阅读说明：本技术 金属钴络合的聚合物及其制备方法和应用 (Metal cobalt complex polymer and preparation method and application thereof ) 是由 邓伟侨 魏效农 张玲 李立 谢勇 高炜 姜磊 焦锋刚 于 2018-09-04 设计创作，主要内容包括：本申请公开了一种金属钴络合的聚合物,并且公开了所述聚合物的制备方法和应用。本申请所提供的聚合物可以在无溶剂无助催化剂的条件下催化二氧化碳与环状烷烃反应生成环状碳酸酯。本申请所提供的聚合物制备方法稳定可靠,步骤较短,有利于节约制备成本。本申请的聚合物作为催化剂时可以多次重复使用,且催化产率没有显著降低。(The application discloses a metal cobalt-complexed polymer, and discloses a preparation method and application of the polymer. The polymer provided by the application can catalyze the reaction of carbon dioxide and cyclic alkane to generate cyclic carbonate under the conditions of no solvent and no promoter. The polymer preparation method provided by the application is stable and reliable, has short steps, and is beneficial to saving the preparation cost. The polymer can be repeatedly used as a catalyst, and the catalytic yield is not obviously reduced.)

1. Metal cobalt complex polymer Co-CMP-A-N + R₃R₄R₅L-, wherein the polymer has a structural unit according to formula I:

wherein A is selected from alkylene of C2-C10; l is^-Selected from Cl^-、Br^-Or I^-；

X is selected from-CH₂CH₂-，-CH(CH₂)₄HC-or-C (CH)₄C-；

R₁Selected from-OAc, -Cl, -Br or-I;

R₂selected from hydrogen, halogen elements, C1-C10 alkyl and-NO₂And a group having a structural formula represented by formula (2):

wherein M is₂₁，M₂₂Independently selected from hydrogen, alkyl of C1-C5, aryl of C6-C18 and substituted aryl of C6-C18;

R₃，R₄，R₅is n-butyl, n-propyl or ethyl, and R₃，R₄，R₅The three groups may be the same or different.

L-is selected from Cl-, Br-or I-;

the polymerization degree of the polymer is 30-100.

2. The polymer of claim 1, wherein the polymer has a structural unit represented by formula I-1, a structural unit represented by formula I-2, a structural unit represented by formula I-3, a structural unit represented by formula I-4, a structural unit represented by formula I-5, a structural unit represented by formula I-6, or a structural unit represented by formula I-7:

3. a process for the preparation of a polymer according to claim 1 or 2, characterized in that it comprises at least the following steps:

a) the intermediate product I is prepared by the reaction of trihalophenol and dihaloalkane

The trihalophenol is at least one selected from compounds having the formula shown in formula II:

the dihaloalkane is selected from at least one of compounds having a chemical formula shown in formula III:

L4-A-L5 formula III

The intermediate product I is selected from at least one compound with a chemical formula shown in a formula IV:

wherein L is₁、L₂、L₃、L₄、L₅Independently selected from Cl, Br or I; l is₆Is L₄And/or L₅；

b) Reacting the intermediate product I with trialkylsilylethylene to prepare an intermediate product II;

the trialkylsilyacetylene is selected from at least one compound with a chemical formula shown in a formula V:

wherein R is₅₁、R₅₂And R₅₃Independently selected from C1-C4 straight or branched chain alkyl groups;

the intermediate product II has at least one of the compounds of the formula shown in formula VI:

c) reacting the intermediate product II with trialkylamine to prepare an intermediate product III;

the trialkylamine is at least one selected from compounds having the formula shown in formula VII:

the intermediate III is selected from at least one compound with a chemical formula shown as a formula VIII:

d) the intermediate product III and a cobalt-based salicylic acid complex Salen-Co-R₁Reacting to obtain the target polymer Co-CMP-A-N + R₃R₄R₅L^-；

The cobalt-based salicylic acid complex Salen-Co-R1 is selected from at least one compound having a chemical formula shown in formula IX:

preferably, the cobalt-based salicylic acid complex Salen-Co-R₁The preparation process comprises the following steps:

1) 5-bromosalicylaldehyde compounds, diamine compounds and cobalt salt compounds react to prepare an intermediate IV (Salen-Co);

the diamine compound is one of ethylenediamine, 1, 2-cyclohexanediamine or o-phenylenediamine;

the cobalt salt compound is cobalt acetate or cobalt dichloride;

the 5-bromosalicylaldehyde compound is selected from at least one compound with the chemical formula shown in formula XII:

the intermediate IV is selected from at least one compound with a chemical formula shown in a formula XIII:

