阅读说明：本技术 一种鎓盐有机催化剂及其制备方法和应用 (Onium salt organic catalyst and preparation method and application thereof ) 是由 伍广朋 郑煜佳 杨贯文 李博 于 2019-11-15 设计创作，主要内容包括：本发明公开了一种鎓盐有机催化剂,具有式(I)所示的结构,其中L为脲或硫脲基团；M为带有电荷的鎓盐结构；y表示脲或硫脲基团的个数,可以是1到100000之间的任意整数；z表示鎓盐基团的个数,可以是1到100000之间的任意整数。本发明还公开了一种鎓盐有机催化剂的制备方法：将任一反应原料W-1和任一反应原料W-2在溶液中混合搅拌,室温下搅拌1～500小时后,去除杂质和有机溶剂,得到鎓盐有机催化剂。本发明还公开了一种鎓盐有机催化剂在制备有机小分子和大分子聚合物中的应用。本发明提供的鎓盐有机催化剂具有易于称量、催化活性高、反应可控等优点；本发明提供的制备方法简单,产率高。(The invention discloses an onium salt organic catalyst, which has a structure shown in a formula (I), wherein L is a urea or thiourea group; m is an onium with a chargeA salt structure; y represents the number of urea or thiourea groups and can be any integer between 1 and 100000; z represents the number of onium salt groups and may be any integer between 1 and 100000. The invention also discloses a preparation method of the onium salt organic catalyst, which comprises the following steps: any one of the reaction raw materials W 1 And any one of the reaction materials W 2 And (3) mixing and stirring the mixture in the solution, and removing impurities and organic solvent after stirring the mixture for 1 to 500 hours at room temperature to obtain the onium salt organic catalyst. The invention also discloses application of the onium salt organic catalyst in preparation of organic micromolecule and macromolecular polymers. The onium salt organic catalyst provided by the invention has the advantages of easy weighing, high catalytic activity, controllable reaction and the like; the preparation method provided by the invention is simple and high in yield.)

1. An onium salt organic catalyst having a structure represented by formula (I):

wherein L is a urea or thiourea group; m is an onium salt structure with a charge; y represents the number of urea or thiourea groups and can be any integer between 1 and 100000; z represents the number of onium salt groups and may be any integer between 1 and 100000;

when y is 1, K is selected from unsubstituted or substituted C₃-C₁₈Alkyl radical, C₃-C₁₈Cycloalkyl radical, C₃-C₁₈Alkenyl radical, C₃-C₁₈Alkynyl, C₇-C₁₈Aryl radical, C₃-C₁₈Heterocyclyl or C₇-C₁₈One or a combination of at least two of the heteroaromatic groups; the substituent is selected from one or a combination of at least two of halogen atoms, branched or straight chain alkyl with 1 to 10 carbon atoms, branched or straight chain alkoxy with 1 to 10 carbon atoms, branched or straight chain cycloalkyl with 3 to 10 carbon atoms, aryl with 6 to 18 carbon atoms and heteroaryl with 5 to 18 carbon atoms;

when y is not less than 2, K is selected from unsubstituted or substituted C₁-C₁₈Alkyl radical, C₃-C₁₈Cycloalkyl radical, C₃-C₁₈Alkenyl, C3-C₁₈Alkynyl, C₆-C₁₈Aryl radical, C₃-C₁₈Heterocyclyl or C₅-C₁₈One or a combination of at least two of the heteroaromatic groups; the substituents being selected from halogen atoms, branched chains having 1 to 10 carbon atomsOr one or a combination of at least two of a linear hydrocarbon group, a branched or linear alkoxy group of 1 to 10 carbon atoms, a branched or linear cycloalkyl group of 3 to 10 carbon atoms, an aryl group of 6 to 18 carbon atoms, and a heteroaryl group of 5 to 18 carbon atoms.

2. The onium salt organic catalyst as claimed in claim 1, wherein L has a structural formula represented by formula (II):

wherein R is₁、R₃、R₄Each independently selected from H, unsubstituted, substituted or one or at least two of the following groups containing O, S, N, Si, P atoms in combination: c₁-C₁₈Alkyl radical, C₃-C₁₈Cycloalkyl radical, C₃-C₁₈Alkenyl, C3-C₁₈Alkynyl, C₆-C₁₈Aryl radical, C₃-C₁₈Heterocyclyl or C₅-C₁₈One or a combination of at least two of the heteroaromatic groups; the substituent is selected from one or a combination of at least two of halogen atoms, branched or straight chain alkyl with 1 to 10 carbon atoms, branched or straight chain alkoxy with 1 to 10 carbon atoms, branched or straight chain cycloalkyl with 3 to 10 carbon atoms, aryl with 6 to 18 carbon atoms and heteroaryl with 5 to 18 carbon atoms; r₂Is O or S;denoted as a connecting bond.

3. The onium salt organic catalyst as claimed in claim 1, wherein said M is selected from one or a combination of at least two of the following structural formulae:

wherein R is₅-R₃₈Each independently selected from H, unsubstituted or substituted C₁-C₁₈Alkyl radical, C₃-C₁₈Cycloalkyl radical, C₃-C₁₈Alkenyl, C3-C₁₈Alkynyl, C₆-C₁₈Aryl radical, C₃-C₁₈Heterocyclyl or C₅-C₁₈One or a combination of at least two of the heteroaromatic groups; the substituent is selected from one or a combination of at least two of halogen atoms, branched or straight chain alkyl with 1 to 10 carbon atoms, branched or straight chain alkoxy with 1 to 10 carbon atoms, branched or straight chain cycloalkyl with 3 to 10 carbon atoms, aryl with 6 to 18 carbon atoms and heteroaryl with 5 to 18 carbon atoms;

x represents a negative ion selected from F^–、Cl^–、Br^–、I^–、NO₃ ^–、CH₃COO^–、CCl₃COO^–、CF₃COO^–、ClO₄ ^–、BF₄ ^–、BPh₄ ^–、N₃ ^–、OH^–P-methylbenzoate, p-methylbenzenesulfonate, o-nitrophenol oxygen, p-nitrophenol oxygen, m-nitrophenol oxygen, 2, 4-dinitrophenol oxygen, 3, 5-dinitrophenol oxygen, 2,4, 6-trinitrophenol oxygen, 3, 5-dichlorophenol oxygen, carbonate, bicarbonate, 3, 5-difluorophenol oxygen, p-nitrophenol oxygen, 3, 5-dichlorophenol oxygen, carbonate, bicarbonate, p,One or a combination of at least two of 3, 5-bis-trifluoromethylphenoxy or pentafluorophenoxy anions;

each R₅-R₃₈Any of the groups in (1) may be bonded to each other to form a ring.

4. An onium salt organic catalyst as claimed in claim 1, wherein said onium salt organic catalyst is:

5. a process for the preparation of an onium salt organic catalyst as claimed in any one of claims 1 to 4, characterized in that the preparation process comprises: any one of the reaction raw materials W₁And any one of the reaction materials W₂Mixing and stirring the mixture in the solution, and removing impurities and organic solvent after stirring the mixture for 1 to 500 hours at room temperature to obtain an onium salt organic catalyst; the reaction raw material W₁And W₂Respectively as follows:

wherein R is₀Is a sulfur atom or an oxygen atom; r'₁、R’₂、R’₃Each independently selected from H, unsubstituted or substituted C₁-C₁₈Alkyl radical, C₃-C₁₈Cycloalkyl radical, C₃-C₁₈Alkenyl, C3-C₁₈Alkynyl, C₆-C₁₈Aryl radical, C₃-C₁₈Heterocyclyl or C₅-C₁₈One or a combination of at least two of the heteroaromatic groups; the substituent is selected from one or a combination of at least two of halogen atoms, branched or straight chain alkyl with 1 to 10 carbon atoms, branched or straight chain alkoxy with 1 to 10 carbon atoms, branched or straight chain cycloalkyl with 3 to 10 carbon atoms, aryl with 6 to 18 carbon atoms and heteroaryl with 5 to 18 carbon atoms;

m is an onium salt structure with a charge; y represents the number of urea or thiourea groups and can be any integer between 1 and 100000; z represents the number of onium salt groups and may be any integer between 1 and 100000.

6. Use of an onium salt organic catalyst as claimed in any one of claims 1 to 4 for the preparation of small organic molecules and macromolecular polymers, characterized in that one or at least two cyclic monomers are polymerized in bulk in contact with the organic catalyst to give the macromolecular polymer; one or more cyclic monomers react with carbon dioxide, carbon disulfide, carbon oxysulfide or carbon monoxide in the presence of an onium salt organic catalyst to obtain cyclic carbonate, cyclic lactone, a cyclic thiocarbonate small molecular compound and a macromolecular polymer.

7. Use of an onium salt organic catalyst as claimed in claim 6 wherein said cyclic monomer is selected from any one or more of the following structural formulae:

Technical Field

The invention relates to the field of catalysis, in particular to development and application of an organic catalyst for preparing organic small-molecule fine chemicals and high-molecular polymer materials.

Background

Compared with metal catalysts, the organic catalyst has the advantages of simple synthesis, low price and low biological toxicity. The most widely studied organic catalysts include heterocyclic carbenes (NHCs), N-heterocyclic bases (NHCBs), hindered Lewis pairs (FLPs), tetrahydroammonium oxides/onium Salts (PTCs), polyphenols, fluoroalcohols, silanediols with co-catalysts, and Ionic Liquids (ILs). The catalytic reaction using hydrogen bond has the advantage of being simple and easy, such as alcohol, polyphenol, carboxylic acid, silanediol, squaramide and thiourea which have been reported recently and are the most widely studied hydrogen bond catalysts. Among them, thiourea or urea is considered to have specific advantages in the aspects of toxicity, sustainability and milder conditions of use, and has the advantages of high catalytic activity, simple preparation, easy modulation of structure and the like.

Although urea and thiourea have good hydrogen bonding effect, urea or thiourea alone often cannot achieve good catalytic efficiency, and quaternary ammonium salt, organic base and the like are generally needed to be used as co-catalysts to form a high-efficiency catalytic system. Recently, a new type of two-component catalyst consisting of strong base and weak acid of urea and thiourea has been reported to show high efficiency, controllability and good chemical selectivity in lactone ring-opening polymerization [ nat. chem.2016,8,1047-]. It is also possible to prepare compounds having more than one group by using urea, thiourea as hydrogen bond donors and varying strong bases (e.g., sodium/potassium alkoxides)High activity novel two-component catalysts [ j.am.chem.soc.2017,139, 1645-1652; macromolecules 2018,51,2048-2053]. Similar to urea and thiourea, Kleij Et al use TEAB (Et 4N)⁺Br^-) And aromatic amide as a two-component catalytic system realizes the fixation of carbon dioxide under the pressure of 10-30 bar, and cyclic carbonate (ACS Catal.2017,7,3532) with high yield is obtained]。

In recent years, the preparation of the organic catalyst containing double functions in the same molecule by intramolecular combination of urea or thiourea and nucleophilic groups has more obvious advantages. For example, Werner et al developed a series of bifunctional ammonium and phosphonium salts for catalyzing the cycloaddition of carbon dioxide and epoxides [ chemcatchem.2015,7,459] to produce various cyclic carbonate compounds. Inspired by urea or thiourea catalysts, Toda and Shirakawa introduced a urea-like group and a quaternary phosphonium salt into one molecule to prepare bifunctional catalysts that can efficiently synthesize cyclic carbonates [ ACS cat.2016, 6,6906; green chem.2016,18,4611 ].

In conclusion, the bifunctional organic catalyst has a synergistic effect of hydrogen bond activation and nucleophilic attack, has a good effect on various organic reactions such as the synthesis of cyclic carbonate by the activation and fixation of carbon dioxide, and shows more excellent performance. Unfortunately, the catalyst has the problems of complex preparation, low activity, difficult structure regulation and the like.

Disclosure of Invention

The invention provides a preparation method of an onium salt organic catalyst, which is simple and has high yield; the invention also provides the application of the onium salt organic catalyst in the preparation of fine chemicals with high added value.

The technical scheme provided by the invention is as follows:

an onium salt organic catalyst having a structure represented by formula (I):

wherein L is a urea or thiourea group; m is an onium salt structure with a charge; y represents the number of urea or thiourea groups and can be any integer between 1 and 100000; z represents the number of onium salt groups and may be any integer between 1 and 100000;

when y is 1, K is selected from any unsubstituted or substituted C₃-C₁₈Alkyl radical, C₃-C₁₈Cycloalkyl radical, C₃-C₁₈Alkenyl radical, C₃-C₁₈Alkynyl, C₇-C₁₈Aryl radical, C₃-C₁₈Heterocyclyl or C₇-C₁₈One or a combination of at least two of the heteroaromatic groups; the substituent is selected from one or a combination of at least two of halogen atoms, branched or straight chain alkyl with 1 to 10 carbon atoms, branched or straight chain alkoxy with 1 to 10 carbon atoms, branched or straight chain cycloalkyl with 3 to 10 carbon atoms, aryl with 6 to 18 carbon atoms and heteroaryl with 5 to 18 carbon atoms;

when y is an integer of 2 or more, K is selected from unsubstituted or substituted C₁-C₁₈Alkyl radical, C₃-C₁₈Cycloalkyl radical, C₃-C₁₈Alkenyl, C3-C₁₈Alkynyl, C₆-C₁₈Aryl radical, C₃-C₁₈Heterocyclyl or C₅-C₁₈One or a combination of at least two of the heteroaromatic groups; the substituent is selected from one or a combination of at least two of halogen atoms, branched or straight chain alkyl with 1 to 10 carbon atoms, branched or straight chain alkoxy with 1 to 10 carbon atoms, branched or straight chain naphthenic base with 3 to 10 carbon atoms, aromatic base with 6 to 18 carbon atoms and heteroaromatic base with 5 to 18 carbon atoms.

Preferably, the structural formula of L is shown as formula (II):

wherein R is₁、R₃、R₄Each independently selected from H, unsubstituted, substituted or containing O, S, N, SiP atoms, or a combination of at least two of the following groups: c₁-C₁₈Alkyl radical, C₃-C₁₈Cycloalkyl radical, C₃-C₁₈Alkenyl, C3-C₁₈Alkynyl, C₆-C₁₈Aryl radical, C₃-C₁₈Heterocyclyl or C₅-C₁₈One or a combination of at least two of the heteroaromatic groups; the substituent is selected from one or a combination of at least two of halogen atoms, branched or straight chain alkyl with 1 to 10 carbon atoms, branched or straight chain alkoxy with 1 to 10 carbon atoms, branched or straight chain cycloalkyl with 3 to 10 carbon atoms, aryl with 6 to 18 carbon atoms and heteroaryl with 5 to 18 carbon atoms; r₂Is O or S;denoted as a connecting bond.

Preferably, M is selected from one or a combination of at least two of the following structural formulae:

wherein R is₅-R₃₈Each independently selected from H, unsubstituted or substituted C₁-C₁₈Alkyl radical, C₃-C₁₈Cycloalkyl radical, C₃-C₁₈Alkenyl, C3-C₁₈Alkynyl, C₆-C₁₈Aryl radical, C₃-C₁₈Heterocyclyl or C₅-C₁₈One or a combination of at least two of the heteroaromatic groups; the substituent is selected from one or a combination of at least two of halogen atoms, branched or straight chain alkyl with 1 to 10 carbon atoms, branched or straight chain alkoxy with 1 to 10 carbon atoms, branched or straight chain cycloalkyl with 3 to 10 carbon atoms, aryl with 6 to 18 carbon atoms and heteroaryl with 5 to 18 carbon atoms;

x represents a negative ion selected from F^–、Cl^–、Br^–、I^–、NO₃ ^–、CH₃COO^–、CCl₃COO^–、CF₃COO^–、ClO₄ ^–、BF₄ ^–、BPh₄ ^–、N₃ ^–、OH^–One or a combination of at least two of p-methylbenzoate, p-methylbenzenesulfonate, o-nitrophenol oxygen, p-nitrophenol oxygen, m-nitrophenol oxygen, 2, 4-dinitrophenol oxygen, 3, 5-dinitrophenol oxygen, 2,4, 6-trinitrophenol oxygen, 3, 5-dichlorophenol oxygen, carbonate, bicarbonate, 3, 5-difluorophenol oxygen, 3, 5-bis-trifluoromethylphenol oxygen, or pentafluorophenol oxygen negative ions;

each R₅-R₃₈Any of the groups in (1) may be bonded to each other to form a ring.

Further preferably, the onium salt organic catalyst is:

the invention also provides a preparation method of the onium salt organic catalyst, which comprises the following steps: any one of the reaction raw materials W₁And any one of the reaction materials W₂Mixing and stirring the mixture in the solution, and removing impurities and organic solvent after stirring the mixture for 1 to 500 hours at room temperature to obtain an onium salt organic catalyst; the reaction raw material W₁And W₂Respectively as follows:

wherein R is₀Is a sulfur atom or an oxygen atom; r'₁、R’₂、R’₃Each independently selected from H, unsubstituted or substituted C₁-C₁₈Alkyl radical, C₃-C₁₈Cycloalkyl radical, C₃-C₁₈Alkenyl, C3-C₁₈Alkynyl, C₆-C₁₈Aryl radical, C₃-C₁₈Heterocyclyl or C₅-C₁₈One or a combination of at least two of the heteroaromatic groups; the substituent is selected from one or a combination of at least two of halogen atoms, branched or straight chain alkyl with 1 to 10 carbon atoms, branched or straight chain alkoxy with 1 to 10 carbon atoms, branched or straight chain cycloalkyl with 3 to 10 carbon atoms, aryl with 6 to 18 carbon atoms and heteroaryl with 5 to 18 carbon atoms;

m is an onium salt structure with a charge; y represents the number of urea or thiourea groups and can be any integer between 1 and 100000; z represents the number of onium salt groups and may be any integer between 1 and 100000.

Wherein the organic solvent is one or more selected from tetrahydrofuran, benzene, toluene, chloroform, hexane, diethyl ether, dichloromethane, ethyl acetate, dimethyl sulfoxide, carbon tetrachloride, 1, 4-dioxane or pyridine.

The reaction equation involved in the above preparation method is as follows:

the invention also provides an application of the onium salt organic catalyst in preparation of organic micromolecules and macromolecular polymers, wherein one or at least two cyclic monomers are subjected to bulk polymerization under the contact of the organic catalyst to obtain the macromolecular polymers; one or more cyclic monomers react with carbon dioxide, carbon disulfide, carbon oxysulfide or carbon monoxide in the presence of an onium salt organic catalyst to obtain cyclic carbonate, cyclic lactone, a cyclic thiocarbonate small molecular compound and a macromolecular polymer.

Preferably, the cyclic monomer is selected from any one or more of the following structural formulae:

the onium salt organic catalyst provided by the invention is a bifunctional organic catalyst containing urea or thiourea and an onium salt, and has the advantages of easiness in weighing, high catalytic activity, reaction controllability (catalytic efficiency and yield are regulated and controlled by changing catalyst concentration, reactant concentration, reaction time, reaction temperature and the like) and the like when being used as the catalyst. The preparation method provided by the invention has the advantages of simple preparation, high yield, low consumption, low cost and the like. The onium salt organic catalyst provided by the invention can be used for effectively synthesizing fine chemicals with high added value, such as cyclic carbonate, thio-cyclic carbonate lactone and the like.

Drawings

FIG. 1 is a digital photograph of onium salt organic catalysts prepared in examples 1-5;

FIG. 2 is a nuclear magnetic resonance image of the onium salt organic catalyst prepared in example 2.

Detailed Description

The invention is described in detail below by way of specific examples:

alkylene oxides and abbreviations therefor

Cyclic lactone and its abbreviation

Example 1

(1) Adding 1mmol of A into a 100mL round-bottom flask, adding 10mL of dichloromethane, stirring to dissolve, adding 1mmol of phenyl isothiocyanate, stirring at room temperature overnight, draining to remove dichloromethane, settling the obtained residue with diethyl ether for several times to remove impurities, and drying to obtain B with yield of 83%, and characterizing the product by nuclear magnetism (deuterated reagent: deuterated chloroform CDCl)₃)。

(2) Adding 1mmol B into 100mL round bottom flask, adding 10mL acetonitrile, adding 1mmol benzyl bromide, stirring at room temperature overnight, draining to remove acetonitrile, precipitating with ethyl acetate for multiple times to remove impurities, and drying to obtain onium salt organic catalyst (catalyst 1) with yield of 87%, and characterizing the product by nuclear magnetism (deuterated reagent: deuterated chloroform CDCl)₃)。

Example 2

(1) Adding 1mmol C into a 100mL round bottom flask, adding 10mL dichloromethane, stirring to dissolve, adding 1mmol phenyl isothiocyanate, stirring at room temperature overnight, draining to remove dichloromethane, settling the obtained residue with diethyl ether for several times to remove impurities, and drying to obtain D with yield of 85%, and characterizing the product by nuclear magnetism (deuterated reagent: deuterated chloroform CDCl)₃)。

(2) 1mmol D was added to a 100mL round bottom flask, 10mL acetonitrile was added thereto, 1.3mmol iodomethane and 1.5mmol potassium carbonate were added, the mixture was stirred at 60 ℃ overnight, the acetonitrile was removed by suction drying, impurities were removed by multiple sedimentation with ether, and drying was carried out to obtain an onium salt organic catalyst (catalyst 2) with a yield of 95%, which was characterized by nuclear magnetism as shown in FIG. 2 (deuterated reagent: deuterated chloroform CDCl)₃)。

Example 3

(1) Adding 1mmol E into a 100mL round-bottom flask, adding 50mL methanol, adding 1mL triethylamine and 1mmol benzaldehyde at low temperature, stirring for reaction for 0.5h, and adding 2mmol NaBH in portions at low temperature₄The reaction was stirred for 1 h. The resulting solution was neutralized with 4mol/L hydrochloric acid (5ml) and extracted with diethyl ether, the ether phase was discarded and the aqueous phase was treated with solid NaHCO₃Neutralizing, extracting with ethyl acetate, draining to remove ethyl acetate, drying to obtain F with yield of 43%, and characterizing the product by nuclear magnetism (deuterated reagent: deuterated chloroform CDCl)₃)。

(2) Adding 1mmol F into 100mL pressure bottle, adding 20mL acetonitrile, 1.5mmol potassium carbonate solid and 2.2mmol methyl iodide, stirring at 50 deg.C for 2 days, filtering to remove potassium carbonate, draining to remove acetonitrile, precipitating with diethyl ether for several times to remove impurities, drying to obtain G with yield of 73%, and characterizing the product by nuclear magnetism (deuterated reagent: deuterated chloroform CDCl)₃)。

(3) To a 100mL round bottom flask was added 1mmol G, to which was added 10mL dichloromethane, stirred to dissolve, 2mL trifluoroacetic acid was added at low temperature, and the reaction was stirred for 2 h. Removing dichloromethane by pumping, precipitating with diethyl ether for multiple times to remove impurities, adding 10mL dichloromethane, adding excess triethylamine and 2mmol phenyl isothiocyanate, stirring for reaction overnight, precipitating with ethyl acetate for multiple times to remove impurities, and drying to obtain onium salt organic catalyst (catalyst 3) with yield of 74%, and characterizing the product by nuclear magnetism (deuterated reagent: deuterated chloroform CDCl)₃)。

Example 4

(1) 1mmol of diethylamine was added to a 100mL pressure bottle, 10mL of acetonitrile and 1.5mmol of potassium carbonate solid were added thereto, 2.5mmol of I were further added, and the mixture was stirred at 50 ℃ and then the reaction mixture was invertedAfter 2 days, the mixture was filtered to remove potassium carbonate, dried to remove acetonitrile, precipitated with diethyl ether several times to remove impurities, and dried to give J in 37% yield, which was characterized by nuclear magnetism (deuterated reagent: deuterated chloroform CDCl)₃)。

(2) To a 100mL round bottom flask was added 1mmol J, 10mL dichloromethane was added and stirred to dissolve, 2mL trifluoroacetic acid was added at low temperature and the reaction stirred for 2 h. The dichloromethane was removed by suction, the impurities were removed by multiple sedimentation with diethyl ether, 10mL of dichloromethane, excess triethylamine and 2mmol of phenylisothiocyanate were added thereto, the mixture was stirred overnight, the impurities were removed by multiple sedimentation with diethyl ether, and drying was carried out to obtain an onium salt organic catalyst (catalyst 4) with a yield of 62%, which was characterized by nuclear magnetism (deuterated reagent: deuterated dimethyl sulfoxide DMSO-d 6).

Example 5

(1) Adding 1mmol piperidine into 100mL pressure bottle, adding 10mL acetonitrile and 1.5mmol potassium carbonate solid, adding 2.5mmol I, stirring at 50 deg.C for 2 days, filtering to remove potassium carbonate, draining to remove acetonitrile, precipitating with diethyl ether for several times to remove impurities, drying to obtain K with yield of 40%, and characterizing the product by nuclear magnetism (deuterated reagent: deuterated chloroform CDCl)₃)。

(2) To a 100mL round bottom flask was added 1mmol K, to which was added 10mL dichloromethane, stirred to dissolve, 2mL trifluoroacetic acid was added at low temperature, and the reaction stirred for 2 h. The dichloromethane was removed by suction, the impurities were removed by multiple sedimentation with diethyl ether, 10mL of dichloromethane, excess triethylamine and 2mmol of phenylisothiocyanate were added thereto, the mixture was stirred overnight, the impurities were removed by multiple sedimentation with diethyl ether, and drying was carried out to obtain an onium salt organic catalyst (catalyst 5) with a yield of 58%, which was characterized by nuclear magnetism (deuterated reagent: deuterated dimethyl sulfoxide DMSO-d 6).

Digital photographs of catalysts 1-5 prepared in examples 1-5, respectively, are shown in fig. 1.

Application examples 1 to 13: method for catalyzing epoxyalkane to open ring to generate cyclic carbonate by using catalysts 1-5

The catalyst prepared in example 1-5 (0.07mmol) was charged into an autoclave, and 35mmol of alkylene oxide was added and charged with 1.2MPa of CO₂And reacting for 20 hours under the given temperature condition. Then releasing carbon dioxide, and taking nuclear magnetism of the reaction liquid to characterize the conversion rate of the monomer. The catalytic results and characterization are shown in table 1.

Table 1 test results of catalytic products of application examples 1-13

Application examples 14 to 18: catalyst 3 for catalytic homopolymerization of cyclic lactone

In a glove box, catalyst 3(0.01mmol) prepared in example 3 was taken and added to a serum bottle, and cyclic lactone (0.01mol), 1ml of toluene, reacted at 80 ℃ for 6 h. And (3) taking reaction liquid to measure nuclear magnetism to represent the conversion rate of the monomer and the selectivity of the product, and drying to obtain the target polyester. The polymer was characterized by GPC. The polymerization results and characterization are shown in Table 2.

TABLE 2 test results for the polymerization products of application examples 14-18

^aM_nNumber average molecular weight, as determined by gel permeation chromatography;^bmolecular weight distribution (PDI) as determined by gel permeation chromatography.

The above-mentioned embodiments are intended to illustrate the technical solutions and advantages of the present invention, and it should be understood that the above-mentioned embodiments are only the most preferred embodiments of the present invention, and are not intended to limit the present invention, and any modifications, additions, equivalents, etc. made within the scope of the principles of the present invention should be included in the scope of the present invention.