CN104624232B - Immobilized carbene catalyst, preparation method thereof, and method for preparing 1,3-dihydroxy acetone by using catalyst - Google Patents
Immobilized carbene catalyst, preparation method thereof, and method for preparing 1,3-dihydroxy acetone by using catalyst Download PDFInfo
- Publication number
- CN104624232B CN104624232B CN201510024406.8A CN201510024406A CN104624232B CN 104624232 B CN104624232 B CN 104624232B CN 201510024406 A CN201510024406 A CN 201510024406A CN 104624232 B CN104624232 B CN 104624232B
- Authority
- CN
- China
- Prior art keywords
- immobilized
- catalyst
- silicon dioxide
- carbone catalyst
- triethylamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a carbene catalyst immobilized by silicon oxide or polystyrene, a preparation method thereof and a method for preparing 1,3-dihydroxy acetone by catalyzing formaldehyde condensation by using the catalyst. A halogen-containing bromized 3-ethyl benzene thiazolium and toxic and harmful triethylamine are not required in the analysis process of 1,3-dihydroxy acetone, the catalyst is convenient to separate and recover and can be used repeatedly. Under an optimized process condition, the conversion rate of paraformaldehyde is close to 100%, and the selectivity of 1,3-dihydroxy acetone is greater than 90%.
Description
Technical field
The present invention relates to a kind of immobilized carbone catalyst, its preparation method and using the catalyst preparation 1,3- dihydroxy
A kind of method of benzylacetone, specifically, the present invention relates to carbone catalyst, its system by silicon oxide or polystyrene-supportedization
Preparation Method and the method for preparing C3H6O3 using the catalyst formaldehyde condensation.
Background technology
1,3-Dihydroxyacetone, abbreviation DHA is simplest three carbon ketose, and outward appearance is white or off-white powder shape knot
Crystalline substance, with sweet, cool taste, easy moisture absorption is simultaneously decomposed.It is generally in the form of dimer, to be lentamente dissolved in 1
In part water or in 15 parts of ethanol, ether is slightly soluble in, but Jing dissolvings or heating are then changed into monomer, monomer is soluble in water or ethanol
Deng organic solvent, fusing point is 75-80 DEG C, and water solublity is more than 250g/L (20 DEG C), stable when pH is 6.0, is a kind of important
Fine chemical material, medicine intermediate and multifunction additive.
In the prior art, the production method of 1,3-Dihydroxyacetone mainly have stiasny method, microbe fermentation method and
Glycerol oxidizing process.The Production by Microorganism Fermentation cycle is long, and low production efficiency, waste liquid amount is big；Glycerol oxidizing process product yield is low, compared with
Low production concentration causes later separation extraction process extremely complex, and the ratio that separation costs account for totle drilling cost is very high, does not economically have
It is advantageous.Compared with above two method, stiasny method has product yield high, and the low advantage of cost of material economically has
There is significant competitiveness.Early in 1984, Toshihiko etc. with paraformaldehyde as raw material, with bromination 3- ethyl-benzothiazole salt
For catalyst, triethylamine is auxiliary agent, and catalysis formaldehyde condensation prepares 1,3-Dihydroxyacetone.Made using N,N-dimethylformamide
For solvent when, reaction yield highest, the conversion ratio of paraformaldehyde is about 98%, and the selectivity of 1,3-Dihydroxyacetone is about 89%
(J.Am.Chem.Soc.,1984,106,4829-4832).University Of Science and Technology Of Hunan's Liu Junfeng et al. with paraformaldehyde as raw material, just
Butanol is solvent, and triethylamine is promoter, and using bromination 3- ethyl-benzothiazole salt catalysis formaldehyde condensation 1,3- dihydroxies are prepared
Benzylacetone, its yield is about 37%, and selectivity is 95-98% (fine chemistry industry, 2013,30 (2), 225-228).
Although the selectivity that above two method prepares 1,3-Dihydroxyacetone is all very high, both approaches 1,
3- ethyl-benzothiazoles salt and triethylamine are all must be added in the building-up process of 3- dihydroxy acetones as catalyst and co-catalysis
Agent, not only operates complex, separation and recovery of catalyst difficulty, and can produce some pairs for containing halogen during the course of the reaction
Product, to the separating-purifying of latter products very big difficulty is brought, and finally have impact on the quality of product.
