CN110117367A - A kind of preparation method of metal cobalt coordination polymer and the application of catalyzing expoxidation of olefines - Google Patents
A kind of preparation method of metal cobalt coordination polymer and the application of catalyzing expoxidation of olefines Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The present invention discloses a kind of preparation method of metal cobalt coordination polymer and the application of catalyzing expoxidation of olefines, it is characterised in that: the basic unit of the metal cobalt coordination polymer includes a divalent cobalt ion, a p-phthalic bridge anion (BDC2‑), (1- imidazolyl methyl) benzene (bix) molecule of Isosorbide-5-Nitrae-two and a water of coordination molecule, Bix and BDC2‑Ligand and Co2+Ion coordination is constructed to form three-dimensional frame structure, and the chemical molecular formula of the cobalt coordination polymer is [Co (BDC) (bix) (H2O)]n, monoclinic system, space group isP21/ c, cell parameter is a=15.486 (2), b=6.5229 (10), c=20.304 (3), α=90.00 °, β=96.433 (2) °, γ=90.00 °, the cobalt coordination polymer catalyst, catalyst preparation are simple, and can with greater activity, it is more highly selective it is styrene catalyzed, hexamethylene is dilute, the pungent alkene epoxidations such as dilute of 1-, the various types of olefins epoxy product prepared is important organic synthesis intermediate, and catalyst separates simply with product, and catalyst can recycled for multiple times, stability is high, greatly reduces catalyst cost.
Description
Technical field
The present invention relates to olefin epoxide catalysis technical field more particularly to a kind of preparation methods of metal cobalt coordination polymer
And the application of catalyzing expoxidation of olefines.
Background technique
Epoxidation reaction of olefines is a kind of important organic reaction process, and product epoxide, which is that a column are important, to be had
Machine intermediate has important application in fine chemistry industry, petrochemical industry and organic synthesis field.Traditional method is using homogeneous
The violent oxidant such as catalyst, such as Metal Schiff _ base complex, metalloporphyrin and organic peracid is magnificent to complete olefin epoxide
Reaction, but there are certain defects for prior synthesizing method, such as: homogeneous catalyst is not readily separated and regenerates, using expensive and acute
Strong strong oxidizer, causes environmental pollution and cost is excessively high, therefore from economical and environmentally friendly angle, synthesizes heterogeneous catalysis
Agent and use environment friendly oxidant are used to be catalyzed the common recognition that reaction has become people's Search green chemistry.
Metal coordinating polymer has the advantages such as porosity height, large specific surface area, skeletal density be light, so that such porous gathers
Close the excellent performance that object material has traditional inorganic porous material incomparable.Based on coordination polymer material as alkene ring
Heterogeneous catalysis is aoxidized, to solve the problem in alkene epoxidation homogeneous reaction, while with hydrogen peroxide or being divided
Sub- oxygen is that the epoxidation reaction of oxygen source is the Green Chemistry of mainstream, has obtained length by the epoxidation reaction of olefines of oxygen source of hydrogen peroxide
The development of foot.The present invention is proposed using oxygen as oxygen source, using cobalt coordination polymer as catalyst, item of the isobutylaldehyde as reducing agent
The epoxidised activity and selectivity of olefin catalytic is studied under part.
Summary of the invention
The invention discloses metal cobalt coordination polymer and preparation method thereof and product as catalyst in olefin epoxide
Change the application in reaction, concrete scheme is as follows:
A kind of metal cobalt coordination polymer, it is characterised in that: the basic unit of the metal cobalt coordination polymer includes a divalent
Cobalt ions, an Isosorbide-5-Nitrae-p-phthalic bridge anion (BDC2-), (1- imidazolyl methyl) benzene (bix) molecule of Isosorbide-5-Nitrae-two and
One water of coordination molecule, cobalt ions are in hexa-coordinate octahedral environment, and equatorial plane is by terephthaldehyde's acid anion
Oxygen atom in three oxygen atoms and a water of coordination molecule constitutes (Co1-O1=2.303 (3) -2.034 (3)), in cobalt ions
Four atoms of the heart and equatorial plane are about coplanar, deviate 0.0460 with equatorial plane, axial position is by ligand bix
Two nitrogen-atoms constitute, (Co1-N2=2.113 (3) and Co1-N4=2.124 (4)), axial angle (N2-Co1-N4) is
177.21(15)°.Bix and BDC2-Ligand and Co2+Ion coordination is constructed to form three-dimensional frame structure, water of coordination between adjacent layer
Molecule and BDC2-There are hydrogen bond actions between middle oxygen atom.Topological analysis learns that cobalt coordination polymer is single node 4- connection cds
Network, node topology symbol are (658).
