CN108465486A - A kind of preparation method and applications of temperature sensitive interfacial catalysis agent - Google Patents
A kind of preparation method and applications of temperature sensitive interfacial catalysis agent Download PDFInfo
- Publication number
- CN108465486A CN108465486A CN201810224056.3A CN201810224056A CN108465486A CN 108465486 A CN108465486 A CN 108465486A CN 201810224056 A CN201810224056 A CN 201810224056A CN 108465486 A CN108465486 A CN 108465486A
- Authority
- CN
- China
- Prior art keywords
- added
- catalysis agent
- temperature sensitive
- product
- interfacial catalysis
- 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.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
- C07C45/294—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with hydrogen peroxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/76—Dehydrogenation
- B01J2231/763—Dehydrogenation of -CH-XH (X= O, NH/N, S) to -C=X or -CX triple bond species
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of preparation method and applications of temperature sensitive interfacial catalysis agent, belong to temperature sensitive interfacial catalysis agent technical field, can solve polyoxometallate and be difficult to H2O2Or O2The problem of to show good catalytic in the lotion catalytic oxidation system of oxidant, the preparation method of the catalyst includes：Terminal groups modification is carried out to the hyper-branched amphipathic polymer with terminal hydroxy group, prepares the polymer that end group is trihydroxy methyl；By trihydroxy methyl terminal groups modification polymer and polyoxometallic acid reactant salt to get interfacial catalysis agent of the present invention.The catalyst can be adsorbed on lotion oil-water interfaces, and in the oxidation reaction of emulsion interface catalytic alcohol, and the separation and recovery of catalyst can be also realized by changing temperature.
Description
Technical field
The invention belongs to temperature sensitive interfacial catalysis agent technical fields, and in particular to a kind of interfacial catalysis agent for having a temperature sensitive performance
Preparation method and its application in lotion catalysis oxidation.
Background technology
Polyoxometallate has fixed nano-scale and sky by one kind that early transition metal atom and oxygen atom form
Between structure multi-metal oxygen cluster compound.Polyoxometallate has both acid and oxidisability, and has unique coordination ability, because
And as one of catalyst important during acid catalysis, oxidation catalysis.However, in the heterogeneous system of organic substrates-water, have
Machine phase/aqueous phase interface area is the important factor in order of such reaction, and polyoxometallate cannot be in organic phase/aqueous phase interface
Upper effectively absorption, thus be difficult to show good catalytic performance.In addition, polyoxometallate has certain dissolving in water
Degree, there is also catalyst loss and difficult separation and recycling problems.
Invention content
The present invention is difficult to for polyoxometallate with H2O2Or O2To be shown in the lotion catalytic oxidation system of oxidant
The problem of good catalytic, the preparation method that a kind of temperature sensitive interfacial catalysis agent is provided and its application in alcohol oxidation reaction.
The present invention adopts the following technical scheme that：
A kind of preparation method of temperature sensitive interfacial catalysis agent, includes the following steps：
1mmol there is the hyper-branched amphipathic polymer of terminal hydroxy group to be dissolved in 100mL tetrahydrofurans, end be then added by the first step
The oxidant of hydroxyl moles 10%-50% reacts at room temperature 12-24h, and product A is settled out in ether, and vacuum drying is for use；
Product A is dissolved in 100mL absolute ethyl alcohols by second step, is added and hyper-branched amphipathic polymer terminal hydroxy group equimolar amounts
Tri methylol amino methane, after being cooled to room temperature, tri methylol amino methane molal quantity 1.5- is added in back flow reaction 4-12h
2.5 times of sodium borohydride reacts 4-24h, and product B is settled out in ether, and vacuum drying is for use；
Third walks, and product B is added in the n,N-Dimethylformamide of 100mL, hyper-branched amphipathic polymer end is then added
The polyoxometallate of 1-2 times of molal quantity of hydroxyl, 60-90 DEG C is reacted 3-10 days, and product, vacuum are settled out in ether after cooling
It is drying to obtain the temperature sensitive interfacial catalysis agent.
The hyper-branched amphipathic polymer has multi-arm, star-like, hyperbranched or dendritic hyper-branched structure.
The HLB value of the hyper-branched amphipathic polymer is 14-30, molecular weight 3000-15000, per moles of polymer
Terminal hydroxy group molal quantity is 3-48mol.
The oxidant is Dess-Martin reagents.
The anion part of the polyoxometallate is [P2V3M15O62]9-, wherein M is Mo or W.
Temperature sensitive interfacial catalysis agent is applied to lotion catalytic oxidation, and process is as follows：
Alcohol and water are added in closed reactor, alcohol is 1 with water molar ratio:5-1:20；Then by H2O2It is added to above-mentioned anti-
It answers in system, H2O2Molal quantity is 1.2 times of alcoholic extract hydroxyl group molal quantity；Add the interface for the 1-5% that quality is reactant gross mass
Catalyst, 40-60 DEG C of reaction temperature react 12-24h, lotion are warming up to 60-90 DEG C, constant temperature stands 2-24h demulsifications, demulsification
Product forms in post analysis water-oil phase, while isolating catalyst.
The alcohol is fatty alcohol or aromatic alcohol.
Beneficial effects of the present invention are as follows：
1. hyper-branched amphipathic polymer is combined with polyoxometallate by C-O-V covalently bondeds by the present invention, it is prepared for
One kind having temperature-sensitive, and can be adsorbed on the catalyst that lotion oil-water interfaces play catalytic action.It is mostly golden in the catalyst
Belong to oxygen hydrochlorate part and provides catalysis oxidation function；Hyper-branched amphipathic polymer part provides Interfacial Adsorption, emulsification and temperature sensitive
Characteristic.In addition, the polyoxometallate of the catalyst and hyper-branched amphipathic polymer avoid catalyst by Covalent bonding together
Loss the problem of.The catalyst can be used for H2O2The lotion catalytic oxidation process of existing alcohol type organic, it is organic at other
The catalytic oxidation process of substrate also has application potential.
2. a kind of temperature sensitive interfacial catalysis agent provided by the present invention is led to by hyper-branched amphipathic polymer with polyoxometallate
Covalent bonding together is crossed to form.With H2O2For in the alcohols organic emulsions catalytic oxidation system of oxidant, which can inhale
It is attached to emulsion interface and plays catalytic action, and there is temperature-sensing property, can realize emulsion breaking and catalyst by changing temperature
Separation and recovery.
Specific implementation mode
Embodiment 1
It is 3000 by the molecular weight of 1mmol, the hyper-branched amphipathic polymer that HLB value is 14（Terminal hydroxy group number is 3mmol）It is dissolved in
In 100mL tetrahydrofurans, the Dess-Martin reagents of 0.3mmol are then added, room temperature reaction for 24 hours, is precipitated in ether and produced
Object, vacuum drying, product is dissolved in 100mL absolute ethyl alcohols, and 3mmol tri methylol amino methanes are added, and back flow reaction 4h is cold
But to 4.5mmol sodium borohydrides after room temperature, are added, reaction for 24 hours, is settled out product in ether, is dried in vacuo, then by product
It is added in the n,N-Dimethylformamide of 100mL, adds (the Bu of 3mmol4N)H4P2V3W15O62, 60 DEG C are reacted 10 days, cold
But product is settled out after in ether, is dried in vacuo up to the temperature sensitive interfacial catalysis agent.
50mmol benzyl alcohols are added to 50mL closed reactors with 250mmol water；60mmol H are then added2O2To above-mentioned
In reaction system；The emulsion catalyst of reactant gross mass 1% is added, is stirred, 40 DEG C of reaction temperature, the reaction time is for 24 hours.It will
Lotion is warming up to 60 DEG C, and constant temperature is stood realizes demulsification for 24 hours.Material composition in organic phase, water phase is analyzed, obtains the catalyst to benzene
The conversion ratio of methanol is 42.5.4%；The selectivity of benzaldehyde is 98.0%.Precipitation is collected, is recycled after acetone washing, drying
Catalyst, under same reaction condition, the catalyst of the recycling is 43.5% to the conversion ratio of benzyl alcohol；The selection of benzaldehyde
Property is 97.5%.
Embodiment 2
It is 9800 by the molecular weight of 1mmol, the hyper-branched amphipathic polymer that HLB value is 30（Terminal hydroxy group number is 24mmol）It is dissolved in
In 100mL tetrahydrofurans, the Dess-Martin reagents of 12mmol are then added, reacts at room temperature 12h, precipitates and produce in ether
Object, vacuum drying, product is dissolved in 100mL absolute ethyl alcohols, addition 24mmol tri methylol amino methanes, back flow reaction 12h,
After being cooled to room temperature, 60mmol sodium borohydrides are added, reacts 4h, product is settled out in ether, are dried in vacuo, then by product
It is added in the n,N-Dimethylformamide of 100mL, adds (the Bu of 48mmol4N)H4P2V3W15O62, 90 DEG C are reacted 3 days, cold
But product is settled out after in ether, is dried in vacuo up to the temperature sensitive interfacial catalysis agent.
50mmol benzyl alcohols are added to 50mL closed reactors with 1000mmol water；60mmol H are then added2O2To above-mentioned
In reaction system；The emulsion catalyst of reactant gross mass 5% is added, is stirred, 60 DEG C of reaction temperature, reaction time 12h.It will
Lotion is warming up to 90 DEG C, and constant temperature stands 6h and realizes demulsification.Material composition in organic phase, water phase is analyzed, obtains the catalyst to benzene
The conversion ratio of methanol is 78.2%；The selectivity of benzaldehyde is 98.4%.Precipitation is collected, is recycled after acetone washing, drying
Catalyst, under same reaction condition, the catalyst of the recycling is 79.0% to the conversion ratio of benzyl alcohol；The selectivity of benzaldehyde
It is 98.5%.
Embodiment 3
It is 15000 by the molecular weight of 1mmol, the hyper-branched amphipathic polymer that HLB value is 22（Terminal hydroxy group number is 48mmol）It is dissolved in
In 100mL tetrahydrofurans, the Dess-Martin reagents of 10mmol are then added, room temperature reaction for 24 hours, is precipitated in ether and produced
Object, vacuum drying, product is dissolved in 100mL absolute ethyl alcohols, addition 48mmol tri methylol amino methanes, back flow reaction 12h,
After being cooled to room temperature, 90mmol sodium borohydrides are added, reacts 8h, product is settled out in ether, are dried in vacuo, then by product
It is added in the n,N-Dimethylformamide of 100mL, adds (the Bu of 60mmol4N)H4P2V3Mo15O62, 70 DEG C are reacted 10 days,
Product is settled out after cooling in ether, is dried in vacuo up to the temperature sensitive interfacial catalysis agent.
50mmol benzyl alcohols are added to 50mL closed reactors with 500mmol water；60mmol H are then added2O2To above-mentioned
In reaction system；The emulsion catalyst of reactant gross mass 2% is added, is stirred, 40 DEG C of reaction temperature, the reaction time is for 24 hours.It will
Lotion is warming up to 70 DEG C, and constant temperature is stood realizes demulsification for 24 hours.Material composition in organic phase, water phase is analyzed, obtains the catalyst to benzene
The conversion ratio of methanol is 73.8%；The selectivity of benzaldehyde is 98.1%.Precipitation is collected, is recycled and urges after ether washing, drying
Agent, under same reaction condition, which is 74.1% to the conversion ratio of benzyl alcohol；The selectivity of benzaldehyde is 98.5%.
Embodiment 4
It is 6000 by the molecular weight of 1mmol, the hyper-branched amphipathic polymer that HLB value is 24（Terminal hydroxy group number is 4mmol）It is dissolved in
In 100mL tetrahydrofurans, the Dess-Martin reagents of 2mmol are then added, reacts at room temperature 16h, precipitates and produce in ether
Object, vacuum drying, product is dissolved in 100mL absolute ethyl alcohols, and 4mmol tri methylol amino methanes are added, and back flow reaction 8h is cold
But to after room temperature, 6mmol sodium borohydrides are added, reacts 4h, product is settled out in ether, is dried in vacuo, then adds product
Enter into the n,N-Dimethylformamide of 100mL, adds (the Bu of 5mmol4N)H4P2V3Mo15O62, 70 DEG C are reacted 10 days, cooling
Product is settled out in ether afterwards, is dried in vacuo up to the temperature sensitive interfacial catalysis agent.
50mmol cyclohexanol is added to 50mL closed reactors with 1000mmol water；60mmol H are then added2O2To above-mentioned
In reaction system；The emulsion catalyst of reactant gross mass 2% is added, is stirred, 60 DEG C of reaction temperature, the reaction time is for 24 hours.It will
Lotion is warming up to 75 DEG C, and constant temperature stands 2h and realizes demulsification.Material composition in organic phase, water phase is analyzed, obtains the catalyst to ring
The conversion ratio of hexanol is 81.5%；The selectivity of cyclohexanone is 99.8%.Precipitation is collected, is recycled and urges after acetone washing, drying
Agent, under same reaction condition, which is 78.2% to the conversion ratio of cyclohexanol；The selectivity of cyclohexanone is 99.6%.
Embodiment 5
It is 8600 by the molecular weight of 1mmol, the hyper-branched amphipathic polymer that HLB value is 20（Terminal hydroxy group number is 12mmol）It is dissolved in
In 100mL tetrahydrofurans, the Dess-Martin reagents of 4mmol are then added, reacts at room temperature 16h, precipitates and produce in ether
Object, vacuum drying, product is dissolved in 100mL absolute ethyl alcohols, addition 12mmol tri methylol amino methanes, back flow reaction 12h,
After being cooled to room temperature, 18mmol sodium borohydrides are added, reacts 4h, product is settled out in ether, are dried in vacuo, then by product
It is added in the n,N-Dimethylformamide of 100mL, adds (the Bu of 12mmol4N)H4P2V3W15O62, 90 DEG C are reacted 3 days, cold
But product is settled out after in ether, is dried in vacuo up to the temperature sensitive interfacial catalysis agent.
50mmol n-octyl alcohols are added to 50mL closed reactors with 1000mmol water；60mmol H are then added2O2To above-mentioned
In reaction system；The emulsion catalyst of reactant gross mass 3% is added, is stirred, 60 DEG C of reaction temperature, the reaction time is for 24 hours.It will
Lotion is warming up to 70 DEG C, and constant temperature stands 6h and realizes demulsification.Material composition in organic phase, water phase is analyzed, obtains the catalyst to just
The conversion ratio of octanol is 52.7%；The selectivity of n-octaldehyde is 73.5%.Precipitation is collected, is recycled and urges after acetone washing, drying
Agent, under same reaction condition, which is 52.5% to the conversion ratio of n-octyl alcohol；The selectivity of n-octaldehyde is 73.0%.
Embodiment 6
It is 3600 by the molecular weight of 1mmol, the hyper-branched amphipathic polymer that HLB value is 16（Terminal hydroxy group number is 6mmol）It is dissolved in
In 100mL tetrahydrofurans, the Dess-Martin reagents of 2mmol are then added, reacts at room temperature 18h, precipitates and produce in ether
Object, vacuum drying, product is dissolved in 100mL absolute ethyl alcohols, addition 6mmol tri methylol amino methanes, back flow reaction 12h,
After being cooled to room temperature, 12mmol sodium borohydrides are added, reacts 4h, product is settled out in ether, are dried in vacuo, then by product
It is added in the n,N-Dimethylformamide of 100mL, adds (the Bu of 12mmol4N)H4P2V3Mo15O62, 90 DEG C are reacted 6 days, cold
But product is settled out after in ether, is dried in vacuo up to the temperature sensitive interfacial catalysis agent.
The 3- phenylpropanols of 50mmol are added to 50mL closed reactors with 1000mmol water；60mmol H are then added2O2It arrives
In above-mentioned reaction system；The emulsion catalyst of reactant gross mass 2% is added, is stirred, 50 DEG C of reaction temperature, the reaction time
24h.Lotion is warming up to 60 DEG C, constant temperature stands 12h and realizes demulsification.Material composition in organic phase, water phase is analyzed, the catalysis is obtained
Agent is 65.3% to the conversion ratio of 3- phenylpropanols；The selectivity of propiophenone is 83.2%.Precipitation is collected, after acetone washing, drying
To recycling catalyst, under same reaction condition, which is 64.2% to the conversion ratio of 3- phenylpropanols；The selection of propiophenone
Property is 83.0%.
Embodiment 7
It is 12000 by the molecular weight of 1mmol, the hyper-branched amphipathic polymer that HLB value is 26（Terminal hydroxy group number is 24mmol）It is dissolved in
In 100mL tetrahydrofurans, the Dess-Martin reagents of 10mmol are then added, reacts at room temperature 20h, precipitates and produce in ether
Object, vacuum drying, product is dissolved in 100mL absolute ethyl alcohols, addition 10mmol tri methylol amino methanes, back flow reaction 8h,
After being cooled to room temperature, 20mmol sodium borohydrides are added, reacts 16h, product is settled out in ether, are dried in vacuo, it then will production
Object is added in the n,N-Dimethylformamide of 100mL, adds (the Bu of 36mmol4N)H4P2V3W15O62, 90 DEG C are reacted 7 days,
Product is settled out after cooling in ether, is dried in vacuo up to the temperature sensitive interfacial catalysis agent.
50mmol isooctanol is added to 50mL closed reactors with 1000mmol water；60mmol H are then added2O2To above-mentioned
In reaction system；The emulsion catalyst of reactant gross mass 1% is added, is stirred, 60 DEG C of reaction temperature, reaction time 18h.It will
Lotion is warming up to 60 DEG C, and constant temperature stands 18h and realizes demulsification.Material composition in organic phase, water phase is analyzed, obtains the catalyst to different
The conversion ratio of octanol is 51.5%；The selectivity of different octanone is 83.2%.Precipitation is collected, is recycled and urges after acetone washing, drying
Agent, under same reaction condition, which is 50.8% to the conversion ratio of isooctanol；The selectivity of different octanone is 82.0%.
Claims (7)
1. a kind of preparation method of temperature sensitive interfacial catalysis agent, it is characterised in that：Include the following steps：
1mmol there is the hyper-branched amphipathic polymer of terminal hydroxy group to be dissolved in 100mL tetrahydrofurans, end be then added by the first step
The oxidant of hydroxyl moles 10%-50% reacts at room temperature 12-24h, and product A is settled out in ether, and vacuum drying is for use；
Product A is dissolved in 100mL absolute ethyl alcohols by second step, is added and hyper-branched amphipathic polymer terminal hydroxy group equimolar amounts
Tri methylol amino methane, after being cooled to room temperature, tri methylol amino methane molal quantity 1.5- is added in back flow reaction 4-12h
2.5 times of sodium borohydride reacts 4-24h, and product B is settled out in ether, and vacuum drying is for use；
Third walks, and product B is added in the n,N-Dimethylformamide of 100mL, hyper-branched amphipathic polymer end is then added
The polyoxometallate of 1-2 times of molal quantity of hydroxyl, 60-90 DEG C is reacted 3-10 days, and product, vacuum are settled out in ether after cooling
It is drying to obtain the temperature sensitive interfacial catalysis agent.
2. a kind of preparation method of temperature sensitive interfacial catalysis agent according to claim 1, it is characterised in that：Described hyper-branched two
Close polymer has multi-arm, star-like, hyperbranched or dendritic hyper-branched structure.
3. a kind of preparation method of temperature sensitive interfacial catalysis agent according to claim 1, it is characterised in that：Described hyper-branched two
The HLB value of close polymer is 14-30, molecular weight 3000-15000, and the terminal hydroxy group molal quantity per moles of polymer is 3-
48mol。
4. a kind of preparation method of temperature sensitive interfacial catalysis agent according to claim 1, it is characterised in that：The oxidant is
Dess-Martin reagents.
5. a kind of preparation method of temperature sensitive interfacial catalysis agent according to claim 1, it is characterised in that：The multi-metal oxygen
The anion part of hydrochlorate is [P2V3M15O62]9-, wherein M is Mo or W.
6. a kind of temperature sensitive interfacial catalysis agent a kind of as described in claim 1 is applied to lotion catalytic oxidation, feature exists
In：Process is as follows：
Alcohol and water are added in closed reactor, alcohol is 1 with water molar ratio:5-1:20；Then by H2O2It is added to above-mentioned reaction
In system, H2O2Molal quantity is 1.2 times of alcoholic extract hydroxyl group molal quantity；It urges at the interface for adding the 1-5% that quality is reactant gross mass
Agent, 40-60 DEG C of reaction temperature react 12-24h, lotion are warming up to 60-90 DEG C, constant temperature stands 2-24h demulsifications, after demulsification
It analyzes product in water-oil phase to form, while isolating catalyst.
7. a kind of temperature sensitive interfacial catalysis agent according to claim 6 is applied to lotion catalytic oxidation, it is characterised in that：
The alcohol is fatty alcohol or aromatic alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810224056.3A CN108465486B (en) | 2018-03-19 | 2018-03-19 | Preparation method and application of temperature-sensitive interface catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810224056.3A CN108465486B (en) | 2018-03-19 | 2018-03-19 | Preparation method and application of temperature-sensitive interface catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108465486A true CN108465486A (en) | 2018-08-31 |
| CN108465486B CN108465486B (en) | 2021-02-02 |
Family
ID=63265426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810224056.3A Active CN108465486B (en) | 2018-03-19 | 2018-03-19 | Preparation method and application of temperature-sensitive interface catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108465486B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109675626A (en) * | 2019-01-11 | 2019-04-26 | 南阳师范学院 | A kind of responsive to temperature type polyoxometallate composite catalyst and its synthetic method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104475156A (en) * | 2014-12-10 | 2015-04-01 | 湖南师范大学 | Method for synthesizing immobilized polyoxometallate material by one step |
| CN103145978B (en) * | 2013-03-25 | 2015-05-13 | 南开大学 | Pegylation polyoxometallate and preparation method thereof |
-
2018
- 2018-03-19 CN CN201810224056.3A patent/CN108465486B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145978B (en) * | 2013-03-25 | 2015-05-13 | 南开大学 | Pegylation polyoxometallate and preparation method thereof |
| CN104475156A (en) * | 2014-12-10 | 2015-04-01 | 湖南师范大学 | Method for synthesizing immobilized polyoxometallate material by one step |
Non-Patent Citations (2)
| Title |
|---|
| YIMING LI等: "Efficient mineralization of phenol by a temperature-responsive polyoxometalate catalyst under wet peroxide oxidation at lower temperatures", 《RSC ADVANCES》 * |
| 吴晓伟: "多金属氧簇/聚合物复合材料的设计合成及在智能催化领域的应用", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109675626A (en) * | 2019-01-11 | 2019-04-26 | 南阳师范学院 | A kind of responsive to temperature type polyoxometallate composite catalyst and its synthetic method |
| CN109675626B (en) * | 2019-01-11 | 2021-12-28 | 南阳师范学院 | Temperature-sensitive polyoxometallate composite catalyst and synthesis method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108465486B (en) | 2021-02-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106582710B (en) | A kind of method that graphene-supported palladium copper nano-catalytic Suzuki reaction prepares biphenyl | |
| CN107442177A (en) | The method that 5 hydroxymethylfurfural selective hydrogenations synthesize 2,5 furyl dimethyl carbinols | |
| CN110560170B (en) | Pd @ MOF material, preparation method thereof and application thereof in biphenyl preparation | |
| CN106008169B (en) | A kind of synthetic method of thymol | |
| CN102627532B (en) | Use of copper alginate | |
| CN106187718A (en) | A kind of preparation method of vanillin | |
| CN107335454A (en) | A kind of loading type Pd3The preparation and its application of Cl cluster catalyst | |
| CN100415791C (en) | Calixarene [4] modified thermosetting phenolic resin and preparation method thereof | |
| CN108465486A (en) | A kind of preparation method and applications of temperature sensitive interfacial catalysis agent | |
| JP2020528446A (en) | New vanillin and / or ethylvanillin, how to prepare them, and their use | |
| Singh et al. | Acid catalyzed 1, 2 Michael addition reaction: a viable synthetic route in designing fullerene core starlike macromolecule | |
| CN112778266B (en) | Iminoguanidine functionalized water-soluble column [5] arene and preparation method and application thereof | |
| Regen | Microenvironment within a solid-phase cosolvent | |
| CN103232324A (en) | Method for preparing (R)-3,5-bis(trifluoromethyl)benzene-ethanol | |
| CN107602516B (en) | Method for synthesizing delta-cyclopentanolide under catalysis of amino acid ionic liquid | |
| CN112094237A (en) | Synthesis method of fluorobenzene imidazole | |
| CN113233983A (en) | Method for catalytically synthesizing linalyl acetate by using acidic deep eutectic solvent | |
| CN111196755A (en) | Preparation method of natural benzaldehyde | |
| Niu et al. | Promotion of organic reactions by interfacial hydrogen bonds on hydroxyl group rich nano-solids | |
| CN109081817A (en) | CuI/ ionic liquid normal temperature and pressure catalysis converts CO2The method for synthesizing 1,3- oxazolidine -2- ketone compounds | |
| CN103665388A (en) | Supermolecule polymer and synthesis method thereof | |
| CN106475143A (en) | (R) the unilateral Fe Anderson type heteropolyacid catalyst modified of 1 (2 hydroxyl 1 phenethyl) thiourea, preparation method and applications | |
| CN109225333A (en) | A kind of preparation method and its usage of three core nickel-vanadium oxygen cluster catalyst | |
| CN109320514B (en) | Immobilized multifunctional compound and preparation and application thereof | |
| CN113880704B (en) | Quick synthesis 18 Method for marking aldehyde compound by O |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |