CN104667978A - Magnetic core-shell structural solid acid material and preparation method thereof - Google Patents
Magnetic core-shell structural solid acid material and preparation method thereof Download PDFInfo
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- CN104667978A CN104667978A CN201410695771.7A CN201410695771A CN104667978A CN 104667978 A CN104667978 A CN 104667978A CN 201410695771 A CN201410695771 A CN 201410695771A CN 104667978 A CN104667978 A CN 104667978A
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Abstract
The invention provides a magnetic core-shell structural solid acid material and a preparation method thereof. The method comprises the following steps: synchronizing magnetic iron oxide by the coprecipitation method; adding vinyl trimethoxy silane to perform hydrolytic condensation to form a magnetic iron oxide core with two bonds on the surface; mixing and copolymerizing a double-bond containing sulfoacid compound monomer and surface-alkenylation magnetic iron oxide core to obtain a core-shell structural solid acid material catalyst. The catalyst is high in heat stability, stable in water, can be in contact with acidic center easily, is high in acid value, and good in catalyzing effect, and can be magnetically absorbed and recovered, and the recycling is simple and convenient.
Description
Technical field
The present invention relates to organic chemical synthesis technical field, particularly a kind of magnetic core-shell structure solid acid material 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, above-mentioned solid acid catalyst have to thermally labile, be difficult to reclaim, industrial use time selling at exorbitant prices problem.
Summary of the invention
For above-mentioned shortcoming, the present invention prepares a kind of magnetic core-shell structure solid acid material, on the basis keeping high catalytic activity, simplifies the removal process of material.Introducing double bond at magnetic oxygenated iron surface, by carrying out hybrid reaction with double bond containing sulfoacid compound, obtaining magnetic core-shell structure solid acid material.
One object of the present invention is to provide a kind of magnetic core-shell structure solid acid material, and this material heat endurance is high; Moisture-stable; Acid centre easily contacts; Acid number is high; Excellent catalytic effect; Absorb by magnetic and reclaim, recycle easy.
For achieving the above object, the present invention is by the following technical solutions:
A kind of magnetic core-shell structure solid acid material preparation method, by Co deposited synthesis magnetic oxide, add vinyltrimethoxy silane to be hydrolyzed condensation, form the magnetic oxide core that surface has double bond, more double bond containing sulfoacid compound monomer is carried out mixing copolymerization with surperficial alkenyl magnetic oxide core and forms magnetic core-shell structure solid acid material.
Further, described double bond containing sulfoacid compound monomer is the one in vinyl sulfonic acid, styrene sulfonic acid, allyl sulphonic acid, methallylsulfonic acid etc.
Preferably, described double bond containing sulfoacid compound monomer is vinyl sulfonic acid.
Another object of the present invention is to provide a kind of magnetic core-shell structure solid acid material preparation method.
For achieving the above object, the present invention is by the following technical solutions:
A preparation method for magnetic core-shell structure solid acid material catalyst as claimed in claim, comprises the following steps:
Step a, prepared by alkenyl magnetic oxide core,
By ferric trichloride and frerrous chloride in molar ratio for 2:1 is dissolved in distilled water, after stirring and dissolving, add the concentrated ammonia liquor of 25%, add the reaction of rear stirring at room temperature, after magnet absorption and separation, washing, obtains magnetic oxide after drying;
By iron oxide, ethanol, water, ammoniacal liquor and VTES carry out mechanical agitation dispersion for 1:30 ~ 150:1 ~ 10:2 ~ 5:0.5 ~ 4 in molar ratio, after room temperature reaction, use magnet absorption and separation, after washing, ethanol is washed, and in baking oven after drying, obtains the magnetic oxide core of surperficial alkenyl;
Step b, the synthesis of magnetic core-shell structure solid acid material,
By magnetic oxide core, double bond containing sulfoacid compound monomer dispersion is in ethanol and water mixed solvent, magnetic oxide core consumption is 0.1 ~ 5.0 times of sulfoacid compound weight, adding azodiisobutyronitrile is initator, after proceeding heating stirring reaction, carry out magnet absorption, reusable heat water washing, by solid drying, obtain magnetic core-shell structure solid acid material.
Preferably, in step a, distilled water consumption is 30 ~ 50 times of ferric trichloride quality.
Preferably, in step a, the consumption of concentrated ammonia liquor of 25% is 3 ~ 10 times of ferric trichloride quality.
Preferably, in step b, in ethanol and water mixed solvent, the volume ratio of second alcohol and water is 1:1.
