CN114308120B

CN114308120B - Phosphorus salt amphiphilic double-functional organic catalyst and preparation method and application thereof

Info

Publication number: CN114308120B
Application number: CN202111661001.7A
Authority: CN
Inventors: 李志波; 王晓武
Original assignee: Qingdao University of Science and Technology
Current assignee: Qingdao University of Science and Technology
Priority date: 2021-12-30
Filing date: 2021-12-30
Publication date: 2024-10-01
Anticipated expiration: 2041-12-30
Also published as: CN114308120A

Abstract

The invention discloses a phosphorus salt amphiphilic bifunctional organic catalyst, and a preparation method and application thereof, and belongs to the field of organic catalyst synthesis and application. The invention solves the problem that the existing organic catalytic system is characterized in that the polymerization reaction can be realized only by mixing nucleophilic and electrophilic reagent two components or multiple components and even adding a cocatalyst or an initiator. The phosphorus salt amphiphilic bifunctional organic catalyst provided by the invention mixes nucleophilic electrophilic groups and initiating species into one catalytic system, has nucleophilic and electrophilic bifunctional sites, and avoids using a complex multicomponent multielement catalytic system. The catalyst can be used for preparing high molecular materials such as polyether, polyester, polycarbonate, polythiocarbonate, polythioether and the like, synthesizing block or random copolymer thereof, and also can be used for preparing fine chemicals of cyclic carbonate, lactone and thio cyclic carbonate by organic micromolecular coupling reaction, and has the characteristics of high efficiency, high selectivity, controllability and the like.

Description

Phosphorus salt amphiphilic double-functional organic catalyst and preparation method and application thereof

Technical Field

The invention relates to a phosphorus salt amphiphilic bifunctional organic catalyst, and a preparation method and application thereof, and belongs to the field of organic catalyst synthesis and application.

Background

Organic catalysts are attractive to scientific researchers because of low cost and availability, low biotoxicity and the like, but compared with the application of the organic catalysts in organic methodologies, the organic catalysts are still in a sprouting period in the field of polymer synthesis preparation, and the polymer materials prepared at present comprise: polyesters, polycarbonates, polyethers, polyamides, polysiloxanes, polyurethanes, and the like.

The organic catalytic systems commonly used at present mainly comprise the following categories: carboxylic acid type catalytic systems, pyridine base type catalytic systems, nitrogen heterocyclic carbene type catalytic systems, nitrogen-containing organic base (guanidino, amidino, amine type) catalytic systems, thiourea/urea+amine or thiourea/urea+base (organic alkali or other bases), phosphazene base type catalytic systems and the like, which have been used for preparing polycarbonate from alkylene oxide and carbon dioxide, preparing polyester from alkylene oxide and epoxy anhydride, preparing polyether from alkylene oxide by ring-opening polymerization, preparing polyester polymer material from cyclic lactone by ring-opening polymerization, preparing polycarbonate from cyclic carbonate by ring-opening polymerization, preparing polyamide from lactam by ring-opening polymerization, preparing polysiloxane from cyclic siloxane by ring-opening polymerization, catalyzing (meth) acrylic ester to polymerize to poly (meth) acrylic ester, and catalyzing vinyl ether to polymerize to functionalized polyethylene.

The polymerization mechanism mainly comprises: electrophilic activated monomer mechanism, nucleophilic activated monomer, nucleophilic activation of initiator, synergistic activation of monomer and initiator, etc. Thiourea/urea + organic base, phosphazene base, carbene, nitrogenous organic base have been reported in the literature as ring-opening polymerization of monomers such as cyclic lactones, alkylene oxides, epoxysilanes, cyclic carbonates, etc., and active species are obtained by activating an initiator to initiate polymerization reaction, thereby realizing chain growth.

The onium salts can be used in polymerization reactions with lewis acid trialkylboron to build acid-base pairs or phosphazene/alcohol/trialkylboron to build multi-component catalytic systems. Trialkylboron is used as Lewis acid and electrophile, which can activate monomer to stabilize active chain end of polymer, onium salt and phosphazene/alcohol have nucleophilic property as initiator, and the bi-component or multicomponent system can raise the activity and controllability of polymerization reaction effectively. Triethylboron and phosphazenes as reported in the literature are used for ring-opening polymerization of alkylene oxide, copolymerization of carbon dioxide and alkylene oxide to prepare polycarbonate, copolymerization of alkylene oxide and hetero atom-alkylene to prepare polycarbonate, copolymerization of epoxy and acid anhydride to prepare polyester, and the like.

However, the existing organic catalytic system is characterized in that the polymerization reaction can be realized only by mixing nucleophilic and electrophilic reagent two components or multiple components and even adding a cocatalyst or an initiator, and the reagent operation, the accuracy and the mechanistic research of the polymerization reaction are difficult; the weighing and measuring of the multiple components increases the error in the experimental operation.

Disclosure of Invention

The invention provides a phosphorus salt amphiphilic bifunctional organic catalyst, a preparation method and application thereof, and aims to solve the problems in the prior art.

The technical scheme of the invention is as follows:

a phosphorus salt amphiphilic double-functional organic catalyst has a structural formula as follows:

Wherein X is an anion, R ¹ and R ² are the same or different substituents, or R ¹ and R ² are bonded or looped through covalent bonds, and n is an integer of 1 or more; y is Wherein R ₁、R₂ and R ₃ are each a hydrogen atom or a combination of one or two or more of a C1-C50 alkyl group, a C3-C50 cycloalkyl group, a C3-C50 alkenyl group, a C3-C50 alkynyl group, a C6-C50 aryl group, a C3-C50 heterocyclic group, and a C5-C50 hetero or full-carbon aromatic group substituted/unsubstituted/containing N, O, P, si, S atoms.

Further defined, Y is BR3 and the organic catalyst has the following structure:

N is an integer of 1 or more, and the chain type is not limited to carbon chains, but may be other hetero atom carbon chains containing hetero atoms such as Si, N, O, P, S; BR ₃ is a cyclic borane or an aliphatic or aromatic borane, and R ₃ has the structure:

Wherein the method comprises the steps of And m is an integer of 1-30 for the connection bond.

Further defined, X is one or a combination of two or more of fluoride, chloride, bromide, iodide, hydroxide, nitrate, azide, tetrafluoroborate, lithium tetrakis (pentafluorophenyl) borate, nickel tetracarbonyl, carbonate, sulfonate, phosphate, hypochlorite, carboxylate, alkoxide, phenoxide.

Further defined, the organic catalyst is of the structure:

Further defined, the substituents on the phosphine are not limited to benzene rings, but may be benzene ring 1-substituted, 2-substituted, 3-substituted, 4-substituted, 5-substituted or multi-ring bridged substituents.

Further defined, the PhO ^- can be a mono-substituted phenol or a poly-substituted phenol.

Further defined, the length of the carbon chain is not limited to 3, but may be an integer greater than 3.

Further defined, the organic catalyst is of the structure:

Further defined, the substituents on the phosphine are not limited to methyl but may be ethyl, propyl, butyl, isobutyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, or methyl 1-substitution, 2-substitution, 3-substitution, 4-substitution, 5-substitution or other polycycloalkyl and substituted polycycloalkyl substituents thereof.

The amphiphilic bifunctional phosphate salt is prepared by carrying out a borohydride reaction on SM containing two unsaturated double bonds and a borohydride reagent containing at least one boron hydrogen bond.

Further defined, the preparation method of the organic catalyst comprises the following steps: mixing SM and a borohydride reagent under inert atmosphere, adding an organic solvent, stirring for 1-144 h at-78-100 ℃, and removing organic matters and impurities after the reaction is finished to obtain the phosphorus salt amphiphilic double-functional organic catalyst.

Further defined, the molar ratio of quaternary phosphonium salt to borohydride reagent in SM is 1: (2-3).

Further defined, the structure of SM is as follows:

Wherein X is a negative ion, R ¹ and R ² are identical or different substituents, or R ¹ and R ² are bonded or looped by covalent bonds.

Further, N is an integer of 1 or more, and the chain type is not limited to carbon chains, but may be other hetero atom carbon chains containing hetero atoms such as Si, N, O, P, S.

Still further defined, R ₁、R₂ and R ₃ are each a hydrogen atom or a combination of one or more of a C1-C50 alkyl group, a C3-C50 cycloalkyl group, a C3-C50 alkenyl group, a C3-C50 alkynyl group, a C6-C50 aryl group, a C3-C50 heterocyclic group, a C5-C50 hetero or full carbon aromatic group substituted/unsubstituted/containing N, O, P, si, S atoms.

Still further defined, the borohydride reagent is a cyclic, aliphatic or aromatic borane containing one or a combination of two or more of the following structures:

Still further defined, the borohydride reagent is 9-borabicyclo (3, 1) -nonane.

Further, the organic solvent is one or more of tetrahydrofuran, benzene, toluene, chloroform, methylene chloride, hexane, diethyl ether, carbon tetrachloride, N-dimethylformamide, ethyl acetate, and 1, 4-dioxane, and is mixed in any ratio.

The application of the phosphorus salt amphiphilic bifunctional organic catalyst in preparing organic micromolecule or high polymer material is that the organic micromolecule or high polymer material is obtained by ring-opening polymerization reaction of one or more than two cyclic monomers under the action of the catalyst, or is obtained by coupling the cyclic monomers with carbon dioxide, carbon disulfide, carbon oxysulfide, isocyanide, isocyanate or carbon monoxide under the action of the catalyst.

Further defined, the specific application method is as follows: the molar ratio of the catalyst to the cyclic monomer is 1: (200-10000) and reacting for 0.16-6 h at-40-25 ℃, the molecular weight of the obtained polymer is in the range of 1-4640 kg/mol, and the molecular weight distribution isIn the range of 1.02 to 1.3.

Further defined, the cyclic monomer comprises one or a combination of more of the following structures:

Further defined, the small organic molecule product is carbon dioxide/carbon disulfide and alkylene oxide/cyclothioalkane which are subjected to catalytic coupling reaction by a catalyst to obtain the cyclic carbonate.

Further defined, the small organic molecule product is a cyclic lactone obtained by catalytic coupling reaction of CO and alkylene oxide.

Further defined, the small organic molecule product is carbon oxysulfide and alkylene oxide/cyclothioalkane which are catalytically coupled by a catalyst to obtain the cyclic thiocarbonate.

Further defined, the polymer is an aliphatic polycarbonate or polyether obtained by catalytic copolymerization of carbon dioxide and alkylene oxide.

Further defined, the polymer is polyether obtained by ring-opening polymerization of alkylene oxide under the catalysis of a catalyst; the cyclic thioether is prepared by catalyzing ring-opening polymerization by a catalyst; polyester obtained by catalyzing alkylene oxide and cyclic anhydride through a catalyst; polyester obtained by catalyzing poly-heteroatom carbonate obtained by copolymerizing heteroatom diene and heteroatom cyclic compound through a catalyst; and (3) polymerizing alkylene oxide and carbon monoxide by using a catalyst to obtain the polyester.

Still further defined, polyether-polyesters, polyester-polycarbonates, polyether-polycarbonate diblock, triblock, multiblock polymers, gradient or random copolymers are prepared by adjusting the order of addition of alkylene oxides, anhydrides, cyclic lactones, carbon dioxide.

Further defined, the organic catalysts CAT1-CAT6 and CAT13-CAT18 are used for catalyzing homo-or copolymerization of Ethylene Oxide (EO), propylene Oxide (PO), butylene Oxide (BO), cyclohexylene oxide (CHO), limonene Oxide (LO), 4-vinylcyclohexene oxide (CVHO) or Allyl Glycidyl Ether (AGE) to obtain polyethers, or for catalyzing copolymerization of Ethylene Oxide (EO), propylene Oxide (PO), butylene Oxide (BO), cyclohexylene oxide (CHO), limonene Oxide (LO), 4-vinylcyclohexene oxide (CVHO) or Allyl Glycidyl Ether (AGE) with CO2 to obtain polycarbonates or cyclic carbonates.

Further defined, the organic catalysts CAT1-CAT6 and CAT13-CAT18 are used for catalyzing copolymerization of Ethylene Oxide (EO), propylene Oxide (PO), butylene Oxide (BO), cyclohexyl oxide (CHO), limonene Oxide (LO), 4-vinylcyclohexene oxide (CVHO) or Allyl Glycidyl Ether (AGE) with cyclic Maleic Anhydride (MA), succinic Anhydride (SA), diethylene Glycol Anhydride (DGA) or Phthalic Anhydride (PA) to obtain polyesters.

Further defined, the organic catalysts CAT1-CAT2 and CAT6 are used to catalyze homo-or copolymerization of EO, PO, BO or AGE to obtain polyethers, and the polymerization is living polymerization.

Further defined, the organic catalysts CAT1-CAT2 and CAT6 are used for catalyzing Lactide (LA), beta-butyrolactone (beta-BL), gamma-butyrolactone (gamma-BL), delta-valerolactone (delta-VL) or epsilon-caprolactone (epsilon-CL) to obtain polyester by ring-opening polymerization or copolymerization.

Further defined, the organic catalysts CAT1-CAT2 and CAT6 are used for catalyzing Ethylene Sulfide (ES), propylene Sulfide (PS), and copolymerizing ethylene sulfide (CHS) with carbon dioxide to obtain the polythiocarbonate; or used for catalyzing 2-phenyl ethylene sulfide (SS) or PS to be copolymerized with CO ₂ to obtain the cyclic thiocarbonate.

Further defined, the organic catalysts CAT1-CAT2 and CAT6 are used for catalyzing the copolymerization of Propylene Oxide (PO) and carbon oxysulfide to obtain polythiocarbonate, or for catalyzing the copolymerization of ethylene oxide (ES) and carbon oxysulfide or carbon disulfide to obtain polythiocarbonate, or for catalyzing the copolymerization of Propylene Oxide (PO) and carbon disulfide to obtain polyether.

Further, the organic catalyst can be used in the presence of a chain transfer agent to control the molecular weight of the polymer (both high and low molecular weight polymers can be prepared), reduce the catalyst dosage, reduce the molecular weight distribution of the polymer, and prepare polymers with functional terminal functional groups (such as ester groups, phenol groups, amino groups, hydroxyl groups, azide groups, etc.).

Further defined is specifically to add one or more alcohol compounds, acid compounds, amine compounds, polyols, polycarboxylic acids, polyols, water as chain transfer agents to the polymerization system to prepare the corresponding polymer polyols or polythiols; or adding one or more polymers with alcoholic hydroxyl, phenolic hydroxyl, amino and carboxyl into a polymerization reaction system as macromolecular chain transfer agents to prepare corresponding block copolymers or graft copolymers.

Further defined, the chain transfer agent comprises one or a combination of more of the following structures:

Wherein the method comprises the steps of Represents the main chain of a macromolecular chain transfer agent, andThe alcoholic hydroxyl group, the phenolic hydroxyl group, the amino group or the carboxylic acid group shown in the main chain does not represent the actual number of functional groups, and the actual number is any integer of 1 or more.

Further, it is contemplated that lewis acids, lewis bases, or other multiple catalysts or cocatalysts may be added to the polymerization system during the preparation of the polymer from the organic catalyst.

The phosphorus salt amphiphilic bifunctional organic catalyst is loaded on inorganic or organic substances to prepare organic micromolecule or high polymer materials, is more beneficial to recycling of the catalyst, and avoids the loss of the catalyst to the greatest extent.

The invention has the following beneficial effects:

(1) The phosphorus salt amphiphilic bifunctional organic catalyst provided by the invention mixes nucleophilic electrophilic groups and initiating species into one catalytic system, has nucleophilic and electrophilic bifunctional sites, and avoids using a complex multicomponent multielement catalytic system.

(2) The phosphorus salt amphiphilic bifunctional organic catalyst provided by the invention also has the characteristics of definite structure, accurate components and synergistic catalysis, which is difficult to achieve by the conventional multi-element system.

(3) The preparation method of the phosphorus salt amphiphilic bifunctional organic catalyst provided by the invention has the characteristics of easily available raw materials, short synthetic route, simplicity and the like.

(4) The phosphorus salt amphiphilic bifunctional organic catalyst provided by the invention is used for preparing high polymer materials such as polyether, polyester, polycarbonate, polythiocarbonate, polythioether and the like, and synthesizing block or random copolymer thereof, and can also be used for preparing fine chemicals such as cyclic carbonate, lactone and thio cyclic carbonate by organic micromolecule coupling reaction, and has the characteristics of high efficiency, high selectivity, controllability and the like.

Drawings

FIG. 1 is a ¹ H NMR spectrum of CAT 1;

FIG. 2 is a ¹ H NMR spectrum of CAT 2;

FIG. 3 is a ¹ H NMR spectrum of pure PPO;

FIG. 4 is a GPC chart of effect example 1;

FIG. 5 is a ¹ H NMR spectrum of Poly (AGE);

FIG. 6 is a ¹ H NMR spectrum of Poly (BO).

Detailed Description

The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.

Example 1

The catalyst CAT1 is synthesized by the following synthetic route:

wherein, The molecular structural formula is as follows:

The preparation process is as follows:

Diallyl diphenylphosphine bromide (173.6 mg,0.5mmol,1 eq.) and 9-borobicyclo [3.3.1] nonane (9-BBN) (122 mg,1.0mmol,2.0 eq.) were dissolved in 10mL chloroform in a flame-dried Schlenk vessel. The reaction mixture was allowed to stir at 80 ℃ for 12 hours. All volatiles were removed and the resulting white solid was washed 3 times with hexane (10 mL) to give the desired product in quantitative yield as shown in FIG. 1 (400 MHz, CDCl ₃, 298K) in the NMR spectrum of product ¹ H.

Example 2

The catalyst CAT2 is synthesized by the following synthetic route:

wherein, The molecular structural formula is as follows:

The preparation process is as follows:

In a flame-dried Schlenk vessel, diallyl diphenylphosphine iodide (307 mg,0.78mmol,1 eq.) and 9-borobicyclo [3.3.1] nonane (9-BBN) (190.4 mg,1.56mmol,2 eq.) were dissolved in 10mL of CHCl ₃. The reaction mixture was allowed to stir at 80 ℃ for 12 hours. All volatiles were removed and the resulting white solid was washed 3 times with hexane (10 mL) to give the desired product in quantitative yield as shown in FIG. 2 (400 MHz, CDCl ₃, 298K) in the product ¹ H NMR spectrum.

Example 3

The catalyst CAT4 is synthesized by the following synthetic route:

The preparation process is as follows:

CAT1 (118.3 mg,0.2mmol,1 eq.) and sodium benzoate (115.3 mg,0.8mmol,4 eq.) were dissolved in 8ml of CHCl ₃ in a flame-dried Schlenk vessel. The reaction mixture was allowed to stir at room temperature for 48 hours. The filtrate was collected by filtration under nitrogen atmosphere, all volatiles were removed, and the resulting white oil was washed 3 times (10 mL) with hexane to obtain the desired white quantitative product.

Example 4

The catalyst CAT5 is synthesized by the following synthetic route:

The preparation process is as follows:

CAT1 (118.3 mg,0.2mmol,1 eq.) and sodium acetate (65.6 mg,0.8mmol,4 eq.) were dissolved in 8ml of chloroform in a flame-dried Schlenk vessel. The reaction mixture was allowed to stir at room temperature for 48 hours. The filtrate was collected by filtration under nitrogen atmosphere, all volatiles were removed, and the resulting white oil was washed 3 times (10 mL) with hexane to obtain the desired white quantitative product.

Example 5

The catalyst CAT6 is synthesized by the following synthetic route:

The preparation process is as follows:

CAT1 (118.3 mg,0.2mmol,1 eq.) and sodium trifluoroacetate (108.8 mg,0.8mmol,4 eq.) were dissolved in 8ml of chloroform in a flame-dried Schlenk vessel. The reaction mixture was allowed to stir at room temperature for 48 hours. The filtrate was collected by filtration under nitrogen atmosphere, all volatiles were removed, and the resulting white oil was washed 3 times (10 mL) with hexane to obtain the desired white quantitative product.

Effect example 1

The catalyst CAT1-CAT6 is used for catalyzing the homopolymerization reaction of propylene oxide, and the synthetic route is as follows:

The preparation process is as follows:

In a glove box, weighing PO and a catalyst into a 5mL pressure-resistant bottle vial with a magnetic stirrer and flame-dried in advance, sealing the vial, taking out, setting the temperature of minus 20-25 ℃ as the reaction temperature, wherein the mol ratio of the PO to the catalyst is 200:1-10000:1, and controlling the reaction time to be 10-120 min. The key data of application examples 1 to 12 are collated in Table 1.

Effect example 2

The catalyst CAT1-CAT6 is used for catalyzing the copolymerization of alkylene oxide and CO ₂, and the synthetic route is as follows:

The preparation process is as follows:

In a glove box, alkylene oxide and a catalyst are added into a reaction kettle, the reaction kettle is filled with carbon dioxide under a certain pressure, and the reaction is carried out under a set temperature condition, and the monomer conversion and the selectivity of the product (the proportion of polycarbonate, polyether and cyclic carbonate) are characterized by nuclear magnetism. The key data for application examples 13-36 are collated in tables 2-5.

TABLE 2

TABLE 3 Table 3

TABLE 4 Table 4

TABLE 5

Effect example 3

The catalyst CAT1-CAT6 is used for catalyzing the copolymerization of alkylene oxide and cyclic anhydride, and the synthetic route is as follows:

The preparation process is as follows:

In a glove box, a proper amount of cyclic anhydride, alkylene oxide and a catalyst are taken, placed in a pressure-resistant bottle and reacted for 10min-12h at the temperature of 60-180 ℃. And taking the reaction liquid to test the nuclear magnetism to represent the monomer conversion rate and the selectivity of the product. After precipitation from methanol, filtration and drying, GPC data of the polymer were analyzed. The key data for application examples 37-53 are collated in tables 6-7.

TABLE 6

TABLE 7

Effect example 4

The catalyst CAT1-CAT6 is used for catalyzing the homopolymerization of the cyclic lactone, and the synthetic route is as follows:

The preparation process is as follows:

In a glove box, adding a proper amount of cyclic lactone monomer and catalyst into a pressure-resistant bottle, adding a certain amount of organic solvent, and reacting for 2-12h at the temperature of-10-80 ℃. And taking the reaction liquid, testing the conversion rate of the nuclear magnetic characterization monomer and the selectivity of the product, filtering the polymer, drying to obtain a polyester target product, and performing GPC (gel permeation chromatography) test analysis on the polyester target product. The key data of application examples 54 to 55 are collated in Table 8.

TABLE 8

Effect example 5

The catalyst CAT7-CAT24 is used for catalyzing the homopolymerization of the cyclic lactone, and the synthetic route is as follows:

The catalyst CAT7-CAT24 was prepared in the same manner as CAT1-CAT 6.

The preparation process is as follows:

in a glove box, adding a proper amount of propylene oxide monomer and catalyst into a pressure-resistant bottle, and reacting for 2-12h at 25-100 ℃. And taking the reaction liquid, and testing the conversion rate of the nuclear magnetic characterization monomer and the selectivity of the product. The key data of application examples 56 to 61 are collated in Table 9.

TABLE 9

Claims

1. The phosphorus salt amphiphilic bifunctional organic catalyst is characterized by comprising the following structural formula:

2. A method for preparing a phosphorus salt amphiphilic bifunctional organic catalyst according to claim 1, wherein the preparation process of the catalyst CAT1 is as follows:

in a flame-dried Schlenk vessel, 0.5mmol of diallyl diphenylphosphine bromide and 1.0mmol of 9-borobicyclo [3.3.1] nonane were dissolved in 10mL of chloroform, stirred at 80℃for 12 hours, all volatiles were removed and the resulting white solid was washed 3 times with 10mL of hexane to give catalyst CAT1;

the preparation process of the catalyst CAT2 comprises the following steps:

In a flame-dried Schlenk vessel, 0.78mmol of diallyl diphenylphosphine iodide and 1.56mmol of 9-borobicyclo [3.3.1] nonane were dissolved in 10mL of CHCl ₃, stirred at 80℃for 12 hours, all volatiles were removed and the resulting white solid was washed 3 times with 10mL of hexane to give catalyst CAT2.

3. The application of the phosphorus salt amphiphilic bifunctional organic catalyst in preparing organic micromolecule or high polymer material is characterized in that the organic micromolecule or high polymer material is obtained by ring-opening polymerization reaction of one or more than two cyclic monomers under the action of a catalyst, or is obtained by coupling the cyclic monomers with carbon dioxide, carbon disulfide, carbon oxysulfide, isocyanide, isocyanate or carbon monoxide under the action of the catalyst;

The specific application method comprises the following steps: the molar ratio of the catalyst to the cyclic monomer is 1: (200-10000) and reacting for 0.16-6 h at-40-25 ℃;

The cyclic monomer is selected from one or more than one of the following structures:

4. The use of a phosphorus salt amphiphilic bifunctional organic catalyst according to claim 3 in the preparation of small organic molecules or high molecular materials, wherein the catalyst is carried out in the presence of a chain transfer agent when preparing a polymer; the chain transfer agent is selected from one or more than one of the following structures: