CN110078702A - A kind of method of poly ion liquid frame catalyst preparation cyclic carbonate - Google Patents
A kind of method of poly ion liquid frame catalyst preparation cyclic carbonate Download PDFInfo
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- CN110078702A CN110078702A CN201910465635.1A CN201910465635A CN110078702A CN 110078702 A CN110078702 A CN 110078702A CN 201910465635 A CN201910465635 A CN 201910465635A CN 110078702 A CN110078702 A CN 110078702A
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- preparation
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- ion liquid
- carbonylation
- cyclic carbonate
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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
- 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
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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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
- 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
- B01J31/063—Polymers comprising a characteristic microstructure
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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
Abstract
The present invention provides a kind of preparation methods of cyclic carbonate, the preparation method includes the following steps: carbon dioxide and diatomic alcohol compounds carbonylation occurring under the catalysis of catalyst, cyclic carbonate is obtained, the catalyst is imidazole type poly ion liquid frame heterogeneous catalyst；Cyclic carbonate ester selectivity with higher and conversion ratio are prepared using the above method, the yield of product circular carbonate products cross reference to related application is up to 69%.Compared to traditional method for preparing cyclic carbonate ester, poly ion liquid frame catalyst used in the present invention has many advantages, such as double activated component, more active sites, high catalytic efficiency, preparation process are simple, stabilization is not easily decomposed, easily separates from liquid phase, industrial application value with higher.
Description
Technical field
The invention belongs to field of catalyst preparation, poly- more particularly, to a kind of imidazole type applied to synthesizing annular carbonate
The preparation method of ionic liquid frame catalyst.
Background technique
Cyclic carbonate, such as ethylene carbonate (EC), propene carbonate (PC), in the conjunction of medicine and fine-chemical intermediate
It is occupied an important position in, can be used as battery electrolyte, aprotic polar solvent, be dimethyl carbonate (transesterification), oxazoline
The initial feed of ketone (cyclic carbonate aminolysis) and polycarbonate (ring-opening polymerisation) etc. is widely used in printing and dyeing, weaving, high score
The industries such as son synthesis and electrochemistry.For cyclic carbonate industrialized production more than 50 years, cyclic carbonate production technology is main
There are oxidative carbonylation of methanol method, propylene oxide ester-interchange method and epoxyethane water legal etc..Oxidative carbonylation of methanol method one way
Yield is low, and propylene oxide ester-interchange method corrosivity is big, deficiency in economic performance, and the legal water of epoxyethane water is than high, energy consumption is high, selectivity
Difference.So needing to develop the new process of energy-saving and environment-friendly green high-efficient, sustainable development is realized.
Carbon dioxide (CO2) and the direct synthesizing annular carbonate of diatomic alcohol compounds there is energy-saving and emission-reduction, safe green etc.
Advantage is concerned in recent years and studies.It is reported at present to pass through CO2With the direct synthesizing annular carbonate of diatomic alcohol compounds
Catalyst have: alkali halide (KI), alkali metal salt (Cs2CO3), transition metal oxide (CeO2、ZrO2), transition gold
Metal complex (Zn (OAc)2) etc..Due to CO2The linear molecule being made of σ key and big pi bond, CO2It is straight with diatomic alcohol compounds
Being bonded into cyclic carbonate is thermodynamics not supporting reactions, reported CO2With the direct synthesis of cyclic carbonic acid of diatomic alcohol compounds
Ester catalysis system usually requires to carry out in high temperature and pressure.On the other hand, there are products to be not readily separated, urges for related homogeneous catalysis system
The low problem of agent utilization rate, and the deficiency that related heterogeneous catalytic system is low there are reactivity.It is novel more therefore, it is necessary to research and develop
Phase catalyst constructs CO2With the efficient heterogeneous catalytic system of the direct synthesizing annular carbonate of diatomic alcohol compounds.
Summary of the invention
It is an object of the invention to provide novel poly ion liquid frame catalyst, the efficient catalytic CO under low pressure, cryogenic conditions2
With the direct synthesizing annular carbonate of glycol.
For this purpose, one of the objects of the present invention is to provide a kind of preparation method of cyclic carbonate, the preparation
Method includes the following steps:
Carbonylation occurs under the catalysis of catalyst for carbon dioxide and diatomic alcohol compounds, obtains cyclic carbonate.
Reaction formula are as follows:
Wherein ,-R is the substituent group of diatomic alcohol compounds.When-R is-H, reactant is ethylene glycol, and product is carbonic acid second
Enester；When-R is-CH3When, reactant is propylene glycol, and product is propene carbonate.
It include poly ion liquid frame in the catalyst.
The poly ion liquid frame has the structure as shown in formula one:
Wherein, X-For the anion of poly ion liquid frame, X-For Br-、OH-Or CO3 2-。
Present invention utilizes poly ion liquid frames as catalyst synthesizing cyclic carbonate ester, and poly ion liquid is utilized
The characteristic of frame double activated component and abundant active site can efficiently activate carbon dioxide and glycol simultaneously, reduce reaction and live
Change energy, improves reactivity.Meanwhile the characteristics of poly ion liquid frame, enables ionic liquid to make as heterogeneous catalysis
With being conducive to the separation of product and the recycling of catalyst.
Preferably, the reaction temperature of the carbonylation is 80~180 DEG C, for example, 80 DEG C, 90 DEG C, 100 DEG C, 110
DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C or 180 DEG C etc..
Preferably, the reaction pressure of the carbonylation be 2~10MPa, for example, 2MPa, 4MPa, 6MPa, 8MPa or
10MPa etc..
Preferably, the reaction time of the carbonylation be 6~for 24 hours, for example, 6h, 8h, 10h, 12h, 14h, 16h,
18h, 20h, 22h or for 24 hours etc..
Preferably, the diatomic alcohol compounds of the carbonylation are ethylene glycol or 1,2-PD etc..
Preferably, the catalyst of the carbonylation is structure shown in formula one, anion X-For Br-、OH-Or CO3 2-
Deng.
Preferably, the mass ratio of the diol reaction object of the carbonylation and catalyst be 1:1~10, for example, 1:
1,1:2,1:3,1:4,1:5,1:6,1:7,1:8,1:9 or 1:10 etc..
Preferably, the solvent of the carbonylation is acetonitrile, methanol or n,N-Dimethylformamide etc..
Preferably, the carbonylation synthesizing annular carbonate method includes the following steps:
Diatomic alcohol compounds, catalyst, solvent are placed in enclosed high pressure reaction kettle and are uniformly mixed, two are passed through in reaction kettle
Carbon oxide gas, the pressure of reaction system maintains model of the temperature of reaction kettle at 80~180 DEG C in the range of 2~10MPa in kettle
In enclosing, progress carbonylation 6~for 24 hours, obtain product circular carbonic ester.
Numberical range of the present invention not only includes enumerated point value, further includes the above-mentioned numerical value not included
Arbitrary point value between range, as space is limited and for concise consideration, range described in the present invention no longer exclusive list includes
Specific point value.
Compared with prior art, the invention has the benefit that
(1) the present invention provides a kind of novel imidazole type poly ion liquid frame heterogeneous catalysts, are catalyzed two using it
Carbonylation occurs for carbonoxide and diatomic alcohol compounds, obtains cyclic carbonate ester；Preparing cyclic carbonate ester using the above method has
Higher selectivity and conversion ratio, the yield of obtained cyclic carbonate ester products is up to 69%.
(2) compared to the previous method for preparing cyclic carbonate ester, poly ion liquid frame catalyst used in the present invention
With double activated component, more active sites, high catalytic efficiency, preparation process is simple, stabilization is not easily decomposed, is easily separated from liquid phase
Many advantages, such as, industrial application value with higher.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.
Illustratively, poly ion liquid frame (formula one, X-For Br-) can synthesize to obtain as follows:
A certain amount of three imidazole radicals benzene monomer and trisbromomethyl monomer are added in 25mL Schlenck reaction flask, is added
A certain amount of alcohol solvent, N2Under protection, 80 DEG C of stirrings are for 24 hours.After reaction, a large amount of white solids are generated, alcohol solvent is used
Wash repeatedly solid product 3 times, later by the dry 12h of synthetic product room temperature in vacuo, obtain white powder substance, as gather from
Sub- liquid frame (formula one, X-For Br-)。
Illustratively, poly ion liquid frame (formula one, X-For OH-) can synthesize to obtain as follows:
In 100mL conical flask, a certain amount of poly ion liquid frame (formula one, X is added-For Br-) and a certain amount of tetrem
Base ammonium hydroxide is added a certain amount of alcohol solvent, is stirred at room temperature for 24 hours.After reaction, solid is washed repeatedly with alcohol solvent
3 times, later by the dry 12h of synthetic product room temperature in vacuo, obtain yellow powder substance, as poly ion liquid frame (formula one,
X-For OH-)。
Illustratively, poly ion liquid frame (formula one, X-For CO3 2-) can synthesize to obtain as follows:
In 100mL conical flask, a certain amount of poly ion liquid frame (formula one, X is added-For Br-) and a certain amount of carbonic acid
Potassium is added a certain amount of aqueous solvent, is stirred at room temperature for 24 hours.After reaction, it is washed with aqueous solvent solid 3 times, will be closed later repeatedly
It is dried in vacuo 12h at product room temperature, obtains yellow powder substance, as poly ion liquid frame (formula one, X-For CO3 2-)。
By the mass ratio of modulation monomer, synthetic, synthesis temperature and generated time, those skilled in the art can
To obtain the poly ion liquid frame of arbitrary structures and the degree of polymerization.
In various embodiments of the present invention, 7890A-FID type gas chromatograph that the yield of product is produced by agilent company
It is quantitative determined.
Embodiment 1
It is anti-that 20mmol ethylene glycol, 1 powder of 100mg poly ion liquid frame and 25ml methanol are placed in 100mL enclosed high pressure
It answers in kettle and is uniformly mixed, carbon dioxide gas is passed through in reaction kettle, the pressure of reaction system maintains reaction kettle temperature in 1MPa in kettle
Degree carries out addition reaction 8h at 100 DEG C, obtains product ethylene carbonate, and the yield of ethylene carbonate is 32%.
The poly ion liquid frame 1 has the structure as shown in compound 1:
Embodiment 2
With embodiment 1, used catalyst is poly ion liquid frame 2, and other conditions are constant.
Embodiment 2 obtains product ethylene carbonate, and the yield of ethylene carbonate is 41%.
It is described that there is the structure as shown in compound 2 from poly ion liquid frame 2:
Embodiment 3
With embodiment 1, used catalyst is poly ion liquid frame 3, and other conditions are constant.
Embodiment 3 obtains product ethylene carbonate, and the yield of ethylene carbonate is 50%.
The poly ion liquid frame 3 has the structure as shown in compound 3:
Embodiment 4
With embodiment 3, used catalyst dosage is 200mg, and other conditions are constant.
Embodiment 4 obtains product ethylene carbonate, and the yield of ethylene carbonate is 54%.
Embodiment 5
With embodiment 4, pressure carbon dioxide used is 2MPa, and other conditions are constant.
Embodiment 5 obtains product ethylene carbonate, and the yield of ethylene carbonate is 58%.
Embodiment 6
With embodiment 5, reaction temperature used is 120 DEG C, and other conditions are constant.
Embodiment 6 obtains product ethylene carbonate, and the yield of ethylene carbonate is 61%.
Embodiment 7
With embodiment 6, the reaction time used is 12h, and other conditions are constant.
Embodiment 7 obtains product ethylene carbonate, and the yield of ethylene carbonate is 65%.
Embodiment 8
With embodiment 7, solvent for use is n,N-Dimethylformamide, and other conditions are constant.
Embodiment 8 obtains product ethylene carbonate, and the yield of ethylene carbonate is 69%.
Embodiment 9
With embodiment 8, glycol compound used is propylene glycol, and other conditions are constant.
Embodiment 9 obtains product propene carbonate, and the yield of propene carbonate is 66%.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
It describes in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (7)
1. a kind of preparation method of cyclic carbonate, which is characterized in that the preparation method includes the following steps:
Carbonylation occurs under the catalysis of catalyst for carbon dioxide and diatomic alcohol compounds, obtains cyclic carbonate；
It include imidazole type poly ion liquid frame in the catalyst；
The poly ion liquid frame has the structure as shown in formula one:
Wherein, X-For the anion of poly ion liquid frame, X-For Br-、OH-Or CO3 2-。
2. preparation method according to claim 1, which is characterized in that preferably, the reaction temperature of the carbonylation
It is 80~180 DEG C.
Preferably, the reaction pressure of the carbonylation is 2~10MPa.
Preferably, the reaction time of the carbonylation be 6~for 24 hours.
3. preparation method according to claim 1 or 2, which is characterized in that preferably, the dihydric alcohol of the carbonylation
The mass ratio of reactant and catalyst is 1:1~10.
Preferably, the solvent of the carbonylation is acetonitrile, methanol or n,N-Dimethylformamide etc..
4. preparation method described according to claim 1~one of 3, which is characterized in that the diatomic alcohol compounds are ethylene glycol
Or 1,2- propylene glycol.
5. preparation method described according to claim 1~one of 4, which is characterized in that in structure shown in formula one, X-For Br-、
OH-Or CO3 2-。
6. preparation method described according to claim 1~one of 5, which is characterized in that the preparation method includes the following steps:
A certain amount of three imidazole radicals benzene monomer and trisbromomethyl monomer are added in 25mL Schlenck reaction flask, is added certain
The alcohol solvent of amount, N2Under protection, 80 DEG C of stirrings are for 24 hours.After reaction, a large amount of white solids are generated, repeatedly with alcohol solvent
Washing solid product 3 times obtains white powder substance, as polyion liquid later by the dry 12h of synthetic product room temperature in vacuo
Body frame.
7. preparation method described according to claim 1~one of 6, which is characterized in that the preparation method includes the following steps:
Diatomic alcohol compounds, poly ion liquid frame catalyst, solvent are placed in enclosed high pressure reaction kettle and are uniformly mixed, reaction
Carbon dioxide gas is passed through in kettle, the pressure of reaction system maintains temperature of reaction kettle 80 in the range of 2~10MPa in kettle
In the range of~180 DEG C, progress carbonylation 6~for 24 hours, obtain cyclic carbonate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112250656A (en) * | 2020-11-03 | 2021-01-22 | 中国科学院过程工程研究所 | Method for catalytically synthesizing cyclic carbonate based on multi-active-center ionic liquid |
| CN114433228A (en) * | 2022-02-10 | 2022-05-06 | 惠州市绿色能源与新材料研究院 | Method for synthesizing cyclic carbonate ester by catalyzing core-shell type polymeric ionic liquid |
| CN114456295A (en) * | 2022-01-27 | 2022-05-10 | 西北师范大学 | Preparation method of porous polyion liquid |
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| CN101376632A (en) * | 2008-09-23 | 2009-03-04 | 赵芳 | Method for synthesizing propylene carbonate ester from CO2 and 1, 2-propanediol |
| CN108117536A (en) * | 2016-11-30 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of method of 1,2-PD and carbon dioxide synthesizing acrylic ester |
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2019
- 2019-05-30 CN CN201910465635.1A patent/CN110078702B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101376632A (en) * | 2008-09-23 | 2009-03-04 | 赵芳 | Method for synthesizing propylene carbonate ester from CO2 and 1, 2-propanediol |
| CN108117536A (en) * | 2016-11-30 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of method of 1,2-PD and carbon dioxide synthesizing acrylic ester |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112250656A (en) * | 2020-11-03 | 2021-01-22 | 中国科学院过程工程研究所 | Method for catalytically synthesizing cyclic carbonate based on multi-active-center ionic liquid |
| CN112250656B (en) * | 2020-11-03 | 2022-06-17 | 中国科学院过程工程研究所 | Method for catalytically synthesizing cyclic carbonate based on multi-active-center ionic liquid |
| CN114456295A (en) * | 2022-01-27 | 2022-05-10 | 西北师范大学 | Preparation method of porous polyion liquid |
| CN114456295B (en) * | 2022-01-27 | 2023-11-24 | 西北师范大学 | Preparation method of porous polyion liquid |
| CN114433228A (en) * | 2022-02-10 | 2022-05-06 | 惠州市绿色能源与新材料研究院 | Method for synthesizing cyclic carbonate ester by catalyzing core-shell type polymeric ionic liquid |
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