CN109453819A - The porous organic polymer carrying transition metal oxide catalyst of carbazyl and application - Google Patents
The porous organic polymer carrying transition metal oxide catalyst of carbazyl and application Download PDFInfo
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- CN109453819A CN109453819A CN201710794499.1A CN201710794499A CN109453819A CN 109453819 A CN109453819 A CN 109453819A CN 201710794499 A CN201710794499 A CN 201710794499A CN 109453819 A CN109453819 A CN 109453819A
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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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
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- 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
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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Abstract
The invention discloses the methods that a kind of porous organic polymer carrying transition metal oxide catalyst of carbazyl prepares P-methoxybenzal-dehyde to methoxy methyl benzene oxidatoin.The catalyst is using carbazyl porous organic polymer as carrier, by back loading transition metal salt, obtains the catalyst of transition metal oxide of carbazyl porous organic polymer load by roasting.Due to there is equally distributed nitrogen-atoms on carbazyl porous organic polymer skeleton, and nitrogen-atoms and metal have certain interaction.Therefore, on the one hand equally distributed nitrogen-atoms has activated metal oxide active site；On the other hand, reduce the loss of active component in reaction process.The catalyst can prepare P-methoxybenzal-dehyde to methoxy toluene with efficient catalytic, and conversion ratio and selectivity can reach 70% or more.Compared with traditional heterogeneous catalyst, the catalyst thermal stability is high, and catalytic activity is good, and active component not easily runs off, the long service life of catalyst.
Description
Technical field
The present invention relates to chemical field, specifically a kind of carbazyl porous organic polymer material back loading cobalt
Manganese oxide catalyst and its application in P-methoxybenzal-dehyde is being prepared to methoxy methyl benzene oxidatoin.
Background technique
P-methoxybenzal-dehyde is also known as anisaldehyde, and generally colourless at normal temperature or flaxen liquid, there have to be lasting
Hawthorn fragrance is a kind of very high fragrance of economic value, is also important organic chemical synthesis intermediate, while still preparing porphin
The intermediate of quinoline class photosensitizer, ammonia card base penicillin etc..Currently, synthesis P-methoxybenzal-dehyde method can be mainly divided into
Anise camphor, phenol, parahydroxyben-zaldehyde, methyl phenyl ethers anisole, is the conjunction of raw material to methoxy toluene etc. at methoxy benzyl alcohol
At route.
From the course for preparing P-methoxybenzal-dehyde to methoxy methyl benzene oxidatoin, using molecular oxygen as oxidant, it is
A kind of more green oxidation process.It is disclosed in patent CN103694093A and uses metalloporphyrin as catalyst, molecular oxygen
The method that prepared by P-methoxybenzal-dehyde to the oxidation of methoxy toluene as oxidant；By porphin in patent CN102070382A
Quinoline metal salt and the porphyrin metal salt being supported on carrier are catalyzed toluene and replace toluene oxidation, react item as catalyst
Part is harsher, and P-methoxybenzal-dehyde yield is lower；It discloses in CN1491930 using CoO-Al2O3(R is co-catalysis to-R
Agent) catalysis to the process of methoxy toluene to aldehyde, obtained preferable effect.
Above case explanation is oxidant using molecular oxygen, designs and prepare high conversion, highly selective and recyclable
Catalyst it is extremely important.Loaded catalyst is a kind of commonly recyclable catalyst, but is often faced with active component
The problems such as loss in various degree, activated centre activity is not high enough, and the selection of carrier is most important to the solution of problem above.
Carbazyl porous organic polymer is a kind of important polymer material, has large specific surface area, and thermal stability is high
The characteristics of, there are very big potentiality as catalyst carrier.Due to being uniformly distributed on carbazyl porous organic polymer skeleton
Nitrogen-atoms, and nitrogen-atoms and metal have certain interaction.Therefore, on the one hand equally distributed nitrogen-atoms has activated metal
Oxide active site；On the other hand, reduce the loss of active component in reaction process.
