CN104588112A - Magnetic bidentate nitrogen-containing tin ligand catalyst and preparation method thereof - Google Patents

Magnetic bidentate nitrogen-containing tin ligand catalyst and preparation method thereof Download PDF

Info

Publication number
CN104588112A
CN104588112A CN201510029516.3A CN201510029516A CN104588112A CN 104588112 A CN104588112 A CN 104588112A CN 201510029516 A CN201510029516 A CN 201510029516A CN 104588112 A CN104588112 A CN 104588112A
Authority
CN
China
Prior art keywords
magnetic
ligand
bidentate
catalyst
preparation
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
Application number
CN201510029516.3A
Other languages
Chinese (zh)
Other versions
CN104588112B (en
Inventor
余照权
张涌
万红亮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SICHUAN FLOWER'S FINE CHEMICAL CO Ltd
Original Assignee
SICHUAN FLOWER'S FINE CHEMICAL CO Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by SICHUAN FLOWER'S FINE CHEMICAL CO Ltd filed Critical SICHUAN FLOWER'S FINE CHEMICAL CO Ltd
Priority to CN201510029516.3A priority Critical patent/CN104588112B/en
Publication of CN104588112A publication Critical patent/CN104588112A/en
Application granted granted Critical
Publication of CN104588112B publication Critical patent/CN104588112B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Catalysts (AREA)

Abstract

The invention discloses a magnetic bidentate nitrogen-containing tin ligand catalyst and a preparation method thereof, relates to a catalyst for esterification and a preparation method of the catalyst and aims at solving the problems that the traditional non-homogeneous phase tin catalyst is difficult to recover after catalytic reaction and remains in a product. The preparation method comprises the following steps: 1, preparing a nitrogen ligand containing an active group; 2, preparing a magnetic bidentate nitrogen-containing ligand; and 3, preparing a magnetic bidentate nitrogen-containing tin ligand. According to the magnetic bidentate nitrogen-containing tin ligand catalyst and the preparation method thereof disclosed by the invention, a tin ligand catalyst with high activity is fixed to nanometer iron oxide particles with superparamagnetism, so that the catalyst can be separated from a reaction system by virtue of an external magnetic field after reaction is finished and can be recycled, and the amount of residues of the catalyst in the product is reduced.

