CN117531540A - Catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol, preparation method and application thereof - Google Patents
Catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol, preparation method and application thereof Download PDFInfo
- Publication number
- CN117531540A CN117531540A CN202311266814.5A CN202311266814A CN117531540A CN 117531540 A CN117531540 A CN 117531540A CN 202311266814 A CN202311266814 A CN 202311266814A CN 117531540 A CN117531540 A CN 117531540A
- Authority
- CN
- China
- Prior art keywords
- glycerol
- catalyst
- carbon dioxide
- carbonate
- synthesizing
- 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
Links
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 204
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 106
- JFMGYULNQJPJCY-UHFFFAOYSA-N 4-(hydroxymethyl)-1,3-dioxolan-2-one Chemical compound OCC1COC(=O)O1 JFMGYULNQJPJCY-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 53
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 53
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000004593 Epoxy Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 84
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 19
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 17
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 239000000376 reactant Substances 0.000 claims description 14
- 239000003431 cross linking reagent Substances 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- -1 vinylbenzyl halide Chemical class 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 238000005956 quaternization reaction Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 5
- KFZYYXVIZOVAFO-UHFFFAOYSA-N 1-ethenyl-4-(iodomethyl)benzene Chemical compound ICC1=CC=C(C=C)C=C1 KFZYYXVIZOVAFO-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- VJJZJBUCDWKPLC-UHFFFAOYSA-N 3-methoxyapigenin Chemical compound O1C2=CC(O)=CC(O)=C2C(=O)C(OC)=C1C1=CC=C(O)C=C1 VJJZJBUCDWKPLC-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- VTPQLJUADNBKRM-UHFFFAOYSA-N 1-(bromomethyl)-4-ethenylbenzene Chemical compound BrCC1=CC=C(C=C)C=C1 VTPQLJUADNBKRM-UHFFFAOYSA-N 0.000 claims description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 claims 1
- 229920000831 ionic polymer Polymers 0.000 abstract description 23
- 239000007788 liquid Substances 0.000 abstract description 23
- 238000005580 one pot reaction Methods 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 235000011187 glycerol Nutrition 0.000 description 57
- 239000002815 homogeneous catalyst Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000003225 biodiesel Substances 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 3
- 150000005676 cyclic carbonates Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- YAUZKNDNVSEDKE-UHFFFAOYSA-N 1-iodoprop-2-enylbenzene Chemical compound C=CC(I)C1=CC=CC=C1 YAUZKNDNVSEDKE-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000003090 exacerbative effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- B01J31/0282—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 aliphatic ring, e.g. morpholinium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers 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
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/26—Nitrogen
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol, a preparation method and application thereof, wherein the catalyst is DBU onium polyion liquid, and is applied to the synthesis of the glycerol carbonate from carbon dioxide, glycerol and an epoxy compound by a one-pot method, and the catalyst is easier to separate and reuse while higher catalytic activity is maintained, so that the operation cost is lower.
Description
Technical Field
The invention relates to the technical field of catalysis, in particular to a catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol, a preparation method and application thereof.
Background
The large use of fossil fuels results in excessive carbon dioxide emissions, exacerbating the greenhouse effect and extreme climate change. Meanwhile, carbon dioxide is widely and abundantly available, low in cost and nontoxic, and is an attractive C1 raw material. The conversion of carbon dioxide into high added value products can not only relieve the greenhouse effect, but also improve the utilization efficiency of waste resources.
The glycerol may originate from the production of renewable energy biodiesel in a yield of about 10wt% of the biodiesel yield. With the rapid development of biodiesel industry, a large amount of surplus glycerol appears, and the price of glycerol drops rapidly due to supply and demand. Meanwhile, the treatment of the excessive crude glycerol brings a certain pressure to the environment. Therefore, the conversion of the glycerol into the chemical product with high added value not only can reduce the pressure caused by the surplus glycerol productivity, but also is beneficial to improving the development economy of the biodiesel industry. Through different chemical reactions, glycerin can be used as a raw material to synthesize various chemical products, such as glycerin carbonate, 1, 3-propanediol, acrolein and the like.
Glycerol carbonate has many excellent properties such as high boiling point, high flash point, low freezing point, low volatility, low toxicity, no odor and pollution, strong polarity, good water solubility, biodegradability, etc. Due to these excellent properties, glycerol carbonate is considered as a green solvent and is widely used in the fields of glues, cosmetics, medicines, dyes, varnishes, detergents, adhesives, biological lubricants, electrolytes, and the like. The glycerin carbonate molecule contains two active groups of hydroxyl and carbonyl, and can react with alcohol, amine, carboxylic acid, isocyanate and the like to produce various derivatives including intermediates of polymers such as polyester, polycarbonate, polyurethane, polyamide and the like.
The preparation of glycerol carbonate from carbon dioxide and glycerol has attracted considerable interest to researchers. The route can realize the co-conversion of a large amount of discharged carbon dioxide and the industrial surplus product glycerol, so that not only can the carbon dioxide be effectively utilized, but also the development of biodiesel industry can be promoted. However, the direct conversion of carbon dioxide and glycerol is thermodynamically limited, and the yield of glycerol carbonate is still low under very severe conditions. As reported in India An Nada, in the eutectic solvent, schiff base is used as a catalyst, molecular sieve is used as a dehydrating agent, and after the reaction is carried out for 24 hours at the temperature of 0.7MPa and 90 ℃, the yield of the glycerin carbonate is only 8 percent. The reaction can be carried out in one pot by adding high energy epoxy compounds, and the process can be divided into two steps which are easy to occur: (1) Cycloaddition of carbon dioxide and an epoxy compound to form a cyclic carbonate; (2) The cyclic carbonate is transesterified with glycerol to form glycerol carbonate and glycol. The university of Sichuan in CN113816852A reports that the efficient synthesis of the glycerol carbonate by the one-pot reaction of carbon dioxide, glycerol and an epoxy compound under mild conditions is realized by utilizing an organic amine halogen salt homogeneous catalyst due to efficient catalytic and mass transfer capacity, so that the yield of the glycerol carbonate is 92%. However, the homogeneous catalyst reported in this patent is difficult to separate from the reaction system, resulting in an increase in cost, and is difficult to be used on a large scale. Heterogeneous catalysts such as MgO-C (Fuel, 2023, 335:126972.) are reported in the literature for catalyzing the "one pot" reaction of carbon dioxide, glycerol and an epoxide to synthesize glycerol carbonate. However, the heterogeneous catalyst gives a maximum of 81% glycerol carbonate yield and the catalytic effect is not ideal. Therefore, it is very important to develop a heterogeneous catalyst for synthesizing glycerol carbonate by a one-pot reaction of carbon dioxide, glycerol and an epoxy compound, which is efficient, easy to separate and stable.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol, a preparation method and application thereof, and overcomes the defect that the catalyst for synthesizing the glycerol carbonate from the existing reaction of carbon dioxide, glycerol and alkylene oxide is difficult to recycle.
The invention is realized in the following way:
in a first aspect, the present invention provides a catalyst for the synthesis of glycerol carbonate from carbon dioxide and glycerol, comprising a polymer comprising units of formula 1;
wherein R is C1-C10 alkyl, X is I - 、Br - Or Cl - 。
It should be noted that, since the nucleophilicity of the halogen anion is critical for ring opening of alkylene oxide, and the protonated organic amine cation also facilitates ring opening of alkylene oxide, the inclusion of the unit of formula 1 may act as a catalyst for the "one pot" synthesis of glycerol carbonate from carbon dioxide, glycerol and an epoxy compound. Wherein R may be a straight-chain alkyl group having 1 to 10 carbon atoms or an alkyl group having a branched chain.
Compared with the reported homogeneous catalyst for synthesizing the glycerin carbonate by a one-pot method of carbon dioxide, glycerin and epoxy compounds, the 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) onium polyion liquid catalyst obtained by the invention has the advantages that the higher catalytic activity is kept, and meanwhile, the polymerization is carried out, the separation and the repeated use are easier, so that the operation cost is lower; compared with the reported homogeneous catalyst for synthesizing the glycerol carbonate by using the carbon dioxide, the glycerol and the epoxy compound through the one-pot method, the DBU onium polyion liquid catalyst has higher catalytic activity and industrial application prospect while being convenient for recycling.
In some alternative embodiments, polymers comprising a repeat of the units described by formula 1 are included.
In some alternative embodiments, polymers comprising a repeat of the units described by formula 2,
wherein CR is a group containing a phenyl group, an alcohol ester group, or an amide group.
In a second aspect, the present invention provides a method for preparing a catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol according to any one of the preceding embodiments, comprising polymerizing monomers formed from 1, 8-diazabicyclo [5.4.0] undec-7-ene and vinylhaloalkylbenzene to obtain the catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol.
When R is methylene, the monomer formed by 1, 8-diazabicyclo [5.4.0] undec-7-ene and vinyl benzyl halide is shown as formula 3, and the monomer shown as formula 3 can be subjected to homopolymerization or copolymerization under the action of a cross-linking agent to obtain the catalyst for synthesizing the glycerol carbonate from the carbon dioxide and the glycerol.
In some alternative embodiments, further comprising the preparation of the monomer: taking 1, 8-diazabicyclo [5.4.0] undec-7-ene and vinyl halogenated alkylbenzene as reactants, and performing quaternization reaction in a first solvent to generate the monomer;
preferably, the molar ratio of 1, 8-diazabicyclo [5.4.0] undec-7-ene to vinylhaloalkylbenzene is from 0.25 to 4:1;
preferably, the initial concentration of vinylhaloalkyl benzene in the first solvent is from 0.1 to 2mol/L;
preferably, the vinylhaloalkylbenzene is one of 4-vinylbenzyl iodide, 4-vinylbenzyl bromide, and 4-vinylbenzyl chloride;
preferably, the first solvent is acetonitrile;
preferably, the temperature of the quaternization reaction is 0-70 ℃ and the time is 4-24 hours;
preferably, after the quaternization reaction is finished, washing the product and performing first vacuum drying to obtain the monomer;
more preferably, the crude product is washed with diethyl ether after the quaternization reaction is complete;
more preferably, the first vacuum drying temperature is 40-80 ℃ and the time is 4-12 h.
In some alternative embodiments, the step of polymerizing includes placing the reactants in a second solvent to perform a polymerization reaction to obtain the catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol; the reactants comprise monomers and an initiator;
preferably, the initiator is azodiisobutyronitrile, and the initiator accounts for 2.5-20wt% of the total mass of the reactants;
preferably, the second solvent is methanol, and the second solvent accounts for 50-200 wt% of the total mass of the reactants;
preferably, the reactant also comprises a cross-linking agent, and the molar ratio of the cross-linking agent to the monomer is 0-4:1;
preferably, the temperature of the polymerization reaction is 60-100 ℃ and the time is 4-24 hours;
preferably, after the polymerization reaction is finished, washing and vacuum drying are carried out on the product for the second time to obtain the catalyst for synthesizing the glycerol carbonate by using the carbon dioxide and the glycerol;
more preferably, the crude product is washed with methanol and ethanol, respectively, after the polymerization reaction is completed;
more preferably, the temperature of the second vacuum drying is 40-80 ℃ and the time is 4-12 h.
In some alternative embodiments, the reactant further comprises a cross-linking agent, wherein the molar ratio of the cross-linking agent to the monomer is 0-4:1;
preferably, the cross-linking agent is at least one of p-vinylbenzene, ethylene glycol dimethacrylate, N-methylene bisacrylamide and polyethylene glycol diacrylate, and the specific structure is shown as follows.
In a third aspect, the present invention provides a method for synthesizing glycerol carbonate from carbon dioxide and glycerol, wherein the catalyst according to any one of the preceding embodiments is used to catalyze the reaction of carbon dioxide, glycerol and an epoxide to synthesize glycerol carbonate.
The glycerol carbonate with high added value is prepared by directly taking carbon dioxide and glycerol as raw materials, is economical and environment-friendly, and accords with the gist of green chemistry.
In some alternative embodiments, the epoxy compound is at least one of ethylene oxide, propylene oxide, epichlorohydrin, epibromohydrin, butylene oxide, hexane oxide, glycidol, styrene oxide, glycidyl ether, and allyl glycerol ether;
and/or the molar ratio of the epoxy compound to the glycerol is 1-10:1, the catalyst is 0.1-20wt% of the glycerol, and the partial pressure of the carbon dioxide is 0.1-5 MPa;
and/or the synthesis reaction temperature is 70-130 ℃ and the synthesis reaction time is 0.5-24 h.
The method for synthesizing the glycerol carbonate has the advantages that the conversion rate of the epoxy compound can reach 98%, the conversion rate of the glycerol can reach 91%, the yield of the glycerol carbonate can reach 91%, and even under the pressure of 0.1MPa carbon dioxide, the yield of the glycerol carbonate can reach 91%.
The invention has the following beneficial effects:
compared with the reported homogeneous catalyst for synthesizing the glycerol carbonate by the carbon dioxide, the glycerol and the epoxy compound through the one-pot method, the DBU onium polyion liquid catalyst is easier to separate and reuse while keeping higher catalytic activity, so that the operation cost is lower; compared with the reported homogeneous catalyst for synthesizing the glycerol carbonate by using the carbon dioxide, the glycerol and the epoxy compound through the one-pot method, the DBU onium polyion liquid catalyst has higher catalytic activity and industrial application prospect while being convenient for recycling.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared spectrum of a polyionic liquid synthesized in the present application, (a) DBUVB, and polyionic liquid synthesized at different DVB/DBU VBI molar ratios, (b) polyionic liquid synthesized with different cross-linking agents and DBUVB.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The following examples of the present application provide a method for the "one pot" synthesis of glycerol carbonate from carbon dioxide, glycerol and an epoxy compound comprising the steps of:
acetonitrile solution of 0.1-2mol/L vinylbenzyl halide in N 2 Stirring at 0-50 deg.c in atmosphere; adding 0.1-2mol/L DBU acetonitrile solution into the vinyl benzyl halide acetonitrile solution according to the molar ratio of DBU to vinyl benzyl halide of 0.25-4:1, and continuously stirring for 4-24 hours at the temperature of 0-70 ℃; washing the crude product for several times by using diethyl ether after the reaction is finished, and drying the washed crude product for 4-12 hours under the vacuum condition that the temperature is 40-80 ℃ and the pressure is 0.01-0.1 MPa, wherein the obtained product is DBU onium ionic liquid monomer.
Mixing the cross-linking agent and DBU onium ionic liquid monomer according to the mol ratio of 0-4:1, and adding the mixture into N 2 Adding an azobisisobutyronitrile initiator accounting for 2.5 to 20 weight percent and methanol accounting for 50 to 200 weight percent based on the total mass of reactants as solvents under the atmosphere; stirring and reacting for 4-24 h at 60-100 ℃; after the reaction is finished, methanol and ethanol are used for washing for a plurality of times respectively, and crude products are obtained through centrifugation; drying the washed crude product for 4-12 hours under the vacuum condition that the temperature is 40-80 ℃ and the pressure is 0.01-0.1 MPa, and obtaining the product which is the DBU onium polyion liquid.
Adding an epoxy compound and glycerin into a reaction kettle according to the mol ratio of 1-10:1, wherein the dosage of the polyion liquid catalyst is 0.1-20wt% of that of the glycerin, charging carbon dioxide with the pressure of 0.1-5 MPa into the reaction kettle, and reacting for 0.5-24 h at the temperature of 70-130 ℃.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1:
1mol/L of 4-vinylbenzyl iodide in acetonitrile in N 2 Stirring at 5 ℃ under the atmosphere; adding 1mol/L DBU acetonitrile solution into 4-vinylbenzyl iodide acetonitrile solution according to the mol ratio of DBU to vinylbenzyl iodide of 1:1, and continuously stirring for 24 hours at 25 ℃; after the reaction was completed, the crude product was washed with diethyl etherAnd 3 times, drying the washed crude product in vacuum for 7 hours at the temperature of 70 ℃ and the pressure of 0.01MPa, wherein the obtained ionic liquid monomer is named DBUVB.
Mixing DVB and DBUVB at a molar ratio of 1:2, at N 2 Adding an azobisisobutyronitrile initiator in an amount of 10wt% and methanol in an amount of 100wt% based on the total mass of the mixture under an atmosphere; stirring at 70 ℃ for reaction for 24 hours; after the reaction is finished, respectively washing for 3 times by using methanol and ethanol, and centrifuging to obtain a crude product; drying the washed crude product for 7 hours under the vacuum condition with the temperature of 70 ℃ and the pressure of 0.01MPa, and obtaining the polyion liquid named as P-DVB-DBUVB-1.
Propylene oxide and glycerin are added into a reaction kettle according to the mol ratio of 4:1, the dosage of the polyion liquid catalyst is 10wt% of that of glycerin, 2MPa of carbon dioxide is filled into the reaction kettle, and the reaction is carried out for 6 hours at 100 ℃. The propylene oxide conversion was 98%, the glycerol conversion was 91%, and the glycerol carbonate yield was 91%.
Example 2:
the catalyst preparation and reaction procedure were the same as in example 1, except that 4-vinylbenzyl iodide in example 1 was replaced with 4-vinylbenzyl chloride. The conversion of propylene oxide obtained by the reaction was 53%, the conversion of glycerin was 42%, and the yield of glycerin carbonate was 36%.
Example 3:
catalyst preparation and reaction procedure the same as in example 1 was followed, substituting EDGMA for DVB in example 1 and giving the polyionic liquid designated P-EDGMA-DBUVB. The conversion of propylene oxide obtained by the reaction was 95%, the conversion of glycerin was 90%, and the yield of glycerin carbonate was 82%.
Example 4:
catalyst preparation and reaction procedure the same as in example 1 was followed, substituting DVB in example 1 with MBAAm and the resulting polyionic liquid was designated P-MBAAm-DBUVBI. The conversion of propylene oxide obtained by the reaction was 98%, the conversion of glycerin was 91%, and the yield of glycerin carbonate was 86%.
Example 5:
catalyst preparation and reaction procedure the same as in example 1 was followed by adjusting the molar ratio of DVB to DBUVB to 0:1 in example 1 and the resulting polyionic liquid was designated as P-DBUVB. The conversion of propylene oxide obtained by the reaction was 98%, the conversion of glycerin was 91%, and the yield of glycerin carbonate was 88%.
Example 6:
catalyst preparation and reaction procedure the same as in example 1 was followed by adjusting the molar ratio of DVB to DBUVB to 1:1 in example 1 and the resulting polyionic liquid was designated P-DVB-DBUVB-2. The conversion of propylene oxide obtained by the reaction was 91%, the conversion of glycerin was 89%, and the yield of glycerin carbonate was 86%.
Example 7:
catalyst preparation and reaction procedure the same as in example 1 was followed by adjusting the molar ratio of DVB to DBUVB to 2:1 in example 1 and the resulting polyionic liquid was designated P-DVB-DBUVB-3. The conversion of propylene oxide obtained by the reaction was 89%, the conversion of glycerin was 87%, and the yield of glycerin carbonate was 85%.
Example 8:
the catalyst preparation and reaction procedure were the same as in example 1, with the molar ratio of propylene oxide to glycerol in example 1 being adjusted to 3:1. The conversion of propylene oxide obtained by the reaction was 95%, the conversion of glycerin was 88%, and the yield of glycerin carbonate was 86%.
Example 9:
the catalyst preparation and reaction procedure were the same as in example 1, and the amount of the catalyst added to the polyionic liquid in example 1 was adjusted to 8% by weight based on glycerin. The conversion of propylene oxide obtained by the reaction was 86%, the conversion of glycerin was 89%, and the yield of glycerin carbonate was 86%.
Example 10:
the catalyst preparation and reaction procedure were the same as in example 1, and the carbon dioxide pressure in example 1 was adjusted to 1.5MPa. The conversion of propylene oxide obtained by the reaction was 91%, the conversion of glycerin was 91%, and the yield of glycerin carbonate was 85%.
Example 11:
the catalyst preparation and the reaction procedure were the same as in example 1, and the reaction temperature in example 1 was adjusted to 90 ℃. The conversion of propylene oxide obtained by the reaction was 89%, the conversion of glycerin was 86%, and the yield of glycerin carbonate was 82%.
Example 12:
the catalyst preparation and reaction procedure were the same as in example 1, with the reaction time in example 1 being set to 4h. The conversion of propylene oxide obtained by the reaction was 87%, the conversion of glycerin was 87%, and the yield of glycerin carbonate was 81%.
Example 13:
the catalyst preparation and reaction procedure were the same as in example 1, with the epichlorohydrin of example 1 being replaced by epichlorohydrin. The conversion of epichlorohydrin obtained by the reaction was 90%, the conversion of glycerin was 52%, and the yield of glycerin carbonate was 51%.
Example 14:
the catalyst preparation and reaction procedure were the same as in example 1, except that propylene oxide in example 1 was replaced with styrene oxide, and the carbon dioxide pressure was adjusted to 0.1MPa. The conversion of styrene oxide obtained by the reaction was 75%, the conversion of glycerin was 84%, and the yield of glycerin carbonate was 83%.
Example 15:
the catalyst preparation and reaction procedure were the same as in example 14, with the reaction time in example 14 being adjusted to 12h. The conversion rate of the styrene oxide obtained by the reaction is 96%, the conversion rate of the glycerin is 91%, and the yield of the glycerin carbonate is 91%.
The catalysts obtained in some of the examples in this application were characterized in that figure 1 shows the infrared spectra of DBUVBI, DBUVBI polymerized with different crosslinking agents in different ratios. As can be seen from the figure, for DBUVB monomer, at 1610cm -1 And 1190cm -1 The c=n bond and the C-N bond on DBU, respectively. 1610cm in P-DBUVB, P-DVB-DBUVB-1, P-DVB-DBUVB-2 and P-DVB-DBUVB-3 polyionic liquids -1 And 1190cm -1 There are respectively stretching vibrational peaks of c=n bonds and C-N bonds, which indicates that DBUVBI was successfully incorporated into the structure of P-DVB-DBUVBI-N polyionic liquids. Polymers synthesized by DBUVB with EDGMA and MBAAm at 1610cm -1 And 1190cm -1 The sites show the stretching vibrational peaks of the c=n and C-N bonds, respectively, as well as the successful incorporation of DBUVBI.
Example 16:
the catalyst in example 1 was subjected to centrifugal separation, washed three times with ethanol, and recovered by vacuum drying; and (3) adding the recovered catalyst into a high-pressure reaction kettle, and entering the next catalytic cycle. The other steps are as described in example 1, and the repeated use results are shown in Table 1.
TABLE 1 reusability Properties of polyionic liquid P-DVB-DBUVB-1
From Table 1, it can be seen that the catalytic activity of the DUB onium polyion liquid catalyst P-DVB-DBUVB-1 is not obviously changed after five times of circulation, which indicates that the DBU onium polyion liquid has good stability and can be recycled for multiple times.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol is characterized by comprising a polymer containing a unit shown in a formula 1;
wherein R is C1-C10 alkyl, X is I - 、Br - Or Cl - 。
2. The catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol according to claim 1, comprising a polymer composed of a repetition of units represented by formula 1.
3. The catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol according to claim 1, comprising a polymer composed of a repetition of units represented by formula 2,
wherein CR is a group containing a phenyl group, an alcohol ester group, or an amide group.
4. A process for preparing a catalyst for the synthesis of glycerol carbonate from carbon dioxide and glycerol as claimed in any one of claims 1 to 3, which comprises polymerizing monomers of 1, 8-diazabicyclo [5.4.0] undec-7-ene and vinylhalogenoalkylbenzene to obtain the catalyst for the synthesis of glycerol carbonate from carbon dioxide and glycerol.
5. The method for preparing a catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol according to claim 4, further comprising the steps of preparing the monomer: taking 1, 8-diazabicyclo [5.4.0] undec-7-ene and vinyl halogenated alkylbenzene as reactants, and performing quaternization reaction in a first solvent to generate the monomer;
preferably, the molar ratio of 1, 8-diazabicyclo [5.4.0] undec-7-ene to vinylbenzyl halide is from 0.25 to 4:1;
preferably, the initial concentration of vinylhaloalkyl benzene in the first solvent is from 0.1 to 2mol/L;
preferably, the vinylhaloalkylbenzene is one of 4-vinylbenzyl iodide, 4-vinylbenzyl bromide, and 4-vinylbenzyl chloride;
preferably, the first solvent is acetonitrile;
preferably, the temperature of the quaternization reaction is 0-70 ℃ and the time is 4-24 hours;
preferably, after the quaternization reaction is finished, washing the product and performing first vacuum drying to obtain the monomer;
more preferably, the crude product is washed with diethyl ether after the quaternization reaction is complete;
more preferably, the first vacuum drying temperature is 40-80 ℃ and the time is 4-12 h.
6. The method for preparing a catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol according to claim 4, wherein the polymerization step comprises placing reactants in a second solvent for polymerization reaction to obtain the catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol; the reactants comprise monomers and an initiator;
preferably, the initiator is azodiisobutyronitrile, and the initiator accounts for 2.5-20wt% of the total mass of the reactants;
preferably, the second solvent is methanol, and the second solvent accounts for 50-200 wt% of the total mass of the reactants;
preferably, the temperature of the polymerization reaction is 60-100 ℃ and the time is 4-24 hours;
preferably, after the polymerization reaction is finished, washing and vacuum drying are carried out on the product for the second time to obtain the catalyst for synthesizing the glycerol carbonate by using the carbon dioxide and the glycerol;
more preferably, the crude product is washed with methanol and ethanol, respectively, after the polymerization reaction is completed;
more preferably, the temperature of the second vacuum drying is 40-80 ℃ and the time is 4-12 h.
7. The method for preparing a catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol according to claim 6, wherein the reactant further comprises a crosslinking agent, and the molar ratio of the crosslinking agent to the monomer is 0-4:1;
preferably, the cross-linking agent is at least one of p-vinylbenzene, ethylene glycol dimethacrylate, N-methylenebisacrylamide and polyethylene glycol diacrylate.
8. A method for synthesizing glycerol carbonate from carbon dioxide and glycerol, which is characterized in that the catalyst of any one of claims 1-3 is used for catalyzing the reaction of carbon dioxide, glycerol and an epoxy compound to synthesize the glycerol carbonate.
9. The method for producing a catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol according to claim 4, wherein said epoxy compound is at least one of ethylene oxide, propylene oxide, epichlorohydrin, bromopropane oxide, butylene oxide, hexane oxide, glycidol, styrene oxide, glycidyl ether and allyl glycerol ether;
and/or the molar ratio of the epoxy compound to the glycerol is 1-10:1, the catalyst is 0.1-20wt% of the glycerol, and the partial pressure of the carbon dioxide is 0.1-5 MPa;
and/or the synthesis reaction temperature is 70-130 ℃ and the synthesis reaction time is 0.5-24 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311266814.5A CN117531540A (en) | 2023-09-27 | 2023-09-27 | Catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311266814.5A CN117531540A (en) | 2023-09-27 | 2023-09-27 | Catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol, preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117531540A true CN117531540A (en) | 2024-02-09 |
Family
ID=89783002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311266814.5A Pending CN117531540A (en) | 2023-09-27 | 2023-09-27 | Catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117531540A (en) |
-
2023
- 2023-09-27 CN CN202311266814.5A patent/CN117531540A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yadav et al. | Polymers based on cyclic carbonates as trait d'union between polymer chemistry and sustainable CO2 utilization | |
| CN112341394B (en) | Method for preparing cyclic carbonate ester by catalysis of hydrogen bond donor functionalized polymeric ionic liquid | |
| CN105143306A (en) | Method for manufacturing polyalkylene carbonate | |
| CN101250258B (en) | Method for producing bio-degradable copolyester by employing composite catalyst | |
| CN106117532A (en) | The synthetic method of a kind of stereoregularity polyester and bimetallic catalyst | |
| CN113278143B (en) | Efficient unsaturated carbon dioxide-based polyol and preparation method thereof | |
| CN114163627A (en) | Double-function double-metal catalyst and its application | |
| CN102746503A (en) | Multifunctional glycidol ether or ester, propylene oxide and carbon dioxide cross-linked terpolymer and preparation method thereof | |
| CN113735705B (en) | Method for catalyzing waste PET (polyethylene terephthalate) polyester to carry out methanol alcoholysis by polyion liquid | |
| CN112851924B (en) | Recyclable nitrogen-containing polycarbonate plastic synthesis method | |
| CN110105540B (en) | Preparation method of glycidyl ester type self-curing epoxy resin | |
| CN117531540A (en) | Catalyst for synthesizing glycerol carbonate from carbon dioxide and glycerol, preparation method and application thereof | |
| CN108722479A (en) | A kind of ionic-liquid catalyst, preparation method and application | |
| Tang et al. | Sustainable Copolymer Synthesis from Carbon Dioxide and Butadiene | |
| CN114505098A (en) | Imidazole type polyion liquid catalyst and preparation method and application thereof | |
| CN101440158A (en) | Furan glycidyl ether or ester-epoxypropane-CO2 copolymer and preparation thereof | |
| CN114891194B (en) | Double-functional polymer catalyst for synthesizing polyester and application thereof | |
| CN112619705A (en) | Catalyst for addition reaction of alkylene oxide and its application | |
| CN116396474A (en) | Hyperbranched polyether ester with multiple purposes and preparation method thereof | |
| CN107383377B (en) | Cyclic polycaprolactone-polyethylene glycol amphiphilic block copolymer, and preparation and application thereof | |
| CN112625007A (en) | Method for preparing glycidyl methacrylate | |
| CN100509913C (en) | Production technique of aliphatic polycarbonate resin | |
| CN104693418B (en) | A kind of epoxy resin cure film of high fat content and its preparation method and application | |
| CN108641073B (en) | Trinuclear organic stannous metal catalyst and preparation method and application thereof | |
| CN113214077A (en) | Method for degrading thermoplastic polyethylene terephthalate |
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 |