Further, the chemical molecular formula of the coordination polymer is [Co (BDC) (bix) (H2O)] n, monoclinic system are empty
Between group beP21/ c, cell parameter be a=15.486 (2), b=6.5229 (10), c=20.304 (3), α=90.00 °, β=
96.433 (2) °, γ=90.00 °.
A kind of preparation method of metal cobalt coordination polymer, characterized by the following steps:
(1) by Cobalt salts CoCl2·6H2O, ligand terephthalic acid (TPA) and 1,4- bis- (1- imidazolyl methyl) benzene are with same substance
Amount is added in deionized water and mixes；
(2) pH is adjusted, the sodium hydroxide of twice of amount of substance is added into reaction mixture, adjusting pH value is 7-9；
(3) above-mentioned mixed liquor is added in hydrothermal reaction kettle, controls 150-170 DEG C of reaction 2-3d of temperature；
(4) it is cooled to room temperature after reaction, filters, washed using methanol and deionized water, cobalt coordination polymer is made.
A kind of application of metal cobalt coordination polymer catalyzing expoxidation of olefines, characterized by the following steps:
(1) by the alkene of certain amount of substance ratio, catalyst cobalt coordination polymer, isobutylaldehyde are dissolved in organic solvent；
(2) oxygen is passed through into above-mentioned reaction solution by flowmeter control flow to be stirred to react, control 20-50 DEG C of its temperature next time
Stream reaction 0-5h；
(3) using test reaction object and product is carried out on Shimadzu QP2010 gas chromatograph-mass spectrometer, pass through by internal standard compound of naphthalene
Internal standard method determines its content and composition；
(4) after reaction, reaction solution carries out makings with solid-phase catalyst and the reaction system of being centrifuged at a high speed, supernatant for catalysis
Analysis obtains epoxy product, while with acetonitrile cleaning catalyst, the catalyst obtained after centrifugation is put to carry out in a vacuum drying oven
Dried recovered, and the epoxidation reaction of olefines in next round can be recycled.
Further, the reaction solution high speed centrifugation is 8000 min-1Separate 3min.
Further, the oxygen is passed through reaction system liquid level or less by gas-guide tube.
Compared with prior art, the present invention has the beneficial effect that:
Catalyst preparation of the present invention is simple, and can with greater activity, it is more highly selective it is styrene catalyzed, hexamethylene is dilute, 1- is pungent dilute etc.
Alkene epoxidation, catalyst separate simply with product, catalyst can recycled for multiple times, stability is high, significantly reduces and urges
Agent cost.
Detailed description of the invention
It to describe the technical solutions in the embodiments of the present invention more clearly, below will be to required in embodiment technical description
Attached drawing to be used does simple introduction, it should be apparent that, drawings in the following description are only some embodiments of the invention,
For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings
Other attached drawings.
Fig. 1 is the metal coordination context diagram for the complex that the present invention obtains.
Fig. 2 is the three-dimensional structure figure for the complex that the present invention obtains.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the present invention
In embodiment, those of ordinary skill in the art's every other implementation obtained without making creative work
Example, belongs to protection scope of the present invention.
In order to reach the purpose of the present invention, as shown in Figs. 1-2, a kind of metal cobalt coordination polymer, the metallic cobalt polycomplexation
The basic unit for closing object includes a divalent cobalt ion, an Isosorbide-5-Nitrae-p-phthalic bridge anion (BDC2-), an Isosorbide-5-Nitrae-two
(1- imidazolyl methyl) benzene (bix) molecule and a water of coordination molecule, cobalt ions are in hexa-coordinate octahedral environment, equatorial plane
Be made of the oxygen atom in three oxygen atoms and a water of coordination molecule in terephthaldehyde's acid anion (Co1-O1=
2.303 (3) -2.034 (3)), four atoms of cobalt ions center and equatorial plane are about coplanar, inclined with equatorial plane
From 0.0460, axial position is made of two nitrogen-atoms on ligand bix, (Co1-N2=2.113 (3) and Co1-N4=
2.124 (4)), axial angle (N2-Co1-N4) is 177.21 (15) °, Bix and BDC2-Ligand and Co2+Ion coordination is constructed
Form three-dimensional frame structure, water of coordination molecule and BDC between adjacent layer2-There are hydrogen bond actions between middle oxygen atom.Topological analysis
Learn that cobalt coordination polymer is single node 4- connection cds network, node topology symbol is (658).
Preferably, the chemical molecular formula of the coordination polymer is [Co (BDC) (bix) (H2O)] n, monoclinic crystal
System, space group areP21/ c, cell parameter be a=15.486 (2), b=6.5229 (10), c=20.304 (3), α=
90.00 °, β=96.433 (2) °, γ=90.00 °.
A kind of preparation method of metal cobalt coordination polymer, includes the following steps:
(1) by cobalt salt CoCl2·6H2O, ligand terephthalic acid (TPA) and 1,4- bis- (1- imidazolyl methyl) benzene are added with same substance amount
Enter in deionized water and mixes；
(2) with the sodium hydroxide of twice of massless is added in reaction mixture, then adjusting above-mentioned molten pH value range is 7-9；
(3) above-mentioned mixed liquor is added in hydrothermal reaction kettle, controls 150-170 DEG C of reaction 2-3d of temperature；
(4) it is cooled to room temperature after reaction, filters, washed respectively with methanol and deionized water, cobalt coordination is obtained after dry
Polymer.
A kind of application of metal cobalt coordination polymer catalyzing expoxidation of olefines, includes the following steps:
(1) by the alkene of certain amount of substance ratio, catalyst cobalt coordination polymer, isobutylaldehyde are dissolved in organic solvent；
(2) oxygen is passed through into above-mentioned reaction solution by flowmeter control flow to be stirred to react, control 20-50 DEG C of its temperature next time
Stream reaction 0-5h；
(3) using test reaction object and product is carried out on Shimadzu QP2010 gas chromatograph-mass spectrometer, pass through by internal standard compound of naphthalene
Internal standard method determines its content and composition；
(4) after reaction, reaction solution carries out makings with solid-phase catalyst and the reaction system of being centrifuged at a high speed, supernatant for catalysis
Analysis obtains epoxy product, while utilizing acetonitrile cleaning catalyst, puts catalyst after centrifugation and does in a vacuum drying oven
It is dry, it recycles and can be recycled in epoxidation reaction of olefines.
Preferably, the reaction solution high speed centrifugation is 8000 min-1Separate 3min.
Preferably, the oxygen is passed through reaction system liquid level or less by gas-guide tube.
One, the preparation of catalyst cobalt coordination polymer
Embodiment 1:
By 0.25 mmol CoCl2·6H2O, 0.25 mmol, terephthalic acid (TPA) (H2BDC) ,-two (1- miaow of 0.25 mmol Isosorbide-5-Nitrae
Oxazolyl methyl) benzene (bix) and 0.5 mmol NaOH mixture be added in 8 mL deionized waters, then with the NaOH of 0.5 mol/L
It is 7.5 that solution, which adjusts pH, and then mixture is put into 25 mL water heating kettles, and 160 oC react 72 h, is cooled to room temperature naturally
Filter, product are washed with deionized water and methanol respectively, are filtered, are obtained catalyst cobalt coordination polymer, 52.6 % of yield.
Embodiment 2:
By 1mmol CoCl2·6H2O, 1 mmol, terephthalic acid (TPA) (H2BDC), 1 mmol Isosorbide-5-Nitrae-two (1- imidazolyl methyl) benzene
(bix) it is added in 50 mL deionized waters with 2 mmol NaOH mixtures, then adjusts pH with the NaOH solution of 0.5 mol/L and be
8.2, then mixture is put into 100 mL water heating kettles, 150 oC react 72 h, are cooled to room temperature filtering, product difference naturally
It is washed with deionized water and methanol, filters, obtain catalyst cobalt coordination polymer, 49.3 % of yield.
Two, cobalt coordination polymer is catalyzed the dilute epoxidation reaction of hexamethylene
Embodiment 3:
Catalyst cobalt coordination polymer is put into baking oven before reaction, 100 DEG C activate 15 minutes.By 4 mmol cyclohexene, 10mg cobalt
Coordination polymer and isobutylaldehyde (12 mmol) are dissolved in 8 mL acetonitrile solvents, are passed through oxygen, and reaction temperature is 25 °C, when reaction
Between be 2 hours.Catalysis is after reaction by reaction solution with 8000 min-1Speed be centrifuged three minutes, solid catalyst and anti-
Liquid is answered to separate, reactants and products are tested on Shimadzu QP2010 gas chromatograph-mass spectrometer, epoxidation of cyclohexene reaction
Conversion ratio is 98.9%, and selectivity is 86.1%, yield 85.1%.Catalyst after separation is washed with acetonitrile, is centrifugated, is dry
Dry, obtained cobalt coordination polymer carries out circulation experiment, and after circulation 6 times, conversion ratio still reaches 95% or more, yield 83% with
On.
Embodiment 4:
Cobalt coordination polymer is put into baking oven before reaction, 100 DEG C activate 15 minutes.By 4 mmol cyclohexene, 10mg cobalt polycomplexation
It closes object and isobutylaldehyde (12 mmol) is dissolved in 8 mL methanol solvates, be passed through oxygen, reaction temperature is 25 °C, the reaction time 2
A hour.Catalysis is after reaction by reaction solution with 8000 min-1Speed be centrifuged three minutes, solid catalyst and reaction solution point
From reactants and products are tested on gas chromatograph-mass spectrometer, and the conversion ratio of epoxidation of cyclohexene reaction is 98.1%, selectivity
It is 85.3%, yield 83.7%.
Embodiment 5:
Cobalt coordination polymer is put into baking oven before reaction, 100 DEG C activate 15 minutes.By 4 mmol cyclohexene, 10mg cobalt polycomplexation
It closes object and isobutylaldehyde (12 mmol) is dissolved in 8 mL trichloropropane solvents, be passed through oxygen, reaction temperature is 25 °C, the reaction time
For 2 hours.Catalysis is after reaction by reaction solution with 8000 min-1Speed be centrifuged three minutes, solid catalyst with react
Liquid separation, reactants and products are tested on gas chromatograph-mass spectrometer, and the conversion ratio of epoxidation of cyclohexene reaction is 97.8%, choosing
Selecting property is 84.9%, yield 83.0%.
Three, the styrene catalyzed epoxidation reaction of cobalt coordination polymer
Embodiment 6:
Cobalt coordination polymer is put into baking oven before reaction, 100 °C activate 15 minutes.By 4 mmol styrene, 10mg cobalt polycomplexation
It closes object and isobutylaldehyde (12 mmol) is dissolved in 8 mL acetonitrile solvents, be passed through oxygen, reaction temperature is 30 °C, and the reaction time is 7
Hour.Catalysis is after reaction by reaction solution with 8000 min-1Speed be centrifuged three minutes, solid catalyst and reaction solution point
From reactants and products are tested on gas chromatograph-mass spectrometer, and the conversion ratio of epoxidation of cyclohexene reaction is 98.3%, selectivity
It is 84.8%, yield 83.3%
Embodiment 7:
Cobalt coordination polymer is put into baking oven before reaction, 100 DEG C activate 15 minutes.By 4 mmol styrene, 10mg cobalt polycomplexation
It closes object and isobutylaldehyde (12 mmol) is dissolved in 8 mL acetonitrile solvents, be passed through oxygen, reaction temperature is 40 °C, and the reaction time is 2
Hour.Catalysis is after reaction by reaction solution with 8000 min-1Speed be centrifuged three minutes, solid catalyst and reaction solution point
From reactants and products are tested on gas chromatograph-mass spectrometer, and the conversion ratio of epoxidation of styrene reaction is 97.1%, selectivity
It is 86.4%, yield 83.9%.
Embodiment 8:
Cobalt coordination polymer is put into baking oven before reaction, 100 DEG C activate 15 minutes.By 4 mmol styrene, 10mg cobalt polycomplexation
It closes object and isobutylaldehyde (12 mmol) is dissolved in 8 mL acetonitrile solvents, be passed through oxygen, reaction temperature is 50 °C, and the reaction time is 1
Hour.Catalysis is after reaction by reaction solution with 8000 min-1Speed be centrifuged three minutes, solid catalyst and reaction solution point
From reactants and products are tested on gas chromatograph-mass spectrometer, and the conversion ratio of epoxidation of cyclohexene reaction is 95.3%, selectivity
It is 83.8%, yield 79.8%.
Four, cobalt coordination polymer is catalyzed the pungent dilute epoxidation reaction of 1-
Embodiment 9:
Cobalt coordination polymer is put into baking oven before reaction, 100 DEG C activate 15 minutes.4 mmol 1- are pungent dilute, 10mg cobalt polycomplexation
It closes object and isobutylaldehyde (12 mmol) is dissolved in 8 mL acetonitrile solvents, be passed through oxygen, reaction temperature is 40 °C, and the reaction time is 2
Hour.Catalysis is after reaction by reaction solution with 8000 min-1Speed be centrifuged three minutes, solid catalyst and reaction solution point
From reactants and products are tested on gas chromatograph-mass spectrometer, and the conversion ratio of epoxidation of cyclohexene reaction is 96.3%, selectivity
It is 92.4%, yield 88.9%.
Five, cobalt coordination polymer is catalyzed the pungent dilute epoxidation reaction of ring
Embodiment 10:
Cobalt coordination polymer is put into baking oven before reaction, 100 DEG C activate 15 minutes.4 mmol rings are pungent dilute, 10mg cobalt polycomplexation
It closes object and isobutylaldehyde (12 mmol) is dissolved in 8 mL acetonitrile solvents, be passed through oxygen, reaction temperature is 40 °C, and the reaction time is 2
Hour.Catalysis is after reaction by reaction solution with 8000 min-1Speed be centrifuged three minutes, solid catalyst and reaction solution point
From reactants and products are tested on gas chromatograph-mass spectrometer, and the conversion ratio of epoxidation of cyclohexene reaction is 95.8%, selectivity
It is 90.6%, yield 86.8%.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (7)
1. a kind of metal cobalt coordination polymer, it is characterised in that: the basic unit of the metal cobalt coordination polymer includes one two
Valence cobalt ions, a p-phthalic bridge anion, (1- imidazolyl methyl) benzene (bix) molecule of Isosorbide-5-Nitrae-two and a coordination
Hydrone, cobalt ions are in hexa-coordinate octahedral environment, and equatorial plane is by three oxygen in terephthaldehyde's acid anion
Oxygen atom in atom and a water of coordination molecule is constituted, and axial position is made of two nitrogen-atoms on ligand bix, Bix and
BDC2-Ligand and Co2+Ion coordination is constructed to form three-dimensional frame structure.
2. a kind of metal cobalt coordination polymer according to claim 1, it is characterised in that: the chemistry of the coordination polymer
Molecular formula is [Co (BDC) (bix) (H2O)] n, monoclinic system, space group areP21/ c, cell parameter are a=15.486 (2), b
=6.5229 (10), c=20.304 (3), α=90.00 °, β=96.433 (2) °, γ=90.00 °.
3. a kind of preparation method of metal cobalt coordination polymer as described in claim 1, it is characterised in that: including walking as follows
It is rapid:
(1) by the Cobalt salts CoCl of same substance amount2·6H2O, ligand terephthalic acid (TPA) and 1,4- bis- (1- imidazolyl methyl)
Benzene and the sodium hydroxide of twice of amount of substance mix, and add appropriate amount of deionized water；
(2) adjusting above-mentioned solution ph range with NaOH solution is 7-9；
(3) above-mentioned mixed liquor is added in hydrothermal reaction kettle, controls 150-170 DEG C of reaction 2-3d of temperature；
(4) it is cooled to room temperature after reaction, filters, washed using methanol and deionized water, cobalt coordination polymer is made.
4. a kind of application of metal cobalt coordination polymer catalyzing expoxidation of olefines as described in claim 1, it is characterised in that: packet
Include following steps:
(1) by the alkene of certain amount of substance ratio, catalyst cobalt coordination polymer, isobutylaldehyde are dissolved in organic solvent；
(2) oxygen is passed through in Xiang Shangshu reaction solution to be stirred, oxygen flow, controller temperature 20-50 are controlled by flowmeter
Back flow reaction 0-5h at DEG C；
(3) using test reaction object and product is carried out on Shimadzu QP2010 gas chromatograph-mass spectrometer, pass through by internal standard compound of naphthalene
Internal standard method determines its content and composition；
(4) after reaction, reaction solution carries out makings with solid-phase catalyst and the reaction system of being centrifuged at a high speed, supernatant for catalysis
Analysis obtains epoxy product, while using being centrifugated after acetonitrile cleaning catalyst, by catalyst put in a vacuum drying oven into
Row drying is recycled and be can be recycled in epoxidation reaction of olefines.
5. the application of metal cobalt coordination polymer catalyzing expoxidation of olefines according to claim 4, it is characterised in that: described
Reaction solution high speed centrifugation is 8000 min-1Separate 3min.
6. the application of metal cobalt coordination polymer catalyzing expoxidation of olefines according to claim 4, it is characterised in that: described
Oxygen is passed through reaction system liquid level or less by gas-guide tube.
7. the application of metal cobalt coordination polymer catalyzing expoxidation of olefines according to claim 4, it is characterised in that: described
Catalyst cobalt coordination polymer is put into baking oven before reaction, 100 DEG C activate 15 minutes.
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