CN109824705A - A kind of preparation method and its usage of bis- (N- (4- carboxyl) phenyl) acid imide Zn complex catalyst - Google Patents
A kind of preparation method and its usage of bis- (N- (4- carboxyl) phenyl) acid imide Zn complex catalyst Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of bis- (N- (4- carboxyl) phenyl) acid imide Zn complex catalyst, this kind of method is by zinc acetate, bis- (N- (4- carboxyl) phenyl) acid imides, triethylamine, water, N, N '-dimethyl Asia amide is placed in a beaker reaction, after completion of the reaction, filtering, filtrate are slowly volatilized, and the crystal of bis- (N- (4- carboxyl) phenyl) acid imide Zn complex catalyst is obtained.The method of the present invention has reaction process simple, and obtained product purity is high, and post-processing is simple.In atmospheric conditions in carbon dioxide cycloaddition reaction, for high conversion rate up to 97.5%, selectivity is up to 97.9%.
Description
Technical field
The invention belongs to catalyst material preparation technical fields, are directed to a kind of bis- (N- (4- carboxyl) phenyl) acyls
The technology of preparing of imines Zn complex catalyst.
Technical background
Metal organic complex is that had by organic ligand and metal ion or cluster by what coordinate bond was self-assembly of
The hybrid inorganic-organic materials of molecule inner pore.There is metal active site abundant composition in metal organic complex, determine
It is with strong lewis acidity and stronger oxidisability, therefore the metal organic complex table in many organic catalytic reactions
Reveal excellent catalysis characteristics.By a large amount of document report (Jiang, et al., Coord.Chem.Rev.2018,362,
1-23).Metal organic complex catalyzes and synthesizes chemistry and has become most promising in metal organic frame scientific domain grind at present
Study carefully one of direction, the extensive concern by chemist.
Simultaneously, it is well known that the excess emissions of carbon dioxide result in global warming.Therefore the catalyzed conversion of carbon dioxide
As chemists' focus of attention field.Wherein, catalysis transform of carbon dioxide generate cyclic carbonate reaction be the most at
One of route of function.However, current catalyst system has in turn resulted in inconvenience there is high temperature and pressure or solvent is used
In industrial problems (KoriA.Andrea, et al, Inorg.Chem.2018,57,13494-13504；EszterFazekas,
et al,Dalton Trans.,2018,47,13106-13112).Therefore, from the point of view of environment and economy, exploitation is more
The catalyst of green still has great importance.
On the basis of document above, according to the idea of development of Green Chemistry, titanium dioxide under a condition of normal pressure is designed
The environmental-friendly metal organic complex efficient catalytic system that carbocyclic ring addition generates cyclic carbonate is very necessary.
By retrieval, patent document related with the present patent application is not yet found.
Summary of the invention
The purpose of this invention is that reaction pressure is excessive, urges in catalyzed conversion carbon dioxide cycloaddition reaction under solution high pressure
The problems such as agent dosage is larger.A kind of preparation method for synthesizing metal organic complex catalyst is provided, in carbon dioxide
Play the role of catalysis in cycloaddition reaction, reaches the target for realizing carbon dioxide cycloaddition under condition of normal pressure.
Mentality of designing of the invention is as follows:
1. inorganic zinc salt and bis- (N- (4- carboxyl) phenyl) imide reactions are constructed into new metal organic complex, from
And metal ion can play the role of catalytic center；
2. being realized being applied in the cycloaddition reaction of carbon dioxide with metallic zinc organic coordination compound catalyst under normal pressure
The highly selective target for obtaining cyclic carbonate of carbon dioxide high conversion.
What the structural information of this kind of catalyst obtained by the following method:
Metal organic complex is obtained by conventional solvent structure, specific description experimental method is as follows:
Reflux under the conditions of acetic acid, which is reacted, with p-aminobenzoic acid first with acid imide has synthesized having in the present invention
Bis- (N- (4- carboxyl) phenyl) acid imides of machine ligand.Then in a clean hydrothermal reaction kettle in sequentially add bis- (N-
(4- carboxyl) phenyl) acid imide (3~6mmol), triethylamine (5~13mmol), Zn (OAc)2(2~7mmol), water (8~
15mL) and N, N '-dimethyl Asia amide (2~5mL), strongly 2~5h of stirring are then charged into stainless steel cauldron, heat up
To 90~120 DEG C, 72h~96h is reacted, is cooled to room temperature after completion of the reaction, obtains dark red color substance.Yield about 32~58%.
Product is characterized, is obtained about bis- (N- (4- carboxyl) phenyl) acyls by single crystal diffraction, powder x-ray diffraction
The accurate information of imines Zn complex.Specific result is as follows:
The molecular formula of crystal is Zn (C38H18N2O8), wherein Zn and bis- (N- (4- carboxyl) phenyl) imido two carboxylics
Oxygen coordination in base anion, is four-coordination environment, can provide the environment of open loop of epoxy compound, at reaction conditions dioxy
Change carbon to be easy in conjunction with the zinc ion of center, to play catalytic action.
This invention mainly synthesis metal organic complex catalyst, it is anti-to be applied to carbon dioxide cycloaddition
It answers.Condition of normal pressure carbon dioxide cycloaddition reaction may be implemented in this kind of catalyst, and high conversion rate is selectively up to up to 97.5%
97.9%.The preparation method reaction process of such catalyst is simple.
Above-mentioned cyclic compound is epoxychloropropane, epoxy bromopropane, propylene oxide, epoxy styrene etc., conversion ratio, choosing
Selecting property passes through gas chromatographic detection.
The purpose of the present invention is what is be achieved through the following technical solutions:
Its molecular structure are as follows:
Molecular formula are as follows: Zn (C38H18N2O8)
Remarks: the space occupancy of two zinc is respectively 0.5 in crystallography, is occupied with four oxygen atom spaces of zinc coordination
Rate is also respectively 0.5, and therefore, the molecular formula of the compound is Zn (C38H18N2O8)
The present invention provides metal organic complex catalyst and has the following characteristics that
1. preparation method is simple and catalyst all has specific molecular structure, be conducive to study mechanism of catalytic reaction.
2. there is catalyst Zn can play catalytic action to carbon dioxide cycloaddition.
Detailed description of the invention
The crystal structure figure of bis- (N- (4- carboxyl) phenyl) the acid imide Zn complex catalyst of Fig. 1
The powder diagram of bis- (N- (4- carboxyl) phenyl) the acid imide Zn complex catalyst of Fig. 2
Specific embodiment
Embodiment 1: compound Zn (C38H18N2O8) preparation
Sequentially add bis- (N- (4- carboxyl) phenyl) acid imides (3mmol) in a clean hydrothermal reaction kettle, three
Ethamine (5mmol), Zn (OAc)2(2mmol), water (8mL) and N, N '-dimethyl Asia amide (2mL), strongly stirring 2h, then
It is fitted into stainless steel cauldron, is warming up to 90 DEG C, react 72h, be cooled to room temperature after completion of the reaction, obtain dark red color substance.It produces
Rate about 34%.
Embodiment 2: compound Zn (C38H18N2O8) preparation
Bis- (N- (4- carboxyl) phenyl) acid imides (4mmol) are sequentially added in a clean hydrothermal reaction kettle,
Triethylamine (8mmol), Zn (OAc)2(4mmol), water (10mL) and N, N '-dimethyl Asia amide (5mL), strongly stirring 3h,
It is then charged into stainless steel cauldron, is warming up to 100 DEG C, react 96h, be cooled to room temperature after completion of the reaction, obtain dark red object
Matter.Yield about 43%.
Embodiment 3: compound Zn (C38H18N2O8) preparation
Bis- (N- (4- carboxyl) phenyl) acid imides (6mmol) are sequentially added in a clean hydrothermal reaction kettle,
Triethylamine (13mmol), Zn (OAc)2(7mmol), water (15mL) and N, N '-dimethyl Asia amide (5mL), strongly stirring 5h,
It is then charged into stainless steel cauldron, is warming up to 120 DEG C, react 80h, be cooled to room temperature after completion of the reaction, obtain dark red object
Matter.Yield about 56%.
Embodiment 4: compound Zn (C38H18N2O8) preparation
Bis- (N- (4- carboxyl) phenyl) acid imides (3mmol) are sequentially added in a clean hydrothermal reaction kettle,
Triethylamine (6mmol), Zn (OAc)2(4mmol), water (10mL) and N, N '-dimethyl Asia amide (4mL), strongly stirring 4h,
It is then charged into stainless steel cauldron, is warming up to 110 DEG C, react 96h, be cooled to room temperature after completion of the reaction, obtain dark red object
Matter.Yield about 50%.
Embodiment 5: compound Zn (C38H18N2O8) preparation
Bis- (N- (4- carboxyl) phenyl) acid imides (3mmol) are sequentially added in a clean hydrothermal reaction kettle,
Triethylamine (7mmol), Zn (OAc)2(4mmol), water (10mL) and N, N '-dimethyl Asia amide (5mL), strongly stirring 5h,
It is then charged into stainless steel cauldron, is warming up to 100 DEG C, react 90h, be cooled to room temperature after completion of the reaction, obtain dark red object
Matter.Yield about 53%.
Embodiment 6: compound Zn (C38H18N2O8) preparation
Bis- (N- (4- carboxyl) phenyl) acid imides (5mmol) are sequentially added in a clean hydrothermal reaction kettle,
Triethylamine (5mmol), Zn (OAc)2(4mmol), water (15mL) and N, N '-dimethyl Asia amide (3mL), strongly stirring 3h,
It is then charged into stainless steel cauldron, is warming up to 90 DEG C, react 72h, be cooled to room temperature after completion of the reaction, obtain dark red object
Matter.Yield about 37%.
Embodiment 7: compound Zn (C38H18N2O8) preparation
Bis- (N- (4- carboxyl) phenyl) acid imides (4mmol) are sequentially added in a clean hydrothermal reaction kettle,
Triethylamine (8mmol), Zn (OAc)2(5mmol), water (9mL) and N, N '-dimethyl Asia amide (5mL), strongly stirring 5h, so
It is fitted into stainless steel cauldron afterwards, is warming up to 120 DEG C, react 96h, be cooled to room temperature after completion of the reaction, obtain dark red color substance.
Yield about 44%.
Embodiment 8: compound Zn (C38H18N2O8) preparation
Bis- (N- (4- carboxyl) phenyl) acid imides (3mmol) are sequentially added in a clean hydrothermal reaction kettle,
Triethylamine (6mmol), ZnCl2(3mmol), water (15mL) and N, N '-dimethyl Asia amide (5mL), strongly stirring 5h, then
It is fitted into stainless steel cauldron, is warming up to 120 DEG C, react 72h, be cooled to room temperature after completion of the reaction, obtain dark red color substance.It produces
Rate about 36%.
Embodiment 9: compound Zn (C38H18N2O8) preparation
Bis- (N- (4- carboxyl) phenyl) acid imides (3mmol) are sequentially added in a clean hydrothermal reaction kettle,
Triethylamine (6mmol), Zn (NO3)2(3mmol), water (15mL) and N, N '-dimethyl Asia amide (5mL), strongly stirring 5h, so
It is fitted into stainless steel cauldron afterwards, is warming up to 120 DEG C, react 72h, be cooled to room temperature after completion of the reaction, obtain dark red color substance.
Yield about 33%.
As shown in table 1, the crystallographic data of bis- (N- (4- carboxyl) phenyl) acid imide Zn complexes
Embodiment 10:Zn (C38H18N2O8) application under catalyst normal pressure to carbon dioxide cycloaddition reaction
Example:
It takes 30mmol epoxide to be placed in 50mL round-bottomed flask, and 50~70mg of catalyst, tetrabutyl phosphonium bromide is added
It is passed through carbon dioxide under ammonium 3~5mol% normal pressure, after reaction 12~for 24 hours is stirred at room temperature, with gas chromatographic detection, in reaction solution
Epoxide almost all is converted into cyclic carbonate, and the data of specific carbon dioxide cycloaddition are shown in Table 2.
Bis- (N- (4- carboxyl) phenyl) the acid imide Zn complexes of table 2 are to epoxide cycloaddition reaction the results list
This bis- (N- (4- carboxyl) phenyl) acid imide Zn complex catalyst as shown in Table 2, for different epoxidations
The cycloaddition reaction for closing object and carbon dioxide all has good effect, and conversion ratio reaches 95% or more, realizes normal pressure item
To the cycloaddition reaction of carbon dioxide under part, solves the problems, such as condition of high voltage carbon dioxide cycloaddition reaction on document.
Claims (5)
1. a kind of preparation method of bis- (N- (4- carboxyl) phenyl) acid imide Zn complex catalyst, it is characterised in that: step
Are as follows: bis- (N- (4- carboxyl) phenyl) acid imides, triethylamine, inorganic zinc are sequentially added in a clean hydrothermal reaction kettle
Salt, reaction dissolvent, are then charged into stainless steel cauldron, are warming up to certain temperature, react strong stirring a period of time, reaction
After be cooled to room temperature, obtain dark red color substance.
2. preparation method according to claim 1, it is characterised in that: bis- (N- (4- carboxyl) phenyl) acid imides: three second
Amine: the ratio between amount of inorganic zinc salt substance is 3 ~ 6:5 ~ 13:2 ~ 7, and solvent for use is water and N, and N '-dimethyl Asia amide reacts molten
Agent is water and N, N '-dimethyl Asia amide water, wherein water and N, the volume ratio of N '-dimethyl Asia amide are as follows: 8 ~ 15:2 ~ 5.
3. preparation method according to claim 1, which is characterized in that strong 2 ~ 5h of mixing time, reaction temperature is 90 ~
120 DEG C, the reaction time is 72h ~ 96h after heating.
4. the preparation method of bis- (N- (4- carboxyl) phenyl) acid imide Zn complex catalyst according to claim 1,
It is characterized by: the inorganic zinc salt is Zn (OAc)2。
5. the preparation method of bis- (N- (4- carboxyl) phenyl) acid imide Zn complexes according to claim 1, feature
It is: the molecular structure of the metallic zinc organic coordination compound catalyst:
。
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| CN111393663A (en) * | 2020-04-07 | 2020-07-10 | 曲靖师范学院 | Perylene bisimide base coordination polymer, preparation method and application thereof |
| CN111514934A (en) * | 2020-04-08 | 2020-08-11 | 四川大学 | Petal-shaped zinc perylenetetracarboxylic acid supermolecule assembly photocatalytic material and preparation method thereof |
| CN115485067A (en) * | 2020-01-09 | 2022-12-16 | 科罗拉多州立大学研究基金会 | Benzoperylene imide photoredox catalysts and methods of using such catalysts |
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| CN111514934A (en) * | 2020-04-08 | 2020-08-11 | 四川大学 | Petal-shaped zinc perylenetetracarboxylic acid supermolecule assembly photocatalytic material and preparation method thereof |
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