CN114308120A - Phosphorus salt amphiphilic bifunctional organic catalyst and preparation method and application thereof - Google Patents

Abstract

The invention discloses a phosphorus salt amphiphilic dual-functional organic catalyst and a preparation method and application thereof, belonging to the field of synthesis and application of organic catalysts. The invention solves the problem that the existing organic catalytic system is characterized in that the polymerization reaction can be realized only by mixing two or more components of nucleophilic reagent and electrophilic reagent 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 a catalytic system, has nucleophilic and electrophilic bifunctional sites, and avoids the use of a complex multicomponent catalytic system. The catalyst can be used for the preparation of high molecular materials such as polyether, polyester, polycarbonate, polythiocarbonate, polythioether and the like, and the synthesis of block or random copolymers thereof, can also be used for carrying out organic small molecule coupling reaction to prepare fine chemicals such as cyclic carbonate, lactone and thio-cyclic carbonate, and has the characteristics of high efficiency, high selectivity, controllability and the like.

Description

Phosphorus salt amphiphilic bifunctional organic catalyst and preparation method and application thereof

technical field

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

Background technique

Organocatalysts have attracted the attention of scientific researchers because of their cheapness, easy availability and low biological toxicity. However, compared with the application of organic catalysts in organic methodology, organic catalysts are still in their infancy in the field of polymer synthesis and preparation. The polymer materials include: polyester, polycarbonate, polyether, polyamide, polysiloxane, polyurethane, etc.

At present, the commonly used organic catalytic systems mainly include the following categories: carboxylic acid catalytic systems, pyridine base catalytic systems, nitrogen heterocyclic carbene catalytic systems, nitrogen-containing organic bases (guanidine, amidine, amine) catalytic systems, sulfur Urea/urea+amine or thiourea/urea+base (strong organic base or other base), phosphazene base catalytic system, etc., these catalytic systems have been used in the preparation of polycarbonate from alkylene oxide and carbon dioxide, alkylene oxide and carbon dioxide. Polyester is prepared by epoxy anhydride, polyether is prepared by ring-opening polymerization of alkylene oxide, polyester polymer material is prepared by ring-opening polymerization of cyclic lactone, polycarbonate is prepared by ring-opening of cyclic carbonate, and polyamide is obtained by ring-opening polymerization of lactam. The ring-opening polymerization of cyclic siloxane is used to prepare polysiloxane, the polymerization of (meth)acrylate is catalyzed to obtain poly(meth)acrylate, and the polymerization of vinyl ether is catalyzed to obtain functionalized polyethylene.

The above-mentioned polymerization mechanism mainly includes: electrophilic activation of monomer mechanism, nucleophilic activation of monomer, nucleophilic activation of initiator, and synergistic activation of monomer and initiator. Thiourea/urea + organic bases, phosphazene bases, carbene, nitrogen-containing organic bases have been reported in the literature as cyclic lactones, alkylene oxides, epoxy silanes, cyclic carbonates and other monomers in the ring-opening polymerization. The initiator obtains active species to initiate the polymerization reaction and realize chain growth.

Onium salts can be used with Lewis acid trialkylboron to construct acid-base pair or phosphazene/alcohol/trialkylboron to construct multi-component catalytic system for polymerization. As Lewis acid and electrophilic reagent, trialkylboron can activate monomers to stabilize polymer active species chain ends. Onium salts and phosphazenes/alcohols have nucleophilic properties as initiators. This two-component or multi-component system can Effectively improve the activity and controllability of the polymerization reaction. As reported in the literature, triethylboron and phosphazene compounds are used for the ring-opening polymerization of alkylene oxide, the copolymerization of carbon dioxide and alkylene oxide to prepare polycarbonate, and the copolymerization of alkylene oxide and heteroatom allene to prepare polycarbonate, Epoxy and acid anhydride copolymerization to prepare polyester, etc.

However, the characteristics of the existing organic catalytic systems are that two or more components of nucleophilic and electrophilic reagents can be mixed or even added with co-catalysts or initiators to realize the polymerization reaction, which brings great advantages to the reagent operation, accuracy and mechanism research of the polymerization reaction. The difficulty is increased; the weighing and measuring of multiple components increases the error of the experimental operation.

SUMMARY OF THE INVENTION

In order to solve the above-mentioned problems in the prior art, the present invention provides a phosphorus salt amphiphilic bifunctional organic catalyst and its preparation method and application.

Technical scheme of the present invention:

A phosphorus salt amphiphilic bifunctional organic catalyst, the structural formula is as follows:

其中R₁、R₂和R₃分别为氢原子或者取代/未取代/含有N、O、P、Si、S原子中一种或两种以上的C1-C50的烷基、C3-C50的环烷基、C3-C50的烯基、C3-C50的炔基、C6-C50的芳基、C3-C50的杂环基、C5-C50的杂或全碳芳香基中的一种或两种以上的组合。In the formula, X is a negative ion, R ¹ and R ² are the same or different substituents, or R ¹ and R ² form a bond or ring through a covalent bond, and n is an integer of 1 or more; Y is

wherein R ₁ , R ₂ and R ₃ are respectively a hydrogen atom or a substituted/unsubstituted/containing one or more of N, O, P, Si, and S atoms of a C1-C50 alkyl group, a C3-C50 ring One or more of alkyl group, C3-C50 alkenyl group, C3-C50 alkynyl group, C6-C50 aryl group, C3-C50 heterocyclic group, C5-C50 hetero or full carbon aryl group The combination.

Further limit, Y is BR3, the organic catalyst is the following structure:

n is an integer of 1 or more, and the type of chain is not limited to carbon chains, but can also be other heteroatom carbon chains containing heteroatoms, such as Si, N, O, P, S; BR ₃ is cyclic borane or aliphatic aromatic or aromatic borane, the structure of R ₃ is as follows:

为连接键，m为1-30的整数。in

is the connection bond, m is an integer from 1 to 30.

Further limited, X is fluoride ion, chloride ion, bromide ion, iodide ion, hydroxide ion, nitrate ion, azide ion, tetrafluoroborate anion, lithium tetrakis(pentafluorophenyl)borate anion, nickel tetracarbonyl A combination of two or more of anions, carbonate ions, sulfonate ions, phosphate ions, hypochlorite ions, carboxylate ions, alkoxy ions, and phenoxy ions.

Further limited, the organic catalyst is the following structure:

For further limitation, the substituent on the phosphine is not limited to the benzene ring, but can also be a 1-substituted, 2-substituted, 3-substituted, 4-substituted, 5-substituted or multi-ring bridged substituent on the benzene ring.

To further define, ^PhO- can be a mono-substituted phenol or a poly-substituted phenol.

For further limitation, the length of the carbon chain is not limited to 3, but can also be a carbon chain that is an integer greater than 3.

Further limited, the organic catalyst is the following structure:

Further limited, the substituent on the phosphine is not limited to methyl, but can also be ethyl, propyl, butyl, isobutyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, or Its methyl group is 1-substituted, 2-substituted, 3-substituted, 4-substituted, 5-substituted or other polycycloalkyl and substituted polycycloalkyl substituents.

To further define, ^PhO- can be a mono-substituted phenol or a poly-substituted phenol.

For further limitation, the length of the carbon chain is not limited to 3, but can also be a carbon chain that is an integer greater than 3.

The above-mentioned amphiphilic bifunctionalization of phosphorus salts is prepared by the hydroboration reaction of SM containing two unsaturated double bonds and a hydroboration reagent containing at least one boron-hydrogen bond.

Further limited, the preparation method of the organic catalyst is as follows: mixing SM and borohydride reagent in an inert atmosphere, adding an organic solvent, stirring at -78-100 ° C for 1-144 h, removing organic matter and impurities after the reaction, and obtaining the phosphorus salt Amphiphilic bifunctional organocatalysts.

To further limit, the molar ratio of quaternary phosphorus salt and hydroboration reagent in SM is 1:(2-3).

To further define, the structure of SM is as follows:

Wherein X is a negative ion, R ¹ and R ² are the same or different substituents, or R ¹ and R ² form a bond or a ring through a covalent bond.

To be further limited, n is an integer of 1 or more, and the type of chain is not limited to carbon chains, but can also be other heteroatom carbon chains containing heteroatoms, such as Si, N, O, P, S.

Further limited, R ₁ , R ₂ and R ₃ are respectively hydrogen atoms or substituted/unsubstituted/containing one or more C1-C50 alkyl groups, C3- One of C50 cycloalkyl group, C3-C50 alkenyl group, C3-C50 alkynyl group, C6-C50 aryl group, C3-C50 heterocyclic group, C5-C50 hetero or full carbon aryl group or combination of two or more.

Further limited, X is fluoride ion, chloride ion, bromide ion, iodide ion, hydroxide ion, nitrate ion, azide ion, tetrafluoroborate anion, tetrakis (pentafluorophenyl) lithium borate anion, tetracarbonyl A combination of two or more of nickel anions, carbonate ions, sulfonate ions, phosphate ions, hypochlorite ions, carboxylate ions, alkoxy ions, and phenoxy ions.

Further limited, the hydroboration reagent is a cyclic, aliphatic or aromatic borane containing one or more of the following structures:

为连接键，m为1-30的整数。in

is the connection bond, m is an integer from 1 to 30.

More specifically, the hydroboration reagent is 9-borabicyclo(3,3,1)-nonane.

Further limited, the organic solvent is tetrahydrofuran, benzene, toluene, chloroform, dichloromethane, hexane, ether, carbon tetrachloride, N,N-dimethylformamide, ethyl acetate, 1,4-dioxane One kind or two or more kinds of rings are mixed in any ratio.

Application of the above-mentioned phosphorus salt amphiphilic bifunctional organic catalyst in the preparation of organic small molecules or polymer materials, wherein the organic small molecules or polymer materials are ring-opened by one or more cyclic monomers under the action of catalysts It is obtained by a polymerization reaction, or is obtained by coupling a cyclic monomer with carbon dioxide, carbon disulfide, carbon sulfide, isothiocyanate, isocyanate or carbon monoxide under the action of a catalyst.

在1.02～1.3的范围内。Further limited, the specific application method is as follows: the catalyst and the cyclic monomer are mixed in a molar ratio of 1:(200-10000), and the reaction is carried out at -40-25°C for 0.16-6h. The molecular weight is in the range of 1～4640kg/mol, and the molecular weight distribution

in the range of 1.02 to 1.3.

Further limited, the cyclic monomer includes one or more combinations of the following structures:

In a further limitation, the organic small molecule product is carbon dioxide/carbon disulfide and alkylene oxide/sulfane through the catalytic coupling reaction of catalyst to obtain cyclic carbonate.

To be further limited, the organic small molecule product is a cyclic lactone obtained by the catalytic coupling reaction of CO and alkylene oxide through a catalyst.

In a further limitation, the organic small molecule product is a cyclic thiocarbonate obtained by catalytic coupling of carbon oxysulfide and alkylene oxide/sulfane through a catalyst.

More specifically, the polymer is an aliphatic polycarbonate or polyether obtained by the catalytic copolymerization of carbon dioxide and alkylene oxide through a catalyst.

It is further limited that the polymer is a polyether obtained by catalyzing ring-opening polymerization of alkylene oxide; a polysulfide obtained by ring-opening polymerization catalyzed by a cyclic sulfide; a polyester obtained by catalyzing an alkylene oxide and a cyclic acid anhydride through a catalyst ; Polyester obtained by the copolymerization of heteroatom allene and heteroatom cyclic compound through catalyst catalysis; polyester obtained by catalyst catalyzed polymerization of alkylene oxide and carbon monoxide.

To be further limited, polyether-polyester, polyester-polycarbonate, polyether-polycarbonate diblock, triblock, multiblock are prepared by adjusting the feeding sequence of alkylene oxide, acid anhydride, cyclic lactone, and carbon dioxide. segmented, gradient or random copolymers.

Further limited, organic catalysts CAT1-CAT6 and CAT13-CAT18 are used to catalyze ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO), cyclohexyl oxide (CHO), limonene oxide ( LO), 4-vinyl epoxycyclohexene (CVHO) or allyl glycidyl ether (AGE) homopolymerization or copolymerization to obtain polyether, or used to catalyze ethylene oxide (EO), propylene oxide (PO ), butylene oxide (BO), epoxycyclohexyl (CHO), limonene oxide (LO), 4-vinyl epoxycyclohexene (CVHO) or allyl glycidyl ether (AGE) copolymerized with CO2 Polycarbonate or cyclic carbonate.

Further limited, organic catalysts CAT1-CAT6 and CAT13-CAT18 are used to catalyze ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO), cyclohexyl oxide (CHO), limonene oxide ( LO), 4-vinyl epoxycyclohexene (CVHO) or allyl glycidyl ether (AGE) with cyclic maleic anhydride (MA), succinic anhydride (SA), diethylene glycol anhydride (DGA) or Polyester is obtained by copolymerization of phthalic anhydride (PA).

More specifically, the organic catalysts CAT1-CAT2 and CAT6 are used to catalyze the homopolymerization or copolymerization of EO, PO, BO or AGE to obtain polyether, and the polymerization reaction is living polymerization.

Further limited, organic catalysts CAT1-CAT2 and CAT6 are used to catalyze lactide (LA), β-butyrolactone (β-BL), γ-butyrolactone (γ-BL), δ-valerolactone (δ -VL) or ε-caprolactone (ε-CL) ring-opening polymerization or copolymerization to obtain polyester.

To further limit, the organic catalysts CAT1-CAT2 and CAT6 are used to catalyze the copolymerization of ethylene sulfide (ES), propylene sulfide (PS), and ethylene sulfide (CHS) with carbon dioxide to obtain polythiocarbonate; or used for catalysis 2-Phenyl thioethane (SS) or PS is copolymerized with _CO to give cyclic thiocarbonates.

Further limited, organic catalysts CAT1-CAT2 and CAT6 are used to catalyze the copolymerization of propylene oxide (PO) and carbon oxysulfide to obtain polythiocarbonate, or to catalyze the copolymerization of ethylene sulfide (ES) with carbon oxysulfide or carbon disulfide. Obtain polythiocarbonate, or be used to catalyze the copolymerization of propylene oxide (PO) and carbon disulfide to obtain polyether.

To further limit, when the organic catalyst prepares the polymer, it can be carried out in the presence of a chain transfer agent, so the molecular weight of the prepared polymer can be regulated (both high and low molecular weight polymers can be prepared), the amount of catalyst is reduced, and the molecular weight of the polymer can be reduced. Distribution, preparation of polymers with functional end functional groups (such as ester groups, phenolic groups, amino groups, hydroxyl groups, azide groups, etc.).

It is further limited, specifically adding one or more alcohol compounds, acid compounds, amine compounds, polyols, polycarboxylic acids, polyols, and water as chain transfer agents in the polymerization reaction system to prepare corresponding polymer polyols or Polythiol; or adding one or more polymers with alcoholic hydroxyl groups, phenolic hydroxyl groups, amino groups, and carboxyl groups as macromolecular chain transfer agents in the polymerization reaction system to prepare corresponding block copolymers or graft copolymers.

Further limited, the chain transfer agent comprises one or more combinations of the following structures:

代表大分子链转移剂的主链，且

主链上所示的醇羟基、酚羟基、氨基或羧酸基不代表官能团的实际个数，实际个数为1以上的任意整数。in

represents the backbone of the macromolecular chain transfer agent, and

The alcoholic hydroxyl group, phenolic hydroxyl group, amino group or carboxylic acid group shown on the main chain does not represent the actual number of functional groups, and the actual number is any integer of 1 or more.

To further limit, when the organic catalyst is used to prepare the polymer, Lewis acid, Lewis base, or other diversified catalysts or co-catalysts may also be added to the polymerization reaction system.

The above-mentioned phosphorus salt amphiphilic bifunctional organic catalyst is supported on inorganic or organic substances for preparing organic small molecules or polymer materials, which is more conducive to the recyclable use of the catalyst and avoids the loss of the catalyst to the greatest extent.

The present invention has the following beneficial effects:

(1) The phosphorous salt amphiphilic bifunctional organic catalyst provided by the present invention combines nucleophilic and electrophilic groups and initiating species into one catalytic system, has nucleophilic and electrophilic bifunctional sites, and avoids the use of complex multi-component catalytic system.

(2) The phosphorous salt amphiphilic bifunctional organic catalyst provided by the present invention also has the characteristics of definite structure, precise components and synergistic catalysis, which is difficult to achieve in the past diversified systems.

(3) The preparation method of the phosphorus salt amphiphilic bifunctional organic catalyst provided by the present invention has the characteristics of easy availability of raw materials, short and simple synthesis route and the like.

(4) Phosphorus salt amphiphilic bifunctional organic catalyst provided by the present invention is used for the preparation of polymer materials such as polyether, polyester, polycarbonate, polythiocarbonate, polysulfide and the like and the block or random copolymerization thereof It can also carry out organic small molecule coupling reaction to prepare fine chemicals such as cyclic carbonate, lactone and thiocyclic carbonate. It has the characteristics of high efficiency, high selectivity and controllability.

Description of drawings

Figure 1 is the ¹ H NMR spectrum of CAT1;

Figure 2 is the ¹ H NMR spectrum of CAT2;

Figure 3 is the ¹ H NMR spectrum of pure PPO;

Fig. 4 is the GPC curve diagram of effect example 1;

Figure 5 is the ¹ H NMR spectrum of Poly(AGE);

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

Detailed ways

The experimental methods used in the following examples are conventional methods unless otherwise specified. The used materials, reagents, methods and instruments, unless otherwise specified, are conventional materials, reagents, methods and instruments in the art, which can be obtained by those skilled in the art through commercial channels.

Example 1

The synthesis of catalyst CAT1, the synthetic route is as follows:

的分子结构式如下：in,

The molecular structure is as follows:

The preparation process is as follows:

In a flame-dried Schlenk vessel, combine diallyldiphenylphosphine bromide (173.6 mg, 0.5 mmol, 1 equiv) and 9-borabicyclo[3.3.1]nonane (9-BBN) (122 mg, 1.0 mmol, 2.0 equiv) was dissolved in 10 mL of chloroform. The reaction mixture was allowed to stir at 80°C for 12 hours. All volatiles were removed and the resulting white solid was washed three times with hexanes (10 mL) to give the desired product in quantitative yield, the ^1H NMR spectrum of the product is shown in Figure 1 (400 MHz, _CDCl3 , 298K).

Example 2

The synthesis of catalyst CAT2, the synthetic route is as follows:

的分子结构式如下：in,

The molecular structure is as follows:

The preparation process is as follows:

In a flame-dried Schlenk vessel, combine diallyldiphenylphosphine iodide (307 mg, 0.78 mmol, 1 equiv) and 9-borabicyclo[3.3.1]nonane (9-BBN) (190.4 mg, 1.56 mmol, 2 equiv) was dissolved in 10 mL of _CHCl3 . The reaction mixture was allowed to stir at 80°C for 12 hours. All volatiles were removed and the resulting white solid was washed three times with hexanes (10 mL) to give the desired product in quantitative yield, the ^1H NMR spectrum of the product is shown in Figure 2 (400 MHz, _CDCl3 , 298K).

Example 3

The synthesis of catalyst CAT4, the synthetic route is as follows:

The preparation process is as follows:

In a flame dried Schlenk vessel, CAT1 (118.3 mg, 0.2 mmol, 1 equiv) and sodium benzoate (115.3 mg, 0.8 mmol, 4 equiv) were dissolved in 8 ml of _CHCl3 . The reaction mixture was allowed to stir at room temperature for 48 hours. The filtrate was collected by filtration under nitrogen to remove all volatiles, and the resulting white oil was washed three times (10 mL) with hexanes to obtain the desired white quantitative product.

Example 4

The synthesis of catalyst CAT5, the synthetic route is as follows:

The preparation process is as follows:

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

Example 5

The synthesis of catalyst CAT6, the synthetic route is as follows:

The preparation process is as follows:

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

Effect example 1

Utilize catalyst CAT1-CAT6 to catalyze the homopolymerization of propylene oxide, and the synthetic route is as follows:

The preparation process is as follows:

In the glove box, weigh PO and catalyst into a 5mL pressure-resistant vial with a magnetic stirrer that was pre-flame-dried, seal the vial out, set -20 to 25°C as the reaction temperature, PO and catalyst The molar ratio is 200:1～10000:1, and the reaction time is controlled at 10～120min. The key data of application examples 1 to 12 are arranged in Table 1.

Effect example 2

Utilize catalyst CAT1-CAT6 to catalyze the copolymerization reaction of alkylene oxide and _CO2 , the synthetic route is as follows:

The preparation process is as follows:

In the glove box, add the alkylene oxide and the catalyst into the reaction kettle, flush the reaction kettle into a certain pressure of carbon dioxide, and carry out the reaction under the set temperature conditions, and characterize the monomer conversion rate and product selectivity by NMR (Proportion of polycarbonate, polyether, cyclic carbonate). The key data of application examples 13 to 36 are arranged in Table 2-5.

Table 2

table 3

Table 4

table 5

Effect example 3

Utilize catalyst CAT1-CAT6 to catalyze the copolymerization of alkylene oxide and cyclic acid anhydride, and the synthetic route is as follows:

The preparation process is as follows:

In the glove box, take an appropriate amount of cyclic acid anhydride, alkylene oxide and catalyst into a pressure-resistant bottle, and react at 60-180°C for 10min-12h. The reaction solution was taken and tested by NMR to characterize the conversion rate of monomers and the selectivity of products. After precipitation from methanol and filter drying, the polymer was analyzed for GPC data. The key data of application examples 37 to 53 are arranged in Table 6-7.

Table 6

Table 7

Effect example 4

Utilize catalyst CAT1-CAT6 to catalyze cyclic lactone homopolymerization, and the synthetic route is as follows:

The preparation process is as follows:

In the glove box, add an appropriate amount of cyclic lactone monomer and catalyst into a pressure-resistant bottle, and add a certain amount of organic solvent, and react at -10℃-80℃ for 2-12h. The reaction solution was taken, the conversion rate of the monomer and the selectivity of the product were characterized by nuclear magnetic resonance, the polymer was filtered, and the polyester target product was obtained after drying, which was subjected to GPC analysis. The key data of Application Examples 54 to 55 are summarized in Table 8.

Table 8

Effect example 5

Utilize catalyst CAT7-CAT24 to catalyze cyclic lactone homopolymerization, and the synthetic route is as follows:

The preparation method of catalysts CAT7-CAT24 is the same as that of CAT1-CAT6.

The preparation process is as follows:

In a glove box, add an appropriate amount of propylene oxide monomer and catalyst into a pressure-resistant bottle, and react at 25°C-100°C for 2-12 hours. The reaction solution was taken and tested by NMR to characterize the conversion rate of monomers and the selectivity of products. The key data of application examples 56 to 61 are summarized in Table 9.

Table 9

Claims (10)

1. A phosphorus salt amphiphilic dual-functional organic catalyst is characterized in that the structural formula of the organic catalyst is as follows:

wherein X is an anion, R¹And R²Are identical or different substituents, or R¹And R²Forming a bond or a ring through a covalent bond, wherein n is an integer of more than 1; y is

Wherein R is₁、R₂And R₃Respectively is one or a combination of more than two of hydrogen atoms or substituted/unsubstituted C1-C50 alkyl, C3-C50 cycloalkyl, C3-C50 alkenyl, C3-C50 alkynyl, C6-C50 aryl, C3-C50 heterocyclic radical, C5-C50 hetero or all-carbon aromatic radical containing one or more than two of N, O, P, Si and S atoms.

2. The amphiphilic bifunctional organic catalyst as claimed in claim 1, wherein Y is BR₃，BR₃Being cyclic boranes or aliphatic or aromatic boranes, R₃The structure of (A) is as follows:

wherein

Is a connecting bond, and m is an integer of 1 to 30.

3. The phosphonium salt amphiphilic bifunctional organic catalyst as claimed in claim 1, wherein X is 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.

4. The amphiphilic bifunctional organic catalyst of any one of claims 1 to 3, wherein the organic catalyst has the following structure:

5. the preparation method of the amphiphilic bifunctional organic phosphorus salt catalyst as claimed in any one of claims 1 to 4, wherein the organic phosphorus salt catalyst is obtained by carrying out a hydroboration reaction on SM containing two unsaturated double bonds and a hydroboration reagent containing at least one boron hydrogen bond;

the structure of the SM is as follows:

wherein X is an anion, R¹And R²Are identical or different substituents, or R¹And R²Forming a bond or a ring through a covalent bond, wherein n is an integer of more than 1;

the hydroboration reagent is ring, aliphatic or aromatic borane containing one or more than two of the following structures:

wherein

Is a connecting bond, and m is an integer of 1 to 30.

6. The method for preparing the amphiphilic bifunctional organic catalyst containing phosphorus salt as claimed in claim 5, wherein the method for preparing the organic catalyst comprises: mixing SM and a hydroboration reagent in an 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 dual-functional organic catalyst;

the organic solvent is one or more than two of tetrahydrofuran, benzene, toluene, chloroform, dichloromethane, hexane, diethyl ether, carbon tetrachloride, N-dimethylformamide, ethyl acetate and 1, 4-dioxane which are mixed in any proportion.

7. The application of the phosphorus salt amphiphilic dual-functional organic catalyst in preparation of organic micromolecules or high molecular materials according to any one of claims 1 to 4 is characterized in that the organic micromolecules or high molecular materials are obtained by ring opening polymerization reaction of one or more than two cyclic monomers under the action of a catalyst, or are obtained by coupling the cyclic monomers with carbon dioxide, carbon disulfide, carbon oxysulfide, isothiocyanate, isocyanate or carbon monoxide under the action of a catalyst;

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

8. The use of the phosphonium salt amphiphilic bifunctional organic catalyst as claimed in claim 7, wherein the cyclic monomer comprises one or more of the following structures:

9. the use of the phosphorus salt amphiphilic bifunctional organic catalyst as claimed in claim 7, wherein the catalyst is used for preparing polymer in the presence of chain transfer agent; the chain transfer agent comprises one or more of the following structures:

wherein

Represents the main chain of a macromolecular chain transfer agent, and

the alcoholic hydroxyl group, phenolic hydroxyl group, amino group or carboxylic acid group shown in the main chain does not represent the actual number of functional groups, and the actual number is an arbitrary integer of 1 or more.

10. The phosphorus salt amphiphilic bifunctional organic catalyst as claimed in claim 1 is loaded on inorganic or organic substances for preparing organic small molecule or high molecular material.

Images