can polyene key inner salt, then carry out acid with acid
Change, obtain the sulfonic functional ion liquid monomer that anion is acid group, then, divinylbenzene is being carried out certainly in acetonitrile
Poly-, form the polymer core containing surface double-bond, finally the ionic liquid monomer of preparation and poly- divinyl benzene nucleus are carried out copolymerization, shape
Become acidic ion liquid parcel polymer core solid-acid material catalyst.
Further, described double bond containing compound is vinyl imidazole, allyl imidazole, 2- vinylpyridine, 4- ethylene
Pyridine, one of triallylamine etc., preferably vinyl imidazole.
Further, described acid is sulphuric acid, hydrochloric acid, phosphoric acid, one of p-methyl benzenesulfonic acid etc., preferably sulphuric acid.
Further object is that providing a kind of acidic ion liquid parcel polymer core solid-acid material catalysis
Agent, this preparation method is simple, high income.
For achieving the above object, the present invention employs the following technical solutions：
A kind of acidic ion liquid wraps up the preparation method of polymer core solid-acid material catalyst, comprises the following steps：
Step a, the preparation of inner salt, with the imidazoles containing ethylene linkage, pyridine or tertiary amine compounds as raw material, add propane sulphur
After lactone or butane sultone mixing, it is stirred at room temperature and obtains inner salt；Wherein contain imidazoles, pyridine or the tertiary amine compounds of ethylene linkage
Mol ratio with propane sultone or butane sultone is 1:1；
Step b, acidifying, inner salt is dissolved in ethanol water mixed solvent, the acid of the amount of material such as addition is entered in room temperature
Row stirring, obtains the ionic liquid solution that homogeneous anion is acid group；
Step c, the preparation of poly- divinyl benzene nucleus, by divinylbenzene, acetonitrile and azodiisobutyronitrile according to mol ratio are
1：(80～200)：0.00001 ratio mixing, heated and stirred is polymerized, is then filtered, acetonitrile is washed, and after ethanol is washed, is drying
It is dried in case, obtain final product poly- divinyl benzene nucleus；
Step d, acidic ion liquid wraps up the synthesis of polymer core solid-acid material, the ionic liquid being obtained in step b
Add poly- divinyl benzene nucleus in solution, the consumption of poly- divinyl benzene nucleus is 1.0～10.0 times of ionic liquid weight, add azo
Bis-isobutyronitrile initiator, heated and stirred is polymerized, and is then filtered, and with ethanol, after water is washed, is dried, obtains final product in baking oven
Acidic ion liquid wraps up polymer core solid-acid material catalyst.
Further, the inner salt obtaining in step a is white solid, after sucking filtration, is more than 99% ether or second with concentration
After acetoacetic ester washing, carry out vacuum drying, obtain inner salt；
Preferably, in ethanol water mixed solvent in step b second alcohol and water volume ratio 1:1.
Preferably, in step c, polymerization temperature is 70 DEG C.
Preferably, in step d, polymerization temperature is 80 DEG C
Preferably, the consumption of initiator is the 0.5% of ionic liquid monomer quality.
Preferably, in step d, drying temperature is 80 DEG C.
Compared with prior art, it is an advantage of the invention that：The thermally-stabilised qualitative height of catalyst of the present invention, heat decomposition temperature exists
More than 200 DEG C；Acid number is high, in more than 3.0mmol/g；Active center distribution, on shell, is more easy to catalytic reaction；Have larger
Surface area；Excellent catalytic effect, to general acid catalyzed reaction such as：Esterification, condensation, alkylation, etherificate etc. have very high catalysis to live
Property；Catalyst reclaims simplicity, can be separated by simple filtration, can be repeated several times use.The acidic ion liquid of present invention synthesis
Parcel polymer core solid-acid material catalyst is with a wide range of applications.
Further, the preparation method of catalyst of the present invention is simple to operate, and yield is high.
Specific embodiment
Below will the present invention is further elaborated by specific embodiment：
Embodiment 1
Vinyl imidazol sulfate ion liquid wraps up the preparation of polymer core solid-acid material
The preparation of the 1st step inner salt
Weigh the vinyl imidazol raw material equal with the amount of substance of Isosorbide-5-Nitrae-butane sultone, obtain after 72h is stirred at room temperature
The solid salt of white, then sucking filtration, washs after 3 times with concentration for 99% ether, 60 DEG C carry out vacuum drying, obtain final product inner salt；
2nd step acidifying
1g inner salt is dissolved in 5g ethanol water mixed solvent, adds the sulphuric acid equal with the amount of substance of inner salt,
It is stirred under room temperature mixing 4h, obtain the ionic liquid solution that corresponding anion is bisulfate ion；
Prepared by the poly- divinyl benzene nucleus of the 3rd step
By divinylbenzene, acetonitrile and azodiisobutyronitrile are 1 according to mol ratio：100：0.00001 ratio mixing,
Carry out heated and stirred polymerization 24h at 70 DEG C, filtered, acetonitrile is washed, ethanol is dried 12h in 80 DEG C of baking ovens after washing and obtains final product poly- two
Ethylene benzene nucleus；
4th step acidic ion liquid parcel polymer core solid acid
Add polymer core in above-mentioned ionic liquid solution, consumption is 1g ionic liquid 2.0g polymer core, add even
Nitrogen bis-isobutyronitrile initiator, consumption is the 0.5% of ionic liquid monomer quality, carries out heated and stirred polymerization 12h, enter at 80 DEG C
Row filters, and with ethanol, water is washed, and 12h is dried obtains final product acidic ion liquid parcel polymer core solid in 80 DEG C of baking ovens
Acid, acid number 3.4mmol/g, 213 DEG C of pyrolysis temperature；
Embodiment 2-6
Except for the following differences, remaining with embodiment 1, alkenyl compound, respectively as shown in table 1, obtains following acidic ionic liquid
Body wraps up polymeric solid acid material catalyst.
Alkenyl compound used by table 1 embodiment 2-6 and the catalyst parameters obtaining
Embodiment 7-8
Except for the following differences, remaining is with embodiment 1, acid respectively as shown in table 2, the catalyst result such as table that different acid obtain
2.
Acid used by table 2 embodiment 7-8 and the catalyst parameters obtaining
Embodiment 9
Catalytic esterification:Having electromagnetic agitation, thermometer, reflux condensing tube, adding in the 100mL three-necked bottle of water knockout drum
Enter 0.1mol citric acid, 0.45mol n-butyl alcohol carries out heated and stirred, acidity is measured by sampling after citric acid is entirely molten, is subsequently adding
The catalyst that 0.25g embodiment 8 is obtained, carries out being heated to reflux stirring, so that the water that reaction produces is separated from water knockout drum, react 4h,
Calculated yield is 99.1%.
Embodiment 10-14
Except for the following differences, remaining with embodiment 9, after reaction terminates, 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, continue reaction, the results are shown in Table 3
The yield of table 3 catalyst difference recovered frequency
Embodiment 15
Catalyzing and condensing reacts:Having electromagnetic agitation, reflux condensing tube, adding in the 100mL three-necked bottle of water knockout drum
0.1mol Ketohexamethylene, 0.15mol ethylene glycol, 10ml hexamethylene and 0.1g embodiment 8 are obtained catalyst, carry out being heated to reflux stirring
The water that reaction produces is made to steam with entrainer azeotropic, reaction 1.5h about, yield reuses 5 times for 99.5%. catalyst, and catalysis is lived
Property does not change.
Embodiment 16
Catalytic alkylation reaction:Having electromagnetic agitation, reflux condensing tube, adding in the 100mL three-necked bottle of water knockout drum
0.1mol catechol, the 0.15mol tert-butyl alcohol and 0.1g embodiment 8 are obtained catalyst, carry out being heated to reflux stirring, reaction 4h is left
The right side, yield is that 91%. catalyst reuse 5 times, and catalysis activity does not change.
Embodiment 17
Catalyst etherifying reacts:Having electromagnetic agitation, reflux condensing tube, adding in the 100mL three-necked bottle of water knockout drum
0.1mol2- naphthols, 0.15mol methanol and 0.1g embodiment 8 are obtained catalyst, carry out being heated to reflux stirring, reaction 6h about,
Yield is that 92%. catalyst reuse 5 times, and catalysis activity does not change.
Claims (9)
1. a kind of acidic ion liquid parcel polymer core solid-acid material catalyst it is characterised in that：Described catalyst adopts
Imidazoles containing ethylene linkage, pyridine and tertiary amine compounds are reacted with propane sultone or butane sultone, obtain containing can polyene key
Inner salt, then be acidified with acid, obtain the sulfonic functional ion liquid monomer that anion is acid group, then, by diethyl
Alkene benzene is carrying out autohemagglutination in acetonitrile, forms the polymer core containing surface double-bond, finally by the ionic liquid monomer of preparation and poly-
Divinyl benzene nucleus carries out copolymerization, forms acidic ion liquid parcel polymer core solid-acid material catalyst；Described containing ethylene linkage
Imidazoles, pyridine and tertiary amine compounds be 2- vinylpyridine, 4-vinylpyridine, one of triallylamine.
2. catalyst according to claim 1 it is characterised in that：Described acid is sulphuric acid, hydrochloric acid, and phosphoric acid, to toluene sulphur
One of acid.
3. a kind of acidic ion liquid as claimed in claim 1 wraps up the preparation side of polymer core solid-acid material catalyst
Method it is characterised in that：
Described preparation method comprises the following steps：
Step a, the preparation of inner salt, with the imidazoles containing ethylene linkage, pyridine or tertiary amine compounds as raw material, add propane sultone
Or after butane sultone mixing, be stirred at room temperature and obtain inner salt；Wherein contain imidazoles, pyridine or tertiary amine compounds and third of ethylene linkage
The mol ratio of alkane sultone or butane sultone is 1:1；
Step b, acidifying, inner salt is dissolved in ethanol water mixed solvent, the acid of the amount of material such as addition is stirred in room temperature
Mix, obtain the ionic liquid solution that homogeneous anion is acid group；
Step c, the preparation of poly- divinyl benzene nucleus, by divinylbenzene, acetonitrile and azodiisobutyronitrile are 1 according to mol ratio：(80
～200)：0.00001 ratio mixing, heated and stirred is polymerized, is then filtered, acetonitrile is washed, after ethanol is washed, do in an oven
Dry, obtain final product poly- divinyl benzene nucleus；
Step d, acidic ion liquid wraps up the synthesis of polymer core solid-acid material, the ionic liquid solution being obtained in step b
The poly- divinyl benzene nucleus of middle addition, the consumption of poly- divinyl benzene nucleus is 1.0～10.0 times of ionic liquid weight, adds azo two different
Butyronitrile initiator, heated and stirred is polymerized, and is then filtered, and with ethanol, after water is washed, is dried, obtains final product acidity in baking oven
Ionic liquid wraps up polymer core solid-acid material catalyst.
4. preparation method according to claim 3 it is characterised in that：The inner salt obtaining in step a is white solid, takes out
After filter, after concentration is more than 99% ether or ethyl acetate is washed, carries out vacuum drying, obtain inner salt.
5. preparation method according to claim 3 it is characterised in that：Second alcohol and water in ethanol water mixed solvent in step b
Volume ratio 1:1.
6. preparation method according to claim 3 it is characterised in that：In step c, polymerization temperature is 70 DEG C.
7. preparation method according to claim 3 it is characterised in that：In step d, polymerization temperature is 80 DEG C.
8. preparation method according to claim 3 it is characterised in that：The consumption of initiator is ionic liquid monomer quality
0.5%.
9. preparation method according to claim 3 it is characterised in that：In step d, drying temperature is 80 DEG C.
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| CN107115892B (en) * | 2017-06-15 | 2019-03-12 | 福州大学 | The preparation of 4- methyl -5- vinylthiazole base polymeric ionic liquid and application |
| CN111036300B (en) * | 2019-12-05 | 2022-07-15 | 浙江赛迅环保科技有限公司 | Novel solid catalyst and application thereof in preparation of 2, 4-dimethyl-6-tert-butylphenol |
| CN111533837B (en) * | 2020-04-20 | 2022-02-11 | 浙江师范大学 | Acidic polymeric ionic liquid and preparation method and application thereof |
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| CN102060738A (en) * | 2010-12-10 | 2011-05-18 | 绍兴文理学院 | Ionic liquid combining B acid site and L acid site as well as preparation method and application thereof |
| CN102633929B (en) * | 2012-03-27 | 2013-11-06 | 绍兴文理学院 | Preparation method of acid ionic liquid mesoporous polymeric material |
| CN103706396B (en) * | 2014-01-06 | 2016-05-11 | 北京化工大学 | Preparation method and the application thereof of one class polydivinylbenezene-ionic liquid-polyacid catalyst |
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