2) the intermediate IV (Salen-Co) and R₁H reaction is carried out to obtain the cobalt-based salicylic acid complex Salen-Co-R₁；

The R is₁H is selected from CH₃COOH, HCl, HBr or HI;

preferably, the specific process of step a) includes dissolving the trihalophenol and the dihaloalkane in a solvent to form a mixed solution, adding a base to the mixed solution, and stirring to react under the protection of an inert gas to obtain an intermediate product I;

wherein the molar ratio of the trihalophenol, the dihaloalkane and the base is 1: (3-5): (5-6).

4. The synthesis method according to claim 3, wherein the solvent is anhydrous acetone, and the base is selected from anhydrous K₂CO₃Anhydrous Na₂CO₃Or anhydrous NaHCO₃The stirring reaction is carried out at the temperature of 50-70 ℃, and the stirring reaction time is 48-60 h.

5. The synthesis method according to claim 3, wherein the specific process of the step b) comprises dissolving the intermediate product I and the trialkylsilyacetylene in a solvent to form a mixed solution, adding a catalyst into the mixed solution, stirring and reacting under the protection of an inert gas, and then adding an alkali to remove the silylyne group to obtain an intermediate product II;

wherein the molar ratio of the intermediate product I to the trialkylsilyacetylene is 1: (3-4), wherein the molar ratio of the alkali to the intermediate product I is (1-1.5): 4;

preferably, the solvent is dry triethylamine and the catalyst is Pd (PPh)₃)₂Cl₂And CuI, the base being selected from anhydrous K₂CO₃Anhydrous Na₂CO₃The stirring reaction is carried out at the temperature of 60-80 ℃, the stirring reaction time is 24-36 h, preferably, the catalyst is used in an amount such that the molar ratio of CuI to intermediate product I is 1: (3-5) Pd (PPh)₃)₂Cl₂And intermediate I in a molar ratio of 1: (10-15).

6. The synthesis method of claim 3, wherein the specific process of step c) comprises dissolving the intermediate product II and trialkylamine in a solvent to form a mixed solution, and stirring the mixed solution under protection of inert gas and protection from light to react;

wherein the molar ratio of the intermediate compound II to the trialkylamine is 2: (3-5).

Preferably, the solvent is chloroform and acetonitrile in a volume ratio of 1: 1, the stirring reaction is carried out at the temperature of 60-80 ℃, and the stirring reaction time is 72-96 h.

7. The synthesis method according to claim 3, wherein the specific process of step d) comprises reacting the intermediate III with the cobalt-based salicylic acid complex Salen-Co-R₁Dissolving the mixture in ｃA solvent to form ｃA mixed solution, and stirring the mixed solution to react in the presence of ｃA catalyst to obtain ｃA target polymer Co-CMP-A-N + R₃R₄R₅L-；

Wherein the molar ratio of the intermediate product III to the cobalt-based salicylic acid complex Salen-Co-R1 is (2-4): 1;

preferably, the catalyst is Pd (PPh)₃)₄And CuI, wherein the dosage of the catalyst is satisfied, and the molar ratio of the CuI to the intermediate product III is 1: (5 to 10) Pd (PPh)₃)₄The molar ratio to intermediate III was 1: (20-30);

preferably, the solvent is anhydrous toluene and dry triethylamine in a volume ratio of 3: 1, the stirring reaction is carried out at 40-90 ℃, and the stirring reaction time is 60-90 hours.

8. Use of a polymer according to claim 1 or 2 or a polymer prepared using a method according to any one of claims 3 to 7, wherein the polymer is used to catalyse the reaction of carbon dioxide with an alkylene oxide to form a cyclic carbonate.

9. The use according to claim 8, wherein the polymer catalyzes the reaction of carbon dioxide with alkylene oxide to form cyclic carbonate by the following steps:

mixing the polymer and the alkylene oxide at a mass ratio of 1: (10-50) feeding, wherein the pressure of carbon dioxide is 0.1-6.0 MPa, and the temperature is 25-120 ℃ and stirring reaction is carried out for 1-72 h to obtain the corresponding cyclic carbonate.

10. Use according to claim 9, characterized in that the cycloalkanes are chosen from ethylene oxide, propylene oxide, epichlorohydrin, 1, 2-butylene oxide, 1, 2-cyclohexene oxide, phenyl ethylene oxide, propylene oxide, cyclohexene oxide, 1, 2-dodecane oxide, 1, 2-epoxy-5-hexene, 2, 3-epoxypropylpropargyl ether, 1,2,7, 8-diepoxyoctane, 1, 2-epoxy-2-methylpropane, trans-2, 3-butylene oxide, trans-1, 2-diphenylethylene oxide, 1-allyloxy-2, 3-propylene oxide, 1, 2-epoxy-3-phenoxypropane, 2-fluoroethylene oxide, 2, 2-difluoroethylene oxide or 1,1, 1-trifluoro-2, 3-propylene oxide.

Technical Field

The application relates to a metal cobalt complex polymer and a preparation method and application thereof, belonging to the field of organic chemistry.

Background

CO₂Gases are the most prominent greenhouse gases in human activities. With the increasing severity of the greenhouse effect, people pay more and more attention to the treatment and absorption of carbon dioxide. Reduction of CO in the atmosphere at present₂There are two main categories of methods: adsorption capture and catalytic conversion. Namely, the organic matter is converted by fixing or adopting a chemical catalytic conversion method, and the high-efficiency implementation of the processes has great significance for the healthy development of the human society. In the field of chemical catalytic conversion, using CO₂The synthesis of cyclic carbonates by cycloaddition with cyclic alkanes is one of the most important routes, by which CO is introduced₂To organic chemicals of higher commercial utility.

Ethylene Carbonate (EC), also known as 1, 3-dioxolanone or Ethylene Carbonate, is a superior organic high boiling point solvent and an intermediate for organic chemical synthesis, as well as other cyclic carbonates, is a basic raw material in organic chemical industry, and is widely used in the fields of printing and dyeing, textiles, electrochemistry, polymer synthesis, and the like. In recent years, research shows that ethylene carbonate can be used for high-energy battery electrolyte with high added value, and synthesis of dimethyl carbonate (DMC) and Ethylene Glycol (EG). More researches show that 3,3,3-trifluoro propylene carbonate (TFPC for short) can replace linear carbonate to obtain better discharge capacity and cycle life, and can greatly improve the safety, voltage resistance and charging cycle performance of the battery. These show the application prospects of cyclic carbonates and the strong demand of the market for them. Ethylene oxide and derivatives thereof and carbon dioxide in the presence of a catalystCan generate corresponding cyclic carbonate under the action, is beneficial to solving CO₂The pollution problem caused by gas emission can supplement the demand of the market for the cyclic carbonate. It is worth noting that most of the currently reported reaction methods require relatively harsh reaction conditions such as high temperature and high pressure (155-200 ℃, 6-9 MPa) and long reaction time, so that industrial production is difficult to carry out, and ethylene oxide is gas at normal temperature and is easy to polymerize, so that a class of reaction methods capable of realizing CO under relatively mild conditions is sought₂The high-efficiency catalyst for catalytic conversion is a problem to be solved urgently at present.

Disclosure of Invention

According to one aspect of the present application there is provided a metallic cobalt complexed polymer having structural units according to formula I:

wherein A is selected from C₂～C₁₀An alkylene group of (a); l is^-Selected from Cl^-、Br^-Or I^-；

X is selected from-CH₂CH₂-，-CH(CH₂)₄HC-or-C (CH)₄C-；

R₁Selected from-OAc, -Cl, -Br or-I;

R₂selected from hydrogen, halogen elements, C₁～C₁₀Alkyl of-NO₂And a group having a structural formula represented by formula (1):

wherein M is₁₁，M₂₂Independently selected from hydrogen, C₁～C₅Alkyl of (C)₆～C₁₈Aryl of (C)₆～C₁₈Substituted aryl of (a);

R₃，R₄，R₅is n-butyl, n-propyl or ethyl, and R₃，R₄，R₅The three groups may be the same or different.

The polymerization degree of the polymer is 30-100.

Preferably, R₁Any one selected from the group consisting of-OAc, -Cl, -Br and-I.

Preferably, R₂Selected from the group consisting of-H, -tBu, -iBu, -NO₂，-Cl，-CH₂NEt₂and-CH₂N(Bn)Et₂Any one of Br.

Preferably, R₃、R₄、R₅Are the same group. Further preferably, R₃、R₄、R₅Are all n-butyl.

Preferably, the polymer has a structural unit shown as a formula I-1, a structural unit shown as a formula I-2, a structural unit shown as a formula I-3, a structural unit shown as a formula I-4, a structural unit shown as a formula I-5, a structural unit shown as a formula I-6 or a structural unit shown as a formula I-7:

according to another aspect of the present application, a process for the preparation of said polymer is provided, comprising at least the following steps:

a) the intermediate product I is prepared by the reaction of trihalophenol and dihaloalkane

The trihalophenol is at least one selected from compounds having the formula shown in formula II:

the dihaloalkane is selected from at least one of compounds having a chemical formula shown in formula III:

L₄-A-L₅formula III

The intermediate product I is selected from at least one compound with a chemical formula shown in a formula IV:

L₁、L₂、L₃、L₄、L₅independently selected from Cl, Br or I; l is₆Is L₄And/or L₅；

b) Reacting the intermediate product I with trialkylsilylethylene to prepare an intermediate product II;

the trialkylsilyacetylene is selected from at least one compound with a chemical formula shown in a formula V:

wherein R is₅₁、R₅₂And R₅₃Independently selected from C1-C4 straight or branched chain alkyl groups;

the intermediate product II has at least one of the compounds of the formula shown in formula VI:

c) reacting the intermediate product II with trialkylamine to prepare an intermediate product III;

the trialkylamine is at least one selected from compounds having the formula shown in formula VII:

the intermediate III is selected from at least one compound with a chemical formula shown as a formula VIII:

d) the intermediate product III and a cobalt-based salicylic acid complex Salen-Co-R₁Reacting to obtain the polymer Co-CMP-A-N⁺R₃R₄R₅L^-；

The cobalt-based salicylic acid complex Salen-Co-R₁At least one selected from compounds having the formula shown in formula IX:

preferably, the cobalt-based salicylic acid complex Salen-Co-R₁The preparation process comprises the following steps:

1) reacting the 5-bromosalicylaldehyde compound with a diamine compound and a cobalt salt to obtain an intermediate IV;

the diamine compound is selected from one of ethylenediamine, 1, 2-cyclohexanediamine or o-phenylenediamine;

the cobalt salt compound is selected from Co (OAc)₂And CoCl₂One of (1);

the 5-bromosalicylaldehyde compound is selected from at least one compound with the chemical formula shown in formula XII:

the intermediate IV is selected from at least one compound with a chemical formula shown in a formula XIII:

2) the intermediates IV and R₁H reaction is carried out to obtain the cobalt-based salicylic acid complex Salen-Co-R₁。

The R is₁H is CH₃COOH, HCl, HBr or HI.

Preferably, the specific process of step a) includes dissolving the trihalophenol and the dihaloalkane in a solvent to form a mixed solution, adding a base to the mixed solution, and stirring under the protection of an inert gas to react to obtain an intermediate product I,

wherein the molar ratio of the trihalophenol, the dihaloalkane and the base is 1: (3-5): (5-6).

Preferably, the solvent is dry acetone, the base is one or more of anhydrous potassium carbonate, anhydrous sodium carbonate and anhydrous sodium bicarbonate, the stirring reaction is carried out at 50-70 ℃, and the stirring reaction time is 48-60 h.

Preferably, the specific process of step b) includes dissolving the intermediate product I and the trialkylsilyacetylene in a solvent to form a mixed solution, adding a catalyst into the mixed solution, stirring for reaction under the protection of an inert gas, adding an alkali to remove the silylynyl group to obtain an intermediate product II,

wherein the molar ratio of the intermediate product I to the trialkylsilyacetylene is 1: (3-4), wherein the molar ratio of the alkali to the intermediate product I is (1-1.5): 4.

preferably, the solvent is dry triethylamine and the catalyst is Pd (PPh)₃)₂Cl₂And CuI, wherein the alkali is one or more of anhydrous potassium carbonate and anhydrous sodium carbonate, the stirring reaction is carried out at the temperature of 60-80 ℃, the stirring reaction time is 24-36 h, preferably, the catalyst is used in an amount meeting the requirement that the molar ratio of the CuI to the intermediate product I is 1: (3-5) Pd (PPh)₃)₂Cl₂And intermediate I in a molar ratio of 1: (10-15).

Preferably, the specific process of step c) includes dissolving the intermediate product II and trialkylamine in a solvent to form a mixed solution, and stirring and reacting under protection of inert gas and in the dark to obtain an intermediate product III;

wherein the molar ratio of the intermediate product II compound to the trialkylamine is 2: (3-4).

Preferably, the solvent is chloroform and acetonitrile in a volume ratio of 1: 1, the stirring reaction is carried out at the temperature of 60-80 ℃, and the stirring reaction time is 72-96 h.

Preferably, the specific process of step d) comprises reacting said intermediate III with said cobalt-based salicylic acid complex Salen-Co-R₁Dissolving the mixture in ｃA solvent to form ｃA mixed solution, and stirring the mixed solution to react in the presence of ｃA catalyst to obtain ｃA target polymer Co-CMP-A-N⁺R₃R₄R₅L^-；

Wherein the intermediate product III and the cobalt-based salicylic acid complex Salen-Co-R₁The molar ratio of (2-4): 1.

preferably, the catalyst is Pd (PPh)₃)₄And CuI, wherein the dosage of the catalyst is satisfied, and the molar ratio of the CuI to the intermediate product III is 1: (5 to 10) Pd (PPh)₃)₄And intermediate III in a molar ratio of 1: (20-30).

Preferably, the solvent is anhydrous toluene and anhydrous triethylamine in a volume ratio of 3: 1, the stirring reaction is carried out at 40-90 ℃, and the stirring reaction time is 60-90 hours.

According to another aspect of the present application, there is provided the use of the polymer or a polymer prepared using the method, wherein the polymer is used to catalyse the reaction of carbon dioxide with an alkylene oxide to cyclic carbonate.

Preferably, the polymer catalyzes a reaction of carbon dioxide and alkylene oxide to form a cyclic carbonate, and the method comprises:

mixing the catalyst and alkylene oxide according to the mass ratio of 1: (10-50) feeding, wherein the pressure of carbon dioxide is 0.1-6.0 MPa, and the temperature is 25-120 ℃ and stirring reaction is carried out for 1-48 h to obtain the corresponding cyclic carbonate.

The ranges of the feeding ratios of the substances mentioned in the invention, including the mass ratio, the volume ratio and the molar ratio, all include any point or range within the range of the ratio.

Catalysis of alkylene oxides with CO with said catalysts₂The reaction formula (c) is as follows:

the reaction process in the formula does not need to add any solvent or cocatalyst; the molar ratio of the alkylene oxide to the catalyst provided by the invention is about (100-2000): 1; in the formula R₆＝-H、-CH₃、-CH₂CH₃、-CH₂CH₂Cl、-CH₂CH₂CH₂CH₃、-Ph、-CH₂Ph, -F or-CF₃And so on.

In this application, C₂～C₁₀、C₁～C₅、C₆～C₁₈And the like refer to the number of carbon atoms involved. Such as "C₁～C₅The "alkyl group" refers to an alkyl group having 1 to 5 carbon atoms.

In the present application, an "alkylene group" is a group formed by losing any two hydrogen atoms on the molecule of an alkane compound. An "alkyl" group is a group formed by the loss of any one hydrogen atom from the molecule of an alkane compound. The alkane compound comprises straight-chain alkane, branched-chain alkane, cycloalkane and cycloalkane with branched chain.

In the present application, "aryl" is a group formed by losing one hydrogen atom on an aromatic ring on an aromatic compound molecule; such as p-tolyl, formed by toluene losing the hydrogen atom para to the methyl group on the phenyl ring.

In the present application, the "halogen" refers to at least one of fluorine, chlorine, bromine and iodine.

As used herein, the term "substituted aryl" refers to an aryl group wherein at least one hydrogen atom is replaced with a substituent selected from the group consisting of halogen, -NO₂And a group having a structural formula represented by formula (2).

The beneficial effects that this application can produce include:

1) the catalyst provided by the application can catalyze the reaction of carbon dioxide and cyclic alkane to generate cyclic carbonate under the condition of no solvent or cocatalyst.

2) The preparation method of the catalyst provided by the application is stable and reliable, has short steps, and is beneficial to saving the preparation cost.

3) The catalyst of the present application can be reused many times.

Drawings

FIG. 1 shows 1,3, 5-tribromo-2- [ (4-bromobutyl) oxy]Process for preparation of benzene¹H NMR；

FIG. 2 shows 1,3, 5-tribromo-2- [ (4-bromobutyl) oxy]Process for preparation of benzene¹³C NMR；

FIG. 3 shows 2- [ (4-bromobutyl) oxy]Of-1, 3, 5-triethynylbenzenes¹H NMR；

FIG. 4 shows 2- [ (4-bromobutyl) oxy]Of-1, 3, 5-triethynylbenzenes¹³C NMR；

FIG. 5 is a drawing of N, N, N-tributyl-4- (2,4, 6-triethynylphenoxy) butane-1-aminylbromide¹H NMR；

FIG. 6 is a drawing of N, N, N-tributyl-4- (2,4, 6-triethynylphenoxy) butane-1-aminylbromide¹³C NMR；

FIG. 7 is an FT-IR of a catalyst monomer molecule herein;

FIG. 8 shows 1,3, 5-tribromo-2- [ (6-bromohexyl) oxy]Process for preparation of benzene¹H NMR；

FIG. 9 shows 1,3, 5-tribromo-2- [ (6-bromohexyl) oxy]Process for preparation of benzene¹³C NMR；

FIG. 10 shows 2- [ (6-bromohexyl) oxy]Of-1, 3, 5-triethynylbenzenes¹H NMR；

FIG. 11 shows 2- [ (6-bromohexyl) oxy]Of-1, 3, 5-triethynylbenzenes¹³C NMR；

FIG. 12 is a drawing of N, N, N-tributyl-6- (2,4, 6-triethynylphenoxy) hexane-1-aminylbromide¹H NMR；

FIG. 13 is a drawing of N, N, N-tributyl-6- (2,4, 6-triethynylphenoxy) hexane-1-aminylbromide¹³C NMR；

FIG. 14 is an FT-IR of a catalyst monomer molecule herein;

FIG. 15 is an FT-IR of a catalyst monomer molecule herein;

FIG. 16 shows 1,3, 5-tribromo-2- [ (8-bromooctyl) oxy group]Process for preparation of benzene¹H NMR；

FIG. 17 shows 1,3, 5-tribromo-2- [ (8-bromooctyl) oxy group]Process for preparation of benzene¹³C NMR；

FIG. 18 shows 2- [ (8-bromooctyl) oxy group]Of-1, 3, 5-triethynylbenzenes¹H NMR；

FIG. 19 is 2- [ (8-bromooctyl) oxy group]Of-1, 3, 5-triethynylbenzenes¹³C NMR；

FIG. 20 is a drawing showing the preparation of N, N, N-tributyl-8- (2,4, 6-triethynylphenoxy) octane-1-aminylbromide¹H NMR；

FIG. 21 is a drawing showing the preparation of N, N, N-tributyl-8- (2,4, 6-triethynylphenoxy) octane-1-aminylbromide¹³C NMR；

FIG. 22 is an FT-IR of a catalyst monomer molecule herein;

FIG. 23 is H-NMR of propylene carbonate;

FIG. 24 is C-NMR of propylene carbonate;

FIG. 25 is H-NMR of ethylene carbonate;

FIG. 26 is C-NMR of ethylene carbonate;

FIG. 27 is H-NMR of 4-chloro-1, 3-dioxolane-2-one;

FIG. 28 is a C-NMR of 4-chloro-1, 3-dioxolane-2-one;

FIG. 29 is H-NMR of 4-ethyl-1, 3-dioxolane-2-one;

FIG. 30 is a C-NMR of 4-ethyl-1, 3-dioxolane-2-one;

FIG. 31 is the H-NMR of 4-butyl-1, 3-dioxolane-2-one;

FIG. 32 is C-NMR of 4-butyl-1, 3-dioxolane-2-one;

FIG. 33 is a H-NMR of 4-fluoro-1, 3-dioxolan-2-one;

FIG. 34 is a C-NMR of 4-fluoro-1, 3-dioxolan-2-one;

FIG. 35 is H-NMR of 4-phenyl-1, 3-dioxolane-2-one;

FIG. 36 is a C-NMR of 4-phenyl-1, 3-dioxolane-2-one;

FIG. 37 is H-NMR of 4-trifluoromethyl-1, 3-dioxolan-2-one;

FIG. 38 is a C-NMR of 4-trifluoromethyl-1, 3-dioxolan-2-one.

Detailed Description

The present application will be described in detail with reference to examples, but the present application is not limited to these examples.

Unless otherwise specified, the raw materials and catalysts in the examples of the present application were all purchased commercially.

In the following examples, the structure shown by formula XI (hereinafter abbreviated as Salen-Co-R)₁) The compound is prepared by adopting a synthesis method in Chinese patent CN 103381370B.

The analysis method in the examples of the present application is as follows:

¹HNMR and¹³c NMR was measured using a BRUKER MERCURY-PLUS 400-MHz type spectrometer instrument.

FT-IR was measured using an Agilent Cary630 Fourier transform Infrared Spectroscopy instrument.