CN111151296A - Magnetic material loaded rhodamine B catalyst, preparation method thereof and catalytic application thereof in phenol synthesis - Google Patents
Magnetic material loaded rhodamine B catalyst, preparation method thereof and catalytic application thereof in phenol synthesis Download PDFInfo
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- CN111151296A CN111151296A CN202010024337.1A CN202010024337A CN111151296A CN 111151296 A CN111151296 A CN 111151296A CN 202010024337 A CN202010024337 A CN 202010024337A CN 111151296 A CN111151296 A CN 111151296A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229940043267 rhodamine b Drugs 0.000 title claims abstract description 42
- 239000000696 magnetic material Substances 0.000 title claims abstract description 34
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 title claims description 5
- 238000003786 synthesis reaction Methods 0.000 title claims description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 42
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 9
- 239000012798 spherical particle Substances 0.000 claims abstract description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012736 aqueous medium Substances 0.000 claims abstract description 7
- 239000003480 eluent Substances 0.000 claims abstract description 7
- 230000033444 hydroxylation Effects 0.000 claims abstract description 7
- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 229910000077 silane Inorganic materials 0.000 claims abstract description 7
- 238000007885 magnetic separation Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 238000000944 Soxhlet extraction Methods 0.000 claims description 2
- 239000012156 elution solvent Substances 0.000 claims description 2
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 4
- 230000005389 magnetism Effects 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000006277 sulfonation reaction Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 1
- 229960001138 acetylsalicylic acid Drugs 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZIQCCIAIROIHHR-UHFFFAOYSA-N benzene;boric acid Chemical compound OB(O)O.C1=CC=CC=C1 ZIQCCIAIROIHHR-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
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- 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
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a preparation method of a magnetic material loaded rhodamine B catalyst, which comprises the following steps: a. uniformly dispersing magnetic ferroferric oxide spherical particles wrapped by silicon dioxide in a toluene solution, and then dropwise adding an organic silicon source to prepare a functionalized magnetic sphere; b. removing unreacted silane by using an organic solvent as an eluent to obtain an amino functionalized magnetic ball; c. dissolving rhodamine B in water, adding an amino functionalized magnetic ball, and reacting in an aqueous medium by adopting an EDC-NHS method to prepare the magnetic material loaded rhodamine B catalyst. Can be applied to the reaction of converting the hydroxylation of the phenylboronic acid into the phenol. The heterogeneous catalyst prepared by the invention can be rapidly recovered under the action of an external magnetic field by utilizing the carrier magnetism, and the recovery efficiency is up to more than 99%; the heterogeneous catalyst has excellent catalytic effect on the reaction of hydroxylation of phenylboronic acid to generate phenol, and can avoid the pollution of the unrecoverable catalyst to the environment in the traditional phenol production process.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a magnetic material loaded rhodamine B catalyst, a preparation method thereof and catalytic application thereof in phenol synthesis.
Background
Phenol is an important raw material for producing certain resins, bactericides, preservatives and medicines (such as aspirin), is recovered from coal tar at the earliest, and most of the phenol is synthesized at present. By the middle of the 60's of the 20 th century, a technical route for producing phenol by the cumene method began to be adopted, and the phenol produced by the process at present accounts for more than 90% of the world phenol yield. Other production processes include toluene chlorination, chlorobenzene and sulfonation. However, because the sulfonation method consumes a large amount of sulfuric acid and caustic soda, only a few sulfonation method devices are reserved in China, and the cumene method production is mainly used step by step, but aluminum trichloride is required to be used as a catalyst in the cumene method production process, cannot be recovered, and causes serious pollution to the environment.
The magnetic nano material has extremely wide application in the technical fields of separation, diagnosis and treatment, catalysis and the like due to the special property of the magnetic nano material. The material has unique characteristics: uniform pore canal, high specific surface area, easy magnetic separation and the like. Particularly, the organic visible light photocatalyst has great application potential in the technical field of catalysis, and organic metal catalysts are loaded on a carrier, but the reports of combining the organic visible light catalyst with a magnetic material are few.
In view of the above, the design and preparation of the magnetic nanomaterial-supported organic visible-light-driven photocatalyst rhodamine B heterogeneous catalyst are technical problems to be solved by the present invention.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a magnetic material loaded rhodamine B catalyst, a preparation method thereof and catalytic application thereof in phenol synthesis, obtains a catalyst which has good catalytic activity and is easy to recover, and is applied to the reaction of converting benzene boric acid hydroxylation into phenol, the catalytic effect is as high as 99% of yield, the catalyst can be rapidly recovered under the action of an external magnetic field, and the recovery efficiency is as high as more than 99%.
The technical scheme adopted by the invention is as follows: a preparation method of a magnetic material loaded rhodamine B catalyst comprises the following steps:
a. uniformly dispersing magnetic ferroferric oxide spherical particles coated with silicon dioxide in a toluene solution, then dropwise adding an organic silicon source, heating to 80-140 ℃ under magnetic stirring for reaction for 5-12 hours, hydrolyzing the organic silicon source under the action of high temperature, coating the organic silicon source on the surface of a magnetic ball to form a functionalized magnetic ball, and performing magnetic separation for later use;
b. refluxing the obtained functionalized magnetic ball for 8-16 hours by using an organic solvent as an eluent through a Soxhlet extractor to remove unreacted silane, and drying to finally obtain the amino functionalized magnetic ball;
c. dissolving rhodamine B in water, adding an amino functionalized magnetic sphere, reacting in an aqueous medium by an EDC-NHS method for 3-8 hours at room temperature, carrying out magnetic separation after the reaction is finished, repeatedly washing with water until filtrate is colorless, and drying to obtain the magnetic material supported rhodamine B catalyst.
Preferably, the organic silicon source is aminopropyltriethoxysilane or aminopropyltrimethoxysilane.
Preferably, the mass ratio of the magnetic ferroferric oxide spherical particles coated by the silicon dioxide to the organic silicon source is 1: 6-10.
Preferably, the soxhlet extraction elution solvent is one of toluene, acetone or ethanol.
Preferably, the mass ratio of the rhodamine B to the amino functionalized magnetic sphere is 1: 20-40.
The magnetic material loaded rhodamine B catalyst prepared by the method can be used for the reaction of converting phenylboronic acid into phenol through hydroxylation, and the reaction formula of the oxidation of toluene is shown as follows:
preferably, the reaction conditions of the catalytic reaction involved in the present invention are: adding a magnetic material loaded rhodamine B catalyst, phenylboronic acid and an organic solvent into a reactor in sequence, finally adding an additive, stirring and reacting at 30-80 ℃, reacting for 12-48 h, and separating by column chromatography to obtain phenol.
The raw materials used in the present invention are commercially available.
Compared with the prior art, the invention has the beneficial effects that:
(1) the heterogeneous catalyst can be quickly recovered under the action of an external magnetic field by utilizing the carrier magnetism, and the recovery efficiency is up to more than 99 percent;
(2) the heterogeneous catalyst loads rhodamine B on the surface of a carrier through a covalent bond, the structure is stable, and the high stability can be still maintained after five times of recovery;
(3) the heterogeneous catalyst has excellent catalytic effect, the yield is up to 99%, the catalytic effect is equivalent to that of the traditional homogeneous catalyst, and the pollution to the environment caused by the fact that the catalyst cannot be recycled in the traditional phenol production process can be avoided.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a magnetic material loaded rhodamine B catalyst prepared by the invention;
FIG. 2 is an infrared spectrogram of the magnetic material loaded rhodamine B catalyst prepared by the invention;
FIG. 3 is a graph showing the separation effect of the catalyst in the reaction solution of the present invention under the action of an external magnetic field;
FIG. 4 is a phenylboronic acid hydroxylation catalytic activity test in accordance with the present invention;
FIG. 5 is a diagram of the catalytic effect of the magnetic material loaded rhodamine B catalyst in cyclic utilization.
In the figure, 1 is a thin-layer chromatogram of the product phenol, 2 is a thin-layer chromatogram of the reaction, and 3-bit raw material phenylboronic acid.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Example 1
(1) Uniformly dispersing 30 g of magnetic ferroferric oxide spherical particles coated by silicon dioxide in a toluene solution, then dropwise adding 200 g of aminopropyltriethoxysilane, heating to 100 ℃ under magnetic stirring for reacting for 8 hours, hydrolyzing a silicon source under the action of high temperature, coating the silicon source on the surface of a magnetic ball to form a functionalized magnetic ball, and performing magnetic separation for later use;
(2) refluxing the obtained functionalized magnetic ball for 8 hours by using an organic solvent toluene as an eluent through a Soxhlet extractor to remove unreacted silane, and drying to finally obtain an amino functionalized magnetic ball;
(3) dissolving 1 g of rhodamine B in water, adding an amino functionalized magnetic ball, reacting in an aqueous medium by an EDC-NHS method for 8 hours at room temperature, carrying out magnetic separation after the reaction is finished, repeatedly washing with water until filtrate is colorless, and drying to obtain a magnetic material loaded rhodamine B catalyst;
(4) adding a magnetic material loaded rhodamine B catalyst, phenylboronic acid and toluene into a reactor in sequence, finally adding an additive, stirring and reacting for 12 hours at 40 ℃, and separating by column chromatography to obtain phenol.
As shown in fig. 3, in the bottle on the left side, the magnetic material loaded rhodamine B catalyst is uniformly distributed in the reaction solution, and the solution is dark red; and a magnet is arranged beside the bottle on the right side, the magnetic material loaded rhodamine B catalyst is positioned on one side of the magnet after being adsorbed by the magnet, and the reaction liquid in the bottle is colorless and transparent.
The magnetic material loaded rhodamine B catalyst of the embodiment is recycled five times for the reaction of hydroxylation of phenylboronic acid to phenol, and the recycling catalytic effect is shown in FIG. 5.
Example 2
(1) Uniformly dispersing 30 g of magnetic ferroferric oxide spherical particles coated by silicon dioxide in a toluene solution, then dropwise adding 240 g of aminopropyltriethoxysilane, heating to 120 ℃ under magnetic stirring for reacting for 8 hours, hydrolyzing a silicon source under the action of high temperature, coating the silicon source on the surface of a magnetic ball to form a functionalized magnetic ball, and performing magnetic separation for later use;
(2) refluxing the obtained functionalized magnetic ball for 8 hours by using an organic solvent acetone as an eluent through a Soxhlet extractor to remove unreacted silane, and drying to finally obtain the amino functionalized magnetic ball;
(3) dissolving 1.5 closantamine B in water, adding an amino functionalized magnetic sphere, reacting in an aqueous medium by an EDC-NHS method for 4 hours at room temperature, carrying out magnetic separation after the reaction is finished, repeatedly washing with water until filtrate is colorless, and drying to obtain a magnetic material loaded rhodamine B catalyst;
(4) adding a magnetic material loaded rhodamine B catalyst, phenylboronic acid and acetonitrile into a reactor in sequence, finally adding an additive, stirring and reacting for 18 hours at 40 ℃, and separating by column chromatography to obtain phenol.
Example 3
(1) Uniformly dispersing 30 g of magnetic ferroferric oxide spherical particles coated by silicon dioxide in a toluene solution, then dropwise adding 180 g of aminopropyl trimethoxysilane, heating to 140 ℃ under magnetic stirring, reacting for 12 hours, hydrolyzing a silicon source under the action of high temperature, coating the silicon source on the surface of a magnetic ball to form a functionalized magnetic ball, and performing magnetic separation for later use;
(2) the obtained functionalized magnetic ball uses ethanol as an eluent, a Soxhlet extractor is used for refluxing for 10 hours to remove unreacted silane, and the amino functionalized magnetic ball is finally obtained after drying;
(3) dissolving 1.8 clodanmine B in water, adding an amino functionalized magnetic sphere, reacting in an aqueous medium by an EDC-NHS method at room temperature for 6 hours, carrying out magnetic separation after the reaction is finished, repeatedly washing with water until filtrate is colorless, and drying to obtain the magnetic material loaded rhodamine B catalyst.
(4) Adding a magnetic material loaded rhodamine B catalyst, phenylboronic acid and acetonitrile into a reactor in sequence, finally adding an additive, stirring and reacting for 12 hours at 80 ℃, and separating by column chromatography to obtain phenol.
Example 4
(1) Uniformly dispersing 30 g of magnetic ferroferric oxide spherical particles coated by silicon dioxide in a toluene solution, then dropwise adding 300 g of aminopropyl trimethoxysilane, heating to 80 ℃ under magnetic stirring for reaction for 5 hours, hydrolyzing a silicon source under the action of high temperature, coating the silicon source on the surface of a magnetic ball to form a functionalized magnetic ball, and performing magnetic separation for later use;
(2) the obtained functionalized magnetic ball uses toluene as an eluent, a Soxhlet extractor is used for refluxing for 5 hours to remove unreacted silane, and the amino functionalized magnetic ball is finally obtained after drying;
(3) dissolving 2-clodamine B in water, adding an amino functionalized magnetic sphere, reacting in an aqueous medium by an EDC-NHS method for 3 hours at room temperature, carrying out magnetic separation after the reaction is finished, repeatedly washing with water until filtrate is colorless, and drying to obtain the magnetic material loaded rhodamine B catalyst.
(4) Adding a magnetic material loaded rhodamine B catalyst, phenylboronic acid and acetonitrile into a reactor in sequence, finally adding an additive, stirring and reacting for 48 hours at 30 ℃, and separating by column chromatography to obtain phenol.
The present invention has been described in detail with reference to the embodiments, but the description is only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The scope of the invention is defined by the claims. The technical solutions of the present invention or those skilled in the art, based on the teaching of the technical solutions of the present invention, should be considered to be within the scope of the present invention, and all equivalent changes and modifications made within the scope of the present invention or equivalent technical solutions designed to achieve the above technical effects are also within the scope of the present invention.
Claims (8)
1. A preparation method of a magnetic material loaded rhodamine B catalyst is characterized by comprising the following steps: the method comprises the following steps:
a. uniformly dispersing magnetic ferroferric oxide spherical particles coated with silicon dioxide in a toluene solution, then dropwise adding an organic silicon source, heating to 80-140 ℃ under magnetic stirring for reaction for 5-12 hours, hydrolyzing the organic silicon source under the action of high temperature, coating the organic silicon source on the surface of a magnetic ball to form a functionalized magnetic ball, and performing magnetic separation for later use;
b. refluxing the obtained functionalized magnetic ball for 8-16 hours by using an organic solvent as an eluent through a Soxhlet extractor to remove unreacted silane, and drying to finally obtain the amino functionalized magnetic ball;
c. dissolving rhodamine B in water, adding an amino functionalized magnetic sphere, reacting in an aqueous medium by an EDC-NHS method for 3-8 hours at room temperature, carrying out magnetic separation after the reaction is finished, repeatedly washing with water until filtrate is colorless, and drying to obtain the magnetic material supported rhodamine B catalyst.
2. The method for preparing the magnetic material supported rhodamine B catalyst as claimed in claim 1, characterized in that: the organic silicon source is aminopropyl triethoxysilane or aminopropyl trimethoxysilane.
3. The method for preparing the magnetic material supported rhodamine B catalyst as claimed in claim 1, characterized in that: the mass ratio of the magnetic ferroferric oxide spherical particles coated by the silicon dioxide to the organic silicon source is 1: 6-10.
4. The method for preparing the magnetic material supported rhodamine B catalyst as claimed in claim 1, characterized in that: the Soxhlet extraction elution solvent is one of toluene, acetone or ethanol.
5. The method for preparing the magnetic material supported rhodamine B catalyst as claimed in claim 1, characterized in that: the mass ratio of the rhodamine B to the amino functional magnetic ball is 1: 20-40.
6. The magnetic material-supported rhodamine B catalyst prepared by the preparation method as described in any one of claims 1 to 5.
7. The magnetic material supported rhodamine B catalyst as claimed in claim 6, which is applied to a reaction for converting phenylboronic acid into phenol through hydroxylation.
8. The catalytic application of the magnetic material loaded rhodamine B catalyst in phenol synthesis as claimed in claim 7, wherein the magnetic material loaded rhodamine B is used as the catalyst, phenylboronic acid and an organic solvent are sequentially added into a reactor, finally an additive is added, stirring reaction is carried out at 30-80 ℃ for 12-48 h, phenol is obtained through separation, and the reaction formula is as follows:
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010024337.1A CN111151296A (en) | 2020-01-09 | 2020-01-09 | Magnetic material loaded rhodamine B catalyst, preparation method thereof and catalytic application thereof in phenol synthesis |
| ZA2021/10130A ZA202110130B (en) | 2020-01-09 | 2021-12-08 | Magnetic material supported rhodamine b catalyst, preparation method thereof and catalytic application in synthesis of phenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010024337.1A CN111151296A (en) | 2020-01-09 | 2020-01-09 | Magnetic material loaded rhodamine B catalyst, preparation method thereof and catalytic application thereof in phenol synthesis |
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| CN111423335A (en) * | 2020-04-21 | 2020-07-17 | 临沂大学 | Method for preparing o-methylbenzamide by safe and green catalysis of polyoxometallate |
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