Summary of the invention
Effective selection for supported catalyst agent carrier set forth above to further activating activities center and subtracts
The problem of few catalyst activity component is lost, uses carbazyl porous organic polymer as catalyst carrier, since it compares table
Area is big, and thermal stability is high, and has equally distributed nitrogen-atoms in polymer backbone, can generate work to metal active centres
Change effect, and since the presence of interaction generates certain stabilization, stabilizing active center is achieved the purpose that with this.This
Invention is polymerize to obtain carbazyl porous organic polymer by carbazolyl monomers, is obtained having in a kind of structural unit and uniformly be divided
The polymer material of the nitrogen-atoms of cloth, then by the method for wet impregnation, active component cobalt, manganese are supported on polymer backbone
On, active and high stability supported cobalt manganese oxide catalyst is obtained by drying and roasting.Under the catalyst action,
The selectivity of conversion ratio and P-methoxybenzal-dehyde to methoxy toluene is up to 70% or more.
According to the present invention, the porous organic polymer carrying transition metal oxide catalyst of the carbazyl can be according to such as
The preparation of lower section method:
1) 1,3,5- tri- (9- carbazyl) benzene is dissolved in anhydrous chloroform, iron chloride is catalyst, under nitrogen atmosphere
24-36h is stirred at room temperature, after reaction, carbazole is obtained by washing, suction filtration, concentrated hydrochloric acid washing, Soxhlet extraction, vacuum drying
Base porous organic polymer.
2) weigh 0.1-2g carbazyl porous organic polymer, be added the 1%-10wt% of carrier quality cobalt salt and/or
Manganese salt is added 2-50ml ethyl alcohol, stirs 12-24h under the conditions of 20-60 DEG C；
3) after impregnating, ethyl alcohol is removed by Rotary Evaporators, the dry 6-12h in 60-120 DEG C of baking oven, in Muffle
With 250-400 DEG C of roasting 2-5h in furnace, the cobalt/cobalt oxide and/or Mn oxide for obtaining the load of carbazyl porous organic polymer are urged
Agent.
According to the present invention, cobalt salt includes one of cobalt chloride, cobalt acetate, cobalt nitrate or two kinds or more；Manganese salt includes chlorine
Change one of manganese, manganese acetate, manganese sulfate or two kinds or more.
According to the present invention, the catalyst can be applicable to the reaction generated to methoxy methyl benzene oxidatoin to methoxy toluene
In；
According to present invention is characterized in that it is described to methoxy toluene prepare P-methoxybenzal-dehyde using autoclave it is anti-
It answers, 60-150 DEG C of reaction temperature, preferably 90-130 DEG C；Reaction time is 1-12h, preferably 6-8h；React oxygen pressure
0.1-2.0MPa, preferably 0.8-1.5MPa；The catalyst amount is the 0.1-100%, preferably 0.5- of substrate quality
2%
The invention discloses a kind of porous organic polymer carrying transition metal oxide catalysts of carbazyl to methoxyl group
The method that toluene oxidation prepares P-methoxybenzal-dehyde.The catalyst is using carbazyl porous organic polymer as carrier, by rear
Carrying transition metal salt obtains the catalyst of transition metal oxide of carbazyl porous organic polymer load by roasting.By
In having equally distributed nitrogen-atoms on carbazyl porous organic polymer skeleton, and nitrogen-atoms has certain phase interaction with metal
With.Therefore, on the one hand equally distributed nitrogen-atoms has activated metal oxide active site；On the other hand, reduce and reacted
The loss of active component in journey.The catalyst can prepare P-methoxybenzal-dehyde, conversion ratio to methoxy toluene with efficient catalytic
It can reach 70% or more with selectivity.Compared with traditional heterogeneous catalyst, the catalyst thermal stability is high, catalytic activity
Good, active component not easily runs off, the long service life of catalyst.
