CN105032485B - A kind of difunctional organic composite type solid acid and preparation method thereof - Google Patents
A kind of difunctional organic composite type solid acid and preparation method thereof Download PDFInfo
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- CN105032485B CN105032485B CN201510305664.3A CN201510305664A CN105032485B CN 105032485 B CN105032485 B CN 105032485B CN 201510305664 A CN201510305664 A CN 201510305664A CN 105032485 B CN105032485 B CN 105032485B
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Abstract
A kind of difunctional organic composite type solid acid proposed by the present invention and preparation method thereof, carrier is used as including silicon oxide pellets, grafting GPPS sulfonic acid on the silicon oxide pellets, in single aqueous phase, catalysis fructose dehydration generation HMF progress is not only improved, is conducive to suppressing the generation of the rehydrated reactions of HMF again, compared to GPPS sulfonic acid PSSH, catalytic performance is significantly improved, and HMF yield reaches 40%.
Description
Technical field
The present invention relates to field of nanocomposite materials, more particularly, to a kind of difunctional organic composite type solid acid.
Background technology
Composite technology be by two or more material of different nature, by method physically or chemically, from
The material with a variety of functions is combined on molecular level.Because various materials make up for each other's deficiencies and learn from each other in performance, collaboration is produced
Effect, so the combination property of obtained composite is better than former composition material, so as to meet a variety of requirements.But
Be conventional composite materials be macroscopically performance plus and and collaboration, with certain limitation, and developing into for nanosecond science and technology is new
Type composite opens new field.
Hydroxymethylfurfural (HMF), as a kind of important biomass derivatives, has been considered to produce fine chemistry,
In the production process of hydroxymethylfurfural, the general GPPS sulfonic acid that is used alone is as catalyst, but its catalytic efficiency is very low, institute
In single aqueous phase, to need a kind of progress for not only improving catalysis fructose dehydration generation HMF, be conducive to suppressing HMF water again again
Close the product of the generation of reaction.
The content of the invention
To solve the problems of the prior art, a kind of difunctional organic composite type solid acid proposed by the present invention, including two
Silica bead is as carrier, grafting GPPS sulfonic acid on the 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 ethanol respectively, by agitator in room temperature
Lower stirring 12h, the solid particle of generation is separated by centrifuge, is dispersed again in ethanol and is centrifuged.Washing below
Process uses ethanol (twice)-water (twice)-ethanol (one time), and the solid finally obtained room temperature under certain air velocity is done
It is dry；
B, initiator graft in silicon oxide pellets surface；
C, GPPS sulfonic acid graft in silicon oxide pellets surface by initiator；
It is preferred that, initiator is that 4- chloromethylbenzene second is dilute, under nitrogen atmosphere protection, is put into flask, by triethoxy
Silane injecting is subsequently added the Pt complex compounds being dissolved in dimethylbenzene into flask, and whole mixture is stirred under the conditions of 45 DEG C,
After reaction terminates, excessive triethoxysilane under the conditions of 45 DEG C by being removed in vacuum, and product passes through post layer
Analysis carrys out separating-purifying；
It is preferred that, the method that GPPS sulfonic acid grafts in silicon oxide pellets surface by initiator is：By the production in b
Thing is dispersed in first alcohol and water, by being ultrasonically formed a stable dispersed system, CuCl, Sodium p-styrenesulfonate and chloromethane
Benzene is well mixed in a nitrogen atmosphere, and whole system is de-gassed using freeze-thaw pump circulation method, adds pentamethyl diethyl
Refine after triamine, polymerisation is carried out under the conditions of 75 DEG C, acquisition product is finally rinsed.
It is preferred that, the dilute ratio with triethoxysilane of 4- chloromethylbenzenes second is：1.2-2.3:1.
Difunctional organic composite type solid acid proposed by the present invention and preparation method thereof has the advantages that：Single
In aqueous phase, catalysis fructose dehydration generation HMF progress is not only improved, is conducive to suppressing the generation of the rehydrated reactions of HMF again, compares
GPPS sulfonic acid PSSH, catalytic performance is significantly improved, and HMF yield reaches 40%.
Embodiment
With reference to embodiment, the present invention is furture elucidated.
Embodiment 1
A kind of difunctional organic composite type solid acid proposed by the present invention, including silicon oxide pellets are as carrier, it is described
Grafting GPPS sulfonic acid on 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 ethanol respectively, by agitator in room temperature
Lower stirring 12h, the solid particle of generation is separated by centrifuge, is dispersed again in ethanol and is centrifuged.Washing below
Process uses ethanol (twice)-water (twice)-ethanol (one time), and the solid finally obtained room temperature under certain air velocity is done
It is dry；
B, initiator graft in silicon oxide pellets surface；
C, GPPS sulfonic acid graft in silicon oxide pellets surface by initiator；
It is preferred that, initiator is that 4- chloromethylbenzene second is dilute, under nitrogen atmosphere protection, is put into flask, by triethoxy
Silane injecting is subsequently added the Pt complex compounds being dissolved in dimethylbenzene into flask, and whole mixture is stirred under the conditions of 45 DEG C,
After reaction terminates, excessive triethoxysilane under the conditions of 45 DEG C by being removed in vacuum, and product passes through post layer
Analysis carrys out separating-purifying；
It is preferred that, the method that GPPS sulfonic acid grafts in silicon oxide pellets surface by initiator is：By the production in b
Thing is dispersed in first alcohol and water, by being ultrasonically formed a stable dispersed system, CuCl, Sodium p-styrenesulfonate and chloromethane
Benzene is well mixed in a nitrogen atmosphere, and whole system is de-gassed using freeze-thaw pump circulation method, adds pentamethyl diethyl
Refine after triamine, polymerisation is carried out under the conditions of 75 DEG C, acquisition product is finally rinsed.
It is preferred that, the dilute ratio with triethoxysilane of 4- chloromethylbenzenes second is：1.2-2.3:1.
The product that the above method is produced is catalyzed fructose dehydration 6 hours under the conditions of 120 DEG C in single aqueous phase,
Comparative example：
Using GPPS sulfonic acid under the conditions of 120 DEG C, fructose dehydration is catalyzed in single aqueous phase 6 hours,
The experiment of HMF yield and conversion ratio and directly addition made using organic composite type solid acid proposed by the present invention are poly-
The HMF yield of the dilute sulfonic acid of benzene second has the following effects that：
The organic composite type solid acid of the proposition of present invention HMF yield in aqueous phase reactions is higher.
The stability test result of HMF yield：Above-mentioned reaction is repeated to the output capacity of HMF after four times：
By the repetition test of four times, catalyst, Neng Gouwen are used as using organic composite type solid acid proposed by the present invention
Ensure calmly 40% or so, and each production rate of comparative example is unstable, it is seen that the production stability of catalyst is strong.
A variety of modifications to embodiment will be apparent for those skilled in the art, determine herein
The General Principle of justice can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, originally
Invention is not intended to be limited to the embodiments shown herein, and is to fit to and principles disclosed herein and features of novelty
Consistent most wide scope.
Claims (1)
1. a kind of difunctional organic composite type solid acid, it is characterised in that including silicon oxide pellets as carrier, the dioxy
Grafting polystyrolsulfon acid on SiClx bead；Comprise the following steps that：
A, prepare silicon oxide pellets：Ammoniacal liquor and tetraethyl orthosilicate are dissolved in ethanol respectively, stirred at room temperature by agitator
12h is mixed, the solid particle of generation is separated by centrifuge, is dispersed again in ethanol and is centrifuged；Washing process below
By the way of twice of ethanol washing, twice of water washing, ethanol are washed one time, the solid finally obtained is in certain air velocity
Lower drying at room temperature；
B, initiator graft in silicon oxide pellets surface；
C, polystyrolsulfon acid graft in silicon oxide pellets surface by initiator, and specific method is：Product in b is disperseed
In first alcohol and water, by being ultrasonically formed a stable dispersed system, CuCl, SSS and chlorotoluene are in nitrogen
It is well mixed, whole system is de-gassed under gas atmosphere using freeze-thaw pump circulation method, adds after pentamethyldiethylene triamine,
Polymerisation is carried out under the conditions of 75 DEG C, acquisition product is finally rinsed；
The initiator is 4- 1-chloro-4-methyl-benzenes, under nitrogen atmosphere protection, is put into flask, triethoxysilane is injected
Into flask, the Pt complex compounds being dissolved in dimethylbenzene are subsequently added, whole mixture is stirred under the conditions of 45 DEG C, when reaction knot
Shu Hou, excessive triethoxysilane under the conditions of 45 DEG C by being removed in vacuum, and product is by column chromatography come separating-purifying；It is described
The ratio of 4- 1-chloro-4-methyl-benzenes and triethoxysilane is：1.2-2.3:1.
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| CN105032485B true CN105032485B (en) | 2017-08-25 |
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| 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 |
| CN108586393B (en) * | 2018-01-31 | 2022-04-22 | 天津工业大学 | Preparation method of 5-hydroxymethylfurfural |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103992425A (en) * | 2014-05-16 | 2014-08-20 | 江苏大学 | Method for preparing macroporous solid acid catalyst by Pickering emulsion polymerization |
| CN104258911A (en) * | 2014-08-29 | 2015-01-07 | 江苏科技大学 | Preparation method of highly cross-linked macroporous/mesoporous solid acid catalyst |
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| FR2853916B1 (en) * | 2003-04-17 | 2006-02-24 | Eastman Kodak Co | METHOD FOR IMPROVING THE OZONE STABILITY OF A MATERIAL FOR IMAGING INKJET PRINTING |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103992425A (en) * | 2014-05-16 | 2014-08-20 | 江苏大学 | Method for preparing macroporous solid acid catalyst by Pickering emulsion polymerization |
| CN104258911A (en) * | 2014-08-29 | 2015-01-07 | 江苏科技大学 | Preparation method of highly cross-linked macroporous/mesoporous solid acid catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 原位聚合SiO2/PSSS纳米复合粒子的制备及其性能;白福顺 等;《纺织学报》;20131130;第34卷(第11期);第6-10页 * |
| 磁性纳米复合粒子表面接枝聚苯乙烯磺酸钠的制备;李艳利 等;《陕西师范大学学报(自然科学版)》;20080531;第36卷(第3期);第65-69页 * |
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Address after: 215138 No. 1 Zhangtangbangxiang, Yangchenghu Town, Xiangcheng District, Suzhou City, Jiangsu Province Patentee after: Suzhou Xiangyuan New Materials Co., Ltd. Address before: 215138 Xiangcheng District, Jiangsu, Weitang Town, the village of the ten figure Patentee before: Suzhou Xiangyuan Speical Fine Chemical Co., Ltd. |
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