CN109675635A - Natural polymer catalyst and preparation method thereof suitable for 2,3,6- oxidation of trimethylphenol - Google Patents
Natural polymer catalyst and preparation method thereof suitable for 2,3,6- oxidation of trimethylphenol Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
- C07C46/06—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring
- C07C46/08—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring with molecular oxygen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/14—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing two or more elements other than carbon, oxygen, nitrogen, sulfur and 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- 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
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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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
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses one kind to be suitable for 2,3,6- pseudocuminol catalysis oxidation preparation 2, the catalyst of 3,5- trimethyl 1,4-benzoquinone, belongs to catalyst preparation technical field, it is made by connection Co (Salphen) and two pyridine compounds and theirs, two pyridine compounds and their includes two pyridyl groups in contraposition, and the nitrogen-atoms in Co atom and two pyridine compounds and theirs in connection Co (Salphen) forms the natural polymer catalyst by coordination key connection；The preparation method of catalyst of the present invention is simple, and can be realized with O2To be catalyzed 2 under oxidant chamber's normal temperature and pressure, 3,6- oxidation of trimethylphenol generates 2,3,5- trimethyl 1,4-benzoquinone, this kind of heterogeneous reaction needs the limitation of hydrogen peroxide, high temperature mostly before overcoming, and in catalyst circulation use process the conversion ratio of substrate, product selectivity can be kept well.
Description
Technical field
The invention belongs to catalyst preparation technical fields, are related to a kind of suitable for 2,3,6-TMP catalysis oxidation system
The catalyst of standby 2,3,5- trimethyl 1,4-benzoquinone, in particular to it is a kind of suitable for the non-covalent poly- of 2,3,6-TMP oxidation
Mixture catalyst and preparation method thereof.
Background technique
2,3,5- trimethyl 1,4-benzoquinone are the important intermediate of synthesising complex E, the synthesis of 2,3,5- trimethyl 1,4-benzoquinone
There are mainly two types of approach, and one is sulfonation-oxidizing process, another kind is a step catalytic oxidation.Sulfonation-oxidizing process environmental pollution
Seriously, it is gradually eliminated；One step catalytic oxidation mild condition, it is environmentally friendly, there is vast potential for future development.
The industrial production of 2,3,5- trimethyl 1,4-benzoquinone mainly passes through the preparation of 2,3,6- pseudocuminol catalysis oxidation at present
It obtains, catalyst is mostly small molecule, such as CuCl2With Co (Salen), O2For oxidant, preferably turn although such catalyst has
Rate and selectivity, but since small molecule stability is poor, the dissolution of reaction process small molecular catalyst causes product and urges
Agent separation is difficult, and catalyst is caused to be difficult to be recycled, and containing wastewater from catalyst pollutes environment, constrains 2,3,5- front threes significantly
The industrial production of base 1,4-benzoquinone, therefore, finding a kind of good cycle, catalytic performance, good catalyst is anxious to be resolved at present
Problem.
Natural polymer has many advantages, such as that synthesis is simple compared with covalent polymer, and structure is clear, but the poor limitation of stability
Application of the natural polymer in heterogeneous catalysis.The stability of coordinate bond between non-covalent bond and covalent bond, with
Coordination is that the natural polymer that driving force is constructed has preferable stability, is had in heterogeneous catalysis latent well
Power.
Summary of the invention
In view of the deficiencies of the prior art, it is suitable for 2,3,6-TMP the purpose of the present invention is to provide one kind to aoxidize
Natural polymer catalyst and preparation method thereof, the catalyst is in the presence of oxygen by 2,3,6-TMP
It is catalytically oxidized to 2,3,5- trimethyl 1,4-benzoquinone, selectivity with higher, and the catalyst can be used repeatedly, substrate
High conversion rate, the selectivity of target product is good.
In order to achieve the above object, the present invention provides following technical schemes:
The present invention provides a kind of natural polymer catalyst suitable for 2,3,6-TMP oxidation, by joining Co
(Salphen) it is made with two pyridine compounds and theirs, two pyridine compounds and their includes two pyridyl groups in contraposition, joins Co
(Salphen) nitrogen-atoms in the Co atom and two pyridine compounds and theirs in is formed described non-total by coordination key connection
Valence polyalcohol catalyst.
Preferably, two pyridine compounds and their is 4,4- bipyridyl, natural polymer catalyst obtained, name
Are as follows: SuP-CSU-1, structure are as follows:
Preferably, two pyridine compounds and their is 1,2-di(4-pyridyl)ethylene, natural polymer obtained
Catalyst, name are as follows: SuP-CSU-2, structure are as follows:
Preferably, two pyridine compounds and their is Isosorbide-5-Nitrae-two (to pyridyl group) benzene, natural polymer obtained is urged
Agent, name are as follows: SuP-CSU-3, structure are as follows:
The inventive concept total as one, the present invention also provides the preparation method of the natural polymer catalyst, packets
Include following steps:
(1) synthesis connection Salphen: using dehydrated alcohol as solvent, the mass ratio of the material of salicylide and o-phenylenediamine is 2~3:
1, N2Protection, reaction mixture stir 3 at 25~80 DEG C~for 24 hours, filtering obtains required target product after recrystallizing；Its
Middle Salphen structure is as follows:
(2) methanol solution of cobalt acetate: being added drop-wise to the tetrahydrofuran solution of connection Salphen by synthesis connection Co (Salphen),
The mass ratio of the material for joining Salphen and cobalt acetate is 1:2~3, reaction mixture stir 3 at 25~80 DEG C~for 24 hours, filter,
It is dried to obtain required target product；Wherein connection Co (Salphen) structure is as follows:
(3) it synthesizes SuP-CSU: using DMF as solvent, joining the mass ratio of the material of Co (Salphen) and two pyridine compounds and theirs
For 1:1, N2Protection, reaction mixture stir 24~48h at 30~100 DEG C, are cooled to room temperature, and methanol and tetrahydro are used after filtering
Furans rope mentions 24~48h to get the natural polymer catalyst.
The present invention also provides the applications of the natural polymer catalyst, using methanol as solvent, in the condition of oxygen
Under, catalysis 2,3,6-TMP is oxidized to 2,3,5- trimethyl 1,4-benzoquinone.
Further, the mass ratio that feeds intake of the catalyst and 2,3,6-TMP is 1:3~10.
Further, for the reaction temperature at 25~65 DEG C, oxygen pressure is 0.1~5MPa, and the catalytic oxidation time is 1
~36h.
The 2,3,6- oxidation of trimethylphenol of the present invention that is catalyzed is at the reaction process of 2,3,5- trimethyl 1,4-benzoquinone are as follows:
For reaction process in above formula using methanol as solvent, oxygen is oxidant.
In order to realize the heterogeneous catalytic oxidation of 2,3,6-TMP, the present invention is using connection Co (Salphen) and two
Pyridine compounds and their reaction is prepared for a kind of natural polymer catalyst, and the polymer is using methanol as solvent, O2For oxidation
The high-selectivity oxidation of 2,3,6-TMP can be achieved under conditions of agent, and can be achieved to urge by simple filtering or centrifugation
Agent efficiently separates, and can be recycled.
Compared with the prior art, technical solution of the present invention bring the utility model has the advantages that
(1) present invention prepares catalyst using methanol as solvent, and oxygen is oxidant at 25~65 DEG C, 0.1~5Mpa item
It is catalyzed 2,3,6-TMP oxidation under part and generates 2,3,5- trimethyl 1,4-benzoquinone, catalysis reaction carries out 1~36h, and reaction turns
Rate is 5%~99%, selectivity > 99% of 2,3,6-TMP, and catalyst can repeatedly use, and is had fine
Industrial applications prospect.
(2) preparation method of catalyst of the present invention is simple, and can be realized with O2To be catalyzed under oxidant chamber's normal temperature and pressure
2,3,6-TMP oxidation generates 2,3,5- trimethyl 1,4-benzoquinone, and this kind of heterogeneous reaction needs double mostly before overcoming
The limitation of oxygen water, high temperature, and in catalyst circulation use process the conversion ratio of substrate, product selectivity can obtain very well
Holding.
Detailed description of the invention
Fig. 1 is connection Salphen1H NMR figure.
Fig. 2 is connection Salphen1C NMR figure.
Fig. 3 is the mass spectrogram for joining Co (Salphen).
Fig. 4 is the FT-IR figure for joining Co (salphen).
Fig. 5 is the UV figure for joining Co (Salphen).
Fig. 6 is that the UV of 4,4- bipyridyl schemes.
The FT-IR that Fig. 7 is Sup-CSU-1 schemes.
The UV that Fig. 8 is Sup-CSU-1 schemes.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, rather than whole embodiments, based on the embodiments of the present invention, ordinary skill
Personnel's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
Present invention will be further explained below with reference to the attached drawings and specific examples.
Embodiment 1
The present invention provides a kind of preparation side of natural polymer catalyst suitable for 2,3,6- oxidation of trimethylphenol
Method, comprising the following steps:
(1) it synthesis connection Salphen: in 500ml three-necked flask, is added 3,3- diaminobenzidine (1g, 4.67mmol)
With 150ml methanol, nitrogen protection, salicylide (2.74g, 22.4mmol) is dissolved in 100ml methanol and is added drop-wise in reaction solution, at room temperature
For 24 hours, filtering, methanol wash to obtain crude product, and THF is recrystallized to give required Salphen compound, wherein joining for stirring
Salphen structure is as follows:
(2) synthesis connection Co (Salphen): in 250ml three-necked flask, be added Salphen (251mg, 0.4mmol) and
100ml THF, ultrasonic dissolution, under nitrogen protection, methanol (30ml) solution of four acetate hydrate cobalts (238mg, 0.95mmol) drips
It is added in the THF solution of connection Salphen, stirs at room temperature for 24 hours, filtering, methanol, water washing obtain required Co (Salphen)
Compound；Wherein connection Co (Salphen) structure is as follows:
(3) synthesize SuP-CSU-1:100ml three-necked flask in, be added connection Co (salphen) (500mg, 0.67mmol) and
4,4- bipyridyls (105mg, 0.67mmol), nitrogen protection, syringe inject 50ml DMF, and 100 DEG C of stirrings for 24 hours, are cooled to room
Temperature, filtering, is mentioned with methanol, THF rope, obtains required SuP-CSU-1, wherein n=10~1000, structure is as follows:
Embodiment 2
The present invention provides a kind of preparation side of natural polymer catalyst suitable for 2,3,6- oxidation of trimethylphenol
Method, comprising the following steps:
(1) it synthesis connection Salphen: in 500ml three-necked flask, is added 3,3- diaminobenzidine (1g, 4.67mmol)
With 150ml methanol, nitrogen protection, salicylide (2.74g, 22.4mmol) is dissolved in 100ml methanol and is added drop-wise in reaction solution, at room temperature
For 24 hours, filtering, methanol wash to obtain crude product, and THF is recrystallized to give required Salphen compound for stirring；
(2) synthesis connection Co (Salphen): in 250ml three-necked flask, be added Salphen (251mg, 0.4mmol) and
100ml THF, ultrasonic dissolution, under nitrogen protection, methanol (30ml) solution of four acetate hydrate cobalts (238mg, 0.95mmol) drips
It is added in the THF solution of Salphen, stirs at room temperature for 24 hours, filtering, methanol, water washing obtain required Co (Salphen) change
Close object；
(3) synthesize SuP-CSU-2:100ml three-necked flask in, be added connection Co (salphen) (500mg, 0.67mmol) and
1,2-di(4-pyridyl)ethylene (122mg, 0.67mmol), nitrogen protection, syringe inject 50ml DMF, 100 DEG C of stirrings
For 24 hours, it is cooled to room temperature, filters, mentioned with methanol, THF rope, obtain required SuP-CSU-2, wherein n=10~1000, structure
It is as follows:
Embodiment 3
The present invention provides a kind of preparation side of natural polymer catalyst suitable for 2,3,6- oxidation of trimethylphenol
Method, comprising the following steps:
(1) it synthesis connection Salphen: in 500ml three-necked flask, is added 3,3- diaminobenzidine (1g, 4.67mmol)
With 150ml methanol, nitrogen protection, salicylide (2.74g, 22.4mmol) is dissolved in 100ml methanol and is added drop-wise in reaction solution, at room temperature
For 24 hours, filtering, methanol wash to obtain crude product, and THF is recrystallized to give required Salphen compound for stirring；
(2) synthesis connection Co (Salphen): in 250ml three-necked flask, be added Salphen (251mg, 0.4mmol) and
100ml THF, ultrasonic dissolution, under nitrogen protection, methanol (30ml) solution of four acetate hydrate cobalts (238mg, 0.95mmol) drips
It is added in the THF solution of Salphen, stirs at room temperature for 24 hours, filtering, methanol, water washing obtain required Co (Salphen) change
Close object；
(3) synthesize SuP-CSU-3:100ml three-necked flask in, be added connection Co (salphen) (500mg, 0.67mmol) and
Isosorbide-5-Nitrae-two (to pyridyl group) benzene (156mg, 0.67mmol), nitrogen protection, syringe inject 50ml DMF, and 100 DEG C are stirred for 24 hours,
It is cooled to room temperature, filters, mentioned with methanol, THF rope, obtain required SuP-CSU-3, wherein n=10~1000, structure is such as
Under:
Embodiment 4
With SuP-CSU-1 catalysis 2,3,6- oxidation of trimethylphenol at the reaction of 2,3,5- trimethyl 1,4-benzoquinone:
The 2,3,6-TMP of the Sup-CSU-1 of 20mg, 68.1mg, methanol 2ml, O2For 0.1Mpa, 30 DEG C of reactions
36h, the conversion ratio of 2,3,6-TMP are 99%, and the selectivity of 2,3,5- trimethyl 1,4-benzoquinone is 99%.
Embodiment 5
With SuP-CSU-2 catalysis 2,3,6- oxidation of trimethylphenol at the reaction of 2,3,5- trimethyl 1,4-benzoquinone:
The 2,3,6-TMP of the Sup-CSU-2 of 20mg, 68.1mg, methanol 2ml, O2For 0.1Mpa, 30 DEG C of reactions
36h, the conversion ratio of 2,3,6-TMP are 99%, and the selectivity of 2,3,5- trimethyl 1,4-benzoquinone is 99%.
Embodiment 6
With SuP-CSU-3 catalysis 2,3,6- oxidation of trimethylphenol at the reaction of 2,3,5- trimethyl 1,4-benzoquinone:
The 2,3,6-TMP of the Sup-CSU-3 of 20mg, 68.1mg, methanol 2ml, O2For 0.1Mpa, 30 DEG C of reactions
36h, the conversion ratio of 2,3,6-TMP are 99%, and the selectivity of 2,3,5- trimethyl 1,4-benzoquinone is 99%.
Embodiment 7
With SuP-CSU-1 catalysis 2,3,6- oxidation of trimethylphenol at the reaction of 2,3,5- trimethyl 1,4-benzoquinone:
The 2,3,6-TMP of the Sup-CSU-1 of 20mg, 68.1mg, methanol 2ml, O2For 1Mpa, 30 DEG C of reaction 3h,
The conversion ratio of 2,3,6-TMP is 99%, and the selectivity of 2,3,5- trimethyl 1,4-benzoquinone is 99%.
Embodiment 8
Catalyst centrifugation after embodiment 7 is reacted after washing, continues to put into catalytic oxidation:
The 2,3,6-TMP of 68.1mg, methanol 2ml, O2For 0.1Mpa, 30 DEG C of reaction 36h, catalyst is for the first time
Circulation, the conversion ratio of 2,3,6-TMP are 99%, and the selectivity of 2,3,5- trimethyl 1,4-benzoquinone is 99%.
Embodiment 9
Catalyst centrifugation after embodiment 8 is reacted after washing, continues to put into catalytic oxidation:
The 2,3,6-TMP of 68.1mg, methanol 2ml, O2For 0.1Mpa, 30 DEG C of reaction 36h, catalyst is for the second time
Circulation, the conversion ratio of 2,3,6-TMP are 99%, and the selectivity of 2,3,5- trimethyl 1,4-benzoquinone is 99%.
Embodiment 10
Catalyst centrifugation after embodiment 9 is reacted after washing, continues to put into catalytic oxidation:
The 2,3,6-TMP of 68.1mg, methanol 2ml, O2For 0.1Mpa, 30 DEG C of reaction 36h, catalyst third time
Circulation, the conversion ratio of 2,3,6-TMP are 99%, and the selectivity of 2,3,5- trimethyl 1,4-benzoquinone is 99%.
Embodiment 11
Catalyst centrifugation after embodiment 9 is reacted after washing, continues to put into catalytic oxidation:
The 2,3,6-TMP of 68.1mg, methanol 2ml, O2For 0.1Mpa, 30 DEG C of reaction 36h, catalyst the 4th time
Circulation, the conversion ratio of 2,3,6-TMP are 98%, and the selectivity of 2,3,5- trimethyl 1,4-benzoquinone is 99%.
Embodiment 12
Catalyst centrifugation after embodiment 9 is reacted after washing, continues to put into catalytic oxidation:
The 2,3,6-TMP of 68.1mg, methanol 2ml, O2For 0.1Mpa, 30 DEG C of reaction 36h, catalyst the 5th time
Circulation, the conversion ratio of 2,3,6-TMP are 96%, and the selectivity of 2,3,5- trimethyl 1,4-benzoquinone is 99%.
Fig. 1 is connection Salphen1H NMR figure, solvent are deuterated CDCl3, from figure it follows that totally 9 kinds of the type of hydrogen, hydrogen
Number ratio be similar to 1:1:1:2:2:2:2:2:2 and target compound meets.
Fig. 2 is connection Salphen13C NMR figure, solvent are deuterated CDCl3, from figure it follows that totally 13 kinds of the type of carbon,
Meet with target compound.
Fig. 3 is the mass spectrogram for joining Co (Salphen), and mode is positive ion mode, from figure it follows that highest peak molecular weight
744.0035 meet with theoretical molecular weight 744.06, illustrate the correct synthesis of target compound.
Fig. 4 is the infrared figure for joining Co (Salphen), from figure it follows that being the peak of C=N key, secondary proof from 1610nm
The correct synthesis of Co (Salphen).
Fig. 5 is the UV figure for joining Co (Salphen), from figure it follows that being attributed to π-the π *, 406nm of aromatic rings from 270nm
Place can be attributed to C=N key n-π * transition as a result, the d-π * electric charge transfer of Co-O key can be attributed at 476nm.
Fig. 6 is the UV figure of 4,4- bipyridyl, from figure it follows that can be attributed to the π-π * of aromatic rings from 270nm.
Fig. 7 is the infrared figure of SuP-CSU-1, from figure it follows that being the peak of C=N key from 1608nm, compared with Co
(Salphen), a small amount of blue shift, the generation of the coordination of side light pyridine N and Co has occurred in C=N key.
The UV that Fig. 8 is SuP-CSU-1 schemes, from figure it follows that the d-π * charge of C=N key n-π * transition and Co-O key turns
Certain red shift has occurred in shifting, it may be possible to caused by the coordination of pyridine N and Co.
Claims (8)
1. a kind of natural polymer catalyst suitable for 2,3,6-TMP oxidation, which is characterized in that by joining Co
(Salphen) it is made with two pyridine compounds and theirs, two pyridine compounds and their includes two pyridyl groups in contraposition, joins Co
(Salphen) nitrogen-atoms in the Co atom and two pyridine compounds and theirs in is formed described non-total by coordination key connection
Valence polyalcohol catalyst.
2. the natural polymer catalyst according to claim 1 suitable for 2,3,6-TMP oxidation, special
Sign is that two pyridine compounds and their is 4,4- bipyridyl, natural polymer catalyst obtained, name are as follows: SuP-
CSU-1, structure are as follows:
3. the natural polymer catalyst according to claim 1 suitable for 2,3,6-TMP oxidation, special
Sign is that two pyridine compounds and their is 1,2-di(4-pyridyl)ethylene, natural polymer catalyst obtained, name
Are as follows: SuP-CSU-2, structure are as follows:
4. the natural polymer catalyst according to claim 1 suitable for 2,3,6-TMP oxidation, special
Sign is that two pyridine compounds and their is Isosorbide-5-Nitrae-two (to pyridyl group) benzene, natural polymer catalyst obtained, name
Are as follows: SuP-CSU-3, structure are as follows:
5. the preparation method of natural polymer catalyst described according to claim 1~any one of 4, which is characterized in that packet
Include following steps:
(1) synthesis connection Salphen: using dehydrated alcohol as solvent, the mass ratio of the material of salicylide and o-phenylenediamine is 2~3:1, N2
Protection, reaction mixture stir 3 at 25~80 DEG C~for 24 hours, filtering obtains required target product after recrystallizing；Wherein join
Salphen structure is as follows:
(2) methanol solution of cobalt acetate synthesis connection Co (Salphen): is added drop-wise to the tetrahydrofuran solution of connection Salphen, connection
The mass ratio of the material of Salphen and cobalt acetate is 1:2~3, reaction mixture stir 3 at 25~80 DEG C~for 24 hours, filtering is done
It is dry to obtain required target product；Wherein connection Co (Salphen) structure is as follows:
(3) synthesize SuP-CSU: using DMF as solvent, the mass ratio of the material for joining Co (Salphen) and two pyridine compounds and theirs is 1:
1, N2Protection, reaction mixture stir 24~48h at 30~100 DEG C, are cooled to room temperature, and methanol and tetrahydrofuran are used after filtering
Rope mentions 24~48h to get the natural polymer catalyst.
6. the application of natural polymer catalyst described according to claim 1~any one of 4, which is characterized in that described non-
Covalent polymer catalyst, using methanol as solvent, under conditions of oxygen, catalysis 2,3,6-TMP is oxidized to 2,
3,5- trimethyl 1,4-benzoquinone.
7. the application of natural polymer catalyst according to claim 6, which is characterized in that the catalyst and 2,3,
The mass ratio that feeds intake of 6- pseudocuminol is 1:3~10.
8. the application of natural polymer catalyst according to claim 6, which is characterized in that the reaction temperature is 25
~65 DEG C, oxygen pressure is 0.1~5MPa, and the catalytic oxidation time is 1~36h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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