In order to solve problems of the prior art, the present invention is urged with paraformaldehyde as raw material using immobilized Cabbeen
Agent, catalysis formaldehyde condensation prepares 1,3-Dihydroxyacetone.The present invention is not used in the building-up process of C3H6O3
Bromination 3- ethyl-benzothiazole salt containing halogen and poisonous and hazardous triethylamine, separation and recovery of catalyst is convenient, and can be again
Use again.Under the process conditions of optimization, the conversion ratio close 100% of paraformaldehyde, the selectivity of 1,3-Dihydroxyacetone is big
In 90%.
The content of the invention
It is an object of the invention to provide a kind of immobilized carbone catalyst, its preparation method, and using the catalyst
The method that catalysis formaldehyde condensation prepares C3H6O3.
According to an aspect of the present invention, the invention provides a kind of immobilized carbone catalyst, its structure is：
Wherein, n is the degree of polymerization of polystyrene support, and it is 100-
10000 integer,Represent silica support.
According to a further aspect in the invention, the invention provides the preparation method of the immobilized carbone catalyst, the party
Method is comprised the following steps：
A) choose the degree of cross linking be chlorine ball that 7, chlorinity is 12.8% as carrier, use the mixed of 1,2- dichloroethanes and ethanol
The swelling 8-16 hours of bonding solvent, the then Cl to include in chlorine ball:The mol ratio of the N included in benzothiazole is 1:1 ratio
Benzothiazole is added thereto to, after back flow reaction 8-16 hour, sucking filtration, washing, is extracted using dehydrated alcohol and is obtained quaternized
Polystyrene resins；
Wherein, the ratio of 1, the 2- dichloroethanes and ethanol is not particularly limited, preferably 1,2- dichloroethanes and second
The mass ratio of alcohol is 1:0.1~100；
B) the quaternized polystyrene resin obtained in step a) is put in the reactor containing dioxane, with chlorine ball
In the Cl that includes:The mol ratio of the N included in triethylamine is 1:1 ratio adds triethylamine, then under nitrogen protection, in
16-28h is reacted at a temperature of 373K, is filtered under nitrogen protection afterwards, and extracted using dehydrated alcohol, obtained final product after vacuum drying
Polystyrene-supported carbone catalyst；
Or,
A ') by the aqueous hydrochloric acid solution of silicon dioxide and 20wt% with 1:6~12 mass ratio mixing, and stir under 373K
The silicon dioxide of activation is filtered, is dried to obtain after reaction 3-6h；
B ') by step a ') in the silicon dioxide of activation for preparing and dry toluene and 3- bromopropyls trimethoxy silane with
Silicon dioxide, dry toluene, the mass ratio of 3- bromopropyl trimethoxy silanes are about 1:10~20:1 mixing, the lower backflow of stirring is anti-
4-12h is answered, is washed using methanol after filtration, after vacuum drying, obtain functionalized SiO 2；
C ') by step b ') in the functionalized SiO 2 for preparing mix with dry toluene, with the functionalized SiO 2
In the Br that includes:The mol ratio of the N included in benzothiazole is 1:1 ratio adds benzothiazole, lower back flow reaction 18- of stirring
30h, is washed after filtration using methanol, after vacuum drying, obtains the supported bromide of silicon dioxide；
D ') by step c ') in the supported bromide of silicon dioxide for preparing mix with dioxane, with the silicon dioxide
The Br included in supported bromide:The mol ratio of the N included in triethylamine is 1:1 ratio adds triethylamine, mixture to exist
Stirring reaction 8-24h under nitrogen protection, under 373K, is filtered under nitrogen protection afterwards, and is extracted using dehydrated alcohol, very
Sky obtains final product the immobilized carbone catalyst of silicon oxide after being dried.
Wherein, the chlorine ball can be bought from market, for example can Polymer Technology company limited purchased from Tianjin Xing Nanyun.
