CN114835854A - Ionic liquid copolymer and method for preparing cyclic carbonate by using same - Google Patents

Ionic liquid copolymer and method for preparing cyclic carbonate by using same Download PDF

Info

Publication number
CN114835854A
CN114835854A CN202210653325.4A CN202210653325A CN114835854A CN 114835854 A CN114835854 A CN 114835854A CN 202210653325 A CN202210653325 A CN 202210653325A CN 114835854 A CN114835854 A CN 114835854A
Authority
CN
China
Prior art keywords
ionic liquid
liquid copolymer
cyclic carbonate
oxide
styrene
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.)
Pending
Application number
CN202210653325.4A
Other languages
Chinese (zh)
Inventor
李跃辉
孙丽伟
范岩
高小龙
孙玉霞
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.)
Lanzhou Institute of Chemical Physics LICP of CAS
Original Assignee
Lanzhou Institute of Chemical Physics LICP of CAS
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 Lanzhou Institute of Chemical Physics LICP of CAS filed Critical Lanzhou Institute of Chemical Physics LICP of CAS
Priority to CN202210653325.4A priority Critical patent/CN114835854A/en
Publication of CN114835854A publication Critical patent/CN114835854A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D317/00Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10Heterocyclic 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
    • C07D317/32Heterocyclic 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
    • C07D317/34Oxygen atoms
    • C07D317/36Alkylene carbonates; Substituted alkylene carbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02Monomers containing only one unsaturated aliphatic radical
    • C08F212/04Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06Hydrocarbons
    • C08F212/08Styrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/34Monomers containing two or more unsaturated aliphatic radicals
    • C08F212/36Divinylbenzene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20General preparatory processes
    • C08G64/32General preparatory processes using carbon dioxide
    • C08G64/34General preparatory processes using carbon dioxide and cyclic ethers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • B01J2231/3411,2-additions, e.g. aldol or Knoevenagel condensations
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/54Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to an ionic liquid copolymer, which is prepared by copolymerizing imidazolium salt containing hydroxyl, carboxyl or amino and rigid molecule containing unsaturated bonds. The ionic liquid copolymer has the advantages of simple structure, easy synthesis, good mechanical stability, high recycling degree and the like, is used as a heterogeneous catalyst for preparing cyclic carbonate by directly reacting low-concentration carbon dioxide and epoxide, does not need additional solvent and additive, has high catalytic activity and selectivity, avoids the steps of gas capture, purification and storage, reduces investment and operation cost, and is suitable for directly converting and utilizing flue gas after large-scale combustion.

Description

Ionic liquid copolymer and method for preparing cyclic carbonate by using same
Technical Field
The invention relates to the technical field of clean catalysis and carbon resource chemical utilization, in particular to an ionic liquid copolymer and a method for preparing cyclic carbonate by using the same.
Background
Carbon dioxide is one of the main greenhouse gases and is a cheap, abundant and nontoxic C1 resource, so that the conversion of carbon dioxide into chemicals and organic fuels with high added values is one of the solutions for alleviating the greenhouse effect and the energy crisis. The reaction of carbon dioxide and epoxide has 100 atom percent of economy, and the obtained cyclic carbonate is a good polar solvent and a pharmaceutical chemical intermediate, and has been widely noticed and researched in recent years.
The common carbon dioxide cycloaddition reaction takes pure carbon dioxide as a gas source, and carries out compression and sealing treatment on mixed gas such as flue gas and the like after being trapped and purified, so that the process has high energy consumption, high operation cost and more operation steps, and the flue gas after being subjected to desulfurization and denitration treatment is directly used as the gas source to react with epoxide, thereby reducing the number of devices and lowering the investment cost. At present, alkali metal salts (Dalton T., 2019, 48, 7527), metal halides (Chinese J. Catal., 2018, 39, 997), ionic liquids (mol. Catal., 2020, 480, 110637, Chinese patent CN 112159387B), metal organic frameworks (Chinese patent CN 107096569) and the like are used as catalysts for the cycloaddition reaction of carbon dioxide, but the catalysts have the problems of high cost, use of cocatalysts, severe reaction conditions, low stability of a catalytic system, difficult regeneration and the like. Therefore, the method has important application value and sustainable development significance for developing a high-efficiency catalyst which is simple to prepare, low in cost, easy to recover and capable of being recycled and realizing direct catalytic conversion of low-concentration carbon dioxide and epoxide.
In view of the fact that ionic liquid has low vapor pressure, good thermal stability, adjustable physicochemical properties and excellent catalytic activity, the preparation of ionic liquid based multiphase catalysts through a specific method has become a research hotspot in recent years, one method is to utilize supported ionic liquid multiphase catalysts, such as imidazole ionic liquid modified metalloporphyrin compounds (chinese patent CN 106008448B), ionic liquid supported mineral substance multiphase catalysts (chinese patent CN 113117747A), hydroxyl functionalized ionic liquid supported catalysts (chinese patent CN 105772081A) and the like to realize the synthesis of cyclic carbonates, however, the used carriers generally have limited loading capacity and short catalyst life; still another way is to prepare ionic liquid polymers, such as polyurethane-based ionic liquid polymers (Green chem., 2013, 15, 1584), quaternary ammonium phosphate polyionic acid liquid (chinese patent CN 105367541B), amino acrylic ionic liquid polymers (chinese patent CN 109134420B), etc., and catalytically synthesize cyclic carbonates, however, some materials have the problems of poor rigidity, high dosage or poor stability, etc. On the other hand, the functionalized organic polymer has high adsorption capacity and affinity, and has good development prospect in the aspect of preparing cyclic carbonate by directly converting low-concentration carbon dioxide (Green chem, 2016, 18, 6493; Chinese patent CN 114014833A). In conclusion, the preparation of the functionalized ionic liquid copolymer with the rigid group is expected to realize the direct capture of low-concentration carbon dioxide in large-scale industrial flue gas and the preparation of the cyclic carbonate.
Disclosure of Invention
The invention aims to solve the technical problem of providing the ionic liquid copolymer which has the advantages of simple structure, good mechanical and chemical stability, easy regeneration and high recycling degree.
Another technical problem to be solved by the invention is to provide a method for preparing cyclic carbonate by using the ionic liquid copolymer.
In order to solve the above problems, the present invention provides an ionic liquid copolymer, which is characterized in that: the copolymer is prepared by copolymerizing imidazolium salt containing hydroxyl, carboxyl or amino and rigid molecules containing unsaturated bonds; the imidazolium salt is selected from one or more of functionalized ionic liquid monomers I-VI shown in the following structural formula:
Figure 758825DEST_PATH_IMAGE001
in the formula: x Is an anion of a functionalized ionic liquid monomer I-VI, and X is selected from Cl, Br, I and BF 4 、PF 6 One of (1); m = 1-6; n = 1-6; the unsaturated bond-containing rigid molecule is selected from styrene (CAS number: 100-42-5),α-methylstyrene (CAS number: 98-83-9), divinylbenzene (CAS number: 1321-74-0), 4-vinyl-1, 1 ' -biphenyl (CAS number: 2350-89-2), 4 ' -divinyl-1, 1 ' -biphenyl (CAS number: 4433-13-0), 2-naphthylethylene (CAS number: 827-54-3), 2-isopropenylnaphthalene (CAS number: 3710-23-4).
The functionalized ionic liquid monomer is I type and IV type, and X is one of Cl and Br.
The rigid molecules containing unsaturated bonds are styrene and divinylbenzene.
The method for preparing the cyclic carbonate by using the ionic liquid copolymer is characterized by comprising the following steps: using ionic liquid copolymer as CO 2 The trapping agent and the heterogeneous catalyst are used for realizing the reaction of low-concentration carbon dioxide and epoxide under the condition of no solvent and no additive to directly prepare the cyclic carbonate.
Said CO 2 The volume concentration is 3-50%.
The epoxides include ethylene oxide (CAS number: 75-21-8), propylene oxide (CAS number: 75-56-9), epichlorohydrin (CAS number: 106-89-8), 2-vinyl ethylene oxide (CAS number: 62249-80-3), 1, 2-butylene oxide (CAS number: 106-88-7), glycidyl ether (CAS number: 13236-02-7), (methoxymethyl) ethylene oxide (CAS number: 930-37-0), 1, 2-pentylene oxide (CAS number: 1003-14-1), cyclohexene oxide (CAS number: 286-20-4), styrene oxide (CAS number: 96-09-3), 2-benzyl ethylene oxide (CAS number: 4436-24-2).
The reaction conditions include that the pressure of mixed gas is 0.5-10 MPa, the reaction temperature is 60-180 ℃, the dosage of the catalyst is 0.1-10 wt% of epoxide, and the reaction time is 1-12 hours.
Compared with the prior art, the invention has the following advantages:
1. the ionic liquid copolymer is prepared by copolymerizing imidazolium salt containing hydroxyl, carboxyl or amino and rigid molecules containing unsaturated bonds, and has the advantages of simple structure, easiness in synthesis, good mechanical stability, high recycling degree and the like.
2. The ionic liquid copolymer prepared by the invention is used as a heterogeneous catalyst for preparing cyclic carbonate by directly reacting low-concentration carbon dioxide with epoxide without additional solvent and additive, has high catalytic activity and selectivity, has a yield of 60-99%, avoids the steps of gas capture, purification and storage, reduces investment and operation cost, and is suitable for direct conversion and utilization of flue gas after large-scale combustion.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is an infrared spectrum characterization of ionic liquid copolymer 1-1 of the present invention.
FIG. 2 is a graph showing the cycle stability test of the ionic liquid copolymer 1-1 of the present invention.
Detailed Description
An ionic liquid copolymer is prepared by copolymerizing imidazolium salt containing hydroxyl, carboxyl or amino and rigid molecule containing unsaturated bond.
The imidazolium salt is selected from one or more of functionalized ionic liquid monomers I-VI shown in the following structural formula:
Figure 216351DEST_PATH_IMAGE001
in the formula: x Is an anion of a functionalized ionic liquid monomer I-VI, and X is selected from Cl, Br, I and BF 4 、PF 6 One of (1); m = 1-6; n =1~ 6. Preferably: i and IV, and X is one of Cl and Br.
The rigid molecule containing unsaturated bonds is selected from styrene (CAS number: 100-42-5),α-methylstyrene (CAS number: 98-83-9), divinylbenzene (CAS number: 1321-74-0), 4-vinyl-1, 1' -biphenyl (CCAS number: 2350-89-2), 4 '-divinyl-1, 1' -biphenyl (CAS No.: 4433-13-0), 2-naphthylethylene (CAS No.: 827-54-3), 2-isopropenylnaphthalene (CAS No.: 3710-23-4). Preferably: styrene and divinylbenzene.
The synthesis method of the ionic liquid copolymer comprises the following steps:
mixing a mixture of 1: 1.1-1: 1.2 heating and refluxing the 1-vinyl imidazole and halogenated alkyl alcohol (or halogenated alkyl acid or halogenated alkylamine) in an absolute ethyl alcohol or acetonitrile solvent at the temperature of 60-80 ℃ for 12-24 hours, and then carrying out reduced pressure distillation, solvent washing and drying to obtain the functionalized ionic liquid monomers I-III.
The functionalized ionic liquid monomers IV-VI are prepared by a two-step method: mixing a mixture of 1: 0.8: 0.9-1: 1.2: 1.1 reacting halogenated alkyl styrene with imidazole and sodium hydroxide (or potassium hydroxide) at high temperature (70-110 ℃) for 6-24 hours to obtain 1- (4-alkyl styrene) imidazole, and then heating and refluxing the 1- (4-alkyl styrene) imidazole and slightly excessive halogenated alkyl alcohol (or halogenated alkyl acid or halogenated alkylamine) in an absolute ethyl alcohol or acetonitrile solvent at 60-80 ℃ for 12-36 hours to obtain the functionalized ionic liquid monomer IV-VI.
And finally, at the temperature of 70-120 ℃, mixing the functionalized ionic liquid monomers I-VI and rigid molecules (styrene, divinyl benzene, 4-vinyl-1, 1 ' -biphenyl, 4 ' -divinyl-1, 1 ' -biphenyl, 2-naphthylethylene and the like) containing unsaturated bonds according to the weight ratio of 1: 0.5-1: 5, mixing the mixture with a free radical initiator azobisisobutyronitrile with the mass of 0.1-5% of the monomer in absolute ethyl alcohol (or toluene), stirring for 0.5-12 hours to obtain a mixed solution, and carrying out vacuum filtration and drying to obtain the ionic liquid copolymer.
A method for preparing cyclic carbonate by using an ionic liquid copolymer comprises the following steps:
simultaneously using the ionic liquid copolymer as CO with the volume concentration of 3-50% 2 The trapping agent and the heterogeneous catalyst react under the conditions of no solvent and no additive, wherein the reaction conditions are that the pressure of mixed gas is 0.5-10 MPa, the reaction temperature is 60-180 ℃, the dosage of the catalyst is 0.1-10 wt% of epoxide, and the reaction time is 1-12 hours, so that low-concentration carbon dioxide and epoxide are realizedThe cyclic carbonate is directly prepared by the reaction, and the yield is 60-99%.
Wherein: epoxides include, but are not limited to, ethylene oxide (CAS number: 75-21-8), propylene oxide (CAS number: 75-56-9), epichlorohydrin (CAS number: 106-89-8), 2-vinyloxirane (CAS number: 62249-80-3), 1, 2-butylene oxide (CAS number: 106-88-7), glycidyl ether (CAS number: 13236-02-7), (methoxymethyl) oxirane (CAS number: 930-37-0), 1, 2-pentylene oxide (CAS number: 1003-14-1), cyclohexene oxide (CAS number: 286-20-4), styrene oxide (CAS number: 96-09-3), 2-benzylethylene oxide (CAS number: 4436-24-2).
EXAMPLE 1 preparation of Ionic liquid copolymer 1-1
Mixing the components in a molar ratio of 1:1.1 heating and refluxing the 1-vinyl imidazole and bromoethanol in absolute ethanol at 60 ℃ for 12 hours, and obtaining bromo-1-hydroxyethyl-3-vinyl imidazolium salt after the reaction is finished by reduced pressure distillation, solvent washing and drying; then, bromo-1-hydroxyethyl-3-vinylimidazolium salt, equimolar styrene and 0.5% of free radical initiator azobisisobutyronitrile are added into toluene, mixed and stirred for 6 hours at 110 ℃ to obtain a mixed solvent, and then the mixed solvent is subjected to vacuum filtration and drying to obtain the ionic liquid copolymer 1-1, wherein the number average molecular weight is 8450.
The obtained ionic liquid copolymer 1-1 was subjected to infrared characterization as shown in FIG. 1. 3309 cm -1 Stretching vibration peak at-OH 3067 cm -1 The vicinity is a stretching vibration peak of C-H bond in cation of imidazole ring, 2924 cm -1 The infrared absorption peak is saturated C-H stretching vibration, 1645 cm -1 Nearby is a characteristic peak of infrared breathing of a benzene ring, 1551 cm -1 1443 cm for skeletal vibration of imidazole ring -1 The absorption peak of saturated carbon-hydrogen bond is near 1064 cm -1 Is the vibration peak of the C-O bond, and in conclusion, the monomer structure and the introduction of the styryl group in the ionic liquid copolymer can be seen.
EXAMPLE 2 preparation of Ionic liquid copolymer 4-2
The imidazole and sodium hydroxide are subjected to melt reaction for 6 hours at 110 ℃ in a molar ratio of 1:1.1 to obtain imidazole sodium salt, then p-chloroethylstyrene and acetonitrile solvent with 1.1 molar equivalent are added, the mixture is heated and refluxed for 12 hours at 80 ℃ to obtain 1-p-ethylstyrylimidazole, and then the mixture is heated and refluxed for 24 hours at 80 ℃ in the acetonitrile solvent with slightly excessive chloroacetic acid to obtain the functionalized ionic liquid 1-carboxymethyl-3-p-ethylstyrylimidazole chloride. And then adding the functionalized ionic liquid, divinylbenzene with the same molar equivalent weight and azodiisobutyronitrile as a free radical initiator with the mass of 0.8 percent of the monomer into toluene, mixing, stirring at 110 ℃ for 12 hours to obtain a mixed solvent, and then carrying out vacuum filtration and drying to obtain the ionic liquid copolymer 4-2 with the number average molecular mass of 10650.
Therefore, the invention can synthesize other types of ionic liquid copolymers in the same way by changing the types of the functionalized ionic liquid and the unsaturated bond-containing rigid molecule.
Example 3 Low CO 2 Synthesis of Cyclic carbonate at concentration:
2 mL of propylene oxide and 2 wt% of ionic liquid copolymer 1-1 were charged in a 100 mL reaction vessel, and 12 vol.% CO was charged 2 CO of 2 /N 2 And (3) controlling the temperature of the mixed gas to be 140 ℃ to react for 10 hours, cooling to room temperature, slowly releasing pressure, and determining the yield of the propylene carbonate by a gas chromatograph by taking dodecane as an internal standard method, wherein the yield is 99%.
Example 4 Low CO 2 Synthesis of Cyclic carbonate at concentration:
the process is as in example 3, and a charge of CO with a concentration of 12% by volume is made 2 CO of (2) 2 /N 2 The mixed gas is adjusted to 4 MPa, other conditions are unchanged, and the yield of the propylene carbonate is 84 percent.
Example 5 Low CO 2 Synthesis of Cyclic carbonate at concentration:
the process is as in example 3, and 20% by volume CO is introduced 2 CO of 2 /N 2 The mixed gas is adjusted to 4 MPa, other conditions are unchanged, and the yield of the propylene carbonate is 99 percent.
Example 6 Low CO 2 Synthesis of Cyclic carbonate at concentration:
the method is the same as example 3, the mass ratio of the ionic liquid copolymer 1-1 to the substrate propylene oxide is 1 wt%, other conditions are unchanged, and the yield of the propylene carbonate is 61%.
Example 7 Low CO 2 Synthesis of Cyclic carbonate at concentration:
the process is the same as example 3, the reaction temperature is 120 ℃, the other conditions are unchanged, and the yield of the propylene carbonate is 73%.
Example 8 Low CO 2 Synthesis of Cyclic carbonate at concentration:
the reaction time was 6 hours as in example 3, the other conditions were unchanged, and the yield of propylene carbonate was 78%.
Example 9 Low CO 2 Synthesis of Cyclic carbonate at concentration:
the method is the same as example 3, the catalyst is the ionic liquid copolymer 4-2 in example 2, other conditions are not changed, and the yield of the propylene carbonate is 95%.
Example 10 catalyst cycling test
The method is the same as example 3, the catalyst is recycled after being filtered and recovered, and the yield of the product propylene carbonate after 10 times of use is still higher than 95%, and is respectively 99%, 98%, 97%, 96% and 95% as shown in figure 2.
EXAMPLE 11 ethylene oxide reaction
The method is the same as example 3, the epoxypropane is replaced by the epoxyethane, the epoxyethane is added into the reaction kettle at low temperature, the reaction temperature is 120 ℃, other conditions are unchanged, and the yield of the ethylene carbonate is 99%.
Example 12 epichlorohydrin reaction
The method is the same as example 3, the epoxy chloropropane is replaced by the epoxy propane, other conditions are not changed, and the yield of the epoxy chloropropylene carbonate is 98 percent.
EXAMPLE 13 glycidyl Ether reaction
The procedure is as in example 3, replacing the propylene oxide with glycidyl ether, otherwise conditions are unchanged and the yield of glycerol carbonate is 95%.
EXAMPLE 14 styrene oxide reaction
The procedure is as in example 3, replacing propylene oxide with styrene oxide, otherwise unchanged, and giving a styrene carbonate yield of 95%.

Claims (7)

1. An ionic liquid copolymer characterized by: the copolymer is prepared by copolymerizing imidazolium salt containing hydroxyl, carboxyl or amino and rigid molecules containing unsaturated bonds; the imidazolium salt is selected from one or more of functionalized ionic liquid monomers I-VI shown in the following structural formula:
Figure DEST_PATH_IMAGE001
in the formula: x Is an anion of a functionalized ionic liquid monomer I-VI, and X is selected from Cl, Br, I and BF 4 、PF 6 One of (1); m = 1-6; n = 1-6; the unsaturated bond-containing rigid molecule is selected from styrene,αOne or more of-methyl styrene, divinyl benzene, 4-vinyl-1, 1 ' -biphenyl, 4 ' -divinyl-1, 1 ' -biphenyl, 2-naphthylethylene and 2-isopropenyl naphthalene.
2. An ionic liquid copolymer according to claim 1 wherein: the functionalized ionic liquid monomer is I type and IV type, and X is one of Cl and Br.
3. An ionic liquid copolymer according to claim 1 wherein: the rigid molecules containing unsaturated bonds are styrene and divinylbenzene.
4. The method of claim 1 for preparing a cyclic carbonate using an ionic liquid copolymer, wherein: using ionic liquid copolymer as CO 2 The trapping agent and the heterogeneous catalyst are used for realizing the reaction of low-concentration carbon dioxide and epoxide under the condition of no solvent and no additive to directly prepare the cyclic carbonate.
5. The method for preparing a cyclic carbonate from an ionic liquid copolymer according to claim 4, wherein: what is needed isCO as described above 2 The volume concentration is 3-50%.
6. The method for preparing a cyclic carbonate from an ionic liquid copolymer according to claim 4, wherein: the epoxide includes ethylene oxide, propylene oxide, epichlorohydrin, 2-vinyl oxirane, 1, 2-butylene oxide, glycidyl ether, (methoxymethyl) ethylene oxide, 1, 2-cyclopentane oxide, cyclohexene oxide, styrene oxide, 2-benzyl oxirane.
7. The method for preparing a cyclic carbonate from an ionic liquid copolymer according to claim 4, wherein: the reaction conditions include that the pressure of mixed gas is 0.5-10 MPa, the reaction temperature is 60-180 ℃, the dosage of the catalyst is 0.1-10 wt% of epoxide, and the reaction time is 1-12 hours.
CN202210653325.4A 2022-06-10 2022-06-10 Ionic liquid copolymer and method for preparing cyclic carbonate by using same Pending CN114835854A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210653325.4A CN114835854A (en) 2022-06-10 2022-06-10 Ionic liquid copolymer and method for preparing cyclic carbonate by using same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210653325.4A CN114835854A (en) 2022-06-10 2022-06-10 Ionic liquid copolymer and method for preparing cyclic carbonate by using same

Publications (1)

Publication Number Publication Date
CN114835854A true CN114835854A (en) 2022-08-02

Family

ID=82574828

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210653325.4A Pending CN114835854A (en) 2022-06-10 2022-06-10 Ionic liquid copolymer and method for preparing cyclic carbonate by using same

Country Status (1)

Country Link
CN (1) CN114835854A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115677928A (en) * 2022-10-28 2023-02-03 浙江理工大学 Difunctional imidazolyl ionic liquid cross-linked copolymer and preparation method and catalytic application thereof

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3002959A (en) * 1956-06-25 1961-10-03 Devoe & Raynolds Co Inc Hydroxyl-containing copolymers and their preparation
CN101024713A (en) * 2006-02-21 2007-08-29 中国科学院化学研究所 Method for preparing chemical crosslink gel lattice polymer electrolyte
JP2013063417A (en) * 2011-02-22 2013-04-11 Osaka Gas Co Ltd Catalyst for cyclic carbonate synthesis, and method for synthesizing cyclic carbonate
US20130274485A1 (en) * 2012-04-13 2013-10-17 Shiey-Shiun HORNG Method of manufacturing cyclic carbonate by using ionic liquid polymer
CN105772081A (en) * 2016-03-07 2016-07-20 华东理工大学 Heterogeneous catalyst and application in cycloaddition preparation of cyclic carbonate by means of epoxy compound
CN108948350A (en) * 2018-06-07 2018-12-07 华东师范大学 A kind of preparation and its application of high crosslinking imidazole ion liquid porous organic polymer
CN109364993A (en) * 2018-12-17 2019-02-22 太原理工大学 For normal pressure catalyzed conversion CO2Poly ion liquid catalyst and preparation method thereof
CN112341394A (en) * 2020-11-03 2021-02-09 中国科学院过程工程研究所 Method for preparing cyclic carbonate ester by catalysis of hydrogen bond donor functionalized polymeric ionic liquid
CN113896704A (en) * 2021-10-19 2022-01-07 中国科学院兰州化学物理研究所 Method for synthesizing cyclic carbonate ester by catalyzing porous self-polymerization ionic liquid
CN114505098A (en) * 2020-11-16 2022-05-17 中国科学院过程工程研究所 Imidazole type polyion liquid catalyst and preparation method and application thereof
CN114539202A (en) * 2022-01-21 2022-05-27 中国科学院兰州化学物理研究所 Method for preparing cyclic carbonate by catalyzing flue gas with imidazole type ionic liquid

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3002959A (en) * 1956-06-25 1961-10-03 Devoe & Raynolds Co Inc Hydroxyl-containing copolymers and their preparation
CN101024713A (en) * 2006-02-21 2007-08-29 中国科学院化学研究所 Method for preparing chemical crosslink gel lattice polymer electrolyte
JP2013063417A (en) * 2011-02-22 2013-04-11 Osaka Gas Co Ltd Catalyst for cyclic carbonate synthesis, and method for synthesizing cyclic carbonate
US20130274485A1 (en) * 2012-04-13 2013-10-17 Shiey-Shiun HORNG Method of manufacturing cyclic carbonate by using ionic liquid polymer
CN105772081A (en) * 2016-03-07 2016-07-20 华东理工大学 Heterogeneous catalyst and application in cycloaddition preparation of cyclic carbonate by means of epoxy compound
CN108948350A (en) * 2018-06-07 2018-12-07 华东师范大学 A kind of preparation and its application of high crosslinking imidazole ion liquid porous organic polymer
CN109364993A (en) * 2018-12-17 2019-02-22 太原理工大学 For normal pressure catalyzed conversion CO2Poly ion liquid catalyst and preparation method thereof
CN112341394A (en) * 2020-11-03 2021-02-09 中国科学院过程工程研究所 Method for preparing cyclic carbonate ester by catalysis of hydrogen bond donor functionalized polymeric ionic liquid
CN114505098A (en) * 2020-11-16 2022-05-17 中国科学院过程工程研究所 Imidazole type polyion liquid catalyst and preparation method and application thereof
CN113896704A (en) * 2021-10-19 2022-01-07 中国科学院兰州化学物理研究所 Method for synthesizing cyclic carbonate ester by catalyzing porous self-polymerization ionic liquid
CN114539202A (en) * 2022-01-21 2022-05-27 中国科学院兰州化学物理研究所 Method for preparing cyclic carbonate by catalyzing flue gas with imidazole type ionic liquid

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115677928A (en) * 2022-10-28 2023-02-03 浙江理工大学 Difunctional imidazolyl ionic liquid cross-linked copolymer and preparation method and catalytic application thereof
CN115677928B (en) * 2022-10-28 2023-10-20 浙江理工大学 Difunctional imidazolyl ionic liquid crosslinked copolymer, preparation method and catalytic application thereof

Similar Documents

Publication Publication Date Title
CN112341394B (en) Method for preparing cyclic carbonate ester by catalysis of hydrogen bond donor functionalized polymeric ionic liquid
CN109364993B (en) For catalytic conversion of CO at normal pressure2Polyion liquid catalyst and preparation method thereof
CN111229320B (en) Metal organic framework composite material grafted with ionic liquid and preparation method and application thereof
CN105732566B (en) A method of preparing ethylene carbonate
CN109970699B (en) Method for synthesizing cyclic carbonate by chemically fixing carbon dioxide under normal temperature and pressure conditions through novel eutectic ionic liquid
Yang et al. Phase-controllable polymerized ionic liquids for CO 2 fixation into cyclic carbonates
CN107519935A (en) A kind of metal Salen organic porous material catalyst for being used to be catalyzed carbon dioxide conversion reaction
CN111514932A (en) Preparation method and application of polyion liquid catalyst
CN114835854A (en) Ionic liquid copolymer and method for preparing cyclic carbonate by using same
CN113912805B (en) Organic porous polymer for catalyzing cycloaddition of epoxide and carbon dioxide
Wan et al. Amide-functionalized organic cationic polymers toward enhanced catalytic performance for conversion of CO2 into cyclic carbonates
Jiang et al. Efficient conversion of CO2 into cyclic carbonates under atmospheric by halogen and metal-free Poly (ionic liquid) s
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
CN113896704A (en) Method for synthesizing cyclic carbonate ester by catalyzing porous self-polymerization ionic liquid
CN115340629B (en) Quaternary ammonium salt polyion liquid and method for preparing cyclic carbonate by using quaternary ammonium salt polyion liquid to catalyze
CN112619705B (en) Alkylene oxide addition reaction catalyst and application thereof
CN115028584B (en) Ionic liquid for producing glutaraldehyde
CN110483404A (en) Glyoxaline ion liquid, poly ion liquid and preparation method and application
CN102049303B (en) Catalyst used in synthesis of propylene carbonate and preparation method and application thereof
CN114433228A (en) Method for synthesizing cyclic carbonate ester by catalyzing core-shell type polymeric ionic liquid
CN109575292B (en) Ion exchange resin and use thereof
CN116920941B (en) Silica-based catalyst loaded with ionic liquid and preparation method and application thereof
CN101921257B (en) Synthesizing method of five-membered cyclic carbonate ester
Zhang et al. Ionic liquid-based advanced porous organic Hyper-Crosslinked polymers (ILHCPs) for CO2 capture and conversion

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
RJ01 Rejection of invention patent application after publication

Application publication date: 20220802

RJ01 Rejection of invention patent application after publication