CN105032485A - Double-functional organic compound type solid acid and preparation method thereof - Google Patents
Double-functional organic compound type solid acid and preparation method thereof Download PDFInfo
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Abstract
The invention provides a double-functional organic compound type solid acid and a preparation method thereof. The double-functional organic compound type solid acid comprises silicon dioxide small balls which are used as carriers; polystyrene sulfonic acid is grafted on the silicon dioxide small balls; in a single water phase, the proceeding of catalyzing fructose to dehydrate to generate HMF is facilitated, and the inhibition on occurrence of an HFM rehydration reaction is also facilitated; and compared with polystyrene sulfonic acid PSSH, the catalytic performance is remarkably improved and the yield of the HFM reaches 40%.
Description
Technical field
The present invention relates to field of nanocomposite materials, especially relate to a kind of difunctional organic composite type solid acid.
Background technology
Composite technology is by two or more material of different nature, by the method for physics or chemistry, is combined into the material with several functions from molecular level.Because various material makes up for each other's deficiencies and learn from each other in performance, produce cooperative effect, so the combination property of the composite obtained is better than former composition material, thus various different requirement can be met.But conventional composite materials be macroscopically performance add and and collaborative, there is certain limitation, and the exploitation developing into advanced composite material (ACM) of nanosecond science and technology opens new field.
Hydroxymethylfurfural (HMF), as a kind of important biomass derivatives, be considered to produce fine chemistry, in the production process of hydroxymethylfurfural, generally be used alone GPPS sulfonic acid as catalyst, but its catalytic efficiency is very low, so in single aqueous phase, need a kind of carrying out both being conducive to catalysis fructose dehydration generation HMF, be conducive to again the product of the generation suppressing the rehydrated reaction of HMF.
Summary of the invention
For solving the problems of the prior art, the difunctional organic composite type solid acid of one that the present invention proposes, comprises silicon oxide pellets as carrier, grafting GPPS sulfonic acid on described silicon oxide pellets.
The preparation method of above-mentioned difunctional organic composite type solid acid, comprises the following steps:
A, prepare silicon oxide pellets: ammoniacal liquor and positive cinnamic acid second vinegar are dissolved in respectively in ethanol, at room temperature stir 12h by agitator, the solid particle of generation is separated by centrifuge, again disperse in ethanol and centrifugation.The ethanol (twice) of washing process Bian below-water (twice)-ethanol (one time), the solid finally obtained is drying at room temperature under certain air velocity;
B, initator graft in silicon oxide pellets surface;
C, GPPS sulfonic acid graft in silicon oxide pellets surface by initator;
Preferably, initator is that 4-chloromethylbenzene second is rare, and under nitrogen atmosphere protection, put into flask, be expelled to by triethoxysilane in flask, add the Pt complex compound be dissolved in dimethylbenzene subsequently, whole mixture stirs under 45 DEG C of conditions,
After reaction terminates, excessive triethoxysilane is by the removing of vacuum under 45 DEG C of conditions, and product carrys out separating-purifying by column chromatography;
Preferably, the method that GPPS sulfonic acid grafts in silicon oxide pellets surface by initator is: be dispersed in by the product in b in first alcohol and water, by the dispersed system that ultrasonic formation one is stable, CuCl, Sodium p-styrenesulfonate and chlorotoluene mix in a nitrogen atmosphere, freeze-thaw pump round-robin method is adopted to carry out degassed to whole system, after adding pentamethyl diethyl refining triamine, under 75 DEG C of conditions, carry out polymerisation, finally carry out flushing and obtain product.
Preferably, described 4-chloromethylbenzene second is rare with the ratio of triethoxysilane is: 1.2-2.3:1.
Difunctional organic composite type solid acid that the present invention proposes and preparation method thereof has following beneficial effect: in single aqueous phase, both the carrying out that the dehydration of catalysis fructose generates HMF had been conducive to, be conducive to again the generation suppressing the rehydrated reaction of HMF, compare GPPS sulfonic acid PSSH, catalytic performance significantly improves, and the productive rate of HMF reaches 40%.
Detailed description of the invention
Below in conjunction with detailed description of the invention, illustrate the present invention further.
Embodiment 1
The difunctional organic composite type solid acid of one that the present invention proposes, comprises silicon oxide pellets as carrier, grafting GPPS sulfonic acid on described silicon oxide pellets.
The preparation method of above-mentioned difunctional organic composite type solid acid, comprises the following steps:
A, prepare silicon oxide pellets: ammoniacal liquor and positive cinnamic acid second vinegar are dissolved in respectively in ethanol, at room temperature stir 12h by agitator, the solid particle of generation is separated by centrifuge, again disperse in ethanol and centrifugation.The ethanol (twice) of washing process Bian below-water (twice)-ethanol (one time), the solid finally obtained is drying at room temperature under certain air velocity;
B, initator graft in silicon oxide pellets surface;
C, GPPS sulfonic acid graft in silicon oxide pellets surface by initator;
Preferably, initator is that 4-chloromethylbenzene second is rare, and under nitrogen atmosphere protection, put into flask, be expelled to by triethoxysilane in flask, add the Pt complex compound be dissolved in dimethylbenzene subsequently, whole mixture stirs under 45 DEG C of conditions,
After reaction terminates, excessive triethoxysilane is by the removing of vacuum under 45 DEG C of conditions, and product carrys out separating-purifying by column chromatography;
Preferably, the method that GPPS sulfonic acid grafts in silicon oxide pellets surface by initator is: be dispersed in by the product in b in first alcohol and water, by the dispersed system that ultrasonic formation one is stable, CuCl, Sodium p-styrenesulfonate and chlorotoluene mix in a nitrogen atmosphere, freeze-thaw pump round-robin method is adopted to carry out degassed to whole system, after adding pentamethyl diethyl refining triamine, under 75 DEG C of conditions, carry out polymerisation, finally carry out flushing and obtain product.
Preferably, described 4-chloromethylbenzene second is rare with the ratio of triethoxysilane is: 1.2-2.3:1.
By the product of said method generation under 120 DEG C of conditions, catalysis fructose dehydration 6 hours in single aqueous phase,
Comparative example:
Use GPPS sulfonic acid under 120 DEG C of conditions, catalysis fructose dehydration 6 hours in single aqueous phase,
The HMF yield that the organic composite type solid acid using the present invention to propose is made and conversion ratio test have following effect with the HMF yield of directly adding GPPS sulfonic acid:
Organic composite type solid acid productive rate of HMF in aqueous phase reactions of proposition of the present invention is higher.
The stability test result of HMF yield: the output capacity of above-mentioned reaction being carried out repeatedly HMF after four times:
Through the repetition test of four times, use the organic composite type solid acid of the present invention's proposition as catalyst, can stablize and ensure about 40%, and each production rate of comparative example is unstable, the production stability of visible catalyst is strong.
To be apparent for those skilled in the art to the multiple amendment of embodiment, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (5)
1. a difunctional organic composite type solid acid, is characterized in that, comprises silicon oxide pellets as carrier, grafting GPPS sulfonic acid on described silicon oxide pellets.
2. the preparation method of difunctional organic composite type solid acid according to claim 1, is characterized in that, comprise the following steps:
A, prepare silicon oxide pellets: ammoniacal liquor and positive cinnamic acid second vinegar are dissolved in respectively in ethanol, at room temperature stir 12h by agitator, the solid particle of generation is separated by centrifuge, again disperse in ethanol and centrifugation; The ethanol (twice) of washing process Bian below-water (twice)-ethanol (one time), the solid finally obtained is drying at room temperature under certain air velocity;
B, initator graft in silicon oxide pellets surface;
C, GPPS sulfonic acid graft in silicon oxide pellets surface by initator.
3. the preparation method of difunctional organic composite type solid acid according to claim 2; it is characterized in that; initator is that 4-chloromethylbenzene second is rare, under nitrogen atmosphere protection, puts into flask; triethoxysilane is expelled in flask; add the Pt complex compound be dissolved in dimethylbenzene subsequently, whole mixture stirs under 45 DEG C of conditions, after reaction terminates; excessive triethoxysilane is by the removing of vacuum under 45 DEG C of conditions, and product carrys out separating-purifying by column chromatography.
4. the preparation method of difunctional organic composite type solid acid according to claim 2, it is characterized in that, the method that GPPS sulfonic acid grafts in silicon oxide pellets surface by initator is: be dispersed in by the product in b in first alcohol and water, by the dispersed system that ultrasonic formation one is stable, CuCl, Sodium p-styrenesulfonate and chlorotoluene mix in a nitrogen atmosphere, freeze-thaw pump round-robin method is adopted to carry out degassed to whole system, after adding pentamethyl diethyl refining triamine, under 75 DEG C of conditions, carry out polymerisation, finally carry out flushing and obtain product.
5. the preparation method of difunctional organic composite type solid acid according to claim 3, is characterized in that, described 4-chloromethylbenzene second is rare with the ratio of triethoxysilane is: 1.2-2.3:1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106902870A (en) * | 2017-02-21 | 2017-06-30 | 湖北硒诺唯新功能化硅胶材料有限公司 | Functionalization material and its production technology with use |
| CN108586393A (en) * | 2018-01-31 | 2018-09-28 | 天津工业大学 | A kind of preparation method of 5 hydroxymethyl furfural |
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| CN103992425A (en) * | 2014-05-16 | 2014-08-20 | 江苏大学 | Method for preparing macroporous solid acid catalyst by Pickering emulsion polymerization |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106902870A (en) * | 2017-02-21 | 2017-06-30 | 湖北硒诺唯新功能化硅胶材料有限公司 | Functionalization material and its production technology with use |
| CN106902870B (en) * | 2017-02-21 | 2018-08-21 | 湖北硒诺唯新功能化硅胶材料有限公司 | Functionalization material and its production technology and use |
| CN108586393A (en) * | 2018-01-31 | 2018-09-28 | 天津工业大学 | A kind of preparation method of 5 hydroxymethyl furfural |
| CN108586393B (en) * | 2018-01-31 | 2022-04-22 | 天津工业大学 | Preparation method of 5-hydroxymethylfurfural |
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