Preferably, in step b, the amount of ethanol and water mixed solvent is 10 ~ 50 times of sulfoacid compound quality.
Preferably, in step b, the consumption of initator is 1% of sulfonic group compound quality.
Preferably, in step b, reaction temperature, wash temperature and baking temperature are 80 DEG C.
Compared with prior art, advantage of the present invention is: the magnetic core-shell structure solid acid catalyst heat endurance of invention synthesis is high, and heat decomposition temperature is more than 180 DEG C; Acid number is high, at more than 2.0mmol/g; Activated centre covers material surface, easy and reactant effect; Excellent catalytic effect, to general acid catalyzed reaction as: esterification, condensation, alkylation, etherificate etc. have very high catalytic activity; Reclaim easy, by magnetic absorption and separation, catalyst can repeatedly use.The magnetic core-shell structure solid acid catalyst of the present invention's synthesis is with a wide range of applications.
Further, the preparation method of magnetic core-shell structure solid of the present invention acid material is simple to operate, reaction temperature and, environmentally friendly, 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 magnetic core-shell structure vinyl sulfonic acid solid acid
1st step alkenyl magnetic oxide core preparation
By ferric trichloride and frerrous chloride in molar ratio for 2:1 is dissolved in distilled water, distilled water consumption is 35 times of ferric trichloride quality, after stirring and dissolving, add the concentrated ammonia liquor of 25%, be 6 times of ferric trichloride quality during consumption, add rear stirring at room temperature reaction 2h, after magnet absorption and separation, wash 3 times, in 80 DEG C of baking ovens after dry 4h, by iron oxide, ethanol, water, ammoniacal liquor and VTES are in molar ratio for 1:80:2:1:2 carries out mechanical agitation dispersion, at room temperature reaction 48h, after magnet absorption and separation, washing and ethanol wash each 3 times, the magnetic oxide core of surperficial alkenyl is obtained after dry 4h in 80 DEG C of baking ovens,
2nd step magnetic core-shell structure solid acid material
By magnetic core, double bond containing sulfoacid compound monomer dispersion is in the ethanol and water mixed solvent of volume ratio 1:1, quantity of solvent is 30 times of sulfonic group compound quality, magnetic core consumption is 1g sulfoacid compound 1.0g, add azodiisobutyronitrile, consumption is 1% of sulfonic group compound quality, proceed heating stirring reaction 12h at 80 DEG C after, carry out magnet absorption, use 80 DEG C of hot washes 3 times again, namely solid dry 12h in 80 DEG C of baking ovens is obtained magnetic core-shell structure solid acid material, acid number 3.2mmol/g, pyrolysis temperature 203 DEG C.
Embodiment 2-3
Except for the following differences, all the other are with embodiment 1, and sulfonic group compound is pressed shown in table 1 respectively, obtain following result
Table 1 embodiment 2-3 sulfonic group compound used and the catalyst parameters obtained
Embodiment 4
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 adds catalyst prepared by 0.15g embodiment, 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 5-9
Except for the following differences, all the other are with embodiment 4, and 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 2
The productive rate of the different recovered frequency of table 2 catalyst
Embodiment 10
Catalyzing and condensing reacts: having electromagnetic agitation, reflux condensing tube, catalyst prepared by 0.1mol cyclohexanone, 0.15mol ethylene glycol, 10ml cyclohexane and 0.1g embodiment 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 99.5%. catalyst reuses 5 times, and catalytic activity does not change.
Embodiment 11
Catalytic alkylation reaction: having electromagnetic agitation, reflux condensing tube, catalyst prepared by 0.1mol catechol, the 0.5mol tert-butyl alcohol and 0.1g embodiment is added in the 100mL three-necked bottle of water knockout drum, carry out heating return stirring, reaction about 4h, yield is that 91%. catalyst reuse 5 times, and catalytic activity does not change.
Embodiment 12
Catalyst etherifying reacts: having electromagnetic agitation, reflux condensing tube, catalyst prepared by 0.1mol2-naphthols, 0.3mol methyl alcohol and 0.1g embodiment is added in the 100mL three-necked bottle of water knockout drum, carry out heating return stirring, reaction about 6h, yield is that 87%. catalyst reuse 5 times, and catalytic activity does not change.
Claims (9)
1. a magnetic core-shell structure solid acid material, it is characterized in that: described catalyst is by Co deposited synthesis magnetic oxide, add vinyltrimethoxy silane to be hydrolyzed condensation, form the magnetic oxide core that surface has double bond, more double bond containing sulfoacid compound monomer is carried out mixing copolymerization with surperficial alkenyl magnetic oxide core and forms magnetic core-shell structure solid acid material catalyst.