Beneficial effects of the present invention:
1, compared with traditional active carbon, silica supports, which has higher
Specific surface area, be easier to load active component；
2, due to the presence of nitrogen-atoms in carbazyl porous organic polymer skeleton, to the electron density of metal active constituent
It has an impact to achieve the purpose that activation；Due to the presence of nitrogen-atoms and metal interaction haved the function that it is stable；From
And obtain active and all relatively high stability catalyst.
3, the catalyst repeat performance is preferable, long service life.
Detailed description of the invention
Fig. 1 is the TEM phenogram of materials A；
Fig. 2 is the infrared spectrum of materials A, B, C, D；
Fig. 3 is the physical absorption figure of materials A.
Specific embodiment
Method provided by the invention is described in detail below with reference to embodiment, but the invention is not limited in any way.
The preparation of 1 materials A of embodiment
1) 2.0g iron chloride is weighed, nitrogen is replaced into, 70ml anhydrous chloroform is added, then 0.8g is added dropwise and is dissolved in 70ml
1 in anhydrous chloroform, 3,5- tri- (9- carbazyl) benzene, stir 36h under room temperature, washed by washing, suction filtration, concentrated hydrochloric acid,
Soxhlet extraction, vacuum drying obtain carbazyl porous organic polymer.
2) 0.2g carbazyl porous organic polymer is weighed, tetra- water cobalt acetate of 40mg is added, 5ml ethyl alcohol is added, at 40 DEG C
Stirring is for 24 hours；
3) after impregnating, ethyl alcohol is removed by rotation steaming method instrument, the dry 12h in 80 DEG C of baking oven, in Muffle furnace
3h is roasted under the conditions of 300 DEG C, obtains materials A.
The preparation of 2 material B-E of embodiment
The preparation method of material B-E is identical as materials A, the difference is that the choosing of metal salt, load capacity and maturing temperature
It selects, obtained material is listed in table 1.
Metal salt, load capacity and the maturing temperature that 1 material B-E of table is used
| Material is compiled | Metal salt | Load capacity (wt%) | Maturing temperature (DEG C) |
| B | CoCl2·6H2O | 3.0 | 350 |
| C | Co(NO3)2·6H2O | 3.0 | 300 |
| D | Co(NO3)2·6H2O | 7.0 | 300 |
| E | Co(O Ac)2·6H2O | 5.0 | 300 |
The preparation of 3 material F of embodiment
1) 2.0g iron chloride is weighed, nitrogen is replaced into, 70ml anhydrous chloroform is added, then 0.8g is added dropwise and is dissolved in 70ml
1 in anhydrous chloroform, 3,5- tri- (9- carbazyl) benzene, stir 36h under room temperature, washed by washing, suction filtration, concentrated hydrochloric acid,
Soxhlet extraction, vacuum drying obtain carbazyl porous organic polymer.
2) 0.2g carbazyl porous organic polymer is weighed, tetra- water manganese acetate of 80mg is added, 5ml ethyl alcohol is added, at 40 DEG C
Stirring is for 24 hours；
3) after impregnating, ethyl alcohol is removed by rotation steaming method instrument, the dry 12h in 80 DEG C of baking oven, in Muffle furnace
3h is roasted under the conditions of 400 DEG C, obtains material F.
Embodiment 4
The 30mg catalyst A and 1.2g of synthesis is added in 60ml autoclave methoxy toluene, 10ml acetonitrile
As reaction dissolvent, oxygen pressure 1.0MPa, reaction temperature is 130 DEG C, reacts 6h.It is cooled to room temperature, uses to the end of reacting
Gas phase analysis method is 70% to methoxy toluene conversion ratio, and the selectivity of P-methoxybenzal-dehyde is 70%.
Embodiment 5
The 30mg catalyst A and 1.2g of synthesis is added in 60ml autoclave methoxy toluene, 10ml acetonitrile
As reaction dissolvent, oxygen pressure 0.2MPa, reaction temperature is 130 DEG C, reacts 6h.It is cooled to room temperature, uses to the end of reacting
Gas phase analysis method is 30% to methoxy toluene conversion ratio, and the selectivity of P-methoxybenzal-dehyde is 60%.
Embodiment 6
The 30mg catalyst A and 1.2g of synthesis is added in 60ml autoclave methoxy toluene, 10ml acetonitrile
As reaction dissolvent, oxygen pressure 1.0MPa, reaction temperature is 80 DEG C, reacts 12h.It is cooled to room temperature, uses to the end of reacting
Gas phase analysis method is 15% to methoxy toluene conversion ratio, and the selectivity of P-methoxybenzal-dehyde is 80%.
Embodiment 7
The 30mg catalyst F and 1.2g of synthesis is added in 60ml autoclave methoxy toluene, 10ml acetonitrile
As reaction dissolvent, oxygen pressure 1.0MPa, reaction temperature is 130 DEG C, reacts 6h.It is cooled to room temperature, uses to the end of reacting
Gas phase analysis method is 50% to methoxy toluene conversion ratio, and the selectivity of P-methoxybenzal-dehyde is 70%.
Embodiment 8
The used catalyst A of embodiment 4 is done into reuse experiment, experimental procedure is completely the same, is repeated four times
It uses, to methoxy toluene conversion ratio 68%, P-methoxybenzal-dehyde selectivity 68%, activity is maintained substantially.
Claims (8)
1. the catalyst of the porous organic polymer carrying transition metal oxide of carbazyl, it is characterised in that: more with carbazyl
Hole organic polymer is that carrier is introduced into transition metal oxide active in the supported on carriers transition metal salt prepared
The heart；Transition metal oxide includes cobalt/cobalt oxide and/or Mn oxide；Quality of the transition metal oxide in catalyst supports
Amount is 1%-10wt%.
2. according to catalyst described in claim 1, it is characterised in that: carbazyl porous organic polymer is as carrier, preparation
It is to be polymerize by the Friedel-Crafts reaction of Ferric Chloride, structural formula are as follows:
3. carrier according to claim 2, it is characterised in that: the carbazyl porous organic polymer carrier can be by
It is prepared according to following steps:
1,3,5- tri- (9- carbazyl) benzene is dissolved in anhydrous chloroform, iron chloride is catalyst, and room temperature is stirred under nitrogen atmosphere
Mix 24-36h；After reaction, by washing, suction filtration, concentrated hydrochloric acid washing, Soxhlet extraction, that vacuum drying obtains carbazyl is porous
Organic polymer.
4. catalyst described in accordance with the claim 1, it is characterised in that: activated centre can be introduced by following steps:
1) 0.1-2g carbazyl porous organic polymer is weighed, the cobalt salt and/or manganese salt of the 1%-10wt% of carrier quality is added,
2-50ml ethyl alcohol is added, stirs 12-24h under the conditions of 20-60 DEG C；
2) after impregnating, ethyl alcohol is removed by Rotary Evaporators, the dry 6-12h in 60-120 DEG C of baking oven, in Muffle furnace
With 250-400 DEG C of roasting 2-5h, cobalt/cobalt oxide and/or the Mn oxide catalysis of carbazyl porous organic polymer load are obtained
Agent.
5. according to the catalyst of claim 4, it is characterised in that: the loading process, cobalt salt include cobalt chloride, cobalt acetate,
One of cobalt nitrate or two kinds or more；Manganese salt includes one of manganese chloride, manganese acetate, manganese sulfate or two kinds or more.
6. a kind of any catalyst of claim 1-5 is generating the anti-of P-methoxybenzal-dehyde to methoxy methyl benzene oxidatoin
Application in answering.
7. applying according to claim 6, it is characterised in that: described to prepare P-methoxybenzal-dehyde to methoxy toluene
Using still reaction, 60-150 DEG C of reaction temperature, preferably 90-130 DEG C；Reaction time is 1-12h, preferably 6-8h；Reaction
Oxygen pressure 0.1-2.0MPa in system, preferably 0.8-1.5MPa.
8. according to application described in claim 6 or 7, it is characterised in that: the catalyst amount is substrate to methoxy methyl
The 0.1-100% of benzene quality, preferably 0.5-2%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110252399A (en) * | 2019-06-11 | 2019-09-20 | 上海大学 | Polymer support loaded catalyst composite material, its application and preparation method |
| CN112604706A (en) * | 2021-01-15 | 2021-04-06 | 荆楚理工学院 | Preparation method and application of nitrogen-containing super-crosslinked polymer-derived Co @ CN catalyst |
| CN112778106A (en) * | 2019-11-05 | 2021-05-11 | 中国科学院大连化学物理研究所 | Method for preparing anisaldehyde by catalytic liquid phase selective oxidation |
| CN113299488A (en) * | 2021-05-31 | 2021-08-24 | 辽宁大学 | Porous carbon material based on nitrogen-rich covalent organic framework structure and preparation method and application thereof |
| CN113828358A (en) * | 2020-06-24 | 2021-12-24 | 万华化学集团股份有限公司 | Mandelic acid oxidation reaction catalyst, preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304779A (en) * | 2012-03-15 | 2013-09-18 | 国家纳米科学中心 | Polycarbazole polymer as well as preparation method and applications thereof |
| CN105126857A (en) * | 2015-07-31 | 2015-12-09 | 齐国良 | Catalyst for catalyzing direct oxidation of toluene to prepare benzaldehyde and preparation method thereof |
| CN106925265A (en) * | 2015-12-30 | 2017-07-07 | 中国科学院过程工程研究所 | A kind of transition metal composite oxide catalytic agent |
-
2017
- 2017-09-06 CN CN201710794499.1A patent/CN109453819B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304779A (en) * | 2012-03-15 | 2013-09-18 | 国家纳米科学中心 | Polycarbazole polymer as well as preparation method and applications thereof |
| CN105126857A (en) * | 2015-07-31 | 2015-12-09 | 齐国良 | Catalyst for catalyzing direct oxidation of toluene to prepare benzaldehyde and preparation method thereof |
| CN106925265A (en) * | 2015-12-30 | 2017-07-07 | 中国科学院过程工程研究所 | A kind of transition metal composite oxide catalytic agent |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110252399A (en) * | 2019-06-11 | 2019-09-20 | 上海大学 | Polymer support loaded catalyst composite material, its application and preparation method |
| CN112778106A (en) * | 2019-11-05 | 2021-05-11 | 中国科学院大连化学物理研究所 | Method for preparing anisaldehyde by catalytic liquid phase selective oxidation |
| CN112778106B (en) * | 2019-11-05 | 2022-06-03 | 中国科学院大连化学物理研究所 | Method for preparing anisaldehyde by catalytic liquid phase selective oxidation |
| CN113828358A (en) * | 2020-06-24 | 2021-12-24 | 万华化学集团股份有限公司 | Mandelic acid oxidation reaction catalyst, preparation method and application thereof |
| CN113828358B (en) * | 2020-06-24 | 2023-12-29 | 万华化学集团股份有限公司 | Mandelic acid oxidation reaction catalyst and preparation method and application thereof |
| CN112604706A (en) * | 2021-01-15 | 2021-04-06 | 荆楚理工学院 | Preparation method and application of nitrogen-containing super-crosslinked polymer-derived Co @ CN catalyst |
| CN112604706B (en) * | 2021-01-15 | 2023-11-10 | 荆楚理工学院 | Preparation method and application of Co@CN catalyst derived from nitrogen-containing super-crosslinked polymer |
| CN113299488A (en) * | 2021-05-31 | 2021-08-24 | 辽宁大学 | Porous carbon material based on nitrogen-rich covalent organic framework structure and preparation method and application thereof |
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