CN117358307A - Quaternary phosphonium salt catalyst for cycloaddition reaction and preparation method and application thereof - Google Patents

Quaternary phosphonium salt catalyst for cycloaddition reaction and preparation method and application thereof Download PDF

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Publication number
CN117358307A
CN117358307A CN202210755158.4A CN202210755158A CN117358307A CN 117358307 A CN117358307 A CN 117358307A CN 202210755158 A CN202210755158 A CN 202210755158A CN 117358307 A CN117358307 A CN 117358307A
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styrene
quaternary phosphonium
phosphonium salt
catalyst
cross
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俞峰萍
戈军伟
金铭
王意
何文军
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins
    • 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
    • C07D317/38—Ethylene carbonate
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention discloses a quaternary phosphonium salt catalyst for cycloaddition reaction, a preparation method and application thereof, wherein the quaternary phosphonium salt catalyst takes styrene cross-linked copolymer resin containing inorganic nano materials as a matrix, and a plurality of quaternary phosphonium salt molecular chains shown in a formula (I) are grafted on the matrix:in formula (I), R 1 、R 2 、R 3 、R 4 Each independently selected from one of hydrogen, alkyl, aryl, ester group, R 1 、R 2 、R 3 Each independently selected from one of alkyl and aryl, n is more than 0, X ‑ Is an anion, and P is a phosphorus element. The quaternary phosphonium salt catalyst for cycloaddition reaction has higher concentration of active center on the surface, so that reactants do not need to diffuse into the catalyst during cycloaddition reactionBecause the surface is more reactive.

Description

Quaternary phosphonium salt catalyst for cycloaddition reaction and preparation method and application thereof
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a cycloaddition reaction catalyst, in particular to a quaternary phosphonium salt catalyst for cycloaddition reaction, and a preparation method and application thereof.
Background
Alkylene carbonates can be prepared by the addition reaction of an epoxy compound with carbon dioxide and are very versatile. In recent years, with the rapid development of the new energy automobile industry, the demand of electrolyte is increasing, and the demand of alkylene carbonate is also increasing. Among these, the production of ethylene carbonate is mainly urea alcoholysis, transesterification and esterification addition of Ethylene Oxide (EO)/carbon dioxide. The esterification addition method of the ethylene oxide and the carbon dioxide accords with the scientific ideas of atomic economy and green chemistry, and the method can effectively utilize the carbon dioxide to synthesize fine chemicals and is widely applied and popularized at present.
The catalysts of the ethylene oxide/carbon dioxide addition system are mainly metal oxides, metal complexes, alkali metals, quaternary ammonium salts, quaternary phosphonium salts, ionic liquids and the like.
Compared with a homogeneous catalyst, the heterogeneous catalyst is characterized in that an active component is immobilized on a catalyst carrier through a physical or chemical method, so that the separation of a subsequent product and the catalyst is facilitated, the catalyst is easy to regenerate and can be repeatedly used.
Although heterogeneous catalytic systems have many advantages, there are still some disadvantages such as catalytic performance of the catalyst, production costs, universality of the feedstock, etc. Therefore, research and development of a heterogeneous catalytic system with high activity, high stability and easy separation are performed, so that the catalytic performance of the heterogeneous catalyst is improved, and the research and development of epoxide/carbon dioxide addition reaction is still hot.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a quaternary phosphonium salt catalyst for cycloaddition reaction, a preparation method and application thereof, and compared with the prior art, the catalyst has active groups with higher concentration on the surface, and the catalyst has the advantages of good catalyst activity, high stability, easy separation of products after reaction and continuous recycling of the catalyst for multiple times.
The invention aims to provide a quaternary phosphonium salt catalyst for cycloaddition reaction, which takes styrene cross-linked copolymer resin containing inorganic nano materials as a matrix, and a plurality of quaternary phosphonium salt molecular chains shown in a formula (I) are grafted on the matrix:
in formula (I), R 1 、R 2 、R 3 、R 4 Each independently selected from one of hydrogen, alkyl, aryl, ester group, R 1 、R 2 、R 3 Each independently selected from one of alkyl and aryl, n is more than 0, X - Is an anion, and P is a phosphorus element.
The quaternary phosphonium salt catalyst for cycloaddition reaction has higher concentration of active centers on the surface, so that reactants do not need to diffuse into the inside of the sphere of the catalyst during cycloaddition reaction, because the surface has higher reactivity.
In a preferred embodiment, in formula (I), R 1 、R 2 、R 3 、R 4 Each independently selected from one of hydrogen, C1-C30 alkyl, C6-C30 aryl, C2-C30 ester, R 1 、R 2 、R 3 Each independently selected from one of C1-C10 alkyl and C6-C20 aryl, n=4-100, X - Is at least one of halogen anions and organic acid radical anions.
In a further preferred embodiment, in formula (I), R 1 、R 2 、R 3 、R 4 Each independently selected from one of hydrogen, C1-C20 alkyl, C6-C20 aryl, C2-C20 ester, R 1 、R 2 、R 3 Each independently selected from one of C1-C5 alkyl, C6-C10 aryl, n=4-40, X - Is chloride, bromide, iodide andone of formate.
In a preferred embodiment, the inorganic nanomaterial-containing styrenic cross-linked copolymer resin is 5wt% to 50wt% (e.g., 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, or 50 wt%) based on 100wt% of the quaternary phosphonium salt catalyst, and the plurality of quaternary phosphonium salt molecular chains represented by formula (I) are 50wt% to 95wt% (e.g., 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, or 95 wt%).
In a further preferred embodiment, the weight of the inorganic nanomaterial-containing styrenic cross-linked copolymer resin is 10wt% to 40wt% based on 100wt% of the quaternary phosphonium salt catalyst, and the weight of the plurality of quaternary phosphonium salt molecular chains represented by formula (I) is 60wt% to 90wt%.
In a preferred embodiment, the inorganic nanomaterial is selected from at least one of carbon nanotubes, graphene, POSS-based compounds, graphite, and fullerenes.
In a further preferred embodiment, the weight content of the inorganic nanomaterial is 0.1wt% to 4wt%, preferably 0.1wt% to 3wt%, more preferably 0.2wt% to 2wt%, based on 100wt% of the total weight of the inorganic nanomaterial-containing styrenic cross-linked copolymer resin.
For example, the inorganic nanomaterial may be present in an amount of 0.1wt%, 0.2wt%, 0.4wt%, 0.6wt%, 0.8wt%, 1wt%, 1.4wt%, 1.8wt%, 2.2wt%, 2.6wt%, 2.8wt%, 3.2wt%, 3.6wt%, or 4wt% based on 100wt% of the total weight of the inorganic nanomaterial-containing styrenic cross-linked copolymer resin.
In a preferred embodiment, the inorganic nanomaterial-containing styrenic cross-linked copolymer resin is obtained as follows: and mixing components comprising a styrene monomer, a cross-linking agent, an inorganic nano material and an initiator, and copolymerizing to obtain the styrene cross-linked copolymer resin containing the inorganic nano material.
In a further preferred embodiment, the styrenic monomer is selected from styrene and its derivatives, preferably at least one from styrene, halogen substituted styrene (e.g. chlorostyrene), halogen substituted alkylstyrene (e.g. p-chloromethylstyrene), α -methylstyrene, alkoxy substituted styrene.
In a still further preferred embodiment, the crosslinking agent is selected from at least one of divinylbenzene, ethylene glycol dimethacrylate, dipropylbenzene, divinylbenzene-methane.
The second object of the present invention is to provide a method for producing a quaternary phosphonium salt catalyst for cycloaddition reaction, preferably for producing the quaternary phosphonium salt catalyst for cycloaddition reaction according to one of the objects of the present invention, wherein the production method comprises: the styrene cross-linked copolymer resin containing the inorganic nano material is sequentially subjected to the following treatment (1) optional chloromethylation treatment, (2) initiation of polymerization of styrene monomers in the presence of a catalyst and a ligand, and further optional chloromethylation treatment, (3) quaternary phosphonium reaction and (4) ion exchange treatment, so that the quaternary phosphonium salt catalyst for the cycloaddition reaction is obtained.
In the present invention, the chloromethylation treatment may be performed by chloromethylation reaction disclosed in the prior art, and may be performed by chloromethylation ether-zinc chloride, or by formaldehyde-hydrogen chloride-zinc chloride, for example, as long as chloromethylation of benzene ring is achieved. By chloromethyl ether is meant chloromethyl alkyl ether, for example selected from chloromethyl methyl ether and/or chloromethyl ethyl ether.
In a preferred embodiment, the inorganic nanomaterial-containing styrenic cross-linked copolymer resin is obtained as follows: and mixing raw materials including a styrene monomer, a cross-linking agent, an inorganic nano material and an initiator, and copolymerizing to obtain the styrene cross-linked copolymer resin containing the inorganic nano material.
In a further preferred embodiment, the styrenic monomer is selected from styrene and its derivatives, preferably at least one of styrene, p-chloromethylstyrene, a-methylstyrene, alkoxy-substituted styrene; and/or the cross-linking agent is at least one selected from divinylbenzene, ethylene glycol dimethacrylate, dipropylbenzene and divinylbenzene-methyl ether; and/or the initiator is at least one selected from benzoyl peroxide, azodiisobutyronitrile, azodiisoheptonitrile, lauroyl peroxide and cumene hydroperoxide.
In a still further preferred embodiment, the weight content of the inorganic nanomaterial is 0.1wt% to 4wt%, preferably 0.1wt% to 3wt%, more preferably 0.2wt% to 2wt%, based on 100wt% of the total weight of the feedstock; and/or the weight content of the styrene monomer is 82wt% to 95wt%; and/or the weight content of the cross-linking agent is 2wt% to 15wt%; and/or the weight content of the initiator is 0.1wt% to 3wt%.
For example, the weight content of the inorganic nanomaterial is 0.1wt%, 0.2wt%, 0.4wt%, 0.6wt%, 0.8wt%, 1wt%, 1.4wt%, 1.8wt%, 2.2wt%, 2.6wt%, 2.8wt%, 3.2wt%, 3.6wt%, or 4wt%, based on 100wt% of the total weight of the raw materials; and/or the mass content of the styrene monomer is 82wt%, 83wt%, 84wt%, 85wt%, 86wt%, 87wt%, 88wt%, 89wt%, 90wt%, 91wt%, 92wt%, 93wt%, 94wt% or 95wt%; and/or the mass content of the cross-linking agent is 2wt%, 4wt%, 6wt%, 8wt%, 10wt%, 12wt%, 14wt% or 15wt%; and/or the mass content of the initiator is 0.1wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt% or 3wt%.
In a preferred embodiment, in preparing the inorganic nanomaterial-containing styrenic cross-linked copolymer resin, the starting material further comprises gelatin, preferably an aqueous solution of gelatin dissolved.
In the invention, the styrene cross-linked copolymer resin containing the inorganic nano material can be directly purchased or prepared by adopting the method, and the conditions for preparing the styrene cross-linked copolymer resin containing the inorganic nano material are all the common conditions disclosed in the prior art.
In a preferred embodiment, when the inorganic nanomaterial-containing styrene cross-linked copolymer resin is prepared using halogen-substituted styrene and/or halogen-substituted alkylstyrene as a styrene monomer, the step (1) is not performed, i.e., the inorganic nanomaterial-containing styrene cross-linked copolymer resin is not subjected to chloromethylation treatment.
In this case, the styrene monomer may be directly polymerized on the surface of the styrene cross-linked copolymer resin of the inorganic nanomaterial.
In another preferred embodiment, when the inorganic nanomaterial-containing styrene-based crosslinked copolymer resin is prepared using a styrene-based monomer other than halogen-substituted styrene and halogen-substituted alkylstyrene, the step (1) is performed, i.e., chloromethylation treatment is performed on the obtained inorganic nanomaterial-containing styrene-based crosslinked copolymer resin.
In a preferred embodiment, when the styrenic monomer in step (2) is selected from halogen-substituted styrenes and/or halogen-substituted alkylstyrenes, step (3) is not performed after the end of step (2), and step (4) is performed directly.
In another preferred embodiment, when the styrenic monomer in step (2) is selected from the group consisting of halogen-substituted styrenes and other styrenic monomers other than halogen-substituted alkylstyrenes, step (3) is performed after step (2) is completed.
In a preferred embodiment, in step (2), the catalyst is selected from cuprous halides, preferably from cuprous chloride and/or diketopromide; and/or the ligand is selected from nitrogen-based ligands, preferably at least one of 2,2' -bipyridine, PMDETA, picolinium, DETA, TREN, CYCLAM.
In a further preferred embodiment, the molar ratio of the catalyst to the ligand is 1 (1-10), preferably 1 (2-5), for example 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10.
In a preferred embodiment, in step (2), the polymerization is carried out under a protective atmosphere, for example nitrogen.
In a preferred embodiment, in step (2), the weight ratio of the total weight of catalyst and ligand to the product of step (1) is (0.08-0.4): 1, preferably (0.1-0.4): 1, for example 0.08:1, 0.1:1, 0.12:1, 0.14:1, 0.16:1, 0.18:1, 0.2:1, 0.22:1, 0.25:1, 0.3:1 or 0.4:1.
In a preferred embodiment, in step (2), the weight ratio of the styrenic monomer to the product of step (1) is (1-6): 1, preferably (2-5): 1, for example 1:1, 2:1, 3:1, 4:1, 5:1 or 6:1.
Wherein when the step (1) is not performed, the product of the step (1) refers to the inorganic nanomaterial-containing styrene-based crosslinked copolymer resin.
In the present invention, the polymerization conditions in the step (2) may be conventional conditions disclosed in the prior art, for example, at 70 to 150℃for 0.2 to 6 hours.
In the present invention, chloromethylation reaction is preferably carried out by using chloromethyl ether and zinc chloride, and preferably, the weight ratio of chloromethyl ether to raw material to be chloromethylated is (2 to 6): 1, for example, 2:1, 3:1, 4:1, 5:1 or 6:1; the weight and the dosage ratio of the zinc chloride to the raw materials to be chloromethylated is (0.2-1): 1, for example 0.2:1, 0.4:1, 0.6:1, 0.8:1 or 1:1. By chloromethyl ether is meant chloromethyl alkyl ether, for example selected from chloromethyl methyl ether and/or chloromethyl ethyl ether.
In a preferred embodiment, in step (3), the quaternary phosphonium reaction is carried out using a P-containing compound represented by formula (II):
in formula (II), R 1 、R 2 、R 3 Each independently selected from one of an alkyl group and an aryl group, preferably one of a C1-C10 alkyl group and a C6-C20 aryl group, more preferably one of a C1-C5 alkyl group and a C6-C10 aryl group.
In a still further preferred embodiment, the weight ratio of the P-containing compound of formula (II) to the product of step (2) is from (0.5 to 3.5): 1, preferably (1.0 to 2.0): 1.
in a preferred embodiment, the quaternary phosphonium reaction of step (3) is carried out in an organic solvent.
In a further preferred embodiment, the organic solvent is selected from at least one of acetonitrile, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran.
In a still further preferred embodiment, the ratio by weight (g/ml) of the volume of the organic solvent to the product of step (2) is from (5 to 10): 1, preferably (6 to 8): 1, for example 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1.
In a preferred embodiment, in step (3), the temperature of the quaternary phosphonium reaction is 50 to 150 ℃ for 12 to 36 hours.
For example, the temperature of the quaternary phosphonium reaction is 50 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃ or 150 ℃ for 12 hours, 15 hours, 18 hours, 20 hours, 22 hours, 25 hours, 28 hours, 30 hours, 32 hours, 34 hours or 36 hours.
In a preferred embodiment, the quaternary phosphonium reaction is followed by a post-treatment, preferably a wash.
In a further preferred embodiment, the post-treatment comprises: and washing by adopting an organic solvent I, an inorganic acid aqueous solution, water and an organic solvent II in sequence.
In a still further preferred embodiment, the organic solvent I is selected from at least one of ethyl acetate, methyl formate, methyl acetate; and/or the inorganic acid aqueous solution is at least one selected from hydrochloric acid aqueous solution, sulfuric acid aqueous solution and nitric acid aqueous solution; and/or the organic solvent II is at least one selected from methanol, ethanol and propanol.
In a preferred embodiment, the ion exchange treatment of step (4) is performed in an aqueous salt-containing solution.
In a further preferred embodiment, the salt is selected from at least one of a halide salt, sodium formate, potassium formate, magnesium formate, calcium formate, sodium acetate, potassium acetate, magnesium acetate, calcium acetate.
Preferably, the concentration of the aqueous salt solution is 0.05 to 2mol/L, preferably 0.1 to 1mol/L, for example 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L or 1mol/L.
Wherein the salt-containing aqueous solution is used in an amount required to bypass the product of step (3), preferably but not limited to the ratio of the weight of the product of step (3) to the volume of the salt-containing aqueous solution (g/ml) of 1 (5-30), preferably (8-20): 1, for example 1:5, 1:8, 1:10, 1:12, 1:15, 1:18, 1:20, 1:25 or 1:30.
In a preferred embodiment, the ion exchange treatment is carried out for 3 to 24 hours, preferably 5 to 10 hours, for example 3 hours, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 22 hours or 24 hours.
The third object of the present invention is to provide a quaternary phosphonium salt catalyst for cycloaddition reaction obtained by the second object of the present invention.
The fourth object of the present invention is to provide a quaternary phosphonium salt catalyst for cycloaddition reaction according to one of the objects of the present invention or a quaternary phosphonium salt catalyst for cycloaddition reaction obtained by the second preparation method according to the second object of the present invention, which is used in the preparation of cyclic carbonate by cycloaddition reaction of alkylene oxide/carbon dioxide.
Preferably, the alkylene oxide has the general formula:
wherein R is 4 -R 7 The radicals are identical or different and are each independently selected from hydrogen, C1-C6-alkyl, C1-C6-haloalkyl or C6-C10-aryl, preferably from hydrogen, methyl, ethyl, propyl, butyl or phenyl; preferably, the alkylene oxide is selected from ethylene oxide and/or propylene oxide.
In a preferred embodiment, the weight ratio of the catalyst to the alkylene oxide is (0.001-1): 1, preferably (0.1-0.3): 1.
For example, the catalyst to alkylene oxide weight ratio is 0.001:1, 0.01:1, 0.05:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, or 1:1.
In a preferred embodiment, the cycloaddition reaction is carried out at a temperature of 60 to 180 ℃, preferably 100 to 160 ℃, at a pressure of 0.1 to 10.0MPa, for a time of 1 to 12 hours.
For example, the cycloaddition reaction temperature is 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, or 180 ℃. The pressure is 0.1MPa, 0.5MPa, 1MPa, 2MPa, 4MPa, 6MPa, 8MPa or 10.0MPa, and the time is 1h, 2h, 4h, 6h, 8h, 10h or 12h.
In a further preferred embodiment, the cycloaddition reaction is carried out at a temperature of 100-160℃and a pressure of 2.0-5.0MPa for a period of 2-5 h.
For example, the cycloaddition reaction is carried out at a temperature of 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃,150 ℃ or 160 ℃, a pressure of 2.0MPa, 2.5MPa, 3.0MPa, 3.5MPa, 4.0MPa, 4.5MPa or 5.0MPa, and a time of 2 hours, 3 hours, 4 hours or 5 hours.
The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein. In the following, the individual technical solutions can in principle be combined with one another to give new technical solutions, which should also be regarded as specifically disclosed herein.
Compared with the prior art, the invention has the following beneficial effects:
(1) The surface of the quaternary phosphonium salt catalyst for cycloaddition reaction contains more quaternary phosphonium salt active sites;
(2) When the quaternary phosphonium salt catalyst is used for preparing alkylene carbonate by the addition reaction of alkylene oxide and carbon dioxide, the quaternary phosphonium salt catalyst has the advantages of high alkylene oxide conversion rate and high alkylene carbonate selectivity;
(3) The quaternary phosphonium salt catalyst for cycloaddition reaction can be used for preparing alkylene carbonate by the addition reaction of alkylene oxide and carbon dioxide, has high catalyst activity and good stability, is easy to separate products after the reaction, can be continuously used for multiple times, and has longer service life.
Drawings
FIG. 1 shows an infrared spectrum of a composite quaternary phosphonium microsphere A1 prepared in example 1.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
In addition, the specific features described in the following embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, so long as the concept of the present invention is not deviated, and the technical solution formed thereby is a part of the original disclosure of the present specification, and also falls within the protection scope of the present invention.
The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art. Examples and comparative examples the chloromethyl ether was chloromethyl methyl ether.
The chlorine content in the examples was determined by oxygen bottle-mercury determination.
[ example 1 ]
60.0 g of styrene, 4.5 g of divinylbenzene and 0.6 g of benzoyl peroxide initiator were put into a 500ml three-necked flask, and then reacted for 1.0 hour with stirring at 60 ℃; subsequently, 0.7 g of octavinyl POSS was added and the stirring was continued for 1 hour to effect the prepolymerization. 300 ml of deionized water solution in which 2.9 g of gelatin had been dissolved was added. Regulating the stirring speed, gradually heating to 78 ℃ at the same time, and reacting for 4 hours; then heating to 90 ℃, reacting for 4 hours, and finally heating to 98 ℃ and reacting for 5 hours. Pouring out the upper liquid after the reaction is finished, washing with hot water at 80 ℃, washing with cold water, filtering, drying in a vacuum oven at 60 ℃, sieving, and collecting composite microspheres with the particle size within the range of 0.35-0.60 mm.
40 g of composite microspheres and 180ml of chloromethyl ether are put into a 500ml three-neck flask, added with room temperature and kept stand for 3 hours, stirring is started, 16 g of zinc chloride is added as a catalyst, the temperature is raised to 60 ℃ for reaction for 4 hours, the reaction is cooled to room temperature after chloromethylation is finished, the chlorinated mother liquor is filtered out, repeatedly washed by methanol, and dried in a vacuum oven for 10 hours at 60 ℃ to obtain 46g of composite chlorine spheres (the chlorine content is 10 wt%).
40.0 g of composite chlorine spheres, 150ml of toluene were charged into a 500ml flask and swollen for 1 hour. 80 g of styrene and 12 g of cuprous chloride/2, 2' -bipyridine (molar ratio 1:2) were then added. The air in the flask was fully replaced with high purity nitrogen, and then reacted at 110℃for 2 hours. After the reaction, the mixture was washed with tetrahydrofuran to obtain a composite modified resin (n.apprxeq.7).
50g of composite modified resin and 250ml of chloromethyl ether are added into a 500ml three-neck flask, the mixture is kept stand at room temperature for 2 hours, stirring is started, 22 g of zinc chloride is added as a catalyst, the temperature is raised to 50 ℃ for reaction for 10 hours, the mixture is cooled to room temperature after chloromethylation is finished, a chlorinated mother liquor is filtered out, the mixture is repeatedly washed by methanol, and the mixture is dried in a vacuum oven at 60 ℃ for 10 hours, so that composite modified chlorine balls (the chlorine content is 15 wt%).
40 g of composite modified chlorine ball, 70 g of tributylphosphine and 200ml of acetonitrile are added into a 500ml three-port bottle, reacted for 24 hours at 80 ℃, cooled to room temperature, filtered, washed by ethyl acetate, 0.1mol/L of HCl, deionized water and methanol in sequence, and then dried for 24 hours at 60 ℃ in vacuum to obtain the composite quaternary phosphonium microsphere A1.
The composite quaternary phosphonium microsphere A1 prepared in example 1 was subjected to infrared spectrogram, and the successful preparation was confirmed.
In a 1000ml three-neck flask, 40 g of composite quaternary phosphonium microsphere A1 and 500ml of NaBr deionized water solution with the concentration of 0.5mol/L are added, and the mixture is stirred at room temperature for ion exchange reaction for 10 hours; washing with deionized water until the washing solution pH=7, and vacuum drying to obtain the nano composite ion exchange resin catalyst Cat-1.
In the nanocomposite ion exchange resin catalyst Cat-1, the weight content of the styrene cross-linked copolymer resin containing the inorganic nanomaterial is 11.6wt percent, and the weight content of the molecular chain shown in the formula (I) is 88.6wt percent (calculated according to a theoretical value after chlorine content measurement).
[ example 2 ]
The procedure of example 1 was repeated, except that: and replacing tributyl phosphorus in the catalyst by triphenylphosphine with equal molar quantity, wherein other conditions are unchanged, and obtaining the catalyst Cat-2.
The composite quaternary phosphonium microsphere prepared in example 2 was subjected to infrared spectrogram, which demonstrates its successful preparation.
[ example 3 ]
The procedure of example 1 was repeated, except that: the tributyl phosphine is replaced by the dimethyl phenyl phosphine with equal molar weight, and other conditions are unchanged, so that the catalyst Cat-3 is obtained.
The composite quaternary phosphonium microsphere prepared in example 3 was subjected to infrared spectrogram, which demonstrates its successful preparation.
[ example 4 ]
The procedure of example 1 was repeated, except that: the catalyst Cat-4 is obtained by replacing the deionized water solution of NaBr of 0.5mol/L with the deionized water solution of NaCl of 0.5mol/L under the same conditions.
[ example 5 ]
The procedure of example 1 was repeated, except that: the catalyst Cat-5 is obtained by replacing the deionized water solution of NaBr of 0.5mol/L with the deionized water solution of NaI of 0.5mol/L under the same conditions.
[ example 6 ]
50.0 g of styrene, 5.6 g of divinylbenzene and 1.2 g of azobisisobutyronitrile initiator were charged into a 500ml three-necked flask, and then reacted at 60℃for 1.0 hour with stirring; subsequently, 0.9 g of carbon nanotubes was added thereto, and stirring was continued for 1 hour to conduct prepolymerization. 300 ml of deionized water solution in which 3.0 g of gelatin had been dissolved was added. Regulating the stirring speed, gradually heating to 78 ℃ at the same time, and reacting for 4 hours; then heating to 90 ℃ for reaction for 5 hours, and finally heating to 98 ℃ for reaction for 5 hours. Pouring out the upper liquid after the reaction is finished, washing with hot water at 80 ℃, washing with cold water, filtering, drying in a vacuum oven at 60 ℃, sieving, and collecting composite microspheres with the particle size within the range of 0.35-0.60 mm.
40 g of composite microspheres and 180ml of chloromethyl ether are put into a 500ml three-neck flask, added with room temperature and kept stand for 3 hours, stirring is started, 15 g of zinc chloride is added as a catalyst, the temperature is raised to 50 ℃ for reaction for 7 hours, the reaction time is cooled to room temperature after chloromethylation is finished, the chlorinated mother liquor is filtered out, repeatedly washed by methanol, and dried in a vacuum oven for 10 hours at 60 ℃ to obtain 49g of composite chlorine spheres (chlorine content 13%).
40.0 g of composite chlorine spheres, 150ml of toluene were charged into a 500ml flask and swollen for 2 hours. Subsequently, 70 g of styrene, 15 g of cuprous chloride/2, 2' -bipyridine (molar ratio 1:2) were added. The air in the flask was fully replaced with high purity nitrogen, and then reacted at 110℃for 2 hours. After the reaction is finished, the composite modified resin is obtained by washing with tetrahydrofuran, wherein n is approximately equal to 5.
50g of composite modified resin A6 and 250ml of chloromethyl ether are added into a 500ml three-neck flask, the mixture is kept stand for 2 hours at room temperature, stirring is started, 22 g of zinc chloride is added as a catalyst, the temperature is raised to 50 ℃ for reaction for 12 hours, the mixture is cooled to the room temperature after chloromethylation is finished, a chlorinated mother liquor is filtered, repeatedly washed by methanol, and the mixture is dried in a vacuum oven for 10 hours at 60 ℃ to obtain composite modified chlorine balls with the chlorine content of 15%.
40 g of composite modified chlorine ball, 80 g of tributylphosphine and 200ml of N, N-dimethylformamide are added into a 500ml three-port bottle, reacted for 24 hours at 120 ℃, cooled to room temperature, filtered, and sequentially treated with methyl acetate and 0.1mol/L of H 2 SO 4 Washing with deionized water and ethanol, and then drying in vacuum at 60 ℃ for 24 hours to obtain the composite quaternary phosphonium microsphere.
The composite quaternary phosphonium microsphere prepared in example 6 was subjected to infrared spectrogram, which demonstrates its successful preparation.
Adding 40 g of composite quaternary phosphonium microspheres into a 1000ml three-neck flask, and stirring 500ml of deionized water solution of KBr with the concentration of 0.5mol/L at room temperature for ion exchange reaction for 10 hours; washing with deionized water until the washing solution pH=7, and vacuum drying to obtain the nano composite ion exchange resin catalyst Cat-6.
In the nanocomposite ion exchange resin catalyst Cat-6, the weight content of the styrene cross-linked copolymer resin containing the inorganic nanomaterial is 14wt%, and the weight content of the molecular chain shown in the formula (I) is 86wt%.
[ example 7 ]
45.0 g of styrene, 2.0 g of dipropenyl benzene and 0.8 g of benzoyl peroxide initiator are put into a 500ml three-neck flask, and then stirred and reacted for 1.0 hour at 60 ℃; subsequently 0.15 g of graphene was added and stirring was continued for 1 hour for prepolymerization. 300 ml of deionized water solution in which 3.0 g of gelatin had been dissolved was added. Regulating the stirring speed, gradually heating to 78 ℃ at the same time, and reacting for 4 hours; then heating to 90 ℃ for reaction for 5 hours, and finally heating to 98 ℃ for reaction for 5 hours. Pouring out the upper liquid after the reaction is finished, washing with hot water at 80 ℃, washing with cold water, filtering, drying in a vacuum oven at 60 ℃, sieving, and collecting composite microspheres with the particle size within the range of 0.35-0.60 mm.
40 g of composite microsphere A7 and 200ml of chloromethyl ether are put into a three-neck flask with 500ml of three-neck flask, the three-neck flask is added with room temperature and kept stand for 3 hours, stirring is started, 25 g of zinc chloride is added as a catalyst, the temperature is raised to 50 ℃ for reaction for 12 hours, the reaction is cooled to the room temperature after chloromethylation is finished, the chlorinated mother liquor is filtered out, repeatedly washed by methanol, and dried in a vacuum oven for 10 hours at 60 ℃ to obtain 50g of composite chlorine spheres (chlorine content is 16%).
40.0 g of composite chlorine spheres, 150ml of toluene were charged into a 500ml flask and swollen for 2 hours. 200 g of styrene, 15 g of cuprous chloride/N, N, N ', N, ' N ' -pentamethyldiethylenetriamine (molar ratio 1:3) were subsequently added. The air in the flask was fully replaced with high purity nitrogen, and then reacted at 110℃for 6 hours. After the reaction, washing with tetrahydrofuran to obtain composite modified resin with n equal to 10.
50g of composite modified resin and 250ml of chloromethyl ether are added into a 500ml three-neck flask, the mixture is kept stand for 2 hours at room temperature, stirring is started, 22 g of zinc chloride is added as a catalyst, the temperature is raised to 50 ℃ for reaction for 12 hours, the mixture is cooled to the room temperature after chloromethylation is finished, a chlorinated mother solution is filtered, repeatedly washed by methanol, and the mixture is dried in a vacuum oven at 60 ℃ for 10 hours, so that composite modified chlorine balls with 18 percent of chlorine content are obtained.
Adding 40 g of composite modified chlorine ball, 80 g of tributylphosphine and 200ml of N, N-dimethylacetamide into a 500ml three-port bottle, reacting for 24 hours at 120 ℃, cooling to room temperature, filtering, and sequentially using methyl acetate and 0.1mol/L HNO 3 Washing with deionized water and ethanol, and then drying in vacuum at 60 ℃ for 24 hours to obtain the composite quaternary phosphonium microsphere.
The composite quaternary phosphonium microsphere prepared in example 7 was subjected to infrared spectrogram, which demonstrates its successful preparation.
Adding 40 g of composite quaternary phosphonium microspheres into a 1000ml three-neck flask, and stirring 500ml of deionized water solution of KBr with the concentration of 0.5mol/L at room temperature for ion exchange reaction for 10 hours; washing with deionized water until the washing solution pH=7, and vacuum drying to obtain the nano composite ion exchange resin catalyst Cat-7.
In the nanocomposite ion exchange resin catalyst Cat-7, the weight content of the styrene cross-linked copolymer resin containing the inorganic nanomaterial is 6wt%, and the weight content of the molecular chain shown in the formula (I) is 94wt%.
Comparative example 1
The procedure of example 1 was repeated, except that: after the composite chlorine ball A1 is obtained, styrene grafting is not carried out, but the composite microsphere A1 is adopted to directly carry out quaternary phosphonium reaction and ion exchange treatment:
60.0 g of styrene, 4.5 g of divinylbenzene and 0.6 g of benzoyl peroxide initiator were put into a 500ml three-necked flask, and then reacted for 1.0 hour with stirring at 60 ℃; subsequently, 0.7 g of octavinyl POSS was added and the stirring was continued for 1 hour to effect the prepolymerization. 300 ml of deionized water solution in which 2.9 g of gelatin had been dissolved was added. Regulating the stirring speed, gradually heating to 78 ℃ at the same time, and reacting for 4 hours; then heating to 90 ℃, reacting for 4 hours, and finally heating to 98 ℃ and reacting for 5 hours. Pouring out the upper liquid after the reaction is finished, washing with hot water at 80 ℃, washing with cold water, filtering, drying in a vacuum oven at 60 ℃, sieving, and collecting composite microspheres with the particle size within the range of 0.35-0.60 mm.
40 g of composite microspheres and 180ml of chloromethyl ether are put into a 500ml three-neck flask, added with room temperature and kept stand for 3 hours, stirring is started, 16 g of zinc chloride is added as a catalyst, the temperature is raised to 60 ℃ for reaction for 4 hours, the mixture is cooled to room temperature after chloromethylation is finished, the chlorinated mother liquor is filtered, repeatedly washed by methanol, and dried in a vacuum oven for 10 hours at 60 ℃ to obtain composite chlorine spheres (chlorine content 10%).
40 g of composite chlorine ball, 70 g of tributylphosphine and 200ml of acetonitrile are added into a 500ml three-port bottle, reacted for 24 hours at 80 ℃, cooled to room temperature, filtered, washed by ethyl acetate, 0.1mol/L of HCl, deionized water and methanol in sequence, and then dried for 24 hours at 60 ℃ in vacuum to obtain the composite quaternary phosphonium microsphere D1.
Adding 40 g of composite quaternary phosphonium microspheres D1 and 500ml of NaBr deionized water solution with the concentration of 0.5mol/L into a 1000ml three-neck flask, and stirring at room temperature for ion exchange reaction for 10 hours; washing with deionized water until the washing solution pH=7, and vacuum drying to obtain the nano composite ion exchange resin catalyst Cat-D1. Experimental example 8 preparation of cyclic carbonate by addition reaction of alkylene oxide/carbon dioxide
The nanocomposite ion exchange resin catalyst Cat-1 prepared in [ example 1 ] was used for the addition reaction of alkylene oxide and carbon dioxide, and experimental conditions were as follows: 50.0 g of ethylene oxide and 2.5 g of catalyst Cat-A1 are added into a 500mL autoclave under the protection of high-purity nitrogen, and 2.0MPa of CO is filled in 2 Heating to 110 ℃, and then charging CO 2 Maintaining the reaction pressure at 2.0MPa, reacting for 2 hours, filtering to remove the catalyst, and measuring the conversion rate C of the ethylene oxide EO 99.2% ethylene carbonate selectivity S EC 99.6%.
The catalyst obtained by other examples is used for carrying out the addition reaction of the alkylene oxide and the carbon dioxide, and has the advantages of high ethylene oxide conversion rate and high ethylene carbonate selectivity.
Comparative example 2 preparation of cyclic carbonate by addition reaction of alkylene oxide/carbon dioxide
Nanocomposite ion exchange resin catalyst Cat-D1 prepared [ comparative example 1 ] was used for epoxyThe addition reaction of alkane and carbon dioxide is carried out under the following experimental conditions: 50.0 g of ethylene oxide and 2.5 g of catalyst Cat-D1 are added into a 500mL autoclave under the protection of high-purity nitrogen, and 2.0MPa of CO is filled in 2 Heating to 110 ℃, and then charging CO 2 Maintaining the reaction pressure at 2.0MPa, reacting for 2 hours, filtering to remove the catalyst, and measuring the conversion rate C of the ethylene oxide EO Ethylene carbonate Selectivity S of 98.3% EC 99.2%.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.

Claims (14)

1. A quaternary phosphonium salt catalyst for cycloaddition reaction takes styrene cross-linked copolymer resin containing inorganic nano material as a matrix, and a plurality of quaternary phosphonium salt molecular chains shown in formula (I) are grafted on the matrix:
in formula (I), R 1 、R 2 、R 3 、R 4 Each independently selected from one of hydrogen, alkyl, aryl, ester group, R 1 、R 2 、R 3 Each independently selected from one of alkyl and aryl, n is more than 0, X - Is an anion, and P is a phosphorus element.
2. The quaternary phosphonium salt catalyst for cycloaddition reaction according to claim 1, wherein in the formula (I), R 1 、R 2 、R 3 、R 4 Each independently selected from one of hydrogen, C1-C30 alkyl, C6-C30 aryl, C2-C30 ester, R 1 、R 2 、R 3 Each independently selected from one of C1-C10 alkyl and C6-C20 aryl, n=4-100, X - Is at least one of halogen anions and organic acid radical anions.
3. The quaternary phosphonium salt catalyst for cycloaddition reaction according to claim 1, wherein the weight of the styrene-based cross-linked copolymer resin containing inorganic nanomaterial is 5 to 50wt% and the weight of the plurality of quaternary phosphonium salt molecular chains represented by formula (I) is 50 to 95wt%, based on 100wt% of the quaternary phosphonium salt catalyst.
4. The quaternary phosphonium salt catalyst for cycloaddition reaction according to any one of claims 1 to 3, wherein the inorganic nanomaterial is at least one selected from the group consisting of carbon nanotubes, graphene, POSS-based compounds, graphite, and fullerenes; preferably, the weight content of the inorganic nanomaterial is 0.1wt% to 4wt%, based on 100wt% of the total weight of the styrenic cross-linked copolymer resin containing the inorganic nanomaterial.
5. The quaternary phosphonium salt catalyst for cycloaddition reaction according to claim 4, wherein the styrenic cross-linked copolymer resin containing inorganic nanomaterial is obtained by: mixing components comprising a styrene monomer, a cross-linking agent, an inorganic nano material and an initiator, and copolymerizing to obtain the styrene cross-linked copolymer resin containing the inorganic nano material;
preferably, the styrene monomer is selected from styrene and derivatives thereof, preferably at least one of styrene, halogen substituted alkylstyrene, alpha-methylstyrene, alkoxy substituted styrene;
preferably, the cross-linking agent is at least one selected from divinylbenzene, ethylene glycol dimethacrylate, dipropylbenzene, and divinylbenzene-based methane.
6. A method for producing a quaternary phosphonium salt catalyst for cycloaddition reaction, preferably for producing a quaternary phosphonium salt catalyst for cycloaddition reaction according to any one of claims 1 to 5, comprising: the styrene cross-linked copolymer resin containing the inorganic nano material is sequentially subjected to the following treatment (1) optional chloromethylation treatment, (2) initiation of polymerization of styrene monomers in the presence of a catalyst and a ligand, and further optional chloromethylation treatment, (3) quaternary phosphonium reaction and (4) ion exchange treatment, so that the quaternary phosphonium salt catalyst for the cycloaddition reaction is obtained.
7. The method according to claim 6, wherein the inorganic nanomaterial-containing styrene-based crosslinked copolymer resin is obtained by: mixing raw materials including a styrene monomer, a cross-linking agent, an inorganic nano material and an initiator, and copolymerizing to obtain the styrene cross-linked copolymer resin containing the inorganic nano material;
preferably, the styrene monomer is selected from styrene and derivatives thereof, preferably at least one of styrene, p-chloromethylstyrene, alpha-methylstyrene, alkoxy-substituted styrene; and/or the cross-linking agent is at least one selected from divinylbenzene, ethylene glycol dimethacrylate, dipropylbenzene and divinylbenzene-methyl ether; and/or the initiator is at least one selected from benzoyl peroxide, azodiisobutyronitrile, azodiisoheptonitrile, lauroyl peroxide and cumene hydroperoxide;
more preferably, the weight content of the inorganic nanomaterial is 0.1wt% to 4wt%, based on 100wt% of the total weight of the raw materials; and/or the weight content of the styrene monomer is 82wt% to 95wt%; and/or the weight content of the cross-linking agent is 2wt% to 15wt%; and/or the weight content of the initiator is 0.1wt% to 3wt%.
8. The method according to claim 6, wherein,
when the styrene cross-linked copolymer resin containing the inorganic nano material is prepared by using halogen-substituted styrene and/or halogen-substituted alkyl styrene as a styrene monomer, the step (1) is not performed; or, when the styrenic cross-linked copolymer resin containing inorganic nanomaterial is prepared using a styrenic monomer other than halogen-substituted styrene and halogen-substituted alkylstyrene, performing the step (1);
and/or the number of the groups of groups,
when the styrenic monomer in step (2) is selected from halogen-substituted styrene and/or halogen-substituted alkylstyrene, not performing step (3) after the end of step (2); or, when the styrenic monomer in the step (2) is selected from the group consisting of halogen-substituted styrene and other styrenic monomers other than halogen-substituted alkylstyrene, the step (3) is performed after the end of the step (2).
9. The process according to claim 6, wherein in step (2),
the catalyst is selected from cuprous halides, preferably from cuprous chloride and/or cupric bromide; and/or the number of the groups of groups,
the ligand is selected from at least one of nitrogen-based ligands, preferably 2,2' -bipyridine, PMDETA, pyridine imine and DETA, TREN, CYCLAM.
10. The process according to claim 6, wherein in step (2),
the molar usage ratio of the catalyst to the ligand is 1 (1-10); and/or the number of the groups of groups,
the weight ratio of the total weight of the catalyst and the ligand to the product of step (1) is (0.08-0.4): 1, and/or,
the weight ratio of the styrene monomer to the product of the step (1) is (1-6): 1.
11. The process according to claim 6, wherein in the step (3),
carrying out the quaternary phosphonium reaction by using a P-containing compound represented by the formula (II):
in formula (II), R 1 、R 2 、R 3 Each independently selected from one of an alkyl group and an aryl group, preferably one of a C1-C10 alkyl group and a C6-C20 aryl group, more preferably one of a C1-C5 alkyl group and a C6-C10 aryl group; preferably, the weight ratio of the compound containing P shown in the formula (II) to the product of the step (2) is (0.5-3.5): 1, a step of;
and/or the number of the groups of groups,
the temperature of the quaternary phosphonium reaction is 50-150 ℃ and the time is 12-36 h;
and/or the number of the groups of groups,
performing post-treatment after the quaternary phosphonium reaction; preferably, the post-treatment comprises: washing sequentially by using an organic solvent I, an inorganic acid aqueous solution, water and an organic solvent II; more preferably, the organic solvent I is at least one selected from ethyl acetate, methyl formate, methyl acetate; and/or the inorganic acid aqueous solution is at least one selected from hydrochloric acid aqueous solution, sulfuric acid aqueous solution and nitric acid aqueous solution; and/or the organic solvent II is at least one selected from methanol, ethanol and propanol.
12. The method according to any one of claims 6 to 11, wherein the ion exchange treatment of step (4) is performed in an aqueous salt-containing solution; preferably, the salt is selected from at least one of halogenated salt, sodium formate, potassium formate, magnesium formate, calcium formate, sodium acetate, potassium acetate, magnesium acetate, calcium acetate; more preferably, the ion exchange treatment is carried out for 3 to 24 hours, preferably 5 to 10 hours.
13. A quaternary phosphonium salt catalyst for cycloaddition reaction obtained by the production process according to any one of claims 6 to 12.
14. The use of the quaternary phosphonium salt catalyst for cycloaddition according to any one of claims 1 to 5 or the quaternary phosphonium salt catalyst for cycloaddition obtained by the production process according to any one of claims 6 to 12 in the production of cyclic carbonates by cycloaddition of alkylene oxide/carbon dioxide, preferably for cycloaddition.
CN202210755158.4A 2022-06-30 2022-06-30 Quaternary phosphonium salt catalyst for cycloaddition reaction and preparation method and application thereof Pending CN117358307A (en)

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