2. sour material according to claim 1, is characterized in that: described double bond containing sulfoacid compound monomer is the one in vinyl sulfonic acid, styrene sulfonic acid, allyl sulphonic acid, methallylsulfonic acid.
3. a preparation method for magnetic core-shell structure solid acid material as claimed in claim 1, is characterized in that,
Described preparation method comprises the following steps:
Step a, prepared by alkenyl magnetic oxide core
By ferric trichloride and frerrous chloride in molar ratio for 2:1 is dissolved in distilled water, after stirring and dissolving, add the concentrated ammonia liquor of 25%, add the reaction of rear stirring at room temperature, after magnet absorption and separation, washing, obtains magnetic oxide after drying;
By iron oxide, ethanol, water, ammoniacal liquor and VTES carry out mechanical agitation dispersion for 1:30 ~ 150:1 ~ 10:2 ~ 5:0.5 ~ 4 in molar ratio, after room temperature reaction, use magnet absorption and separation, after washing, ethanol is washed, in baking oven after drying, obtain the magnetic oxide core of surperficial alkenyl;
Step b, the synthesis of magnetic core-shell structure solid acid material
By magnetic oxide core, double bond containing sulfoacid compound monomer dispersion is in ethanol and water mixed solvent, magnetic oxide core consumption is 0.1 ~ 5.0 times of sulfoacid compound weight, adding azodiisobutyronitrile is initator, after proceeding heating stirring reaction, carry out magnet absorption, reusable heat water washing, by solid drying, obtain magnetic core-shell structure solid acid material.
4. method according to claim 3, is characterized in that: in step a, distilled water consumption is 30 ~ 50 times of ferric trichloride quality.
5. method according to claim 3, is characterized in that: in step a, the consumption of concentrated ammonia liquor of 25% is 3 ~ 10 times of ferric trichloride quality.
6. method according to claim 3, is characterized in that: in step b, in ethanol and water mixed solvent, the volume ratio of second alcohol and water is 1:1.
7. method according to claim 3, is characterized in that: in step b, the amount of ethanol and water mixed solvent is 10 ~ 50 times of sulfoacid compound quality.
8. method according to claim 3, is characterized in that: in step b, the consumption of initator is 1% of sulfonic group compound quality.
9. method according to claim 3, is characterized in that: in step b, reaction temperature, wash temperature and baking temperature are 80 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109365004A (en) * | 2018-11-28 | 2019-02-22 | 武汉工程大学 | A kind of magnetic solid acid catalyst and its application for extracting saponin |
| CN111138611A (en) * | 2020-01-06 | 2020-05-12 | 河北科技大学 | Preparation method and application of magnetic sulfonated polystyrene molecular brush |
| CN112958151A (en) * | 2021-02-26 | 2021-06-15 | 曲阜师范大学 | Mesoporous poly-L-proline catalyst for catalytic synthesis of spiroindolone compounds and preparation method and application thereof |
-
2014
- 2014-11-26 CN CN201410695771.7A patent/CN104667978A/en active Pending
Non-Patent Citations (2)
| Title |
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| XUEZHENG LIANG ET AL: "Novel carbon-based strong acid catalyst from starch and its catalytic activities for acetalization", 《J MATER SCI》 * |
| XUEZHENG LIANG: "Novel Ionic Liquid Supported on a Magnetic Core and Its Catalytic Activities", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109365004A (en) * | 2018-11-28 | 2019-02-22 | 武汉工程大学 | A kind of magnetic solid acid catalyst and its application for extracting saponin |
| CN109365004B (en) * | 2018-11-28 | 2022-03-18 | 武汉工程大学 | Magnetic solid acid catalyst and application thereof in extracting saponin |
| CN111138611A (en) * | 2020-01-06 | 2020-05-12 | 河北科技大学 | Preparation method and application of magnetic sulfonated polystyrene molecular brush |
| CN112958151A (en) * | 2021-02-26 | 2021-06-15 | 曲阜师范大学 | Mesoporous poly-L-proline catalyst for catalytic synthesis of spiroindolone compounds and preparation method and application thereof |
| CN112958151B (en) * | 2021-02-26 | 2022-05-10 | 曲阜师范大学 | Mesoporous poly-L-proline catalyst for catalytic synthesis of spiroindolone compounds, and preparation method and application thereof |
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