Description

Nitrogenous tin ligand catalyst of a kind of magnetic bidentate and preparation method thereof
Technical field
The present invention relates to a kind of Catalysts and its preparation method for esterification, be specifically related to a kind of Catalysts and its preparation method of nitrogenous tin part of the esterification for stearic acid and ethylene glycol.
Background technology
Esterification is the important reaction of the class in organic synthesis, and the glycol stearate utilizing the esterification of stearic acid and ethylene glycol to produce is a kind of daily use chemicals auxiliary agent, is widely used in various detergent product.Organotin catalysts has very high catalytic activity, has as the glycol stearate produced during catalyst the advantage that color and luster is good, purity is high.But it is not catalyst can remain in the product, easy to be recycled.
Summary of the invention
Object of the present invention is just for the deficiencies in the prior art, provides nitrogenous tin ligand catalyst of a kind of magnetic bidentate and preparation method thereof, solves the problem that in existing esterification, organotin catalysts easily remains, not easily reclaims.
The nitrogenous tin ligand catalyst of magnetic bidentate provided by the invention, its structural formula is:
，
In formula, n is 1 ~ 5, R is CH 3(CH 2) m, wherein m=0 ~ 5; Fe xo yfor Fe 2o 3or Fe 3o 4.
It prepares by the following method:
(1) preparation is containing active group nitrogen ligand: be obtained by reacting containing active group nitrogen ligand by silane coupler and alkyl diamine agitating heating; Wherein the ratio of the amount of substance of silane coupler and alkyl diamine is 1 ~ 5 ︰ 1, is heated with stirring to 70 DEG C ~ 150 DEG C, then reacts 2 ~ 10 hours at 70 DEG C ~ 150 DEG C, through rotating pressure-decreasing distillation, obtains containing active group nitrogen ligand; Further optimal technical scheme is, the ratio of the amount of substance of silane coupler and alkyl diamine is 2 ︰ 1, and reaction temperature is 90 DEG C ~ 100 DEG C, and the reaction time is 6 ~ 8 hours; Wherein, silane coupler is selected from vinyltrimethoxy silane, 3-r-chloropropyl trimethoxyl silane, 3-chloropropyl triethoxysilane and 3-bromopropyl trimethoxy silane, and alkyl diamine is selected from 1,3 propane diamine, Isosorbide-5-Nitrae butanediamine and 1,5 pentanediamines.
(2) magnetic bidentate containing n-donor ligand is prepared: under nitrogen protection, will containing active group nitrogen ligand and magnetic Fe xo ynano particle joins in solvent I successively, be stir under the condition of 70 DEG C ~ 150 DEG C to obtain magnetic bidentate containing n-donor ligand in temperature, reflux 8 ~ 36 hours, be cooled to room temperature, utilize externally-applied magnetic field to be separated with solvent I by magnetic bidentate containing n-donor ligand, then wash 3 ~ 6 times with toluene or ethanol respectively, then drying under reduced pressure, obtain magnetic bidentate containing n-donor ligand, wherein containing active group nitrogen ligand and Fe xo ythe mol ratio of nano particle is 3 ~ 10 ︰ 1, and the mol ratio containing active group nitrogen ligand and solvent I is 1 ︰ 120 ~ 180, and solvent I is toluene or absolute ethyl alcohol, Fe xo yfor Fe 2o 3or Fe 3o 4; Further optimal technical scheme is, containing active group nitrogen ligand and Fe xo ythe mol ratio of nano particle is 4 ︰ 1, and the mol ratio containing active group nitrogen ligand and solvent I is 1 ︰ 140, and the temperature conditions of stirring is 100 DEG C, and the stirring and refluxing time is 18h.
(3) the nitrogenous tin part of magnetic bidentate is prepared: under nitrogen protection, by R- 2snCl 2join in solvent II with magnetic bidentate nitrogen ligands according to the ratio that mol ratio is 0.8 ~ 1.8 ﹕ 1, stirring and refluxing 8 ~ 36 hours at temperature is 50 ~ 80 DEG C, being cooled to room temperature utilizes externally-applied magnetic field to be separated with solvent II by nitrogenous for magnetic bidentate tin part, 3 times are washed with ethanol, drying under reduced pressure, obtains the nitrogenous tin ligand catalyst of magnetic bidentate; Wherein solvent II is ethanol, propyl alcohol or butanols, R- 2snCl 2middle R is CH 3(CH 2) m, m=0 ~ 5.Further optimal technical scheme is, R- 2snCl 2be 1.1 ︰ 1 with the mol ratio of magnetic bidentate containing n-donor ligand, the temperature conditions of stirring is 70 DEG C, and the stirring and refluxing time is 24h.
The reaction equation that the present invention prepares the nitrogenous tin ligand catalyst of magnetic bidentate is:
Wherein, R is CH 3(CH 2) m, wherein m is=0 ~ 5.
The invention has the beneficial effects as follows: the nitrogenous tin ligand catalyst of magnetic bidentate of the present invention is to have the magnetic particle of superparamagnetism as carrier, the magnetic particle of superparamagnetism does not have magnetic in the external world without during magnetic field, be magnetized when applying magnetic field, the external world and have magnetic, when magnetic field is withdrawn from, magnetic disappears.By nitrogen tin part in silane coupler load, during the reaction of this catalyst stearic acid and ethylene glycol, have higher catalytic activity at a lower temperature, product purity is greater than 99%, and color and luster is more shallow.After catalyst recovery of the present invention, recycle five catalytic activitys without obvious reduction, product yield is still more than 90%.The catalyst utilizing the inventive method to prepare can be magnetized by externally-applied magnetic field, when removing externally-applied magnetic field, magnetic disappears, therefore magnetic bidentate nitrogen tin ligand catalyst of the present invention can realize when externally-applied magnetic field and being separated of reaction system, relative to the separation method of other catalyst, there is simple timesaving advantage, and decrease catalyst in the product residual.
Magnetic bidentate nitrogen tin ligand catalyst of the present invention is used for the esterification of catalysis stearic acid and ethylene glycol.
Detailed description of the invention
In order to the object of the present invention of understanding clearly, technical scheme and beneficial effect, below the present invention is described further, but not by protection scope of the present invention limit in the examples below.
Embodiment one:
(1) containing the preparation of active group nitrogen ligand: take silane coupler and alkyl diamine, wherein the ratio of the amount of substance of silane coupler and alkyl diamine is 1 ﹕ 1, be heated with stirring to 70 DEG C ~ 150 DEG C, then react 2 ~ 10 hours at 70 DEG C ~ 150 DEG C, through rotating pressure-decreasing distillation, obtain the nitrogen ligand containing active group; Wherein silane coupler is selected from vinyltrimethoxy silane, 3-r-chloropropyl trimethoxyl silane, 3-chloropropyl triethoxysilane and 3-bromopropyl trimethoxy silane, and alkyl diamine is selected from 1,3 propane diamine, Isosorbide-5-Nitrae butanediamine or 1,5 pentanediamines
(2) preparation of magnetic bidentate containing n-donor ligand: under nitrogen protection, will contain nitrogen ligand and the magnetic Fe of active group xo ynano particle joins in solvent I successively, be stir under the condition of 70 DEG C ~ 150 DEG C in temperature, reflux 8 ~ 36 hours, be cooled to room temperature, externally-applied magnetic field is utilized magnetic bidentate nitrogen ligands and solvent I to be separated, and then respectively with toluene, ethanol washing 3 ~ 6 times, then drying under reduced pressure, obtain magnetic bidentate nitrogen ligands, wherein containing nitrogen ligand and the Fe of active group xo ynano particle mol ratio is 3:1, and be 1:120 containing the nitrogen ligand of active group and solvent I mol ratio, solvent I is toluene or absolute ethyl alcohol, Fe xo yfor Fe 2o 3or Fe 3o 4;
(3) preparation of the nitrogenous tin part of magnetic bidentate: under nitrogen protection, by R- 2snCl 2join in solvent II with magnetic bidentate containing n-donor ligand according to the ratio that mol ratio is 0.8 ﹕ 1, stirring and refluxing 8 ~ 36 hours at temperature is 50 ~ 80 DEG C, being cooled to room temperature utilizes externally-applied magnetic field magnetic bidentate nitrogen tin part and solvent to be separated, 3 times are washed with ethanol, drying under reduced pressure, obtains magnetic bidentate nitrogen tin ligand catalyst.Wherein solvent II is ethanol, propyl alcohol or butanols.
Embodiment two:
The present embodiment is identical with embodiment one, and the ratio unlike the amount of substance of silane coupler in step (1) and alkyl diamine is 5 ﹕ 1.
Embodiment three:
The present embodiment is identical with embodiment one, and the ratio unlike the amount of substance of silane coupler in step (1) and alkyl diamine is 2 ﹕ 1.
Embodiment four:
The present embodiment is identical with embodiment three, and be 90 DEG C ~ 100 DEG C unlike the temperature of agitating heating in step (1), the reaction time is 6 ~ 8 hours.
Embodiment five:
The present embodiment is identical with embodiment two, unlike the nitrogen ligand and the Fe that contain active group in step (2) xo ynano particle mol ratio is 10:1, is 1:180 containing the nitrogen ligand of active group and solvent I mol ratio.
Embodiment six:
The present embodiment is identical with embodiment three, unlike the nitrogen ligand and the Fe that contain active group in step (2) xo ynano particle mol ratio is 4:1, is 1:140 containing the nitrogen ligand of active group and solvent I mol ratio.
Embodiment seven:
The present embodiment is identical with embodiment six, and be 100 DEG C unlike the temperature conditions stirred in step (2), the stirring and refluxing time is 18h.
Embodiment eight:
The present embodiment is identical with embodiment five, unlike R-in step (3) 2snCl 2be 1.8 ﹕ 1 with the mol ratio of magnetic bidentate containing n-donor ligand.
Embodiment nine:
The present embodiment is identical with embodiment six, unlike R-in step (3) 2snCl 2be 1.1 ﹕ 1 with the mol ratio of magnetic bidentate containing n-donor ligand.
Embodiment ten:
The present embodiment is identical with embodiment nine, and be 70 DEG C unlike the temperature conditions stirred in step (3), the stirring and refluxing time is 24h.
Adopt following verification experimental verification beneficial effect of the present invention:
Adopt the magnetic bidentate nitrogenous tin ligand catalyst catalysis stearic acid of above-described embodiment gained and the esterification of ethylene glycol, experimental procedure and result as described below:
Experimental procedure: add 0.9 mol stearic acid in the there-necked flask that paddle, thermometer and division box be housed, 0.5 mol ethylene glycol and 0.1% (gross mass) catalyst, pass into nitrogen, be heated to 180 DEG C, utilize division box in time except the water generated in dereaction.React after 6 hours and stop reaction, use high performance liquid chromatography testing result.Result display conversion ratio is greater than 99%.
When adopting the reaction of the magnetic bidentate nitrogenous tin ligand catalyst catalysis stearic acid of above-described embodiment gained and ethylene glycol, after catalyst recovery, reuse 5 times, catalytic activity there is no obvious decline, experimental procedure and result as described below:
Experimental procedure: add 0.9 mol stearic acid in the there-necked flask that paddle, thermometer and division box be housed, 0.5 mol ethylene glycol and 0.1% (gross mass) catalyst, pass into nitrogen, be heated to 180 DEG C, utilize division box in time except the water generated in dereaction.React after 6 hours and stop reaction.After reaction terminates, an additional magnet, is adsorbed on bottom there-necked flask by magnetic bidentate nitrogen tin catalyst, pours out upper solution, use high performance liquid chromatography testing result.Drying under reduced pressure after magnetic bidentate nitrogen tin catalyst ethanol washs 3 times, continues to test next time.
As mentioned above, then repeat 4 experiments, each experiment uses the catalyst that last time, experiment was reclaimed.
Present embodiment gained magnetic bidentate nitrogen tin catalyst reuses five times, and product yield is all higher than 90%, and the catalytic activity of catalyst there is no obvious reduction, and product yield as shown in Table 1.
Magnetic bidentate nitrogen tin ligand catalyst of the present invention is to have the magnetic particle of superparamagnetism as carrier, the magnetic particle of superparamagnetism does not have magnetic in the external world without during magnetic field, be magnetized when applying magnetic field, the external world and have magnetic, when magnetic field is withdrawn from, magnetic disappears.By nitrogen tin part in silane coupler load, during the reaction of this catalyst stearic acid and ethylene glycol, have higher catalytic activity at a lower temperature, product purity is greater than 99%, and color and luster is more shallow.After catalyst recovery of the present invention, recycle five catalytic activitys without obvious reduction, product yield is still more than 90%.The catalyst utilizing the inventive method to prepare can be magnetized by externally-applied magnetic field, when removing externally-applied magnetic field, magnetic disappears, therefore magnetic bidentate nitrogen tin ligand catalyst of the present invention can realize when externally-applied magnetic field and being separated of reaction system, relative to the separation method of other catalyst, there is simple timesaving advantage, and decrease catalyst in the product residual.

Claims (10)

1. the nitrogenous tin ligand catalyst of magnetic bidentate, is characterized in that: its structural formula is:
，
In formula, n is 1 ~ 5, R is CH 3(CH 2) m, wherein m=0 ~ 5; Fe xo yfor Fe 2o 3or Fe 3o 4.
2. the preparation method of the nitrogenous tin ligand catalyst of a kind of magnetic bidentate according to claim 1, is characterized in that: comprise following preparation process:
(1) preparation is containing active group nitrogen ligand: distill through rotating pressure-decreasing after silane coupler and alkyl diamine agitating heating being reacted and obtain containing active group nitrogen ligand;
(2) magnetic bidentate containing n-donor ligand is prepared: under nitrogen protection, will containing active group nitrogen ligand and magnetic Fe xo ynano particle joins in solvent I successively, is stirring and refluxing 8 ~ 36 hours under the condition of 70 DEG C ~ 150 DEG C, is cooled to room temperature in temperature, after utilizing externally-applied magnetic field to be separated solvent I, wash 3 ~ 6 times with toluene or ethanol, then drying under reduced pressure, obtains magnetic bidentate containing n-donor ligand; Wherein, solvent I is toluene or absolute ethyl alcohol, Fe xo yfor Fe 2o 3or Fe 3o 4;
(3) the nitrogenous tin part of magnetic bidentate is prepared: under nitrogen protection, by R- 2snCl 2according to mol ratio, (ratio of 0.8 ~ 1.8) ︰ 1 joins in solvent II with magnetic bidentate containing n-donor ligand, it is stirring and refluxing 8 ~ 36 hours under the condition of 50 ~ 80 DEG C in temperature, be cooled to room temperature, after utilizing externally-applied magnetic field to be separated solvent II, 3 times are washed with ethanol, drying under reduced pressure, obtains the nitrogenous tin ligand catalyst of magnetic bidentate; Wherein solvent II is ethanol, propyl alcohol or butanols, R- 2snCl 2middle R is CH 3(CH 2) m, m=0 ~ 5.
3. the preparation method of the nitrogenous tin ligand catalyst of a kind of magnetic bidentate according to claim 2, it is characterized in that: in described step (1), the ratio of the amount of substance of silane coupler and alkyl diamine is 1 ~ 5 ︰ 1, reaction temperature is 70 DEG C ~ 150 DEG C, and the reaction time is 2 ~ 10 hours.
4. the preparation method of the nitrogenous tin ligand catalyst of a kind of magnetic bidentate according to claim 3, it is characterized in that: in described step (1), the ratio of the amount of substance of silane coupler and alkyl diamine is 2 ︰ 1, reaction temperature is 90 DEG C ~ 100 DEG C, and the reaction time is 6 ~ 8 hours.
5. the preparation method of the nitrogenous tin ligand catalyst of a kind of magnetic bidentate according to claim 2, it is characterized in that: in described step (1), silane coupler is selected from vinyltrimethoxy silane, 3-r-chloropropyl trimethoxyl silane, 3-chloropropyl triethoxysilane and 3-bromopropyl trimethoxy silane, alkyl diamine is selected from 1,3 propane diamine, 1,4 butanediamine and 1,5 pentanediamines.
6. the preparation method of the nitrogenous tin ligand catalyst of a kind of magnetic bidentate according to claim 2, is characterized in that: containing active group nitrogen ligand and Fe in described step (2) xo ythe mol ratio of nano particle is that (3 ~ 10) ︰ 1, the mol ratio containing active group nitrogen ligand and solvent I is 1 ︰ (120 ~ 180).
7. the preparation method of the nitrogenous tin ligand catalyst of a kind of magnetic bidentate according to claim 6, is characterized in that: containing active group nitrogen ligand and Fe in described step (2) xo ythe mol ratio of nano particle is 4 ︰ 1, and the mol ratio containing active group nitrogen ligand and solvent I is 1 ︰ 140.
8. the preparation method of the nitrogenous tin ligand catalyst of a kind of magnetic bidentate according to claim 2, is characterized in that: the temperature conditions stirred in described step (2) is 100 DEG C, and the stirring and refluxing time is 18h.
9. the preparation method of the nitrogenous tin ligand catalyst of a kind of magnetic bidentate according to claim 2, is characterized in that: R-in described step (3) 2snCl 2be 1.1 ︰ 1 with the mol ratio of magnetic bidentate containing n-donor ligand.
10. the preparation method of the nitrogenous tin ligand catalyst of a kind of magnetic bidentate according to claim 2, is characterized in that: the temperature conditions stirred in described step (3) is 70 DEG C, and the stirring and refluxing time is 24h.
CN201510029516.3A 2015-01-21 2015-01-21 Magnetic bidentate nitrogen-containing tin ligand catalyst and preparation method thereof Active CN104588112B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510029516.3A CN104588112B (en) 2015-01-21 2015-01-21 Magnetic bidentate nitrogen-containing tin ligand catalyst and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510029516.3A CN104588112B (en) 2015-01-21 2015-01-21 Magnetic bidentate nitrogen-containing tin ligand catalyst and preparation method thereof

Publications (2)

Publication Number Publication Date
CN104588112A true CN104588112A (en) 2015-05-06
CN104588112B CN104588112B (en) 2017-05-10

Family

ID=53114366

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510029516.3A Active CN104588112B (en) 2015-01-21 2015-01-21 Magnetic bidentate nitrogen-containing tin ligand catalyst and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104588112B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107442169A (en) * 2017-08-15 2017-12-08 太原理工大学 A kind of catalyst for loading chloride organotin and nitrogen-containing compound and its preparation method and application

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090247783A1 (en) * 2008-04-01 2009-10-01 Eastman Chemical Company Carbonylation process
CN101757948A (en) * 2010-01-29 2010-06-30 黑龙江省科学院石油化学研究院 Preparation method of magnetic sulfur-containing bidentate palladium ligand catalyst
CN102432849A (en) * 2011-08-04 2012-05-02 南京工业大学 Polymerizing production method for transparent amorphous copolyester
CN102489330A (en) * 2011-11-28 2012-06-13 黑龙江省科学院石油化学研究院 Preparation method of magnetic nitrogen-containing bidentate palladium ligand catalyst
CN102500418A (en) * 2011-11-28 2012-06-20 黑龙江省科学院石油化学研究院 Magnetic bidentate imide palladium ligand catalyst and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090247783A1 (en) * 2008-04-01 2009-10-01 Eastman Chemical Company Carbonylation process
CN101757948A (en) * 2010-01-29 2010-06-30 黑龙江省科学院石油化学研究院 Preparation method of magnetic sulfur-containing bidentate palladium ligand catalyst
CN102432849A (en) * 2011-08-04 2012-05-02 南京工业大学 Polymerizing production method for transparent amorphous copolyester
CN102489330A (en) * 2011-11-28 2012-06-13 黑龙江省科学院石油化学研究院 Preparation method of magnetic nitrogen-containing bidentate palladium ligand catalyst
CN102500418A (en) * 2011-11-28 2012-06-20 黑龙江省科学院石油化学研究院 Magnetic bidentate imide palladium ligand catalyst and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107442169A (en) * 2017-08-15 2017-12-08 太原理工大学 A kind of catalyst for loading chloride organotin and nitrogen-containing compound and its preparation method and application
CN107442169B (en) * 2017-08-15 2020-02-07 太原理工大学 Catalyst loaded with chlorine-containing organotin and nitrogen-containing compound and preparation method and application thereof

Also Published As

Publication number Publication date
CN104588112B (en) 2017-05-10

Similar Documents

Publication Publication Date Title
Shebl Synthesis and spectroscopic studies of binuclear metal complexes of a tetradentate N2O2 Schiff base ligand derived from 4, 6-diacetylresorcinol and benzylamine
CN107899611B (en) Organic catalyst with visible light catalytic asymmetric photocatalytic hydroxylation performance, preparation method and application thereof
CN107552074A (en) A kind of preparation method for being used to produce the solid acid catalyst of the double isobutyrates of the pentanediol of 2,2,4 trimethyl 1,3
CN103230805A (en) Method for preparing magnetic hydrotalcite loaded nano-palladium catalyst
CN106513028B (en) A kind of catalyst and preparation method thereof and the application in reduction nitro compound
CN101011669A (en) Method for preparing chitose magnetic microsphere metal palladium complex catalyst
CN106008401A (en) Preparation method of N-formamide compound
CN107670690B (en) Iron-based cyano-containing anionic imidazole ionic liquid catalyst and preparation method and application thereof
CN113603580B (en) Method for synthesizing methacrylic acid by decarboxylation of itaconic acid
CN108722488B (en) Bimetal center metal-organic framework material for enhancing Lewis acidity and preparation method thereof
CN104588112B (en) Magnetic bidentate nitrogen-containing tin ligand catalyst and preparation method thereof
CN102500418B (en) Preparation method of magnetic bidentate imide palladium ligand catalyst
CN104817583B (en) Carbon bridging bisamide base ytterbium and its preparation and the application in catalysis aldehyde and amine amide are combined to react
CN101550069B (en) Method for synthesizing propylene glycol methyl ether
CN103706404A (en) Magnetic composite microsphere for catalyzing CO2 and epoxy compound cycloaddition reaction as well as preparation method and application thereof
CN104926650A (en) Method for catalyzing eneyne cycloisomerization reaction with cerium-dioxide-loaded gold nanoparticles
CN102515104A (en) Method for preparing hydrogen chloride and silicon dioxide by hydrolyzing silicon tetrachloride in organic solvent
CN110330515B (en) Nitrogen-oxygen mixed ligand zinc complex and preparation method thereof
CN107417741B (en) Diethylenetriamine vanadium (III)-tungsten (VI)-vanadium (IV)-oxygen cluster compound and its synthetic method
CN102992369B (en) Recycling method for catalyst alumina
CN108948055B (en) 8-methylquinoline gem-diboron compound and preparation method thereof
CN106513045A (en) (R)-1(2-(naphthyl) ethyl) thiourea unilateral modified Fe-Anderson type heteropolyacid catalyst, preparing method and application of (R)-1(2-(naphthyl) ethyl) thiourea unilateral modified Fe-Anderson type heteropolyacid catalyst
CN113072452A (en) Method for catalytically synthesizing o-aminophenol
CN104549503B (en) A kind of support type organic tin catalyst and its preparation method and application
CN105195228A (en) Fe3O4-loaded chiral catalyst and preparation method and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant