CN108636450B - Polyion liquid composite material and preparation method and application thereof - Google Patents

Polyion liquid composite material and preparation method and application thereof Download PDF

Info

Publication number
CN108636450B
CN108636450B CN201810345759.1A CN201810345759A CN108636450B CN 108636450 B CN108636450 B CN 108636450B CN 201810345759 A CN201810345759 A CN 201810345759A CN 108636450 B CN108636450 B CN 108636450B
Authority
CN
China
Prior art keywords
product
composite material
reacting
cooling
room temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810345759.1A
Other languages
Chinese (zh)
Other versions
CN108636450A (en
Inventor
兰东辉
易兵
区泽堂
谭年元
伍水生
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Institute of Engineering
Original Assignee
Hunan Institute of Engineering
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hunan Institute of Engineering filed Critical Hunan Institute of Engineering
Priority to CN201810345759.1A priority Critical patent/CN108636450B/en
Publication of CN108636450A publication Critical patent/CN108636450A/en
Application granted granted Critical
Publication of CN108636450B publication Critical patent/CN108636450B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B01J31/0292—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 immobilised on a substrate
    • B01J31/0295—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 immobilised on a substrate by covalent attachment to the substrate, e.g. silica
    • 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
    • B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a preparation method of a polyion liquid composite material, which comprises the following steps: (1) ultrasonically dispersing a carrier in an organic solvent, then adding a silane coupling reagent, and reacting at 60-120 ℃ for 12-48 h to obtain a product A; (2) cooling and centrifugally washing the product A, then adding a solvent and organic amine, and reacting at 60-120 ℃ for 12-48 h to obtain a product B; (3) and cooling the product B, adding dihalogenated hydrocarbon, reacting at 30-100 ℃ for 12-48 h to obtain a product C, cooling the product C, centrifuging, washing, drying and grinding to obtain the composite material. The method adopts a cross-linking strategy to create a plurality of ionic liquid active sites in an organic amine single molecule and simultaneously realize that a plurality of sites of polyionic liquid are connected with a carrier by covalent bonds, the material has a plurality of functional groups such as hydroxyl, ionic liquid and amine, and can efficiently catalyze epoxide and CO under the conditions of no solvent and mild conditions2Cyclic carbonate is prepared by cycloaddition reaction, and the catalyst has excellent cycle performance.

Description

Polyion liquid composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a polyion liquid composite material for catalyzing cycloaddition reaction of carbon dioxide and epoxide to synthesize cyclic carbonate and a preparation method thereof.
Background
The hawaii monna astronomical observatory measurement results show that: CO in the atmosphere2The concentration increased by 3.05ppm over 2015 years, which is much higher than the annual average growth rate of 2ppm for the last decade. CO in the atmosphere2The concentration is increased year by year, which leads to the intensification of the greenhouse effect, and the survival and the development of human beings are seriously threatened. From another perspective, CO2And is a cheap, nontoxic and renewable C1 resource, and is used for producing methanol, salicylic acid, urea, carbonate, polycarbonate and the like. Wherein, CO is used2The cyclic carbonate with high added value is synthesized by cycloaddition reaction with epoxide, which not only accords with the principles of green chemistry and 100% atom economy, but also meets the strategic requirements of sustainable development, and is a technology of 'one arrow double carving'.
At present, there is a large amount of CO2The cycloaddition catalyst includes homogeneous catalysts such as organic bases, metal salts, Ionic Liquids (ILs), metal complexes, etc., and heterogeneous catalysts such as metal oxides, supported catalysts, organic metal framework materials, carbon materials, etc., have been reported in succession. The homogeneous catalyst has high catalytic activity, but the catalyst is difficult to recover, and the product needs to be purified by distillation; although the heterogeneous catalyst is simple to separate, the heterogeneous catalyst generally has the disadvantages of harsh reaction conditions, solvent and/or auxiliary agent requirements, and incapability of obtaining activity and mechanical properties and/or stability at the same time. Researchers can fix ILs with high activity on carriers such as silicon-based materials and the like to solve the problem of difficult separation of homogeneous catalysts, but the problems of poor activity due to limited loading capacity and easy loss of active components exist. Research and development of efficient CO catalysis under mild conditions without solvent and auxiliary agent2A heterogeneous catalyst for the cycloaddition reaction having good mechanical properties and stability is CO2Difficulty in study of cycloaddition reaction. Earlier researches find that the synergistic effect of a hydrogen bond donor and an anion can promote the ring-opening activation of epoxide, and organic base is favorable for CO2The synergistic effect of the three is beneficial to CO2And cycloaddition reaction of epoxide. The loading of active sites is a key factor in determining the activity of the catalyst. Therefore, the invention adopts the strategy of multi-group cooperative catalysis and active site crosslinking, simultaneously improves the solid loading capacity and stability of the catalyst, and develops the efficient catalysis of CO under mild conditions2And (3) a polyion liquid composite material of cycloaddition reaction.
Disclosure of Invention
The invention aims to provide a preparation method of a high-efficiency stable polyion liquid composite material, and the polyion liquid composite material prepared by the method has excellent performance and can efficiently and selectively catalyze CO under mild conditions and without any solvent or auxiliary agent2And epoxide cycloaddition reaction to synthesize the cyclic carbonate, and the activity of the catalyst is almost unchanged after the catalyst is recycled for many times.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a preparation method of a polyion liquid composite material comprises the following steps:
(1) ultrasonically dispersing a carrier with rich hydroxyl on the surface in an organic solvent at room temperature, then adding a certain amount of silane coupling reagent, and reacting at 60-120 ℃ for 12-48 h to obtain a product A;
(2) cooling the product A obtained in the step (1), centrifuging and washing to remove unreacted silane coupling reagent, then adding organic amine rich in nitrogen and organic solvent, and reacting at 60-120 ℃ for 12-48 h to obtain a product B;
(3) and (3) cooling the product B obtained in the step (2), adding a certain amount of dihalogenated hydrocarbon, reacting at 30-100 ℃ for 12-48 h to obtain a product C, cooling the product C to room temperature, centrifugally washing the product C for 5 times by using an organic solvent, drying the product C in a vacuum drying oven at 60 ℃ for 24h, and finally grinding the product C to obtain the polyion liquid composite material.
Preferably, the carrier with the surface rich in hydroxyl is selected from graphene oxide, cellulose and SiO2One or more of sol, MCM-41 or SBA-15.
Preferably, the organic solvent in step (1), step (2) and step (3) is one or more selected from the group consisting of toluene, dichloromethane, acetonitrile, N-dimethylformamide and tetrahydrofuran.
Preferably, the silane coupling agent in step (1) is one or more selected from gamma-chloropropyltrimethoxysilane, gamma-chloromethyltrimethoxysilane, gamma-chloropropyltriethoxysilane, or gamma-bromopropyltrimethoxysilane.
Preferably, the mass ratio of the carrier to the silane coupling agent in the step (1) is 1: 1-30.
Preferably, the nitrogen-rich organic amine in step (1) is one or more of triethylene tetramine, tetramethyl guanidine, metformin, hexamethylene tetramine or bis-thiourea.
Preferably, the mass ratio of the added amount of the nitrogen-rich organic amine to the silane coupling reagent in the step (1) is 1: 0.2-10.
Preferably, the dihalo-hydrocarbon in the step (3) is one or more selected from 1, 2-dibromoethane, 1, 4-dibromobutane, p-dibenzyl bromide, p-dibenzyl chloride, 1, 6-dibromohexane or 1, 8-dibromooctane; the molar ratio of the adding amount of the dihalohydrocarbon to the organic amine is 1 to (0.1-10).
In addition, the invention also claims the polyion liquid composite material prepared by the preparation method and the polyion liquid composite material prepared by the preparation method in epoxide and CO2The application of cycloaddition reaction in synthesizing cyclic carbonate comprises the following specific steps: adding catalyst polyion liquid composite material powder and liquid epoxide into a self-made high-pressure reaction kettle at room temperature, and introducing CO under continuous stirring2Raising the system pressure to 0.1-3 MPa, then raising the temperature of the reaction kettle to 30-120 ℃, reacting for 2-48 h at the temperature, cooling the reaction kettle to room temperature after the reaction is finished, and slowly releasing unreacted CO2And finally, filtering to remove the catalyst in the reaction liquid, and distilling to remove unreacted epoxide to obtain the cyclic carbonate.
Preferably, the epoxide is one or more of ethylene oxide, epichlorohydrin, propylene oxide, butylene oxide, cyclohexene oxide, cyclopentene oxide or styrene oxide; the mass ratio of the polyion liquid composite material to the epoxide is (0.01-0.2) to 1.
Compared with the prior art, the invention has the technical effects that:
according to the invention, firstly, a polyion liquid precursor-organic amine is immobilized on the surface of a carrier and generates an ionic liquid in situ, and then a strategy of crosslinking dihalohydrocarbon and unsaturated amine on the surface of the carrier is adopted to synthesize the polyion liquid composite material, so that agglomeration in the polyion liquid synthesis process is avoided, a plurality of ionic liquid active sites can be created in a single molecule of organic amine, and the covalent bond connection between the plurality of ionic liquid active sites and the carrier is realized at the same time. The polyion liquid composite material prepared by the invention is rich in various active groups such as hydroxyl, ionic liquid and alkaline site, and the various active groups in the molecule have synergistic effect, so that the polyion liquid composite material can efficiently catalyze CO under the conditions of no solvent, no assistant and mild conditions (even normal temperature and normal pressure)2And epoxide cycloaddition reaction to synchronously realize CO2Emission reduction and resource utilization. The invention firstly combines the polyion liquid and the inorganic material by covalent bonds and applies the polyion liquid and the inorganic material to catalyze CO2The technology not only expands the variety of novel high polymer materials, but also promotes the application of the novel high polymer materials in the field of catalysis.
Drawings
FIG. 1 is a FT-IR spectrum of materials prepared in example 1(b) of the present invention and comparative example 1 (a);
FIG. 2 is XPS (N) of materials prepared in example 1(b) of the present invention and comparative example 1(a)ls) Spectra.
Detailed Description
The technical scheme of the invention is further explained by combining the embodiment as follows:
the selectivity and yield of the target products in the following examples and comparative examples of the present invention were analyzed by using Agilent 7820A, a gas chromatograph manufactured by Agilent Co., Ltd, equipped with a TCD detector and RTX-1 capillary chromatography 0(30 m. times.0.25 mm. times.0.25 μm).
Example 1
A preparation method of a polyion liquid composite material comprises the following steps:
(1) ultrasonically dispersing 0.2g of graphene oxide in a mixed solution of 30mL of toluene and 30mL of DMF at room temperature, then adding 1mL of gamma-chloropropyltrimethoxysilane, and reacting for 24h at 100 ℃ to obtain a product A;
(2) cooling the product A obtained in the step (1), washing by centrifugal ethanol to remove unreacted silane coupling reagent, then adding 60mL of acetonitrile and 0.56g of hexamethylenetetramine, and reacting at 60 ℃ for 24h to obtain a product B;
(3) and (3) cooling the product B obtained in the step (2), adding 1mL of dibromobutane, reacting at 60 ℃ for 48h to obtain a product C, cooling the product C to room temperature, centrifuging and washing the product C for 5 times by using acetonitrile, drying the product C in a vacuum drying oven at 60 ℃ for 24h, and finally grinding the product C to obtain the polyion liquid composite material marked as GO-B.
Example 2
A preparation method of a polyion liquid composite material comprises the following steps:
(1) 0.5g of SiO are added at room temperature2Ultrasonically dispersing the sol in 60mL of toluene, then adding 1mL of gamma-chloropropyltrimethoxysilane, and reacting for 48 hours at 110 ℃ to obtain a product A;
(2) cooling the product A obtained in the step (1), washing by using centrifugal ethanol to remove unreacted silane coupling reagent, then adding 60mL of DMF and 0.56g of hexamethylenetetramine, and reacting at 60 ℃ for 24h to obtain a product B;
(3) cooling the product B obtained in the step (2), adding 1mL of dibromoethane, reacting at 60 ℃ for 48h to obtain a product C, cooling the product C to room temperature, centrifugally washing the product C with acetonitrile for 5 times, drying the product C in a vacuum drying oven at 60 ℃ for 24h, and finally grinding the product C to obtain the polyion liquid composite material marked as SiO2-E。
Example 3
A preparation method of a polyion liquid composite material comprises the following steps:
(1) ultrasonically dispersing 0.5g MCM-41 into 60mL of toluene at room temperature, then adding 1mL of gamma-bromopropyltrimethoxysilane, and reacting for 12 hours at 110 ℃ to obtain a product A;
(2) cooling the product A obtained in the step (1), washing by using centrifugal ethanol to remove unreacted silane coupling reagent, then adding 60mL of DMF and 0.56g of hexamethylenetetramine, and reacting at 60 ℃ for 24h to obtain a product B;
(3) and (3) cooling the product B obtained in the step (2), adding 1mL of P-dibenzyl bromide, reacting at 60 ℃ for 24h to obtain a product C, cooling the product C to room temperature, centrifuging and washing the product C for 5 times by using acetonitrile, drying the product C in a vacuum drying oven at 60 ℃ for 24h, and finally grinding the product C to obtain the polyion liquid composite material marked as MCM-41-P.
Example 4
A preparation method of a polyion liquid composite material comprises the following steps:
(1) ultrasonically dispersing 0.5g of SBA-15 into 60mL of toluene at room temperature, then adding 1mL of gamma-chloropropyltriethoxysilane, and reacting for 12h at 110 ℃ to obtain a product A;
(2) cooling the product A obtained in the step (1), washing by using centrifugal ethanol to remove unreacted silane coupling reagent, then adding 60mL of DMF and 0.56g of hexamethylenetetramine, and reacting at 60 ℃ for 24h to obtain a product B;
(3) and (3) cooling the product B obtained in the step (2), adding 1mL of 1, 8-dibromooctane, reacting at 60 ℃ for 24h to obtain a product C, cooling the product C to room temperature, centrifuging and washing the product C for 5 times by using acetonitrile, drying the product C in a vacuum drying oven at 60 ℃ for 24h, and finally grinding the product C to obtain the polyion liquid composite material SBA-15-PE.
Example 5
A preparation method of a polyion liquid composite material comprises the following steps:
(1) ultrasonically dispersing 0.2g of graphene oxide in a mixed solution of 30mL of toluene and 30mL of DMF at room temperature, then adding 1mL of gamma-chloropropyltriethoxysilane, and reacting for 24h at 100 ℃ to obtain a product A;
(2) cooling the product A obtained in the step (1), washing with centrifugal ethanol to remove unreacted silane coupling reagent, then adding 60mL of acetonitrile and 0.8mL of triethylene tetramine, and reacting at 60 ℃ for 24h to obtain a product B;
(3) and (3) cooling the product B obtained in the step (2), adding 1mL of dibromobutane, reacting at 60 ℃ for 48h to obtain a product C, cooling the product C to room temperature, centrifuging and washing the product C for 5 times by using acetonitrile, drying the product C in a vacuum drying oven at 60 ℃ for 24h, and finally grinding the product C to obtain the polyion liquid composite material marked as GO-TB.
Example 6
A preparation method of a polyion liquid composite material comprises the following steps:
(1) ultrasonically dispersing 0.2g of graphene oxide in a mixed solution of 30mL of toluene and 30mL of DMF at room temperature, then adding 1mL of gamma-chloropropyltrimethoxysilane, and reacting for 24h at 100 ℃ to obtain a product A;
(2) cooling the product A obtained in the step (1), washing by using centrifugal ethanol to remove unreacted silane coupling reagent, then adding 60mL of acetonitrile and 1mL of tetramethylguanidine, and reacting at 60 ℃ for 24h to obtain a product B;
(3) and (3) cooling the product B obtained in the step (2), adding 1mL of dibromobutane, reacting at 60 ℃ for 48h to obtain a product C, cooling the product C to room temperature, centrifuging and washing the product C for 5 times by using acetonitrile, drying the product C in a vacuum drying oven at 60 ℃ for 24h, and finally grinding the product C to obtain the polyion liquid composite material marked as GO-TE.
Comparative example 1
A preparation method of a composite material comprises the following steps:
(1) ultrasonically dispersing 0.2g of graphene oxide in a mixed solution of 30mL of toluene and 30mL of DMF at room temperature, then adding 1mL of gamma-chloropropyltrimethoxysilane, and reacting for 24h at 100 ℃ to obtain a product A;
(2) cooling the product A obtained in the step (1), washing by centrifugal ethanol to remove unreacted silane coupling reagent, then adding 60mL of acetonitrile and 0.56g of hexamethylenetetramine, and reacting at 60 ℃ for 24h to obtain a product B;
(3) and (3) cooling the product B obtained in the step (2) to room temperature, then centrifugally washing the product B for 5 times by using acetonitrile, then placing the product B in a vacuum drying oven at 60 ℃ for drying for 24 hours, and finally grinding the product B to obtain black powder recorded as GO-H.
Comparative example 2
A preparation method of a composite material comprises the following steps:
(1) ultrasonically dispersing 0.2g of graphene oxide in a mixed solution of 30mL of toluene and 30mL of DMF at room temperature, then adding 1mL of gamma-chloropropyltrimethoxysilane, and reacting for 24h at 100 ℃ to obtain a product A;
(2) cooling the product A obtained in the step (1), washing by centrifugal ethanol to remove unreacted silane coupling reagent, then adding 60mL of acetonitrile and 0.8mL of tri-n-butylamine, and reacting at 60 ℃ for 24h to obtain a product B;
(3) and (3) cooling the product B obtained in the step (2) to room temperature, then centrifugally washing the product B for 5 times by using acetonitrile, then placing the product B in a vacuum drying oven at 60 ℃ for drying for 24 hours, and finally grinding the product B to obtain black powder recorded as GO-T.
Epoxide and CO2Cycloaddition reaction to prepare cyclic carbonate:
example 7
At room temperature, 0.2g of GO-B, 0.15g of internal standard substance biphenyl and 28.6mmol of propylene oxide are sequentially added into a 30mL high-pressure reaction kettle, and 2MPa CO is introduced into the kettle under the stirring of room temperature2Then putting the reaction kettle into a reactor with magnetic forceReacting for 4 hours at 120 ℃ in a stirred oil bath reactor, cooling the reaction kettle in cold water after the reaction is finished, and then releasing CO2Taking out the reactant, centrifuging, taking the supernatant for GC analysis: the yield of propylene carbonate was 99.8% with a selectivity of 100%.
Example 8
Sequentially adding SiO into a 30mL high-pressure reaction kettle at room temperature20.04g of E, 0.15g of biphenyl as an internal standard substance and 28.6mmol of propylene oxide, and introducing 4MPa CO under stirring at room temperature2Then putting the reaction kettle into an oil bath reactor with magnetic stirring to react for 5 hours at 120 ℃, putting the reaction kettle into cold water to cool after the reaction is finished, and then releasing CO2Taking out the reactant, centrifuging, taking the supernatant for GC analysis: the yield of propylene carbonate was 95.8% with a selectivity of 99.7%.
Example 9
At room temperature, sequentially adding 0.2g of MCM-41-P, 0.15g of internal standard substance biphenyl and 28.6mmol of propylene oxide into a 30mL high-pressure reaction kettle, and introducing 2MPa CO under the condition of room temperature stirring2Then putting the reaction kettle into an oil bath reactor with magnetic stirring to react for 12 hours at the temperature of 80 ℃, putting the reaction kettle into cold water to cool after the reaction is finished, and then releasing CO2Taking out the reactant, centrifuging, taking the supernatant for GC analysis: the yield of propylene carbonate was 99.2% with a selectivity of 99.8%.
Example 10
Sequentially adding 0.3g of SBA-15-PE, 0.15g of internal standard substance biphenyl and 28.6mmol of propylene oxide into a 30mL high-pressure reaction kettle at room temperature, and introducing 2MPa CO under the condition of room temperature stirring2Then putting the reaction kettle into an oil bath reactor with magnetic stirring to react for 2 hours at 120 ℃, putting the reaction kettle into cold water to cool after the reaction is finished, and then releasing CO2Taking out the reactant, centrifuging, taking the supernatant for GC analysis: the yield of propylene carbonate was 93.4% with a selectivity of 99.8%.
Example 11
At room temperature, 0.2g of GO-TB, 0.15g of internal standard substance biphenyl and 28.6mmol of propylene oxide are sequentially added into a 30mL high-pressure reaction kettle, and 2MPa CO is introduced into the kettle under the condition of room temperature stirring2Then, thenPutting the reaction kettle into an oil bath reactor with magnetic stirring to react for 4 hours at 100 ℃, putting the reaction kettle into cold water to cool after the reaction is finished, and then releasing CO2Taking out the reactant, centrifuging, taking the supernatant for GC analysis: the yield of propylene carbonate was 99.4% with a selectivity of 99.8%.
Example 6
At room temperature, 0.1g of GO-TE, 0.15g of internal standard substance biphenyl and 28.6mmol of propylene oxide are sequentially added into a 30mL high-pressure reaction kettle, and 2MPa CO is introduced into the kettle under the stirring of room temperature2Then putting the reaction kettle into an oil bath reactor with magnetic stirring to react for 4 hours at 110 ℃, putting the reaction kettle into cold water to cool after the reaction is finished, and then releasing CO2Taking out the reactant, centrifuging, taking the supernatant for GC analysis: the yield of propylene carbonate was 93.8% with a selectivity of 99.7%.
Example 7
At room temperature, 0.2g of GO-B, 0.15g of internal standard substance biphenyl and 14.3mmol of epichlorohydrin are sequentially added into a 30mL high-pressure reaction kettle, and 0.1MPa of CO is introduced into the kettle under the stirring of room temperature2Then putting the reaction kettle into an oil bath reactor with magnetic stirring to react for 48 hours at 30 ℃, putting the reaction kettle into cold water to cool after the reaction is finished, and then releasing CO2Taking out the reactant, centrifuging, taking the supernatant for GC analysis: the yield of the product cyclic carbonate was 91.7% with a selectivity of 99.5%.
Example 8
At room temperature, 0.2g of GO-B, 0.15g of internal standard substance biphenyl and 14.3mmol of epichlorohydrin are sequentially added into a 30mL high-pressure reaction kettle, and 1MPa CO is introduced into the kettle under the condition of room temperature stirring2Then putting the reaction kettle into an oil bath reactor with magnetic stirring to react for 12 hours at 60 ℃, putting the reaction kettle into cold water to cool after the reaction is finished, and then releasing CO2Taking out the reactant, centrifuging, taking the supernatant for GC analysis: the yield of the product cyclic carbonate was 93.8% with a selectivity of 99.6%.
Example 9
At room temperature, 0.2g of GO-B, 0.15g of internal standard substance biphenyl and 14.3mmol of epichlorohydrin are sequentially added into a 30mL high-pressure reaction kettle, and the mixture is introduced into the high-pressure reaction kettle while stirring at room temperature1MPa CO2Then putting the reaction kettle into an oil bath reactor with magnetic stirring to react for 8 hours at the temperature of 80 ℃, putting the reaction kettle into cold water to cool after the reaction is finished, and then releasing CO2Taking out the reactant, centrifuging, taking the supernatant for GC analysis: the yield of the product cyclic carbonate was 98.2% with a selectivity of 99.4%.
Comparative example 3
At room temperature, 0.2g of GO-T, 0.15g of internal standard substance biphenyl and 14.3mmol of epichlorohydrin are sequentially added into a 30mL high-pressure reaction kettle, and 0.1MPa of CO is introduced into the kettle under room temperature stirring2Then putting the reaction kettle into an oil bath reactor with magnetic stirring to react for 48 hours at 30 ℃, putting the reaction kettle into cold water to cool after the reaction is finished, and then releasing CO2Taking out the reactant, centrifuging, taking the supernatant for GC analysis: the yield of the product cyclic carbonate was 1.8% with a selectivity of 99.8%.
Comparative example 4
At room temperature, 0.2g of GO-H, 0.15g of internal standard substance biphenyl and 14.3mmol of epichlorohydrin are sequentially added into a 30mL high-pressure reaction kettle, and 0.1MPa of CO is introduced into the kettle under the stirring of room temperature2Then putting the reaction kettle into an oil bath reactor with magnetic stirring to react for 48 hours at 30 ℃, putting the reaction kettle into cold water to cool after the reaction is finished, and then releasing CO2Taking out the reactant, centrifuging, taking the supernatant for GC analysis: the yield of the product cyclic carbonate was 14.2% with a selectivity of 99.8%.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (6)

1. The preparation method of the polyion liquid composite material is characterized by comprising the following steps:
(1) ultrasonically dispersing a carrier with rich hydroxyl on the surface in an organic solvent at room temperature, then adding a certain amount of silane coupling reagent, and reacting at 60-120 ℃ for 12-48 h to obtain a product A;
(2) cooling the product A obtained in the step (1), centrifuging and washing to remove unreacted silane coupling reagent, then adding an organic solvent and organic amine rich in nitrogen, and reacting at 60-120 ℃ for 12-48 h to obtain a product B;
(3) cooling the product B obtained in the step (2), adding a certain amount of dihalogenated hydrocarbon, reacting at 30-100 ℃ for 12-48 h to obtain a product C, cooling the product C to room temperature, centrifugally washing the product C for 5 times by using an organic solvent, drying the product C in a vacuum drying oven at 60 ℃ for 24h, and finally grinding the product C to obtain the polyion liquid composite material;
wherein the carrier with the surface rich in hydroxyl is selected from graphene oxide, cellulose and SiO2One or more of sol, MCM-41 or SBA-15;
wherein, the organic solvent in the step (1), the step (2) and the step (3) is one or more selected from toluene, dichloromethane, acetonitrile, N-dimethylformamide or tetrahydrofuran;
wherein, the silane coupling reagent in the step (1) is one or more selected from gamma-chloropropyltrimethoxysilane, gamma-chloromethyltrimethoxysilane, gamma-chloropropyltriethoxysilane or gamma-bromopropyltrimethoxysilane;
wherein, the organic amine rich in nitrogen in the step (2) is one or more selected from triethylene tetramine, tetramethylguanidine, metformin, hexamethylene tetramine or bisthiourea; the mass ratio of the added amount of the organic amine rich in nitrogen to the silane coupling reagent is 1: 0.2-10.
2. The preparation method according to claim 1, wherein the mass ratio of the carrier to the silane coupling agent in the step (1) is 1: 1 to 30.
3. The production method according to claim 1, wherein the dihalo-hydrocarbon in the step (3) is one or more selected from 1, 2-dibromoethane, 1, 4-dibromobutane, p-dibromobenzyl, p-dichlorobenzyl, 1, 6-dibromohexane or 1, 8-dibromooctane; the molar ratio of the adding amount of the dihalohydrocarbon to the nitrogen-rich organic amine is 1: 0.1-10.
4. The polyion liquid composite material prepared by the preparation method according to any one of claims 1 to 3.
5. A polyion liquid composite material as claimed in claim 4 in the presence of an epoxide and CO2The application of the cycloaddition reaction in synthesizing the cyclic carbonate is characterized by comprising the following specific steps: adding catalyst polyion liquid composite material and liquid epoxide into a high-pressure reaction kettle at room temperature, and introducing CO under continuous stirring2Raising the system pressure to 0.1-3 MPa, then raising the temperature of the reaction kettle to 30-120 ℃, reacting for 2-48 h at the temperature, cooling the reaction kettle to room temperature after the reaction is finished, and slowly releasing unreacted CO2And finally, filtering to remove the catalyst in the reaction liquid, and distilling to remove unreacted epoxide to obtain the cyclic carbonate.
6. Use according to claim 5, characterized in that the epoxide is one or more of ethylene oxide, epichlorohydrin, propylene oxide, butylene oxide, cyclohexene oxide, cyclopentene oxide or styrene oxide; the mass ratio of the polyion liquid composite material to the epoxide is (0.01-0.2) to 1.
CN201810345759.1A 2018-04-09 2018-04-09 Polyion liquid composite material and preparation method and application thereof Active CN108636450B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810345759.1A CN108636450B (en) 2018-04-09 2018-04-09 Polyion liquid composite material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810345759.1A CN108636450B (en) 2018-04-09 2018-04-09 Polyion liquid composite material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN108636450A CN108636450A (en) 2018-10-12
CN108636450B true CN108636450B (en) 2021-02-09

Family

ID=63746415

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810345759.1A Active CN108636450B (en) 2018-04-09 2018-04-09 Polyion liquid composite material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN108636450B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110729464B (en) * 2019-10-23 2020-10-20 商丘师范学院 Annular nano germanium dioxide/polyion liquid composite material and preparation method and application thereof
CN112295599A (en) * 2020-10-29 2021-02-02 中国科学院过程工程研究所 Application of restricted-domain multi-site ionic liquid catalyst in synthesis of cyclic carbonate
CN112844473B (en) * 2021-01-19 2023-08-11 中科南京绿色制造产业创新研究院 Alumina-supported polyion liquid catalyst and preparation method and application thereof
CN112705261B (en) * 2021-02-01 2021-12-21 福州大学 Preparation method of Pickering emulsion guanidino ionic liquid catalytic system for ester exchange reaction
CN112980335A (en) * 2021-03-08 2021-06-18 西北工业大学深圳研究院 Electrorheological polishing solution containing polyion liquid/nano abrasive composite particles and preparation method thereof
CN113265024B (en) * 2021-04-14 2022-10-28 南京工业大学 Binuclear imidazole polyion liquid material and preparation method and application thereof
CN116371464B (en) * 2023-02-10 2024-05-17 华东师范大学 Polyionic liquid-hydrotalcite composite material, preparation method and catalytic application

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5302717A (en) * 1992-10-15 1994-04-12 Monsanto Company Preparation of urethane and carbonate products
CN101108843B (en) * 2006-07-20 2011-04-06 中国科学院过程工程研究所 Method of synthesizing circularity carbonic acid ester containing water or moisture architecture
JP2011524401A (en) * 2008-06-18 2011-09-01 ビーエーエスエフ ソシエタス・ヨーロピア Method for producing glycidyl ester
CN102816182B (en) * 2012-09-10 2015-09-30 南昌航空大学 A kind of dication ionic liquid of Han Phosphonium and Synthesis and applications thereof
CN103159731B (en) * 2013-02-19 2015-10-28 浙江大学 A kind of difunctionalization ionic liquid that adopts traps the method with chemical recycling of carbon dioxide simultaneously
CN104926782B (en) * 2015-05-13 2018-08-17 南昌航空大学 The method that isothiuronium salts ionic liquid prepares cyclic carbonate
CN106279094B (en) * 2016-07-14 2019-03-29 中国科学院过程工程研究所 A kind of method of Thiourea preparing cyclic carbonate by catalyzing with ionic liquid

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
二氧化碳资源化为环状碳酸酯的新型碳基催化剂研究;兰东辉;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20170215(第2期);全文 *
功能化离子液体催化CO_固定反应的机理研究;李萍;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20160615(第6期);全文 *

Also Published As

Publication number Publication date
CN108636450A (en) 2018-10-12

Similar Documents

Publication Publication Date Title
CN108636450B (en) Polyion liquid composite material and preparation method and application thereof
CN112341394B (en) Method for preparing cyclic carbonate ester by catalysis of hydrogen bond donor functionalized polymeric ionic liquid
CN110105321B (en) Method for synthesizing cyclic carbonate by catalyzing carbon dioxide through eutectic ionic liquid
CN106946706B (en) Method for preparing dimethyl carbonate by direct reaction of carbon dioxide and methanol
CN109225337B (en) MOFs (metal-organic frameworks) -encapsulated ionic liquid catalyst and preparation and application thereof
EP2910540B1 (en) Novel ruthenium complex and method for preparing methanol and diol
CN112778533B (en) Porphyrin-based porous organic polymer, preparation method thereof and synthesis method of cyclic carbonate
CN106279094B (en) A kind of method of Thiourea preparing cyclic carbonate by catalyzing with ionic liquid
CN105732566B (en) A method of preparing ethylene carbonate
CN111362901B (en) Method for synthesizing cyclic carbonate by catalyzing carbon dioxide with fluoroalcohol functionalized ionic liquid
CN105521825A (en) Catalyst for preparing phenol by benzene oxidation, and preparation method and application thereof
CN112169836A (en) Porous ionic polymer heterogeneous catalyst and method for catalytically synthesizing N-formamide by using same
CN114437364A (en) Metal coupled triazine porous organic framework, construction method thereof and CO catalysis2Application of coupling with epoxide to prepare cyclic carbonate
CN110078702A (en) A kind of method of poly ion liquid frame catalyst preparation cyclic carbonate
CN102580775A (en) Schiff base complex catalyst for synthesizing diphenyl carbonate through oxidative carbonylation of phenol
CN104926782B (en) The method that isothiuronium salts ionic liquid prepares cyclic carbonate
CN107537576B (en) Immobilized catalyst of silane coupling molecular sieve and double-salt ionic liquid
CN113117747A (en) Interfacial ionic liquid supported catalyst for synthesizing cyclic carbonate from carbon dioxide
CN105622560A (en) Preparation method of theta-lactone
CN105665022B (en) A kind of CO2Bifunctional catalyst of cyclic carbonate ester and preparation method thereof is prepared with epoxide cycloaddition
CN115340629B (en) Quaternary ammonium salt polyion liquid and method for preparing cyclic carbonate by using quaternary ammonium salt polyion liquid to catalyze
CN112246284B (en) Single-molecule load type metal-organic framework material, preparation method thereof and application thereof in catalytic conversion of carbon dioxide
CN115894871A (en) Metal porphyrin-based porous ionic polymer and preparation method and application thereof
CN108586344A (en) Hydroxy functionalized pyrazolium ion liquid and the method for utilizing its catalytically synthesizing cyclic carbonate ester
CN114433228A (en) Method for synthesizing cyclic carbonate ester by catalyzing core-shell type polymeric ionic liquid

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant