Polynuclear phosphoborane catalyst as well as preparation method and application thereof

Abstract

The invention discloses a polynuclear phosphoborane catalyst as well as a preparation method and application thereof, and belongs to the field of chemical synthesis and chemical catalysis. The catalyst is constructed by combining a borane component and an organophosphorus nitrile base ligand, has strong basicity of organophosphorus nitrile base and a multi-center borane Lewis acid site, and can efficiently activate monomers and stabilize active species through acid-base synergism. The preparation method comprises the following steps: taking hexachlorocyclotriphosphazene or octachlorocyclotetraphosphazene as a raw material, carrying out alkylene substitution to obtain a precursor, and reacting the precursor with a hydroboration reagent, so that the synthetic route is simple, and the raw material is easy to obtain. The catalyst can efficiently catalyze epoxide homopolymerization and epoxide and anhydride copolymerization, low-molecular-weight polyether and polyester with controllable structures can be prepared with high selectivity, the molecular weight distribution of the product is narrow, and the application prospect is wide.

Description

Technical Field

[0001] This invention relates to the fields of chemical synthesis and chemical catalysis, specifically a polynuclear phosphoborane catalyst, its preparation method, and its uses. Background Technology

[0002] In the fields of chemical synthesis and chemical catalysis, ring-opening polymerization (ROP) and ring-opening copolymerization (ROCOP) are core technological pathways for preparing high-performance polymer materials such as polyethers and polyesters. These materials are widely used in packaging, pharmaceuticals, engineering materials, and many other fields. The polymerization efficiency, product structure controllability, and mild reaction conditions of cyclic monomers (such as epoxides and acid anhydrides) directly depend on the performance of the catalyst. Therefore, developing efficient and highly selective catalytic systems is a core research focus and key requirement in this field.

[0003] Phosphazene compounds (also known as phosphorazenes) possess excellent basicity and structural tunability due to their characteristic phosphorus-nitrogen (P=N) double bonds, making them widely used in anionic polymerization catalysis. They are suitable for the polymerization reactions of various monomers, including epoxides, cyclosiloxanes, and lactams. The structure of the organophosphazene base is the core factor determining its catalytic performance; its basicity and steric hindrance directly affect monomer activation efficiency, active species stability, and product selectivity.

[0004] In existing technologies, catalysts such as cyclotriphosphazene base CTPB and phosphazene salt P5Cl have been shown to form loose ion pairs with borane Lewis acids, exhibiting certain catalytic activity in the copolymerization reaction of epoxides and carbon dioxide. However, these catalytic systems still have significant technical drawbacks: 1. Traditional phosphazene catalysts often rely on a single active site to function, lacking synergistic optimization of monomer activation, active species stabilization, and chain growth regulation, which limits polymerization efficiency, especially in multi-monomer copolymerization where it is difficult to balance reaction rate and product selectivity.

[0005] 2. Polymers prepared by existing catalysts often suffer from problems such as wide molecular weight distribution, non-uniform end group structure, and difficulty in precisely controlling low molecular weight products, which cannot meet the requirements of high-end materials for refined polymer structure.

[0006] 3. Most catalytic systems require auxiliary conditions such as high temperature and high pressure to achieve effective catalytic activity, which not only increases the complexity of the process and production cost, but may also lead to product contamination or an increase in side reactions.

[0007] 4. Existing phosphazene-borane composite catalysts are mostly designed for specific monomer combinations, and have poor adaptability to different types of cyclic monomers (such as epoxides and acid anhydrides), making it difficult to achieve efficient catalytic preparation of multiple polymers (polyethers, polyesters, etc.) with a single catalyst. Summary of the Invention

[0008] Based on previous research and existing problems, this invention proposes a polynuclear phosphoborane catalyst, its preparation method, and its applications after further research and analysis. The polynuclear phosphoborane catalyst system has the advantages of high activity and easy synthesis, and can be applied to the field of catalytic polymerization with high efficiency and selectivity, greatly expanding the types and application fields of organophosphazenes and organoboron catalysts.

[0009] To achieve the above objectives, the present invention provides the following technical solution: A polynuclear phosphoborane catalyst has the following general structural formula: The skeleton of cyclotriphosphazene is: [P3N3] Where X represents -R1-(CH2) n -BY2 group; The skeleton of cyclotetraphosphazene is: [P4N4] Where X represents -R1-(CH2) n -BY2 group; Among them, BY2 is independently selected from 9-boronbicyclo[3.3.1]nonane derivative group, cyclopentaborane derivative group, cyclohexylborane derivative group, dicyclohexylborane derivative group, diphenylborane derivative group or 3-methylcyclopentaborane derivative group; The derivatized group is a monovalent organoboron group formed by replacing one BH bond on a boron atom in the listed parent borane (the precursor is borane-tetrahydrofuran complex, borane-dimethyl sulfide complex, or free borane hydride), and the bonding mode is through the boron atom bonded to the methylene (-CH2-); R1 is independently selected from N, O, -NH or -CH2; n is a positive integer from 1 to 3 (n=1 corresponds to an allyl derivatized chain, n=2 corresponds to a butenyl derivatized chain, and n=3 corresponds to a pentenyl derivatized chain); The catalyst has an organophosphazene base framework and a multi-center borane Lewis acidic site, which together form a synergistic acid-base pair.

[0010] Preferably, the degree of Cl atom substitution in the cyclotriphosphazene skeleton is 100%, and the degree of Cl atom substitution in the cyclotetraphosphazene skeleton is 100%. The number of Lewis acid sites in multicenter boranes is regulated by the degree of substitution on the phosphazene skeleton. The number of acid sites = the number of substituted Cl atoms or twice the number of substituted Cl atoms. The hexachlorocyclotriphosphazene skeleton can introduce a maximum of 12 acid sites, and the octachlorocyclotetraphosphazene skeleton can introduce a maximum of 16 acid sites.

[0011] This invention also proposes a method for preparing a polynuclear phosphoborane catalyst, comprising the following steps: reacting a phosphazene precursor compound containing an olefin-substituted group with a borohydride reagent HBY2 in an organic solvent via a borohydride reaction, wherein the olefin-substituted phosphazene precursor compound contains an allyl, butenyl, or pentenyl group, respectively, for the values ​​of n=1, 2, and 3 mentioned above; the reaction temperature is 25–60 °C, the reaction time is 12–48 h, the molar ratio of the phosphazene precursor compound containing an olefin-substituted group to the borohydride reagent is 1:(1–16), and the polynuclear phosphoborane catalyst is obtained by purification after the reaction.

[0012] Preferably, the organic solvent is selected from at least one of benzene, toluene, xylene, and tetrahydrofuran; The borohydride reagent HBY2 is selected from at least one of 9-boronbicyclo[3.3.1]nonane, cyclopentylborane, cyclohexylborane, dicyclohexylborane, diphenylborane, and 3-methylcyclopentylborane.

[0013] The preparation method of phosphazene precursor compounds containing olefin substituents is as follows: using hexachlorocyclotriphosphazene or octachlorocyclotetraphosphazene as raw materials, reacting with olefin amines, olefin lithium, olefin Grignard reagents or olefin alcohols in an organic solvent in the presence of an acid-binding agent; The reaction temperature is 0–150℃, the reaction time is 1–72 h, and the molar ratio of raw materials, reaction reagents and acid-binding agents is 1:(1–16):(1–16).

[0014] Preferably, the acid-binding agent is selected from at least one of triethylamine, sodium carbonate, sodium bicarbonate, sodium hydroxide, and potassium hydroxide; The organic solvent is selected from at least one of benzene, toluene, xylene, and tetrahydrofuran; The olefin-based lithium or olefin-based Grignard reagent includes at least one of allyl lithium, allyl lithium, allyl magnesium bromide, 2-methylallyl magnesium bromide, and 4-pentenyl magnesium bromide.

[0015] The present invention also proposes a method for preparing a polymer, using the aforementioned polynuclear phosphoborane catalyst, wherein the polymer is a polyether, the reaction is carried out in the presence of a chain transfer agent, the reaction temperature is -20 to 80°C, and the reaction time is 0.1 to 72 h; The polymer is polyester, and the reaction is carried out in the presence of a chain transfer agent and an organic solvent at a temperature of 80–150 °C for a time of 0.1–72 h.

[0016] Preferably, when the polymer is a polyether, the reactive monomer is at least one epoxide monomer selected from at least one of propylene oxide, ethylene oxide, butane oxide, hexane oxide, and octane oxide.

[0017] Preferably, when the polymer is a polyester, the reactant monomer is a combination of at least two monomers and the reaction is carried out in an organic solvent. The monomers are selected from at least two of cyclohexane oxide, propylene oxide, ethylene oxide, butane oxide, hexane oxide, octane oxide, glutaric anhydride, phthalic anhydride, perphthalic anhydride, and succinic anhydride. The organic solvent is selected from at least one of benzene, toluene, dichloromethane, and tetrahydrofuran.

[0018] Preferably, the chain transfer agent is 1,4-terephthalic acid (BDM), ethylene glycol, 1,3-propanediol or 1,4-butanediol; When the monomer is propylene oxide, the number-average molecular weight of the polyether is 1.4 to 60.0 kg / mol and the molecular weight distribution is 1.03 to 2.16 by adjusting the molar ratio of chain transfer agent to monomer to 0.01 to 1:20. When the molar ratio of the monomers propylene oxide and phthalic anhydride is 2:1, polyesters can be prepared with a number average molecular weight of 25.4–47.5 kg / mol and a molecular weight distribution of 1.06–1.14.

[0019] Compared with the prior art, the present invention provides a polynuclear borane catalyst, its preparation method and uses, which have the following beneficial effects: This invention proposes combining borane components with organophosphazene bases to construct novel polynuclear phospharonane catalysts. The catalyst design draws inspiration from the structural features of organophosphazene bases, introducing multiple Lewis acid sites by embedding multi-center borane structures into the phosphazene base framework. This structural design effectively activates chain transfer agents and monomers and stabilizes active species during the polymerization process, thereby significantly improving catalytic efficiency.

[0020] This invention develops a series of polynuclear phosborane catalysts based on the hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene skeletons by introducing different olefinic substituents. The synthesized polynuclear phosborane catalysts have the following characteristics: by adjusting the skeleton structure of the organophosphazene core (hexachlorocyclotriphosphazene or octachlorocyclotetraphosphazene), the basicity and steric hindrance effect of the catalyst can be adjusted, thereby meeting the needs of different catalytic systems; by selecting different substituents, the number and structure of the introduced boron centers can be controlled, thereby further improving the steric hindrance effect and catalytic activity.

[0021] The synthesis of the catalyst of this invention is based on a one-step, highly efficient hydroboration reaction between an allyl-containing phosphazene precursor compound and a hydroboration reagent. This method has mild reaction conditions, a simple operation process, and relatively readily available raw materials, which is conducive to the large-scale preparation of the catalyst.

[0022] The catalyst system can efficiently and selectively catalyze the ring-opening polymerization (ROP) and ring-opening copolymerization (ROCOP) of various cyclic monomers (such as epoxides, cyclic esters, cyclic carbonates, etc.), and is suitable for preparing polymers with diverse structures (such as polyethers, polyesters, etc.).

[0023] This invention successfully constructs a novel type of organophosphazene-multi-center organoboron catalyst. Its unique structure can be systematically regulated by changing the substituent (R1), boron center (BY2), and phosphazene skeleton, which greatly expands the types and application range of organophosphazene-organoboron catalysts and has important research value and broad application prospects. Attached Figure Description

[0024] Figure 1 The polynuclear borane catalyst CAT1 provided in Example 1 of this invention. 1 HNMR spectrum; Figure 2 The polynuclear borane catalyst CAT1 provided in Example 1 of this invention. 11 BNMR spectrum; Figure 3 The polynuclear phosphoborane catalyst CAT4 provided in Example 2 of this invention. 1 HNMR spectrum; Figure 4 The polynuclear phosphoborane catalyst CAT4 provided in Example 2 of this invention. 11 BNMR spectrum; Figure 5 It is the polynuclear phosphoborane catalyst CAT25 provided in Example 3 of this invention. 1 HNMR spectrum; Figure 6 It is the polynuclear phosphoborane catalyst CAT25 provided in Example 3 of this invention. 11 BNMR spectrum; Figure 7 The polyether provided in Example 7 of this invention is... 1 HNMR spectrum; Figure 8 This is the GPC spectrum of the polyether provided in Application Example 7 of this invention; Figure 9 The polyether provided in Example 16 of this invention. 1 HNMR spectrum; Figure 10 This is the GPC spectrum of the polyether provided in Application Example 16 of the present invention; Figure 11 The polyether provided in Application Example 19 of this invention 1 HNMR spectrum; Figure 12 This is the GPC spectrum of the polyether provided in Application Example 19 of this invention; Figure 13 The polyester provided in Application Example 22 of this invention 1 HNMR spectrum; Figure 14 This is the GPC spectrum of the polyester provided in Application Example 22 of the present invention. Detailed Implementation

[0025] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments.

[0026] Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0027] The present invention preferably proposes the following 33 catalysts: The following is a detailed record of the specific preparation methods and performance experiments of the above 33 catalysts: Example 1 The precursor for catalyst CAT1 was prepared by reacting hexachlorocyclotriphosphazene with allylamine hydrochloride, and the specific operation is as follows: Hexachlorocyclotriphosphazene (4.0 g, 11.51 mmol) and allylamine hydrochloride (8.0 g, 85.51 mmol) were added to a Schlenk flask pre-filled with toluene (70 mL), followed by the dropwise addition of triethylamine (23.5 mL, 169.07 mmol). The solution was heated to 110 °C. o Heated at C for 72 h. The reaction mixture was filtered and concentrated under vacuum to obtain a solid product. The solid product was dried under vacuum at room temperature for 18 h, with a yield of 81%.

[0028] 1 HNMR (400MHz, CDCl3) δ5.89(m,6H),5.18(dq,6H),5.01(dq,6H),3.53(m,12H),2.23(br,6H). 31 PNMR (162MHz, CDCl3) δ 18.26. The CAT1 catalyst precursor was selected and prepared with 9-boron bicyclic [3.3.1]nonane (9-BBN) to prepare the polynuclear phosphoborane catalyst CAT1. The specific operation is as follows: In the glove box, the catalyst CAT1 precursor hexamethyleneaminocyclotriphosphazene was placed... (0.5 g, 1.06 mmol) was added to a pre-dried solvent storage bottle equipped with a magnetic stir bar, and 9-boronbicyclo[3.3.1]nonane (0.5 min THF) (18.7 mL, 6.36 mmol) was added dropwise. The solution was heated to 60 °C. o The mixture was heated at C for 48 h. The reaction mixture was concentrated under vacuum to obtain a crude solid product, which was further purified by washing three times with pentane. The white solid product CAT1 was dried under vacuum at room temperature for 18 h. Yield: 99%.

[0029] 1 HNMR (400MHz, CDCl3) δ2.90(m,12H),2.20(m,6H),1.72(m,84H),1.30(m,12H),1.16(m,12H). 31 PNMR (162MHz, CDCl3) δ 18.68. 11 BNMR (128MHz, CDCl3) δ 82.89. Example 2 The CAT2 catalyst precursor was selected and prepared with cyclopentadienoic borane to prepare the polynuclear phosphoroborane catalyst CAT2, in the same way as CAT1.

[0030] Example 3 The CAT3 catalyst precursor was selected and cyclohexylborane was used to prepare the polynuclear phosphoroborane catalyst CAT3, which was prepared in the same way as CAT1.

[0031] Example 4 The precursor for catalyst CAT4 was prepared by reacting hexachlorocyclotriphosphazene with diallylamine, and the specific steps are as follows: Hexachlorocyclotriphosphazene (4.0 g, 11.51 mmol) and diallylamine (23.1 mL, 184.16 mmol) were added to a Schlenk flask pre-filled with toluene (70 mL), followed by the dropwise addition of triethylamine (23.5 mL, 169.07 mmol). The mixture was heated to 110 °C. o Heated at C for 72 h. Filter the reaction mixture and concentrate under vacuum to obtain an oily product. Dry the oily product under vacuum at room temperature for 18 h. Yield 50%.

[0032] 1 HNMR (400MHz, CDCl3) δ5.79(m,12H),5.08(m,24H),3.57(m,24H). 31 PNMR (162MHz, CDCl3) δ 21.22. The CAT4 catalyst precursor was prepared by reacting 9-boron bicyclic [3.3.1]nonane (9-BBN) with the catalyst precursor. The specific operation is as follows: In the glove box, the catalyst CAT4 precursor, dodecaallylaminocyclotriphosphazene, is... (0.5 g, 0.70 mmol) was added to a pre-dried solvent storage bottle equipped with a magnetic stir bar, and 9-boronbicyclo[3.3.1]nonane (0.5 min THF) (16.9 mL, 8.43 mmol) was added dropwise. The solution was heated to 60 °C. o Heated at C for 48 h. The reaction mixture was concentrated under vacuum to obtain a crude solid product, which was further purified by washing three times with pentane. The white solid product CAT4 was dried under vacuum at room temperature for 18 h. Yield 99%.

[0033] 1 HNMR (400MHz, CDCl3) δ3.01(m,12H),1.75(m,84H),1.30(m,12H),1.20(m,12H). 31 PNMR (162MHz, CDCl3) δ 21.74. 11 BNMR (128MHz, CDCl3) δ 87.96. Example 5 The CAT5 catalyst precursor was selected and prepared with cyclopentadienoic borane to prepare the polynuclear phosphoroborane catalyst CAT5, in the same way as CAT4.

[0034] Example 6 The CAT6 catalyst precursor was selected and cyclohexylborane was used to prepare the polynuclear phosphoroborane catalyst CAT6, which was prepared in the same way as CAT4.

[0035] Example 7 The precursor for catalyst CAT7 was prepared by reacting hexachlorocyclotriphosphazene with allyl magnesium bromide, and the specific operation is as follows: Hexachlorocyclotriphosphazene (4.0 g, 11.51 mmol) and allyl magnesium bromide (92.1 mL, 92.08 mmol) were added to a Schlenk flask and incubated at 67°C. o Heated at C for 72 h. Filter the reaction mixture and concentrate under vacuum to obtain an oily product. Dry the oily product under vacuum at room temperature for 18 h. Yield 65%.

[0036] The CAT7 catalyst precursor was selected and prepared with 9-boron bicyclic [3.3.1]nonane (9-BBN) to prepare the polynuclear phosphoborane catalyst CAT7. The specific operation is as follows: In the glove box, the catalyst CAT7 precursor hexamethylenecyclotriphosphazene was placed... (0.5 g, 1.31 mmol) was added to a pre-dried solvent storage bottle equipped with a magnetic stir bar, and 9-boronbicyclo[3.3.1]nonane (0.5 min THF) (15.7 mL, 7.86 mmol) was added dropwise. The solution was heated to 60 °C. o Heated at C for 48 h. The reaction mixture was concentrated under vacuum to obtain a crude solid product, which was further purified by washing three times with pentane. The white solid product CAT7 was dried under vacuum at room temperature for 18 h. Yield 99%.

[0037] Example 8 The CAT8 catalyst precursor was selected and prepared with cyclopentadienoic borane to prepare the polynuclear phosphoroborane catalyst CAT8, in the same way as CAT7.

[0038] Example 9 The CAT9 catalyst precursor was selected and cyclohexylborane was used to prepare the polynuclear phosphoroborane catalyst CAT9, and the preparation method was the same as that for CAT7.

[0039] Example 10 The precursor for catalyst CAT10 was prepared by reacting hexachlorocyclotriphosphazene with allyl alcohol, and the specific operation is as follows: Hexachlorocyclotriphosphazene (4.0 g, 11.51 mmol) and allyl alcohol (5.8 mL, 85.51 mmol) were added to a Schlenk flask pre-filled with toluene (70 mL), followed by the dropwise addition of triethylamine (23.5 mL, 169.07 mmol). The mixture was heated to 110 °C. o Heated at C for 72 h. The reaction mixture was filtered and concentrated under vacuum to obtain a solid product. The solid product was dried under vacuum at room temperature for 18 h, yield 54%.

[0040] The CAT10 catalyst precursor was prepared by reacting 9-boron bicyclic [3.3.1]nonane (9-BBN) with the catalyst precursor. The specific operation is as follows: In the glove box, the catalyst CAT10 precursor hexamethyleneoxycyclotriphosphazene was placed... (0.5 g, 1.04 mmol) was added to a pre-dried solvent storage bottle equipped with a magnetic stir bar, and 9-boronbicyclo[3.3.1]nonane (0.5 min THF) (12.5 mL, 6.24 mmol) was added dropwise. The solution was heated to 60 °C. o Heated at C for 48 h. The reaction mixture was concentrated under vacuum to obtain a crude solid product, which was further purified by washing three times with pentane. The white solid product CAT10 was dried under vacuum at room temperature for 18 h. Yield 99%.

[0041] Example 11 The CAT11 catalyst precursor was selected and prepared with cyclopentadienoic borane to prepare the polynuclear phosphoroborane catalyst CAT11, which was prepared in the same way as CAT10.

[0042] Example 12 The CAT12 catalyst precursor was selected and prepared with cyclohexylborane to prepare the polynuclear phosphoroborane catalyst CAT12, which was prepared in the same way as CAT10.

[0043] Example 13 The precursor for catalyst CAT13 was prepared by reacting octachlorocyclotetraphosphazene with allylamine hydrochloride, and the specific operation is as follows: Octachlorocyclotetraphosphazene (4.0 g, 8.63 mmol) and allylamine hydrochloride (6.5 g, 69.04 mmol) were added to a Schlenk flask pre-filled with toluene (70 mL), followed by the dropwise addition of triethylamine (19.2 mL, 138.08 mmol) at 110 °C. o Heated at C for 72 h. The reaction mixture was filtered and concentrated under vacuum to obtain a solid product. The solid product was dried under vacuum at room temperature for 18 h, yield 54%.

[0044] The CAT13 catalyst precursor was selected and prepared with 9-boron bicyclic [3.3.1]nonane (9-BBN) to prepare the polynuclear phosphoborane catalyst CAT13. The specific operation is as follows: In the glove box, the catalyst CAT13 precursor octaallylaminocyclotetraphosphazene was placed... (0.5 g, 0.80 mmol) was added to a pre-dried solvent storage bottle equipped with a magnetic stir bar, and 9-boronbicyclo[3.3.1]nonane (0.5 min THF) (12.8 mL, 6.40 mmol) was added dropwise. The solution was heated to 60 °C. o Heated at C for 48 h. The reaction mixture was concentrated under vacuum to obtain a crude solid product, which was further purified by washing three times with pentane. The white solid product CAT13 was dried under vacuum at room temperature for 18 h. Yield 99%.

[0045] Example 14 The CAT14 catalyst precursor was selected and prepared with cyclopentadienoic borane to prepare the polynuclear phosphoroborane catalyst CAT14, which was prepared in the same way as CAT13.

[0046] Example 15 The CAT15 catalyst precursor was selected and prepared with cyclohexylborane to prepare the polynuclear phosphoroborane catalyst CAT15, which was prepared in the same way as CAT13.

[0047] Example 16 Octachlorocyclotetraphosphazene and diallylamine were selected to prepare the catalyst CAT16 precursor, and the specific operation is as follows: Octachlorocyclotetraphosphazene (4.0 g, 8.63 mmol) and diallylamine (8.5 mL, 69.04 mmol) were added to a Schlenk flask pre-filled with toluene (70 mL), followed by the dropwise addition of triethylamine (19.2 mL, 138.08 mmol). The mixture was heated to 110 °C. o Heated at C for 72 h. The reaction mixture was filtered and concentrated under vacuum to obtain a solid product. The solid product was dried under vacuum at room temperature for 18 h, with a yield of 63%.

[0048] The CAT16 catalyst precursor was selected and prepared with 9-boron bicyclic [3.3.1]nonane (9-BBN) to prepare the polynuclear phosphoborane catalyst CAT16. The specific operation is as follows: In the glove box, the catalyst CAT16 precursor hexadecylaminocyclotetraphosphazene was placed... (0.5 g, 0.53 mmol) was added to a pre-dried solvent storage bottle equipped with a magnetic stir bar, and 9-boronbicyclo[3.3.1]nonane (0.5 min THF) (17.0 mL, 8.48 mmol) was added dropwise. The solution was heated to 60 °C. o Heated at C for 48 h. The reaction mixture was concentrated under vacuum to obtain a crude solid product, which was further purified by washing three times with pentane. The white solid product CAT16 was dried under vacuum at room temperature for 18 h. Yield 99%.

[0049] Example 17 The CAT17 catalyst precursor was selected and prepared with cyclopentadienoic borane to prepare the polynuclear phosphoroborane catalyst CAT17, which was prepared in the same way as CAT16.

[0050] Example 18 The CAT18 catalyst precursor was selected and cyclohexylborane was used to prepare the polynuclear phosphoroborane catalyst CAT18, which was prepared in the same way as CAT16.

[0051] Example 19 Octachlorocyclotetraphosphazene was selected to prepare the catalyst CAT19 precursor with allyl magnesium bromide. The specific operation is as follows: Octachlorocyclotetraphosphazene (4.0 g, 8.63 mmol) and allyl magnesium bromide (69.0 mL, 69.04 mmol) were added to a Schlenk flask and heated to 67 °C. o Heated at C for 72 h. Filter the reaction mixture and concentrate under vacuum to obtain an oily product. Dry the oily product under vacuum at room temperature for 18 h. Yield 48%.

[0052] The CAT19 catalyst precursor was selected and prepared with 9-boron bicyclic [3.3.1]nonane (9-BBN) to prepare the polynuclear phosphoborane catalyst CAT19. The specific operation is as follows: In the glove box, the catalyst CAT19 precursor octaallylcyclotetraphosphazene was placed... (0.5 g, 0.98 mmol) was added to a pre-dried solvent storage bottle equipped with a magnetic stir bar, and 9-boronbicyclo[3.3.1]nonane (0.5 minTHF) (15.7 mL, 7.84 mmol) was added dropwise. The solution was heated to 60 °C. o Heated at C for 48 h. The reaction mixture was concentrated under vacuum to obtain a crude solid product, which was further purified by washing three times with pentane. The white solid product CAT19 was dried under vacuum at room temperature for 18 h. Yield 99%.

[0053] Example 20 The CAT20 catalyst precursor was selected and prepared by cyclopentadienoic borane in the same way as CAT19.

[0054] Example 21 The precursor of catalyst CAT21 was selected and cyclohexylborane was used to prepare polynuclear phosphoroborane catalyst CAT21, and the preparation method was the same as that of CAT19.

[0055] Example 22 The precursor for catalyst CAT22 was prepared by reacting octachlorocyclotetraphosphazene with allyl alcohol, and the specific steps are as follows: Octachlorocyclotetraphosphazene (4.0 g, 8.63 mmol) and allyl alcohol (4.7 mL, 69.04 mmol) were added to a Schlenk flask pre-filled with toluene (70 mL), followed by the dropwise addition of triethylamine (19.2 mL, 138.08 mmol). The mixture was heated to 110 °C. o Heated at C for 72 h. The reaction mixture was filtered and concentrated under vacuum to obtain a solid product. The solid product was dried under vacuum at room temperature for 18 h, yield 43%.

[0056] The CAT22 catalyst precursor was prepared by reacting 9-boron bicyclic [3.3.1]nonane (9-BBN) with the catalyst precursor. The specific operation is as follows: In the glove box, the catalyst CAT22 precursor octaallyloxycyclotetraphosphazene was placed... (0.5 g, 0.79 mmol) was added to a pre-dried solvent storage bottle equipped with a magnetic stir bar, and 9-boronbicyclo[3.3.1]nonane (0.5 min THF) (12.6 mL, 6.32 mmol) was added dropwise. The solution was heated to 60 °C. o Heated at C for 48 h. The reaction mixture was concentrated under vacuum to obtain a crude solid product, which was further purified by washing three times with pentane. The white solid product CAT22 was dried under vacuum at room temperature for 18 h. Yield 99%.

[0057] Example 23 The precursor of catalyst CAT23 was selected and prepared with cyclopentadienoic borane to prepare polynuclear phosphoroborane catalyst CAT23, in the same way as CAT22.

[0058] Example 24 The precursor of catalyst CAT24 was selected and cyclohexylborane was used to prepare polynuclear phosphoroborane catalyst CAT24, and the preparation method was the same as that of CAT22.

[0059] Example 25 The precursor for catalyst CAT25 was prepared by reacting hexachlorocyclotriphosphazene with N-methylallylamine, and the specific steps are as follows: Hexachlorocyclotriphosphazene (4.0 g, 11.51 mmol) and N-methylallylamine (8.9 mL, 92.08 mmol) were added to a Schlenk flask pre-filled with toluene (70 mL), followed by the dropwise addition of triethylamine (25.6 mL, 184.16 mmol). The mixture was heated to 110 °C. o Heated at C for 72 h. Filter the reaction mixture and concentrate under vacuum to obtain an oily product. Dry the oily product under vacuum at room temperature for 18 h. Yield 78%.

[0060] 1 HNMR (400MHz, CDCl3) δ5.77(m,6H),5.15(m,12H),3.56(m,12H),2.54(m,18H). 31 PNMR (162MHz, CDCl3) δ 24.27. The CAT25 catalyst precursor was prepared by combining 9-boron bicyclic [3.3.1]nonane (9-BBN). The specific procedures are as follows: In the glove box, the catalyst CAT25 precursor N-hexamethylallylcyclotriphosphazene was placed... (0.5 g, 0.90 mmol) was added to a pre-dried solvent storage bottle equipped with a magnetic stir bar, and 9-boronbicyclo[3.3.1]nonane (0.5 min THF) (10.8 mL, 5.40 mmol) was added dropwise. The solution was heated to 60 °C. o Heated at C for 48 h. The reaction mixture was concentrated under vacuum to obtain a crude solid product, which was further purified by washing three times with pentane. The white solid product CAT25 was dried under vacuum at room temperature for 18 h. Yield 99%.

[0061] 1 HNMR (400MHz, CDCl3) δ2.89(m,12H),2.55(m,12H),1.70(m,84H),1.23(m,18H). 31PNMR (162MHz, CDCl3) δ 24.58. 11 BNMR (128MHz, CDCl3) δ 88.51. Example 26 The CAT26 precursor was selected and prepared with cyclopentadienoic borane to prepare the polynuclear phosphoroborane catalyst CAT26, in the same manner as CAT25.

[0062] Example 27 The precursor of catalyst CAT27 was selected and cyclohexylborane was used to prepare polynuclear phosphoroborane catalyst CAT27, and the preparation method was the same as that of CAT25.

[0063] Example 28 The precursor for catalyst CAT28 was prepared by reacting hexachlorocyclotriphosphazene with allylamine hydrochloride, and the specific steps are as follows: Hexachlorocyclotriphosphazene (4.0 g, 11.51 mmol) and allylamine hydrochloride (8.0 g, 85.51 mmol) were added to a Schlenk flask pre-filled with toluene (70 mL), followed by the dropwise addition of triethylamine (23.5 mL, 169.07 mmol). The solution was heated to 110 °C. o Heated at C for 72 h. Filter the reaction mixture and concentrate under vacuum to obtain a solid product. Dry the solid product under vacuum at room temperature for 18 h. Yield 81%.

[0064] 1 HNMR (400MHz, CDCl3) δ5.89(m,6H),5.18(dq,6H),5.01(dq,6H),3.53(m,12H),2.23(br,6H). 31 PNMR (162MHz, CDCl3) δ 18.26. The CAT28 catalyst precursor was prepared by combining 9-boron bicyclic [3.3.1]nonane (9-BBN). The specific procedures are as follows: In the glove box, the catalyst CAT28 precursor hexamethyleneaminocyclotriphosphazene was placed... (0.5 g, 1.06 mmol) was added to a pre-dried solvent storage bottle equipped with a magnetic stir bar, and 9-boronbicyclo[3.3.1]nonane (0.5 min THF) (3.1 mL, 1.06 mmol) was added dropwise. The solution was heated at 60 °C. o Heated at C for 48 h. The reaction mixture was concentrated under vacuum to obtain a crude solid product, which was further purified by washing three times with pentane. The white solid product CAT28 was dried under vacuum at room temperature for 18 h. Yield 99%.

[0065] 1HNMR (400MHz, CDCl3) δ5.85(m,5H),5.15(m,5H),4.89(m,5H),3.49(m,10H),2.73(m,12H),2.22(m,6H),1.68(m,14H),1.30(m,2H),1.25(m,2H). 31 PNMR (162MHz, CDCl3) δ 18.35. 11 BNMR (128MHz, CDCl3) δ 82.46. Example 29 The precursor of catalyst CAT29 was selected and prepared with cyclopentadienoic borane to prepare polynuclear phosphoroborane catalyst CAT29, in the same way as CAT28.

[0066] Example 30 The CAT30 catalyst precursor was selected and prepared by cyclohexylborane to prepare the polynuclear phosphoroborane catalyst CAT30, which was prepared in the same way as CAT28.

[0067] Example 31 The precursor for catalyst CAT31 was prepared by reacting hexachlorocyclotriphosphazene with allylamine hydrochloride, and the specific operation is as follows: Hexachlorocyclotriphosphazene (4.0 g, 11.51 mmol) and allylamine hydrochloride (8.0 g, 85.51 mmol) were added to a Schlenk flask pre-filled with toluene (70 mL), followed by the dropwise addition of triethylamine (23.5 mL, 169.07 mmol). The solution was heated to 110 °C. o Heated at C for 72 h. Filter the reaction mixture and concentrate under vacuum to obtain a solid product. Dry the solid product under vacuum at room temperature for 18 h. Yield 81%.

[0068] 1 HNMR (400MHz, CDCl3) δ5.89(m,6H),5.18(dq,6H),5.01(dq,6H),3.53(m,12H),2.23(br,6H). 31 PNMR (162MHz, CDCl3) δ 18.26. The CAT31 catalyst precursor was prepared by reacting 9-boron bicyclic [3.3.1]nonane (9-BBN) with the catalyst precursor. The specific operation is as follows: In the glove box, the catalyst CAT31 precursor hexamethyleneaminocyclotriphosphazene was placed... (0.5 g, 1.06 mmol) was added to a pre-dried solvent storage bottle equipped with a magnetic stir bar, and 9-boronbicyclo[3.3.1]nonane (0.5 min THF) (9.3 mL, 3.18 mmol) was added dropwise. The solution was then heated at 60 °C.o The mixture was heated at C for 48 h. The reaction mixture was concentrated under vacuum to obtain a crude solid product, which was further purified by washing three times with pentane. The white solid product CAT31 was dried under vacuum at room temperature for 18 h. Yield: 99%.

[0069] 1 HNMR (400MHz, CDCl3) δ5.82(m,3H),5.13(m,3H),4.90(m,3H),3.53(m,6H),2.58(m,12H),2.34(m,6H),1.71(m,42H),1.33(m,6H),1.28(m,6H). 31 PNMR (162MHz, CDCl3) δ 18.47. 11 BNMR (128MHz, CDCl3) δ 82.85. Example 32 The CAT32 precursor was selected and cyclopentadienoic borane was used to prepare the polynuclear phosphoroborane catalyst CAT32, which was prepared in the same way as CAT31.

[0070] Example 33 The CAT33 catalyst precursor was selected and prepared with cyclohexylborane to prepare the polynuclear phosphoroborane catalyst CAT33, which was prepared in the same way as CAT31.

[0071] The following are examples of the application of polynuclear borane catalysts in polymerization reactions.

[0072] Application Example 1: Utilizing CAT1 to catalyze the homopolymerization of propylene oxide (PO) In a glove box, add CAT1 (20 μL, 0.01 mmol), 1,4-phenylenediamine (BDM) (1.38 mg, 0.01 mmol), and PO (0.7 mL, 10.0 mmol) to a pre-dried 10 mL pressure-resistant bottle equipped with a magnetic stirrer at 25°C. o The reaction was carried out at C for 6 min, and the reaction was quenched after completion. A portion of the reaction solution was taken for analysis, and the conversion rate was 99%. The number-average molecular weight was determined by GPC. M n It is 22.6 kg / mol, and the molecular weight distribution is... Ð It is 1.51.

[0073] Application Example 2: Utilizing CAT1 to catalyze the homopolymerization of propylene oxide (PO) In a glove box, add CAT1 (20 μL, 0.01 mmol), BDM (1.38 mg, 0.01 mmol), and PO (1.4 mL, 20.0 mmol) to a pre-dried 10 mL pressure-resistant bottle equipped with a magnetic stirrer. Heat to 25 °C. o The reaction was carried out at C for 15 min, and the reaction was quenched after completion. A portion of the reaction solution was taken for analysis, and the conversion rate was 99%. The number-average molecular weight was determined by GPC. M n It is 41.2 kg / mol, and the molecular weight distribution is... Ð It is 1.57.

[0074] Application Example 3: Utilizing CAT1 to catalyze the homopolymerization of propylene oxide (PO) In a glove box, add CAT1 (20 μL, 0.01 mmol), BDM (1.38 mg, 0.01 mmol), and PO (3.5 mL, 50.0 mmol) to a pre-dried 10 mL pressure-resistant bottle equipped with a magnetic stirrer at 25°C. o The reaction was carried out at C for 20 min, and the reaction was quenched after completion. A portion of the reaction solution was taken for analysis, and the conversion rate was 57%. The number-average molecular weight was determined by GPC. M n It is 44.1 kg / mol, and the molecular weight distribution is... Ð It is 1.54.

[0075] Application Example 4: Utilizing CAT1 to catalyze the homopolymerization of propylene oxide (PO) In a glove box, add CAT1 (20 μL, 0.01 mmol), BDM (1.38 mg, 0.01 mmol), and PO (7.0 mL, 100.0 mmol) to a pre-dried 10 mL pressure-resistant bottle equipped with a magnetic stirrer at 25°C. o The reaction was carried out at C for 40 min, and the reaction was quenched after completion. A portion of the reaction solution was taken for analysis, and the conversion rate was 52%. The number-average molecular weight was determined by GPC. M n It is 60.0 kg / mol, and the molecular weight distribution is... Ð It is 1.60.

[0076] Application Example 5: Utilizing CAT1 to catalyze the homopolymerization of propylene oxide (PO) In a glove box, add CAT1 (20 μL, 0.01 mmol), BDM (13.8 mg, 0.1 mmol), and PO (1.4 mL, 20.0 mmol) to a pre-dried 10 mL pressure-resistant bottle equipped with a magnetic stirrer. Heat to 25 °C. o The reaction was carried out at C for 120 min, and the reaction was quenched after completion. A portion of the reaction solution was taken for analysis, and the conversion rate was 99%. The number-average molecular weight was determined by GPC. M n It is 9.6 kg / mol, and the molecular weight distribution is... Ð It is 1.12.

[0077] Application Example 6: Utilizing CAT1 to catalyze the homopolymerization of propylene oxide (PO) In a glove box, add CAT1 (20 μL, 0.01 mmol), BDM (27.6 mg, 0.2 mmol), and PO (1.4 mL, 20.0 mmol) to a pre-dried 10 mL pressure-resistant bottle equipped with a magnetic stirrer at 25°C. o The reaction was carried out at C for 210 min, and the reaction was quenched after completion. A portion of the reaction solution was taken for analysis, and the conversion rate was 99%. The number-average molecular weight was determined by GPC. M n It is 5.6 kg / mol, and the molecular weight distribution is... Ð It is 1.05.

[0078] Application Example 7: Utilizing CAT1 to catalyze the homopolymerization of propylene oxide (PO) In a glove box, add CAT1 (20 μL, 0.01 mmol), BDM (69.1 mg, 0.5 mmol), and PO (1.4 mL, 20.0 mmol) to a pre-dried 10 mL pressure-resistant bottle equipped with a magnetic stirrer at 25°C. o The reaction was carried out at C for 300 min. After the reaction was completed, the reaction was quenched, and a portion of the reaction solution was taken for analysis. The conversion rate was 99%. The number-average molecular weight was determined by GPC. M n It is 2.4 kg / mol, and the molecular weight distribution is... Ð It is 1.04.

[0079] Application Example 8: Utilizing CAT1 to catalyze the homopolymerization of propylene oxide (PO) In a glove box, add CAT1 (20 μL, 0.01 mmol), BDM (138.0 mg, 1 mmol), and PO (1.4 mL, 20.0 mmol) to a pre-dried 10 mL pressure-resistant bottle equipped with a magnetic stirrer. Heat to 25 °C. o The reaction was carried out at C for 360 min. After the reaction was completed, the reaction was quenched, and a portion of the reaction solution was taken for analysis. The conversion rate was 99%. The number-average molecular weight was determined by GPC. M n It is 1.4 kg / mol, and the molecular weight distribution is... Ð It is 1.05.

[0080] Application Example 9: Utilizing CAT4 to catalyze the homopolymerization of propylene oxide (PO) In a glove box, add CAT4 (20 μL, 0.01 mmol), BDM (1.38 mg, 0.01 mmol), and PO (0.7 mL, 10.0 mmol) to a pre-dried 10 mL pressure-resistant bottle equipped with a magnetic stirrer at 25°C. o The reaction was carried out at C for 5 min, and the reaction was quenched after completion. A portion of the reaction solution was taken for analysis, and the conversion rate was 99%. The number-average molecular weight was determined by GPC. M n It is 21.5 kg / mol, and the molecular weight distribution is... Ð It is 2.00.

[0081] Application Example 10: Homopolymerization of propylene oxide (PO) catalyzed by CAT4 In a glove box, add CAT4 (20 μL, 0.01 mmol), BDM (1.38 mg, 0.01 mmol), and PO (1.4 mL, 20.0 mmol) to a pre-dried 10 mL pressure-resistant bottle equipped with a magnetic stirrer at 25°C. o The reaction was carried out at C for 10 min, and the reaction was quenched after completion. A portion of the reaction solution was taken for analysis, and the conversion rate was 99%. The number-average molecular weight was determined by GPC. M n It is 38.6 kg / mol, and the molecular weight distribution is... Ð It is 1.98.

[0082] Application Example 11: Utilizing CAT4 to catalyze the homopolymerization of propylene oxide (PO) In a glove box, add CAT4 (20 μL, 0.01 mmol), BDM (1.38 mg, 0.01 mmol), and PO (3.5 mL, 50.0 mmol) to a pre-dried 10 mL pressure-resistant bottle equipped with a magnetic stirrer at 25°C. o The reaction was carried out at C for 15 min. After the reaction was completed, the reaction was quenched, and a portion of the reaction solution was taken for analysis. The conversion rate was 65.3%. The number-average molecular weight was determined by GPC. M n It is 55.8 kg / mol, and the molecular weight distribution is... Ð It is 1.88.

[0083] Application Example 12: Using CAT4 to catalyze the homopolymerization of propylene oxide (PO) In a glove box, add CAT4 (20 μL, 0.01 mmol), BDM (1.38 mg, 0.01 mmol), and PO (7.0 mL, 100.0 mmol) to a pre-dried 10 mL pressure-resistant bottle equipped with a magnetic stirrer. Heat to 25 °C. o The reaction was carried out at C for 40 min, and the reaction was quenched after completion. A portion of the reaction solution was taken for analysis, and the conversion rate was 68%. The number-average molecular weight was determined by GPC. M n It is 54.5 kg / mol, and the molecular weight distribution is... Ð It is 2.16.

[0084] Application Example 13: Homopolymerization of propylene oxide (PO) catalyzed by CAT4 In a glove box, add CAT4 (20 μL, 0.01 mmol), BDM (13.8 mg, 0.1 mmol), and PO (1.4 mL, 20.0 mmol) to a pre-dried 10 mL pressure-resistant bottle equipped with a magnetic stirrer. Heat to 25 °C. o The reaction was carried out at C for 38 min, and the reaction was quenched after completion. A portion of the reaction solution was taken for analysis, and the conversion rate was 99%. The number-average molecular weight was determined by GPC. M n It is 11.9 kg / mol, and the molecular weight distribution is... Ð It is 1.39.

[0085] Application Example 14: Homopolymerization of propylene oxide (PO) catalyzed by CAT4 In a glove box, add CAT4 (20 μL, 0.01 mmol), BDM (27.6 mg, 0.2 mmol), and PO (1.4 mL, 20.0 mmol) to a pre-dried 10 mL pressure-resistant bottle equipped with a magnetic stirrer at 25°C. o The reaction was carried out at C for 46 min, and the reaction was quenched after completion. A portion of the reaction solution was taken for analysis, and the conversion rate was 99%. The number-average molecular weight was determined by GPC. M n It is 7.3 kg / mol, and the molecular weight distribution is... Ð It is 1.38.

[0086] Application Example 15: Homopolymerization of propylene oxide (PO) catalyzed by CAT4 In a glove box, add CAT4 (20 μL, 0.01 mmol), BDM (69.1 mg, 0.5 mmol), and PO (1.4 mL, 20.0 mmol) to a pre-dried 10 mL pressure-resistant bottle equipped with a magnetic stirrer at 25°C. o The reaction was carried out at C for 76 min, and the reaction was quenched after completion. A portion of the reaction solution was taken for analysis, and the conversion rate was 99%. The number-average molecular weight was determined by GPC. M n It is 3.2 kg / mol, and the molecular weight distribution is... Ð It is 1.06.

[0087] Application Example 16: Homopolymerization of propylene oxide (PO) catalyzed by CAT4 In a glove box, add CAT4 (20 μL, 0.01 mmol), BDM (138.0 mg, 1 mmol), and PO (1.4 mL, 20.0 mmol) to a pre-dried 10 mL pressure-resistant bottle equipped with a magnetic stirrer. Heat to 25 °C. o The reaction was carried out at C for 97 min, and the reaction was quenched after completion. A portion of the reaction solution was taken for analysis, and the conversion rate was 99%. The number-average molecular weight was determined by GPC. M n It is 2.1 kg / mol, and the molecular weight distribution is... Ð It is 1.06.

[0088] Application Example 17: Using CAT25 to catalyze the homopolymerization of propylene oxide (PO) In a glove box, add CAT25 (20 μL, 0.01 mmol), BDM (1.38 mg, 0.01 mmol), and PO (1.4 mL, 20.0 mmol) to a pre-dried 10 mL pressure-resistant bottle equipped with a magnetic stirrer at 25°C. o The reaction was carried out at C for 78 min, and the reaction was quenched after completion. A portion of the reaction solution was taken for analysis, and the conversion rate was 99%. The number-average molecular weight was determined by GPC. M n It is 37.4 kg / mol, and the molecular weight distribution is... Ð It is 1.35.

[0089] Application Example 18: Using CAT25 to catalyze the homopolymerization of propylene oxide (PO) In a glove box, add CAT25 (20 μL, 0.01 mmol), BDM (13.8 mg, 0.1 mmol), and PO (1.4 mL, 20.0 mmol) to a pre-dried 10 mL pressure-resistant bottle equipped with a magnetic stirrer at 25°C. o The reaction was carried out at C for 236 min, and the reaction was quenched after completion. A portion of the reaction solution was taken for analysis, and the conversion rate was 99%. The number-average molecular weight was determined by GPC. M n It is 14.1 kg / mol, and the molecular weight distribution is... Ð It is 1.07.

[0090] Application Example 19: Using CAT25 to catalyze the homopolymerization of propylene oxide (PO) In a glove box, add CAT25 (20 μL, 0.01 mmol), BDM (27.6 mg, 0.2 mmol), and PO (1.4 mL, 20.0 mmol) to a pre-dried 10 mL pressure-resistant bottle equipped with a magnetic stirrer at 25 °C. o The reaction was carried out at C for 540 min, and the reaction was quenched after completion. A portion of the reaction solution was taken for analysis, and the conversion rate was 99%. The number-average molecular weight was determined by GPC. M n It is 8.4 kg / mol, and the molecular weight distribution is... Ð It is 1.06.

[0091] Application Example 20: Homopolymerization of propylene oxide (PO) catalyzed by CAT28 In a glove box, add CAT28 (20 μL, 0.01 mmol), BDM (27.6 mg, 0.2 mmol), and PO (1.4 mL, 20.0 mmol) to a pre-dried 10 mL pressure-resistant bottle equipped with a magnetic stirrer at 25°C. o The reaction was carried out at C for 20 hours. After the reaction was completed, the reaction was quenched, and a portion of the reaction solution was taken for analysis. The conversion rate was 99%. The number-average molecular weight was determined by GPC. M n It is 8.3 kg / mol, and the molecular weight distribution is... Ð It is 1.03.

[0092] Application Example 21: Using CAT31 to catalyze the homopolymerization of propylene oxide (PO) In a glove box, add CAT31 (20 μL, 0.01 mmol), BDM (27.6 mg, 0.2 mmol), and PO (1.4 mL, 20.0 mmol) to a pre-dried 10 mL pressure-resistant bottle equipped with a magnetic stirrer at 25°C. o The reaction was carried out at C for 14 hours. After the reaction was completed, the reaction was quenched, and a portion of the reaction solution was taken for analysis. The conversion rate was 99%. The number-average molecular weight was determined by GPC. M n It is 8.4 kg / mol, and the molecular weight distribution is... Ð It is 1.04.

[0093] Application Example 22: Utilizing CAT1 to catalyze the copolymerization of propylene oxide (PO) and phthalic anhydride (PA). In a glove box, add CAT1 (20 μL, 0.01 mmol), BDM (1.38 mg, 0.01 mmol), PO (0.3 mL, 4.0 mmol), PA (0.3 g, 2.0 mmol), and 1.7 mL of toluene to a pre-dried 10 mL pressure-resistant bottle equipped with a magnetic stirrer at 100°C. o The reaction was carried out at C for 30 min, and the reaction was quenched after completion. A portion of the reaction solution was taken for analysis, and the conversion rate was 99%. The number-average molecular weight was determined by GPC. M n It is 25.4 kg / mol, and the molecular weight distribution is... Ð It is 1.07.

[0094] Application Example 23: Utilizing CAT1 to catalyze the copolymerization of propylene oxide (PO) and phthalic anhydride (PA). In a glove box, add CAT1 (20 μL, 0.01 mmol), BDM (1.38 mg, 0.01 mmol), PO (0.6 mL, 8.0 mmol), PA (0.6 g, 4.0 mmol), and 6.8 mL of toluene to a pre-dried 10 mL pressure-resistant bottle equipped with a magnetic stirrer at 100°C. o The reaction was carried out at C for 60 min, and the reaction was quenched after completion. A portion of the reaction solution was taken for analysis, and the conversion rate was 99%. The number-average molecular weight was determined by GPC. M n It is 47.5 kg / mol, and the molecular weight distribution is... Ð It is 1.14.

[0095] Application Example 24: Utilizing CAT28 catalyst for the copolymerization of propylene oxide (PO) and phthalic anhydride (PA). In a glove box, add CAT28 (20 μL, 0.01 mmol), BDM (1.38 mg, 0.01 mmol), PO (0.6 mL, 8.0 mmol), PA (0.6 g, 4.0 mmol), and 6.8 mL of toluene to a pre-dried 10 mL pressure bottle equipped with a magnetic stirrer at 100°C. o The reaction was carried out at C for 2 hours. After the reaction was completed, the reaction was quenched, and a portion of the reaction solution was taken for analysis. The conversion rate was 86%. The number-average molecular weight was determined by GPC. M n It is 40.8 kg / mol, and the molecular weight distribution is... Ð It is 1.06.

[0096] Application Example 25: Utilizing CAT31 to catalyze the copolymerization of propylene oxide (PO) and phthalic anhydride (PA). In a glove box, add CAT31 (20 μL, 0.01 mmol), BDM (1.38 mg, 0.01 mmol), PO (0.6 mL, 8.0 mmol), PA (0.6 g, 4.0 mmol), and 6.8 mL of toluene to a pre-dried 10 mL pressure bottle equipped with a magnetic stirrer at 100°C. o The reaction was carried out at C for 7 hours. After the reaction was completed, the reaction was quenched, and a portion of the reaction solution was taken for analysis. The conversion rate was 99%. The number-average molecular weight was determined by GPC. M n It is 45.3 kg / mol, and the molecular weight distribution is... Ð It is 1.16.

[0097] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit them. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. However, these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions claimed by the present invention.

Claims

1. A polynuclear phosphoborane catalyst, characterized in that, It has the following general structural formula: The skeleton of cyclotriphosphazene is: [P3N3] Where X represents -R1-(CH2) n -BY2 group; The skeleton of cyclotetraphosphazene is: [P4N4] Where X represents -R1-(CH2) n -BY2 group; Among them, BY2 is independently selected from 9-boronbicyclo[3.3.1]nonane derivative group, cyclopentaborane derivative group, cyclohexylborane derivative group, dicyclohexylborane derivative group, diphenylborane derivative group or 3-methylcyclopentaborane derivative group; The derived group is a monovalent organoboron group formed by replacing one BH bond on the boron atom of the listed parent boranes, and the bonding mode is through the boron atom bonded to the methylene (-CH2-); R1 is independently selected from N, O, -NH or -CH2; n is a positive integer from 1 to 3; The catalyst has an organophosphazene base framework and a multi-center borane Lewis acidic site, which together form a synergistic acid-base pair.

2. The polynuclear phosphoborane catalyst according to claim 1, characterized in that, The degree of Cl atom substitution in the cyclotriphosphazene skeleton is 100%, and the degree of Cl atom substitution in the cyclotetraphosphazene skeleton is 100%. The number of Lewis acid sites in multicenter boranes is regulated by the degree of substitution on the phosphazene skeleton. The number of acid sites = the number of substituted Cl atoms or twice the number of substituted Cl atoms. The hexachlorocyclotriphosphazene skeleton can introduce a maximum of 12 acid sites, and the octachlorocyclotetraphosphazene skeleton can introduce a maximum of 16 acid sites.

3. A method for preparing the polynuclear borane catalyst according to claim 1 or 2, characterized in that, Includes the following steps: A phosphazene precursor containing an olefinic group was subjected to a hydroboration reaction with a hydroboration reagent HBY2 in an organic solvent. The olefinic group in the phosphazene precursor was allyl, butenyl, or pentenyl. The reaction temperature was 25–60 °C, the reaction time was 12–48 h, and the molar ratio of the olefinic phosphazene precursor to the hydroboration reagent was 1:(1–16). After the reaction was completed, the precursor was purified to obtain a polynuclear phosphaborane catalyst.

4. The method for preparing a polynuclear phosphoborane catalyst according to claim 3, characterized in that, The organic solvent is selected from at least one of benzene, toluene, xylene, and tetrahydrofuran; The borohydride reagent HBY2 is selected from at least one of 9-boronbicyclo[3.3.1]nonane, cyclopentylborane, cyclohexylborane, dicyclohexylborane, diphenylborane, and 3-methylcyclopentylborane.

5. The method for preparing a polynuclear phosphoborane catalyst according to claim 3, characterized in that, The preparation method of phosphazene precursor compounds containing olefin substituents is as follows: using hexachlorocyclotriphosphazene or octachlorocyclotetraphosphazene as raw materials, reacting with olefin amines, olefin lithium, olefin Grignard reagents or olefin alcohols in an organic solvent in the presence of an acid-binding agent; The reaction temperature is 0–150℃, the reaction time is 1–72 h, and the molar ratio of raw materials, reaction reagents and acid-binding agents is 1:(1–16):(1–16).

6. The method for preparing a polynuclear phosphoborane catalyst according to claim 5, characterized in that, The acid-binding agent is selected from at least one of triethylamine, sodium carbonate, sodium bicarbonate, sodium hydroxide, and potassium hydroxide; The organic solvent is selected from at least one of benzene, toluene, xylene, and tetrahydrofuran; The olefin-based lithium or olefin-based Grignard reagent includes at least one of allyl lithium, allyl lithium, allyl magnesium bromide, 2-methylallyl magnesium bromide, and 4-pentenyl magnesium bromide.

7. A method for preparing a polymer, characterized in that, The reaction is carried out using the polynuclear phosphoborane catalyst as described in claim 1 or 2, with the polymer being polyether, in the presence of a chain transfer agent, at a reaction temperature of -20 to 80°C, and for a reaction time of 0.1 to 72 h. The polymer is polyester, and the reaction is carried out in the presence of a chain transfer agent and an organic solvent at a temperature of 80–150 °C for a time of 0.1–72 h.

8. The method for preparing a polymer according to claim 7, characterized in that, When the polymer is a polyether, the reactive monomer is at least one epoxide monomer selected from at least one of propylene oxide, ethylene oxide, butane oxide, hexane oxide, and octane oxide.

9. A method for preparing a polymer according to claim 7, characterized in that, When the polymer is polyester, the reactant monomer is a combination of at least two monomers and the reaction is carried out in an organic solvent. The monomers are selected from at least two of cyclohexane oxide, propylene oxide, ethylene oxide, butane oxide, hexane oxide, octane oxide, glutaric anhydride, phthalic anhydride, perphthalic anhydride, and succinic anhydride. The organic solvent is selected from at least one of benzene, toluene, dichloromethane, and tetrahydrofuran.

10. A method for preparing a polymer according to claim 7, characterized in that, The chain transfer agent is 1,4-terephthalic acid (BDM), ethylene glycol, 1,3-propanediol, or 1,4-butanediol; When the monomer is propylene oxide, the number-average molecular weight of the polyether is 1.4 to 60.0 kg / mol and the molecular weight distribution is 1.03 to 2.16 by adjusting the molar ratio of chain transfer agent to monomer to 0.01 to 1:

20. When the molar ratio of the monomers propylene oxide and phthalic anhydride is 2:1, polyesters can be prepared with a number average molecular weight of 25.4–47.5 kg / mol and a molecular weight distribution of 1.06–1.14.

Images