Specifically react as shown in formulas below 1 or reaction equation 2：
Reaction equation 1
Reaction equation 2
According to a further aspect in the invention, it provides a kind of using above-mentioned immobilized carbone catalyst catalysis formaldehyde condensation
The method for preparing 1,3-Dihydroxyacetone, the method is comprised the following steps：
It is separately added into paraformaldehyde, solvent and the immobilized carbone catalyst in reactor at room temperature, stirs, together
When be warming up to 100~150 DEG C, under nitrogen protection react 0.5~5h product is obtained.
The solvent can for ethanol, isopropanol, 1,4- dioxane, 1,3- dioxolanes, N,N-dimethylformamide,
N,N-dimethylacetamide, dimethyl sulfoxide or its mixture, preferably isopropanol, N,N-dimethylacetamide, 1,3- dioxies
Five rings, dimethyl sulfoxide or its mixture.
The solvent load is 2~10 times of paraformaldehyde quality.
The immobilized carbone catalyst consumption is 0.1~2 times of paraformaldehyde quality, preferably 0.1~0.4 times, more
Preferably 0.15~0.35 times, more preferably 0.22~0.3 times.
The reaction temperature is 100 DEG C~150 DEG C, preferably 140 DEG C~150 DEG C；The response time is 0.5~5 hour,
Preferably 1~4 hour, more preferably 2~4 hours.
After the completion of reaction, reactant liquor can be separated and recovered into catalyst, 1, the 3- dihydroxy for obtaining through simple filtration
Acetone soln directly carries out liquid-phase chromatographic analysis.
The advantage of the present invention includes：1st, the present invention is not used containing halogen in the building-up process of C3H6O3
Bromination 3- ethyl-benzothiazole salt and poisonous and hazardous triethylamine, product separation purification is easy, good product quality；2nd, the present invention
The immobilized carbone catalyst catalysis activity for being used is good, and the once through yield of 1,3-Dihydroxyacetone is high, and catalyst is separated
Reclaim convenient, can reuse.
Description of the drawings
Fig. 1 is the proton nmr spectra of the DHA prepared according to embodiments of the invention 3；
Fig. 2 is the carbon-13 nmr spectra of the DHA prepared according to embodiments of the invention 3.
Specific embodiment
The present invention is illustrated referring to specific embodiment.It will be appreciated by those skilled in the art that these embodiments are only
For the purpose of illustrating the invention, and never in any form the scope of the present invention is limited.
Each raw material sources in embodiment：Chlorine ball, Tianjin Xing Nanyun can Polymer Technology company limited；1,2- dichloroethanes,
Chinese medicines group Beijing chemical reagent company limited；Dehydrated alcohol, Chinese medicines group Beijing chemical reagent company limited；Benzothiazole,
Chinese medicines group Beijing chemical reagent company limited；Triethylamine, Chinese medicines group Beijing chemical reagent company limited；Silicon dioxide, state
Beijing chemical reagent company limited of medicine group；Hydrochloric acid, Chinese medicines group Beijing chemical reagent company limited；Dry toluene, traditional Chinese medicines collection
Beijing chemical reagent company limited of group；Paraformaldehyde, Chinese medicines group Beijing chemical reagent company limited；Absolute methanol, traditional Chinese medicines collection
Beijing chemical reagent company limited of group；Dioxane, Chinese medicines group Beijing chemical reagent company limited；Isopropanol, Chinese medicines group
Beijing chemical reagent company limited；DMAC N,N' dimethyl acetamide；Chinese medicines group Beijing chemical reagent company limited；Dimethyl is sub-
Sulfone, Chinese medicines group Beijing chemical reagent company limited.
Embodiment 1
40g chlorine balls are weighed, the mixed solvent with the ethanol of 1, the 2- dichloroethanes and 200mL of 500mL is molten as sweller
It is swollen overnight, next day is according to the Cl included in chlorine ball：The mol ratio of the N included in benzothiazole is 1:1 ratio adds benzo thiophene
Azoles, back flow reaction 12h, sucking filtration extracts 12h after washing using dehydrated alcohol, and brown color quaternized polystyrene resin is obtained.
The quaternized polystyrene resin for obtaining is put in the 500mL reactors containing 250mL dioxane, according to institute
The Cl included in the quaternized polystyrene resin stated：The mol ratio of the N included in triethylamine is 1:1 ratio adds three second
Amine, mixture under nitrogen protection with stirring reaction 24h under 373K.After reaction terminates, filtered under nitrogen protection, and will
After filter cake is using 500mL dehydrated alcohol extracting 10h, vacuum drying obtains final product immobilized carbone catalyst.
Embodiment 2
Weigh 50g silicon dioxide to be put in the there-necked flask of 500mL, add the 20% of 300mL aqueous hydrochloric acid solution, in
Stirring reaction 4h under 373K.Then, filter, be dried to obtain the silica supports of activation.Silicon dioxide after activation is put into
In the four-hole boiling flask of 1L, 400mL dry toluenes and 50mL 3- bromopropyl trimethoxy silanes are added, heated back under mechanical agitation
Stream reaction 10h, the methanol after filtration using 300mL is washed 3 times, after vacuum drying, obtains functionalized SiO 2.Use Fo Erha
It is 11.6% that moral method measures the content of bromine atoms.
The functionalized SiO 2 for obtaining is added in the four-hole boiling flask of 1L, 300mL dry toluenes is added, according to function
Change the Br that silicon dioxide is included：The mol ratio of the N included in benzothiazole is 1:1 ratio adds benzothiazole, mechanical agitation
Lower back flow reaction 18h, the methanol after filtration using 300mL is washed 3 times, after vacuum drying, obtains the supported bromine of silicon dioxide
Salt.
The supported bromide of the silicon dioxide for obtaining is put in the 1L reactors containing 500mL dioxane, according to two
The Br included in the supported bromide of silicon oxide：The mol ratio of the N included in triethylamine is 1:1 ratio adds triethylamine, mixes
Compound stirring reaction 12h under 373k under nitrogen protection.After reaction terminates, filtered under nitrogen protection, and by filter cake
After using 500mL dehydrated alcohol extracting 10h, vacuum drying obtains final product immobilized carbone catalyst.
Embodiment 3
9.01g paraformaldehydes, the 1,3- dioxolanes of 90mL and 2.53g are separately added into in 150mL reactors under room temperature
The described immobilized carbone catalyst obtained in embodiment 1, strength mechanical agitation, while temperature programming is to 140 DEG C, nitrogen is protected
The lower reaction 2.0h of shield.After reaction terminates, reactant liquor is separated by filtration recovery catalyst, the 1,3-Dihydroxyacetone solution for obtaining
Directly carry out efficient liquid phase chromatographic analysis.The conversion ratio close 100% of paraformaldehyde, the selectivity of 1,3-Dihydroxyacetone is
92.37%.
The nuclear magnetic spectrogram of the C3H6O3 obtained according to the embodiment is as shown in Figures 1 and 2.
As shown in figure 1,1(500MHz, D in H NMR spectras2O), the group peak between δ=4.5~5.0 be solvent peak, δ=
Peak between 4.0~4.5 is the H peaks on methylene-CH2, and the peak between δ=3.0~3.5 is the H peaks on-OH, both faces
Product ratio about 2, meets the quantity ratio of the upper Hs upper with-OH of-CH2.
As shown in Fig. 213(500MHz, D in C NMR spectras2O), the group peak near δ=212 is unsaturation C on carbonyl
Absworption peak, then corresponding to the saturation C peak on methylene-CH2, the nuclear-magnetism carbon spectrum of product is also demonstrated that at the group peak near δ=64
Crystallization products obtained therefrom is consistent with DHA structures.
Embodiment 4
Except being obtained in embodiment 1 using what is adopted in the catalyst alternate embodiment 3 for obtaining in example 2
The catalyst beyond, with conditioned response same as Example 3, its analysis result shows, the conversion ratio of paraformaldehyde connects
Nearly 100%, the selectivity of 1,3-Dihydroxyacetone is 95.01%.
Embodiment 5~7
In using table 1 below in addition to listed catalyst amount, mode same as Example 3 prepares 1,3- dihydroxies
Benzylacetone, its specific experiment result is listed in table 1.
Table 1
| Embodiment title | Solid-supported catalyst consumption | Conversion ratio % | Selectivity % |
| Embodiment 5 | 1.51g | 89.04 | 90.16 |
| Embodiment 6 | 2.05g | 96.75 | 92.93 |
| Embodiment 7 | 3.01g | ≈100 | 88.42 |
Embodiment 8~10
In addition to response time in using table 2 below, mode same as Example 3 prepares 1,3-Dihydroxyacetone,
Its specific experiment result is listed in table 2.
Table 2
| Embodiment title | Response time | Conversion ratio % | Selectivity % |
| Embodiment 8 | 1.0h | 72.54 | 90.62 |
| Embodiment 9 | 3.0h | ≈100 | 93.08 |
| Embodiment 10 | 4.0h | ≈100 | 85.11 |
Embodiment 11~23
In addition to reaction temperature in using table 3 below, the identical mode of embodiment 3 prepares 1,3-Dihydroxyacetone, its
Specific experiment result is listed in table 3.
Table 3
| Embodiment title | Reaction temperature, DEG C | Conversion ratio % | Selectivity % |
| Embodiment 11 | 120 | 55.29 | 87.44 |
| Embodiment 12 | 130 | 70.36 | 89.19 |
| Embodiment 13 | 150 | ≈100 | 81.63 |
Embodiment 14~16
In addition to solvent in using table 4 below, the identical mode of embodiment 3 prepares 1,3-Dihydroxyacetone, and its is concrete
Experimental result is listed in table 4.
Table 4
| Embodiment title | Solvent species | Conversion ratio % | Selectivity % |
| Embodiment 14 | Isopropanol | ≈100 | 86.97 |
| Embodiment 15 | DMAC N,N' dimethyl acetamide | ≈100 | 93.15 |
| Embodiment 16 | Dimethyl sulfoxide | ≈100 | 82.06 |
Embodiment 17
Take the catalysis described in traditional bromination 3- ethyl-benzothiazole salt and triethylamine catalyst system and catalyzing alternate embodiment 3
Agent, with embodiment 3, its specific experiment result is listed in table 5 to other conditions.
| Embodiment title | Catalyst system and catalyzing | Conversion ratio % | Selectivity % |
| Embodiment 17 | Bromination 3- ethyl-benzothiazole salt, triethylamine | ≈100 | 83.23 |
However, because bromination 3- ethyl-benzothiazole salt and triethylamine catalyst system and catalyzing are all small molecules, follow-up catalyst
Reclaim difficult.
Supported catalyst is employed in the present invention, is not only easily reclaimed, and with high activity, using the present invention
Catalyst can cause the reaction for preparing C3H6O3 that there is high conversion and high selectivity.
Claims (10)
1. a kind of immobilized carbone catalyst, it has following structure：
Wherein, n is the degree of polymerization of polystyrene support, and it is the integer of 100-10000,Represent silica support.
2. a kind of method of the immobilized carbone catalyst prepared described in claim 1, the method comprising the steps of：
A) choose the degree of cross linking be chlorine ball that 7, chlorinity is 12.8% as carrier, use the mixing of 1,2- dichloroethanes and ethanol molten
Solvent swell 8-16 hour, the then Cl to include in chlorine ball：The mol ratio of the N included in benzothiazole is 1:1 ratio is to it
Middle addition benzothiazole, after back flow reaction 8-16 hour, sucking filtration, washing, is extracted using dehydrated alcohol and obtains quaternized polyphenyl
Vinyl；
B) the quaternized polystyrene resin obtained in step a) is put in the reactor containing dioxane, to wrap in chlorine ball
The Cl for containing:The mol ratio of the N included in triethylamine is 1:1 ratio adds triethylamine, then under nitrogen protection, in 373K's
At a temperature of react 16-28h, filter under nitrogen protection afterwards, and extracted using dehydrated alcohol, polyphenyl second is obtained after vacuum drying
The immobilized carbone catalyst of alkene；
Or,
A ') by silicon dioxide and the combined of the 20wt% of excess, and filter after stirring reaction 3-6h under 373K,
It is dried to obtain the silicon dioxide of activation；
B ') by step a ') in the silicon dioxide of activation for preparing mix with dry toluene and 3- bromopropyl trimethoxy silanes, stir
Lower back flow reaction 4-12h is mixed, is washed using methanol after filtration, after vacuum drying, obtain functionalized SiO 2；
C ') by step b ') in the functionalized SiO 2 for preparing mix with dry toluene, included with the functionalized SiO 2
Br:The mol ratio of the N included in benzothiazole is 1:1 ratio adds benzothiazole, lower back flow reaction 18-30h of stirring, mistake
Washed using methanol after filter, after vacuum drying, obtain the supported bromide of silicon dioxide；
D ') by step c ') in the supported bromide of silicon dioxide for preparing mix with dioxane, it is immobilized with the silicon dioxide
The Br included in the bromide of change：The mol ratio of the N included in triethylamine is 1:1 ratio adds triethylamine, and mixture is in nitrogen
Stirring reaction 8-24h under protection, under 373K, is filtered under nitrogen protection afterwards, and is extracted using dehydrated alcohol, and vacuum is done
The immobilized carbone catalyst of silicon oxide is obtained after dry.
3. it is a kind of to prepare 1,3- dihydroxy third using immobilized carbone catalyst catalysis formaldehyde condensation according to claim 1
The method of ketone, the method comprising the steps of：
It is separately added into paraformaldehyde, solvent and the immobilized carbone catalyst in reactor at room temperature, stirs, while rises
Temperature is reacted 0.5~5h and prepares 1,3-Dihydroxyacetone to 100~150 DEG C, under nitrogen protection.
4. method according to claim 3, wherein, the solvent is ethanol, isopropanol, Isosorbide-5-Nitrae-dioxane, 1,3- bis-
Oxygen five rings, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide or its mixture.
5. method according to claim 4, wherein, the solvent is isopropanol, N,N-dimethylacetamide, 1,3- dioxies
Five rings, dimethyl sulfoxide or its mixture.
6. the method according to any one of claim 3 to 5, wherein, the solvent load for paraformaldehyde quality 2~
10 times.
7. the method according to any one of claim 3 to 5, wherein, the immobilized carbone catalyst consumption is poly
0.1~2 times of formaldehyde quality.
8. the method according to any one of claim 3 to 5, wherein, the immobilized carbone catalyst consumption is poly
0.1~0.4 times of formaldehyde quality.
9. the method according to any one of claim 3 to 5, wherein, the immobilized carbone catalyst consumption is poly
0.15~0.35 times of formaldehyde quality.
10. the method according to any one of claim 3 to 5, wherein, the response time is 1~4 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510024406.8A CN104624232B (en) | 2015-01-16 | 2015-01-16 | Immobilized carbene catalyst, preparation method thereof, and method for preparing 1,3-dihydroxy acetone by using catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510024406.8A CN104624232B (en) | 2015-01-16 | 2015-01-16 | Immobilized carbene catalyst, preparation method thereof, and method for preparing 1,3-dihydroxy acetone by using catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104624232A CN104624232A (en) | 2015-05-20 |
| CN104624232B true CN104624232B (en) | 2017-05-17 |
Family
ID=53203753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510024406.8A Active CN104624232B (en) | 2015-01-16 | 2015-01-16 | Immobilized carbene catalyst, preparation method thereof, and method for preparing 1,3-dihydroxy acetone by using catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104624232B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114887658B (en) * | 2022-05-12 | 2024-03-05 | 合肥工业大学 | Dendritic mesoporous silica microsphere supported carbene catalyst and application thereof in catalyzing carbon dioxide to synthesize cyclic carbonate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012143188A (en) * | 2011-01-12 | 2012-08-02 | Kansai Univ | Method for producing immobilized catalyst membrane, immobilized catalyst membrane and transmembrane reaction method |
| CN103274911A (en) * | 2013-05-09 | 2013-09-04 | 浙江金伯士药业有限公司 | Novel preparation method of 1,3-dihydroxyl-2-acetone |
-
2015
- 2015-01-16 CN CN201510024406.8A patent/CN104624232B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012143188A (en) * | 2011-01-12 | 2012-08-02 | Kansai Univ | Method for producing immobilized catalyst membrane, immobilized catalyst membrane and transmembrane reaction method |
| CN103274911A (en) * | 2013-05-09 | 2013-09-04 | 浙江金伯士药业有限公司 | Novel preparation method of 1,3-dihydroxyl-2-acetone |
Non-Patent Citations (1)
| Title |
|---|
| 苯并噻唑盐催化多聚甲醛合成1,3-二羟基丙酮;刘俊峰，等;《精细化工》;20130228;第30卷(第2期);摘要、第1实验部分 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104624232A (en) | 2015-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106967216B (en) | A kind of covalent organic framework material and the preparation method and application thereof of imines connection | |
| CN104069891B (en) | The preparation method of the immobilized HP catalyst of a kind of polymer microballoon | |
| CN101648134B (en) | Copper and silicon catalyst for preparing ethanediol by hydrogenating dimethyl oxalate and preparation method thereof | |
| CN105294447B (en) | A kind of method for being catalyzed hydrogenation of chloronitrobenzene and preparing aniline | |
| CN104492495A (en) | Ionic liquid immobilized magnetic solid acid material catalyst and preparation method thereof | |
| CN103638970B (en) | A kind of method of marsh gas purifying in fixing bed | |
| CN100415791C (en) | Calixarene [4] modified thermosetting phenolic resin and preparation method thereof | |
| CN104624232B (en) | Immobilized carbene catalyst, preparation method thereof, and method for preparing 1,3-dihydroxy acetone by using catalyst | |
| CN107739444A (en) | Based on amino functional YbIIIMetal-organic framework material of six core molecule construction units and its preparation method and application | |
| CN103212444A (en) | Synthesis method of organic-inorganic hybrid porous solid material with quadruple catalysis and adsorption functions | |
| CN102500301B (en) | Preparation method and product of polymer microsphere with core-shell structure and hollow structure | |
| CN106946800A (en) | A kind of synthetic method of (1H, the 3H) diketone of quinazoline 2,4 and its derivative | |
| CN102309986A (en) | Catalyst used for producing promoter N-t-butyl benzothiazole sulfonamide and its preparation method | |
| CN108043461A (en) | It is a kind of to use g-C3N4/ UiO-66/NiPt catalyst is to the method for levulic acid catalytic hydrogenation | |
| CN107537576A (en) | The solid-supported catalyst of silane coupled molecular sieve and double salt ion liquid | |
| CN107746452A (en) | Palladium load different-phase catalyst based on micro- mesoporous phenolic resin and preparation method thereof | |
| CN111517949B (en) | Method for synthesizing ethylene glycol phenyl ether methacrylate | |
| CN108586193A (en) | A method of preparing 1,3-PD using 3- methoxy methyl propionates | |
| CN104525252A (en) | Immobilized ionic liquid solid acid catalyst and preparation method thereof | |
| CN104262127A (en) | Brush-type difluoro monomer and synthetic method thereof | |
| CN106582622A (en) | Easy-recycling palladium-supporting modified montmorillonite catalyst preparation method and applications of easy-recycling palladium-supporting modified montmorillonite catalyst in Suzuki reaction | |
| CN107744834A (en) | A kind of supported palladium Raney nickel synthesized for alkene epoxidation and Bisphenol F and preparation method | |
| CN109942570B (en) | Conjugated microporous polymer based on phenothiazine, preparation method and high-efficiency catalysis application | |
| CN101653733B (en) | Catalyst for preparing glyoxal by oxidizing aldehyde and preparation method thereof | |
| CN113856494A (en) | Preparation and application of metal organic framework filled mixed matrix membrane with photoresponse |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 100070 Beijing city Fengtai District Haiying Road No. 6 Building No. 6 hospital Applicant after: BEIJING RISUN TECHNOLOGY CO., LTD. Address before: 100070 Beijing city Fengtai District Haiying Road No. 6 Building No. 6 hospital Applicant before: Beijing Xuyang Chemical Technology Research Institute Co., Ltd. |
|
| COR | Change of bibliographic data | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |