Application of diquaternary ammonium salt catalyst containing phenyl borate in preparing five-membered ring carbonate

Abstract

The invention relates to an application of a catalyst containing phenyl borate diquaternary ammonium salt for preparing five-membered ring carbonate. The catalyst contains a phenyl borate structure in the structure of the catalyst containing phenyl borate diquaternary ammonium salt, and the oxygen atom and the quaternary ammonium salt are connected by a carbon chain. Under the catalytic condition of the phenyl borate diquaternary ammonium salt, carbon dioxide and an epoxy compound are used to prepare the five-membered ring carbonate, the amount of the catalyst is 0.01-5% of the mass of the epoxy compound, the reaction temperature is 60-200 DEG C, the reaction pressure is 0.1-20MPa, the reaction time is 1-100h, and the five-membered ring carbonate product with a yield and purity greater than 98% can be obtained. The five-membered ring carbonate is prepared by catalysis of the present invention without adding other co-catalysts, and has the advantages of easy availability of catalyst raw materials, simple preparation method, stable structure, high catalytic efficiency, and recyclable application.

Description

Technical Field

[0001] The invention belongs to the technical field of catalyst application, and in particular relates to the application of a diquaternary ammonium salt catalyst containing phenyl borate in preparing five-membered ring carbonate. Background Art

[0002] Reducing the amount of carbon dioxide can effectively prevent the rise in global surface temperature, melting of glaciers and abnormal climate. Countries around the world pay close attention to the green utilization technology of carbon dioxide, develop green, high-tech fine chemical industry chains, and increase the added value of products. The reaction of carbon dioxide and alkylene oxide to prepare cyclic carbonates is an effective carbon fixation method and one of the important ways to recycle carbon dioxide. Cyclic carbonates are important industrial raw materials and can be used as battery electrolytes, polar solvents and chemical intermediates. Due to the thermodynamic stability and kinetic inertness of carbon dioxide, the key to the synthesis of cyclic carbonates from carbon dioxide and alkylene oxide is how to activate carbon dioxide with relatively stable thermodynamic properties.

[0003]

[0004] The catalysts reported for synthesizing five-membered ring carbonates (as shown in Scheme 1) from carbon dioxide and epoxy compounds are mainly: alkali metal and alkali metal halide catalysts, such as LiBr (Tetrahedron, 2005, 61, 1835); quaternary ammonium salt and quaternary phosphonium salt catalysts, such as molten tetrabutylammonium bromide (Organic Letters, 2002, 4 (15): 2561-2563.); ionic liquid catalysts, such as 1-alkyl-3-methylimidazolium salts ([Cn-min]X) (Chemical Communications, 2003, 39 (7): 896-897.); metal complex catalysts, such as Salen ligands (Journal of American Chemical Society, 2001, 123 (46): 11498-11499.) and other types. Although the above catalysts show better catalytic activity, there are also some problems. On the one hand, the above catalysts require the addition of other co-catalysts to participate in the reaction. On the other hand, in the process of scale-up preparation, there are still problems such as high synthesis cost, complex process, and low scale-up catalytic efficiency, which seriously restrict the progress of industrialization. Therefore, it is particularly important to choose high-efficiency and low-cost catalysts and new catalysts and reaction systems. Summary of the invention

[0005] In order to overcome the shortcomings of the prior art, the present invention provides an application of a diquaternary ammonium salt catalyst containing phenyl borate for preparing a five-membered ring carbonate. When the present invention is used to catalyze carbon dioxide and an epoxy compound to prepare a five-membered ring carbonate, no other co-catalyst needs to be added, the raw materials for catalyst synthesis are cheap and easily available, and the preparation method is simple.

[0006] To achieve the above object, the technical solution adopted by the present invention is:

[0007] The invention discloses an application of a bis-quaternary ammonium salt catalyst containing phenyl borate for preparing a five-membered ring carbonate. Under the condition that the bis-quaternary ammonium salt catalyst containing phenyl borate is used as a single catalyst, carbon dioxide and an epoxide react to prepare the five-membered ring carbonate.

[0008] Preferably, the structure of the phenyl borate diquaternary ammonium salt catalyst is a phenyl borate structure, and the oxygen atom and the quaternary ammonium salt are connected by a carbon chain.

[0009] Preferably, the structural formula of the diquaternary ammonium salt catalyst containing phenyl borate is as shown in (I):

[0010]

[0011] Wherein R1, R2, and R3 are respectively one of CH3, CH3CH2, CH3CH2CH2, (CH3)2CH, CH3CH2CH2CH2, and (CH3)3C groups; R1, R2, and R3 may be the same group or different groups; n represents the number of the same unit carbon; and X represents one of fluorine, chlorine, bromine, and iodine.

[0012] The catalyst is prepared by reacting phenylboric acid with a tertiary amine containing a terminal hydroxyl group to form phenylboric acid ester, and the phenylboric acid ester containing a tertiary amine is reacted with a halogenated hydrocarbon to form a phenylboric acid ester diquaternary ammonium salt catalyst, which can be prepared by referring to the method reported in the literature (Journal of Organometallic Chemistry, 2019, 142, 891, 72-77; Macromolecular Rapid Communications, 2013, 34 (19), 1580-1584) or by a similar method.

[0013] Preferably, the amount of the catalyst used is 0.01 to 5% of the mass of the epoxy compound.

[0014] Preferably, the reaction temperature is 60-200° C., the reaction pressure is 0.1-20 MPa, and the reaction time is 1-100 h.

[0015] Preferably, the amount of the catalyst used is 0.1 to 2% of the mass of the epoxy compound.

[0016] Preferably, the reaction temperature is 100-150° C., the reaction pressure is 10-15 MPa, and the reaction time is 6-13 h.

[0017] Preferably, the catalyst is one of the following: 2,2'-((phenylboranediyl)dioxy)bis(N,N,N-trimethylethyl quaternary ammonium bromide), 2,2'-((phenylboranediyl)dioxy)bis(N-ethyl-N,N-dimethylethyl quaternary ammonium chloride), 3,3'-((phenylboranediyl)dioxy)bis(N,N-dimethyl-N-propylpropane-1-iodide quaternary ammonium salt), 3,3'-((phenylboranediyl)dioxy)bis(N,N-dimethyl-N-propylpropane-1-iodide quaternary ammonium salt bis(N,N-dimethylbutane-1-quaternary ammonium bromide), N,N'-(((phenylboranediyl)dioxy))bis(propane-3,1-diyl))bis(N,N-dimethylbutane-1-quaternary ammonium chloride), N,N'-(((phenylboranediyl)dioxy))bis(propane-3,1-diyl))bis(N,N-dimethylbutane-1-quaternary ammonium chloride), N,N'-(((phenylboranediyl)dioxy))bis(propane-3,1-diyl))bis(N,N-dimethylpentane-1-quaternary ammonium iodide).

[0018] Preferably, the epoxy compound is one of ethylene oxide, propylene oxide, epichlorohydrin, di-4-epoxycyclohexane, 2,3-butylene oxide, and 2-phenylpropylene oxide.

[0019] Compared with the prior art, the beneficial effects of the present invention are:

[0020] The catalytic preparation of the five-membered ring carbonate by the present invention does not require the addition of other co-catalysts, and has the advantages of easy availability of catalyst raw materials, simple preparation method, stable structure, high catalytic efficiency, and recyclability. DETAILED DESCRIPTION

[0021] The present invention is further described below in conjunction with specific embodiments, but the scope of the present invention is not limited thereto. A person skilled in the art can and should know that any simple change or replacement based on the essential spirit of the present invention should fall within the scope of protection required by the present invention.

[0022] Example 1

[0023] 0.2g of catalyst 2,2'-((phenylboranediyl)dioxy)bis(N,N,N-trimethylethyl quaternary ammonium bromide) was placed in a stainless steel autoclave, and replaced with nitrogen / carbon dioxide three times. Then 100g of 2,3-butylene oxide was added to the autoclave, and the system pressure was maintained at 5MPa. Stirring was started. The temperature of the autoclave was raised to 110°C, and stirring was maintained for 8h. The reaction was stopped and cooled to room temperature. The product was collected with a yield of 99.6% and a purity of 99.0%.

[0024] Example 2

[0025] 0.1g of catalyst 2,2'-((phenylboranediyl)dioxy)bis(N-ethyl-N,N-dimethylethyl quaternary ammonium chloride) was placed in a stainless steel autoclave, and replaced with nitrogen / carbon dioxide three times. Then 40g of propylene oxide was added to the autoclave, and the system pressure was maintained at 6MPa. Stirring was started. The temperature of the autoclave was raised to 100°C, and stirring was maintained for 5h. The reaction was stopped and cooled to room temperature. The product was collected with a yield of 99% and a purity of 98.7%.

[0026] Example 3

[0027] 0.3g of catalyst 3,3'-((phenylboranediyl)dioxy)bis(N,N-dimethyl-N-propylpropane-1-iodide quaternary ammonium salt) was placed in a stainless steel autoclave, replaced with nitrogen / carbon dioxide three times, and then 100g of epichlorohydrin was added to the autoclave. The system pressure was maintained at 4MPa and stirring was started. The temperature of the autoclave was raised to 100°C and stirring was maintained for 6h. The reaction was stopped and cooled to room temperature. The product was collected with a yield of 99% and a purity of 99.1%.

[0028] Example 4

[0029] 0.1g of catalyst 3,3'-((phenylboranediyl)dioxy)bis(N,N-dimethyl-N-propylpropane-1-quaternary ammonium bromide salt) was placed in a stainless steel autoclave, replaced with nitrogen / carbon dioxide three times, and then 100g of di-4-epoxycyclohexane was added to the autoclave. The system pressure was maintained at 10MPa and stirring was started. The temperature of the autoclave was raised to 100°C and stirring was maintained for 8h. The reaction was stopped and cooled to room temperature. The product was collected with a yield of 98.3% and a purity of 98.6%.

[0030] Example 5

[0031] 1.0g catalyst N,N'-(((phenylboranediyl)dioxy))bis(propane-3,1-diyl))bis(N,N-dimethylbutane-1-chlorinated quaternary ammonium salt) was placed in a stainless steel autoclave, replaced with nitrogen / carbon dioxide three times, and then 100g of 2-phenylpropylene oxide was added to the autoclave. The system pressure was maintained at 6MPa and stirring was started. The temperature of the autoclave was raised to 120°C and stirring was maintained for 8h. The reaction was stopped and cooled to room temperature. The product was collected with a yield of 99.3% and a purity of 99.1%.

[0032] Example 6

[0033] 0.4g of catalyst N,N'-(((phenylboranediyl)dioxy)bis(propane-3,1-diyl))bis(N,N-dimethylpentane-1-iodide quaternary ammonium salt) was placed in a stainless steel autoclave, and replaced with nitrogen / carbon dioxide three times. Then 100g of epoxidized soybean oil was added to the autoclave, the system pressure was maintained at 5MPa, and stirring was started. The temperature of the autoclave was raised to 120°C, and stirring was maintained for 6h, the reaction was stopped, and the reaction was cooled to room temperature. The product was collected with a yield of 99.0% and a purity of 99.3%.

[0034] Example 7

[0035] 0.2g of catalyst 2,2'-((phenylboranediyl)dioxy)bis(N,N,N-trimethylethyl quaternary ammonium bromide) was placed in a stainless steel autoclave, and replaced with nitrogen / carbon dioxide three times. Then 100g of 1,4-butanediol diglycidyl ether was added to the autoclave, the system pressure was maintained at 3MPa, and stirring was started. The temperature of the autoclave was raised to 110°C, and stirring was maintained for 7h, the reaction was stopped, and the reaction was cooled to room temperature. The product was collected with a yield of 99.2% and a purity of 98.9%.

[0036] Example 8

[0037] 0.1g of catalyst 2,2'-((phenylboranediyl)dioxy)bis(N-ethyl-N,N-dimethylethyl quaternary ammonium chloride) was placed in a stainless steel autoclave, and replaced with nitrogen / carbon dioxide three times. Then 100g of ethylene oxide was added to the autoclave, and the system pressure was maintained at 2MPa. Stirring was started. The temperature of the autoclave was raised to 130°C, and stirring was maintained for 8h. The reaction was stopped and cooled to room temperature. The product was collected with a yield of 99.0% and a purity of 99.4%.

[0038] Finally, it should be noted that the above embodiments are only used to illustrate rather than limit the technical solutions of the present invention. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that the present invention can still be modified or replaced by equivalents. Any modification or partial replacement that does not depart from the spirit and scope of the present invention should be included in the scope of the claims of the present invention.

Claims

1. An application of a diquaternary ammonium salt catalyst containing phenyl borate for preparing a five-membered ring carbonate, characterized in that: Under the condition that diquaternary ammonium salt of phenyl borate is used as a single catalyst, carbon dioxide reacts with an epoxy compound to prepare a five-membered ring carbonate; the structural formula of the diquaternary ammonium salt of phenyl borate catalyst is shown as (I): ； Wherein R1, R2, and R3 are respectively one of CH3, CH3CH2, CH3CH2CH2, (CH3)2CH, CH3CH2CH2CH2, and (CH3)3C groups; n represents the number of carbon atoms in the same unit, and X represents one of fluorine, chlorine, bromine, and iodine.

2. The use of the phenyl borate diquaternary ammonium salt catalyst for preparing five-membered ring carbonate according to claim 1, characterized in that: The amount of the catalyst used is 0.01 to 5% of the mass of the epoxy compound.

3. The use of the phenyl borate diquaternary ammonium salt catalyst for preparing five-membered ring carbonate according to claim 2, characterized in that: The reaction temperature is 60-200° C., the reaction pressure is 0.1-20 MPa, and the reaction time is 1-100 h.

4. The use of the phenyl borate diquaternary ammonium salt catalyst for preparing five-membered ring carbonate according to claim 2, characterized in that: The amount of catalyst used is 0.1 to 2% of the mass of the epoxy compound.

5. The use of the diquaternary ammonium salt catalyst containing phenyl borate ester for preparing five-membered ring carbonate according to claim 4, characterized in that: The reaction temperature is 100-150°C, the reaction pressure is 10-15MPa, and the reaction time is 6-13h.

6. The use of the diquaternary ammonium salt catalyst containing phenyl borate ester for preparing five-membered ring carbonate according to claim 1, characterized in that: The catalyst is one of the following: 2,2'-((phenylboranediyl)dioxy)bis( N , N , N -trimethylethyl quaternary ammonium bromide), 2,2'-((phenylboranediyl)dioxy)bis( N -ethyl- N , N -dimethylethyl chloride quaternary ammonium salt), 3,3'-((phenylboranediyl)dioxy)bis( N , N -Dimethyl- N -propylpropane-1-iodide quaternary ammonium salt), 3,3'-((phenylboranediyl)dioxy)bis( N , N -Dimethyl- N -propylpropane-1-bromide quaternary ammonium salt), N , N '-(((phenylboranediyl)dioxy))bis(propane-3,1-diyl))bis( N , N -dimethylbutane-1-quaternary ammonium chloride), N , N '-(((phenylboranediyl)dioxy))bis(propane-3,1-diyl))bis( N , N -dimethylbutane-1-quaternary ammonium chloride), N , N '-(((phenylboranediyl)dioxy)bis(propane-3,1-diyl))bis( N , N -dimethylpentane-1-iodide quaternary ammonium salt).

7. The use of the diquaternary ammonium salt catalyst containing phenyl borate ester for preparing five-membered ring carbonate according to claim 6, characterized in that: The epoxy compound is one of ethylene oxide, propylene oxide, epichlorohydrin, di-4-epoxycyclohexane, 2,3-butylene oxide, 2-phenylpropylene oxide, epoxy soybean oil, and 1,4-butanediol diglycidyl ether.

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