CN107903238A - A kind of method that copper-based catalysts prepare cyclic carbonate - Google Patents
A kind of method that copper-based catalysts prepare cyclic carbonate Download PDFInfo
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- CN107903238A CN107903238A CN201711274166.2A CN201711274166A CN107903238A CN 107903238 A CN107903238 A CN 107903238A CN 201711274166 A CN201711274166 A CN 201711274166A CN 107903238 A CN107903238 A CN 107903238A
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- copper
- cyclic carbonate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—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
- C07D317/10—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
- 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
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—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
- C07D317/44—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 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—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 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
Abstract
The invention discloses a kind of method that copper-based catalysts prepare cyclic carbonate, raw material is used as by the use of carbon dioxide and epoxides, join pyrroles's capillary copolymer material as heterogeneous catalyst to be conjugated copper porphyrin bipyridyl/conjugation copper porphyrin, tetra-n-butyl ammonium bromide is co-catalyst, in the case where normal temperature and pressure is solvent-free, efficient green catalytically synthesizing cyclic carbonate ester is realized.The major advantage of this method is that method for preparing catalyst is simple, and cost is low, and catalytic activity is high, and structural behaviour is stablized, easily recycling, repeats and utilizes;Reaction condition is gentle, speed is fast and safe operation, suitable for large-scale industrial production.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of zinc based catalyst prepares the side of cyclic carbonate
Method.
Background technology
With the progress of the development human civilization of society, especially industrial great development with rapid changepl. never-ending changes and improvements, for fossil energy
The consumption requirements in source increasingly increase.A large amount of with fossil fuel use, and the concentration of carbon dioxide quickly raises, and becomes a kind of master
Greenhouse gases are wanted, cause a series of environment and ecological problem.Meanwhile carbon dioxide is used as a kind of widely distributed, rich reserves, honest and clean
Valency is easy to get, is renewable, is nontoxic, one resource of non-flammable preferable carbon.No matter from the angle that environmental protection or renewable resource utilize
Degree considers that the research in terms of the capture and chemical conversion of carbon dioxide is all of great significance.Using carbon dioxide as Material synthesis
Organic carbonate is exactly an exemplary of its recycling, has been realized in industrialized production at present.
Organic carbonate is a kind of green chemical with characteristics such as higher boiling, low-steam pressure, low toxicities, has been widely used in
The multiple fields such as solvent, detergent, lithium battery electrolytes, fuel additive.Organic carbonate can be divided into linear carbonate
And cyclic carbonate.Wherein cyclic carbonate is widely used as the electrolyte of lithium battery, with the fast development of new energy, market pair
It is increasing in the demand of high-quality cyclic carbonate.
From the perspective of Green Chemistry and sustainable development, using carbon dioxide and epoxides as Material synthesis carbonic ester
Provide a kind of safe and clean, sustainable, high atom economy new way.Current industrialized carbon dioxide and ring
The process that oxygen prepares cyclic carbonate mainly has two kinds of catalyst system and catalyzings:Polyethylene glycol/potassium iodide system and quaternary ammonium salt system.The former
Iodine can be generated during the reaction, causes finished product to turn to be yellow, and product quality declines;And the pressure that the latter needs during the reaction
Power is higher, to the security of production operation, more demanding, the equipment cost height for performance that equipment is pressure-resistant.
At present, with CO2It is raw material with cyclic carbonate, in the reaction system of synthesizing annular carbonate, has developed
A series of catalyst, as quaternary ammonium salt, quaternary alkylphosphonium salts, organic base, ionic liquid, metal oxide, metal complex, feature are organic
Polymeric material and metalloporphyrin etc..2013, the research group of Deng et al. was using salen Al/Co and three ethynylbenzenes to be single
Body, by Sonogashira coupling reactions, is prepared for microporous polymer catalyst Al-CMP and Co-CMP, in the reaction system
In achieve preferable catalytic effect, and the just desirable good yield under normal temperature and pressure conditions, while catalyst may be used also
Recycling [Nat.Commun., 2013,4,1-7].2016, Xiao Fengshou taught seminar with tetravinyl Cob altporphyrin
For monomer, by the method for radical polymerization, catalyst Co/POP-TPP is made, at 29 DEG C, when pressure is 0.1MPa, reaction
24h, achieve it is satisfied as a result, catalyst can circulation and stress use, and by low concentration CO2As research object, have
Certain industrial application value [J.Catal., 2016,338,202].
The content of the invention
The technical problems to be solved by the invention are deposited inefficient in a mild condition for the current reaction system
Problem, there is provided a kind of synthesis step is simple, raw material is cheap and easy to get, high catalytic efficiency, the stable heterogeneous catalyst easily recycled, normal
Under normal temperature and pressure, condition of no solvent, efficient catalytic is converted into cyclic carbonate, can be widely applied to field of industrial production.
In order to solve the above technical problems, the present invention uses following technical scheme:
A kind of method that copper-based catalysts prepare cyclic carbonate, using carbon dioxide and epoxides as raw material, to be conjugated copper
Porphyrin bipyridyl/conjugation copper porphyrin connection pyrroles's capillary copolymer material is heterogeneous catalyst, and tetra-n-butyl ammonium bromide is co-catalysis
Agent, in the case where normal temperature and pressure is solvent-free, reacts 12-48h, has synthesized cyclic carbonate in high yield, and heterogeneous catalyst separation is simple,
Washable recycling, and can realize and repeatedly use(More than 20 times).
The conjugation copper porphyrin bipyridyl capillary copolymer material uses Scholl coupling reactions, with copper tetraphenylporphyrin
It is monomer with 2,2- bipyridyls, uses anhydrous AlCl3Catalyst preparation obtains, its structural formula is as follows:
。
Conjugation copper porphyrin connection pyrroles's capillary copolymer material uses Scholl coupling reactions, with copper tetraphenylporphyrin
It is monomer with pyrroles, uses anhydrous AlCl3Catalyst preparation obtains, its structural formula is as follows:
。
The epoxide is propylene oxide, epoxy butane, epoxychloropropane, epoxy bromopropane, styrene oxide, benzene
Base glycidol ether or cyclohexene oxide.
The dosage of the heterogeneous catalyst active component is 0.2~0.5mol% of epoxide dosage.
The dosage of the co-catalyst is 3.6~7.2mol% of epoxides.
The beneficial effects of the invention are as follows:1) present invention utilizes and is conjugated copper porphyrin capillary copolymer material and tetran-butylphosphonium bromide
Ammonium is realized under normal temperature and pressure conditions, efficient catalytic CO2 and epoxides synthesizing annular carbonate as dual-component catalyst,
Mass energy is saved, reduces the requirement to press device in production, substantially increases the security of operation;2) catalyst is used
Measure that low, high catalytic efficiency, reaction time is short, product is easily isolated purifying, operated easy to actual industrial;3) need not add any
Organic solvent, it is environmentally protective;4) catalyst raw material used in is easy to get, cost is low, synthesis is quick and easy.
Embodiment
The present invention is further described in the examples below, but the merely illustrative purposes of discussion of these embodiments, should not
It is interpreted the implementation limitation of the present invention.
Embodiment 1
The method that the copper-based catalysts of the present embodiment prepare cyclic carbonate, step are as follows:
Into the stainless steel autoclave of 10mL, 50mg is sequentially added(Active ingredient copper 0.4mol%)Catalyst conjugation copper
Porphyrin bipyridyl capillary copolymer material, 12.5mmol propylene oxide and 0.9mmol co-catalyst tetra-n-butyl ammonium bromides, are passed through
Carbon dioxide and to keep pressure be 0.1MPa, under the conditions of temperature is 25 DEG C, after stirring 48h, room temperature cooling, slowly release is remaining
Carbon dioxide after, filter to isolate catalyst, after purification cyclic carbonate separation yield be 94%.
Embodiment 2
The method that the copper-based catalysts of the present embodiment prepare cyclic carbonate, step are as follows:
Into the stainless steel autoclave of 10mL, 50mg is sequentially added(Active ingredient copper 0.2mol%)Catalyst conjugation copper
Porphyrin bipyridyl capillary copolymer material, 12.5mmol epoxy butanes and 0.9mmol co-catalyst tetra-n-butyl ammonium bromides, are passed through
Carbon dioxide and to keep pressure be 0.1MPa, under the conditions of temperature is 25 DEG C, after stirring 48h, room temperature cooling, slowly release is remaining
Carbon dioxide after, filter to isolate catalyst, after purification cyclic carbonate separation yield be 92%.
Embodiment 3
The method that the copper-based catalysts of the present embodiment prepare cyclic carbonate, step are as follows:
Into the stainless steel autoclave of 10mL, 50mg is sequentially added(Active ingredient copper 0.5mol%)Catalyst conjugation copper
Porphyrin bipyridyl capillary copolymer material, 12.5mmol epoxychloropropane and 0.9mmol co-catalyst tetra-n-butyl ammonium bromides, lead to
It is 0.1MPa to enter carbon dioxide and keep pressure, and under the conditions of temperature is 25 DEG C, after stirring 48h, room temperature cooling, slowly release is surplus
After remaining carbon dioxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 95%.
Embodiment 4
The method that the copper-based catalysts of the present embodiment prepare cyclic carbonate, step are as follows:
Into the stainless steel autoclave of 10mL, 50mg is sequentially added(Active ingredient copper 0.3mol%)Catalyst conjugation copper
Porphyrin bipyridyl capillary copolymer material, 12.5mmol epoxy bromopropanes and 0.9mmol co-catalyst tetra-n-butyl ammonium bromides, lead to
It is 0.1MPa to enter carbon dioxide and keep pressure, and under the conditions of temperature is 25 DEG C, after stirring 48h, room temperature cooling, slowly release is surplus
After remaining carbon dioxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 94%.
Embodiment 5
The method that the copper-based catalysts of the present embodiment prepare cyclic carbonate, step are as follows:
Into the stainless steel autoclave of 10mL, 50mg is sequentially added(Active ingredient copper 0.3mol%)Catalyst conjugation copper
Porphyrin bipyridyl capillary copolymer material, 12.5mmol styrene oxides and 0.675mmol co-catalyst tetra-n-butyl ammonium bromides,
It is 0.1MPa to be passed through carbon dioxide and keep pressure, under the conditions of temperature is 25 DEG C, after stirring 24h, and room temperature cooling, slowly release
After remaining carbon dioxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 88%.
Embodiment 6
The method that the copper-based catalysts of the present embodiment prepare cyclic carbonate, step are as follows:
Into the stainless steel autoclave of 10mL, 50mg is sequentially added(Active ingredient copper 0.2mol%)Catalyst conjugation copper
Porphyrin bipyridyl capillary copolymer material, 12.5mmol phenyl glycidyl ethers and 0.45mmol co-catalyst tetran-butylphosphonium bromides
Ammonium, it is 0.1MPa to be passed through carbon dioxide and keep pressure, under the conditions of temperature is 25 DEG C, after stirring 12h, and room temperature cooling, slowly
After discharging remaining carbon dioxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 78%.
Embodiment 7
The method that the copper-based catalysts of the present embodiment prepare cyclic carbonate, step are as follows:
Into the stainless steel autoclave of 10mL, 50mg is sequentially added(Active ingredient copper 0.4mol%)Catalyst conjugation copper
Porphyrin bipyridyl capillary copolymer material, 12.5mmol cyclohexene oxides and 0.675mmol co-catalyst tetra-n-butyl ammonium bromides,
It is 0.1MPa to be passed through carbon dioxide and keep pressure, under the conditions of temperature is 25 DEG C, after stirring 36h, and room temperature cooling, slowly release
After remaining carbon dioxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 89%.
Embodiment 8
The method that the copper-based catalysts of the present embodiment prepare cyclic carbonate, step are as follows:
Into the stainless steel autoclave of 10mL, 50mg is sequentially added(Active ingredient copper 0.45mol%)Catalyst conjugation copper
Porphyrin joins pyrroles's capillary copolymer material, 12.5mmol propylene oxide and 0.9mmol co-catalyst tetra-n-butyl ammonium bromides, is passed through
Carbon dioxide and to keep pressure be 0.1MPa, under the conditions of temperature is 25 DEG C, after stirring 48h, room temperature cooling, slowly release is remaining
Carbon dioxide after, filter to isolate catalyst, after purification cyclic carbonate separation yield be 96%.
Embodiment 9
The method that the copper-based catalysts of the present embodiment prepare cyclic carbonate, step are as follows:
Into the stainless steel autoclave of 10mL, 50mg is sequentially added(Active ingredient copper 0.3mol%)Catalyst conjugation copper
Porphyrin joins pyrroles's capillary copolymer material, 12.5mmol epoxy butanes and 0.9mmol co-catalyst tetra-n-butyl ammonium bromides, is passed through
Carbon dioxide and to keep pressure be 0.1MPa, under the conditions of temperature is 25 DEG C, after stirring 48h, room temperature cooling, slowly release is remaining
Carbon dioxide after, filter to isolate catalyst, after purification cyclic carbonate separation yield be 92%.
Embodiment 10
The method that the copper-based catalysts of the present embodiment prepare cyclic carbonate, step are as follows:
Into the stainless steel autoclave of 10mL, 50mg is sequentially added(Active ingredient copper 0.5mol%)Catalyst conjugation copper
Porphyrin joins pyrroles's capillary copolymer material, 12.5mmol epoxychloropropane and 0.9mmol co-catalyst tetra-n-butyl ammonium bromides, leads to
It is 0.1MPa to enter carbon dioxide and keep pressure, and under the conditions of temperature is 25 DEG C, after stirring 36h, room temperature cooling, slowly release is surplus
After remaining carbon dioxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 96%.
Embodiment 11
The method that the copper-based catalysts of the present embodiment prepare cyclic carbonate, step are as follows:
Into the stainless steel autoclave of 10mL, 50mg is sequentially added(Active ingredient copper 0.4mol%)Catalyst conjugation copper
Porphyrin joins pyrroles's capillary copolymer material, 12.5mmol epoxy bromopropanes and 0.9mmol co-catalyst tetra-n-butyl ammonium bromides, leads to
It is 0.1MPa to enter carbon dioxide and keep pressure, and under the conditions of temperature is 25 DEG C, after stirring 48h, room temperature cooling, slowly release is surplus
After remaining carbon dioxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 95%.
Embodiment 12
The method that the copper-based catalysts of the present embodiment prepare cyclic carbonate, step are as follows:
Into the stainless steel autoclave of 10mL, 50mg is sequentially added(Active ingredient copper 0.3mol%)Catalyst conjugation copper
Porphyrin joins pyrroles's capillary copolymer material, 12.5mmol styrene oxides and 0.9mmol co-catalyst tetra-n-butyl ammonium bromides, leads to
It is 0.1MPa to enter carbon dioxide and keep pressure, and under the conditions of temperature is 25 DEG C, after stirring 48h, room temperature cooling, slowly release is surplus
After remaining carbon dioxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 90%.
Embodiment 13
The method that the copper-based catalysts of the present embodiment prepare cyclic carbonate, step are as follows:
Into the stainless steel autoclave of 10mL, 50mg is sequentially added(Active ingredient copper 0.2mol%)Catalyst conjugation copper
Porphyrin joins pyrroles's capillary copolymer material, 12.5mmol phenyl glycidyl ethers and 0.45mmol co-catalyst tetran-butylphosphonium bromides
Ammonium, it is 0.1MPa to be passed through carbon dioxide and keep pressure, under the conditions of temperature is 25 DEG C, after stirring 12h, and room temperature cooling, slowly
After discharging remaining carbon dioxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 88%.
Embodiment 14
The method that the copper-based catalysts of the present embodiment prepare cyclic carbonate, step are as follows:
Into the stainless steel autoclave of 10mL, 50mg is sequentially added(Active ingredient copper 0.2mol%)Catalyst conjugation copper
Porphyrin joins pyrroles's capillary copolymer material, 12.5mmol cyclohexene oxides and 0.9mmol co-catalyst tetra-n-butyl ammonium bromides, leads to
It is 0.1MPa to enter carbon dioxide and keep pressure, and under the conditions of temperature is 25 DEG C, after stirring 48h, room temperature cooling, slowly release is surplus
After remaining carbon dioxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 91%.
The content of active component is on the basis of the dosage of epoxide in above-described embodiment.
Claims (6)
1. a kind of method that copper-based catalysts prepare cyclic carbonate, it is characterised in that by the use of carbon dioxide and epoxides as
Raw material, joins pyrroles's capillary copolymer material as heterogeneous catalyst, tetra-n-butyl bromine to be conjugated copper porphyrin bipyridyl/conjugation copper porphyrin
Change ammonium is co-catalyst, in the case where normal temperature and pressure is solvent-free, reacts 12-48h, realizes efficient green catalysis carbon dioxide synthesis ring
Shape carbonic ester.
2. the method that copper-based catalysts according to claim 1 prepare cyclic carbonate, it is characterised in that:The conjugation copper
Porphyrin bipyridyl capillary copolymer material uses Scholl coupling reactions, is single with copper tetraphenylporphyrin and 2,2- bipyridyl
Body, uses anhydrous AlCl3Catalyst preparation obtains, its structural formula is as follows:
。
3. the method that copper-based catalysts according to claim 1 prepare cyclic carbonate, it is characterised in that:The conjugation copper
Porphyrin connection pyrroles's capillary copolymer material uses Scholl coupling reactions, using copper tetraphenylporphyrin and pyrroles as monomer, uses
Anhydrous AlCl3Catalyst preparation obtains, its structural formula is as follows:
。
4. the method that copper-based catalysts according to claim 1 prepare cyclic carbonate, it is characterised in that:The epoxidation
Compound is propylene oxide, epoxy butane, epoxychloropropane, epoxy bromopropane, styrene oxide, phenyl glycidyl ether or oxidation
Cyclohexene.
5. the method that copper-based catalysts according to claim 1 prepare cyclic carbonate, it is characterised in that:The multiphase is urged
The dosage of agent active component is 0.2~0.5mol% of epoxide dosage.
6. the method that copper-based catalysts according to claim 1 prepare cyclic carbonate, it is characterised in that:The co-catalysis
The dosage of agent is 3.6~7.2mol% of epoxides.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103435623A (en) * | 2013-09-05 | 2013-12-11 | 中国科学院长春应用化学研究所 | Metalloporphyrin complex and preparation method thereof, and preparation method of polycarbonate |
CN103987714A (en) * | 2011-09-21 | 2014-08-13 | 国立大学法人冈山大学 | Metal porphyrin complex, method for producing same, carbon dioxide immobilization catalyst comprising same, and method for producing cyclic carbonic acid ester. |
CN106831698A (en) * | 2016-12-20 | 2017-06-13 | 中山大学 | A kind of method of heterogeneous catalysis synthesizing annular carbonate |
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2017
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Publication number | Priority date | Publication date | Assignee | Title |
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CN103987714A (en) * | 2011-09-21 | 2014-08-13 | 国立大学法人冈山大学 | Metal porphyrin complex, method for producing same, carbon dioxide immobilization catalyst comprising same, and method for producing cyclic carbonic acid ester. |
CN103435623A (en) * | 2013-09-05 | 2013-12-11 | 中国科学院长春应用化学研究所 | Metalloporphyrin complex and preparation method thereof, and preparation method of polycarbonate |
CN106831698A (en) * | 2016-12-20 | 2017-06-13 | 中山大学 | A kind of method of heterogeneous catalysis synthesizing annular carbonate |
Non-Patent Citations (1)
Title |
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SHUANG MENG等: ""A facile approach to prepare porphyrinic porous aromatic frameworks for small hydrocarbon separation"", 《J. MATER. CHEM. A》 * |
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