Polymeric polynuclear boron organocatalysts, methods of making and using the same

Abstract

The application belongs to the field of catalyst synthesis, and relates to a polymer polynuclear boron organic catalyst, a preparation method and application thereof, the preparation method of the catalyst comprises the following steps: adding tetrahydrofuran into a catalyst precursor, then adding a borohydride reagent drop by drop, heating the reaction mixture at 25-80 DEG C for 22-26 h, vacuum concentrating the reaction mixture to obtain a crude product, purifying the crude product by washing with pentane for 2-5 times, and vacuum drying the product at normal temperature for 10-14 h to obtain the catalyst; the catalyst precursor and a preparation method thereof are also provided; the polymer polynuclear boron organic catalyst provided by the application has the advantages of high activity, simple preparation method and low cost, and the catalyst can control the polymer substrate type and the polymer type by adjusting the reaction conditions, the catalytic system and the substrate, and can efficiently prepare polymers such as polyether, polyester and polycarbonate due to the synergistic effect of the polynuclear boron center, so that the types of the organic catalyst and the polymer are greatly expanded.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of catalyst synthesis, and particularly relates to a polymer polynuclear boron organic catalyst and a preparation method and application thereof. BACKGROUND

[0002] The development of new catalysts and the innovation of catalytic technology continuously promote the development of synthetic chemistry and material science. As a pioneer in the field of catalysts, metal catalysts have shown their superior catalytic performance. Among metal catalysts and enzyme catalysts, bimetallic centers or multimetallic centers have a synergistic effect and exhibit better catalytic performance than mononuclear metal catalysts. In such reactions, metal centers act as Lewis acids and electrophilic centers, which can activate substrates and stabilize active species. However, the metal residues and recycling problems of metal catalysts limit their further application in certain chemical and material fields.

[0003] Organic catalysts have attracted the attention of researchers due to their low cost, low biological toxicity, etc., and have gradually shown superior performance in organic synthetic methodology and polymer material synthesis. Compared with the application of organic catalysts in organic methodology, organic catalysts are still in the embryonic stage in the field of polymer synthesis and preparation. The prepared polymer materials include polyesters, polycarbonates, polyethers, polyamides, polysiloxanes, polyurethanes, etc., which have a wide range of applications in our daily life. Boron, as a common Lewis acid, has good electrophilicity and has shown excellent reactivity in organic methodology and polymerization reactions. Based on this, the application provides a polymer polynuclear boron system, which is applied to polymerization reactions, and develops an economical, effective and environmentally friendly polymerization process. SUMMARY

[0004] The application aims to solve the above problems in the prior art, and provides a polymer polynuclear boron organic catalyst and a preparation method and application thereof. The polymer polynuclear boron system includes a preparation method of a catalyst precursor and a preparation method of a polymer polynuclear boron organic catalyst. The polymer polynuclear boron organic catalyst disclosed in the application has the advantages of high activity and easy availability, and can be efficiently and selectively applied to the field of catalytic polymerization, greatly expanding the types and application fields of organic catalysts.

[0005] The polymer is used as a skeleton to synthesize the polyboron catalyst with multiple Lewis acid centers, which can better activate monomers and stabilize active species, and embodies the synergistic effect of multiple boron centers. When the polymer polyboron becomes useless after the polymerization reaction stops, the polymer polyboron is disposed after polymerization. In order to improve the utilization rate of the polymer polyboron, the polymer polyboron can be recycled after polymerization and used in the next polymerization reaction, so that the performance and quality of the formed polymer are not changed, and the recycling can make the polymerization process economic and environment-friendly.

[0006] The technical scheme of the present application is:

[0007] The present application provides a polymer polynuclear boron organic catalyst, which has the structure as shown in formula I or formula II:

[0008]

[0009] Preferably, the polymer polynuclear boron organic catalyst has any of the following structures:

[0010]

[0011]

[0012] n is the length of the carbon chain, which is an integer greater than 1, preferably n is any integer between 85 and 95, for example, it can be 85, 86, 87, 88, 89, 90, 91, 92, 93, 94 or 95, more preferably n is 90, 91 or 92;

[0013] m is the length of the carbon chain, which is an integer greater than 1, preferably m is any integer between 85 and 95; for example, it can be 85, 86, 87, 88, 89, 90, 91, 92, 93, 94 or 95, more preferably m is 90, 91 or 92;

[0014] x is the length of the carbon chain, which is any integer between 0 and 3;

[0015] y is the length of the carbon chain, which is any integer between 1 and 5;

[0016] R 1 is one of hydrogen, methyl, ethyl, butyl, phenyl or substituted phenyl;

[0017] BR2 is any of the following structures:

[0018]

[0019] The present application also provides a preparation method of the polymer polynuclear boron organic catalyst, comprising the following steps:

[0020] adding tetrahydrofuran to the catalyst precursor, then adding dropwise a borohydride reagent (HBR2), heating the reaction mixture at 25-80°C for 22-26h, vacuum concentrating the reaction mixture to obtain a crude product, purifying the crude product by washing with pentane for 2-5 times, then vacuum drying at room temperature for 10-14h to obtain the catalyst;

[0021] wherein the borohydride reagent comprises any one of 9-borabicyclo[3.3.1]nonane, cyclopentylborane, cyclohexylborane, dicyclohexylborane or 3-methylcyclopentylborane;

[0022] the catalyst precursor is catalyst precursor 1 or catalyst precursor 2, the molar ratio of the catalyst precursor 1 to the borohydride reagent is 1:(1.02-3)n, and the molar ratio of the catalyst precursor 2 to the borohydride reagent is 1:(1.02-3)m;

[0023] wherein the n is an integer greater than 1, preferably the n is an integer between 85-95, more preferably n is 90, 91 or 92; and the m is an integer greater than 1, preferably the m is an integer between 85-95; more preferably m is 90, 91 or 92.

[0024] The molar ratio of the catalyst precursor 1 to the borohydride reagent is any ratio within the range of 1:(1.02-3)n, for example, it can be 1:1.02n, 1:1.05n, 1:1.2n, 1:1.3n, 1:1.5n, 1:1.6n, 1:1.9n, 1:2.0n, 1:2.2n, 1:2.3n, 1:2.4n, 1:2.5n, 1:2.7n or 1:3n, etc.; preferably, the molar ratio is 1:2.4n.

[0025] The molar ratio of the catalyst precursor 2 to the borohydride reagent is any ratio within the range of 1:(1.02-3)m, for example, it can be 1:1.02m, 1:1.05m, 1:1.2m, 1:1.3m, 1:1.5m, 1:1.6m, 1:1.9m, 1:2.0m, 1:2.2m, 1:2.3m, 1:2.4m, 1:2.5m, 1:2.7m or 1:3m, etc.; preferably, the molar ratio is 1:2.4m.

[0026] The reaction temperature can be any temperature within the range of 25-80°C, such as 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 72°C, 75°C, or 80°C, etc., the reaction time can be any value within the range of 22-26h, such as 22h, 22.5h, 23h, 24h, 25h, 25.5h, or 26h, etc., and the drying time can be any value within the range of 10-14h, such as 10h, 11h, 12h, 12.5h, 13h, 13.5h, or 14h, etc.

[0027] The amount of tetrahydrofuran added in the above step is 3mL per mmol of catalyst precursor;

[0028] Pentane is used for washing the crude product, and thus the amount of pentane used is controlled to be just enough to cover the crude product.

[0029] Further, the present application also provides a catalyst precursor, which is a polymer having a terminal olefin double bond, including catalyst precursor 1 or catalyst precursor 2, and the chemical structural formula is as follows:

[0030]

[0031] The preferred structural formula is as follows:

[0032]

[0033] wherein n is the length of the carbon chain, which is an integer greater than 1, preferably n is any integer between 85 and 95, such as 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, or 95, more preferably n is 90, 91, or 92;

[0034] m is the length of the carbon chain, which is an integer greater than 1, preferably m is any integer between 85 and 95, such as 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, or 95, more preferably m is 90, 91, or 92;

[0035] x is the length of the carbon chain, which is any integer between 0 and 3;

[0036] y is the length of the carbon chain, which is any integer between 1 and 5;

[0037] R is one of hydrogen, methyl, ethyl, butyl, phenyl, or substituted phenyl.

[0038] Further, the preparation steps of the catalyst precursor 1 are as follows:

[0039] A polymer of 4-vinylphenol monomer and a halogenated alkene in a molar ratio of 1 : (10-20) are weighed out and dissolved in acetonitrile, anhydrous potassium carbonate is added and heated at a temperature of 60-70°C for 10-14 hours, left to stand at room temperature, the residue after filtration is washed 2-5 times with dichloromethane, dried by rotary evaporation and then washed 1-3 times with pentane, and dried under vacuum at room temperature for 10-14 hours to obtain catalyst precursor 1.

[0040] The polymer of 4-vinylphenol monomer is poly(4-vinylphenol); the halogenated alkene is one or more of allyl bromide, 4-bromo-1-butene or 5-bromo-1-pentene.

[0041] The molar ratio of the polymer of 4-vinylphenol monomer and the halogenated alkene is any ratio within the range of 1 : (10-20), for example, it can be 1 : 10, 1 : 12, 1 : 15, 1 : 17, 1 : 19 or 1 : 20, etc., and preferably, the molar ratio is 1 : 10.

[0042] The molar ratio of the anhydrous potassium carbonate and the polymer of 4-vinylphenol monomer is (5-10) : 1, and the ratio can be any ratio within the range, for example, 5 : 1, 6 : 1, 7 : 1, 8 : 1, 9 : 1, 9.5 : 1 or 10 : 1, etc., and preferably, the molar ratio of the anhydrous potassium carbonate and the polymer of 4-vinylphenol monomer is 6.6 : 1.

[0043] The temperature is any temperature value within the range of 60-70°C, for example, it can be 60°C, 62°C, 65°C, 67°C, 68°C or 70°C, etc.; the heating time is any value within the range of 10-14 hours, for example, it can be 10 hours, 11 hours, 12 hours, 12.5 hours, 13 hours, 13.5 hours or 14 hours, etc.; and the vacuum drying time is any value within the range of 10-14 hours, for example, it can be 10 hours, 11 hours, 12 hours, 12.5 hours, 13 hours, 13.5 hours or 14 hours, etc.

[0044] Further, the preparation steps of the catalyst precursor 2 are as follows:

[0045] A styrene monomer and a conjugated diene monomer in a molar ratio of (5-15) : 1 are weighed out and dissolved in cyclohexane, sec-butyllithium is added and stirred at room temperature for 2.5-3.5 hours, then quenched with a small amount of methanol, the colorless mixture is precipitated in methanol 1-3 times, the product is recovered by filtration, and the product is dried under high vacuum overnight to obtain a fine white powder, which is the catalyst precursor 2.

[0046] The styrene monomer is preferably styrene, and the conjugated diene monomer is 1,3-cyclohexadiene.

[0047] In the above preparation method, the molar ratio of the styrene monomer and the conjugated diene monomer is any ratio in the range of (5-15) : 1, for example, it can be 5:1, 6:1, 8:1, 8.5:1, 9:1, 9.5:1, 10:1, 12:1, 13:1 or 15:1, etc., and preferably, the molar ratio is 8.9:1.

[0048] In the above preparation method, the amount of the sec-butyl lithium added is controlled such that the molar ratio of the sec-butyl lithium and the conjugated diene monomer is (0.01-0.1) : 1, and the specific ratio can be any ratio in the range of (0.01-0.1) : 1, for example, it can be 0.01:1, 0.02:1, 0.032:1, 0.04:1, 0.056:1, 0.07:1, 0.08:1, 0.09:1 or 0.1:1, etc. Preferably, the molar ratio of the sec-butyl lithium and the conjugated diene monomer is 0.056:1.

[0049] The above stirring time is any value in the range of 2.5-3.5 h, for example, it can be 2.5 h, 2.7 h, 2.9 h, 3 h, 3.2 h, 3.3 h or 3.5 h, etc.

[0050] The application also provides an application of the polymer polynuclear boron organic catalyst in catalyzing a polymerization reaction to prepare a polymer, the polymerization reaction is ring-opening polymerization, and the polymer prepared by polymerization includes polyether, polyester, polycarbonate and the like; wherein,

[0051] The polymer prepared by catalyzing the homopolymerization of the epoxy monomer is polyether;

[0052] The polycarbonate prepared by catalyzing the copolymerization of the epoxy monomer and carbon dioxide;

[0053] The polyester prepared by catalyzing the copolymerization of the epoxy monomer and cyclic anhydride and the like.

[0054] Further, the application also provides an application of the polymer polynuclear boron organic catalyst in preparing an organic small molecule, and the organic small molecule prepared is a cyclic carbonate prepared by coupling an epoxy monomer and carbon dioxide.

[0055] Further, the epoxy monomer includes but is not limited to the following structure:

[0056]

[0057]

[0058] Further, the application of the catalyst in the polymerization to prepare the polyether includes the following steps:

[0059] In a glove box, the catalyst is weighed into a pre-flame dried pressure-resistant bottle with a magnet, the molar ratio of the epoxy monomer, the catalyst and the initiator is 200:1:0.5-10000:1:0.5, the pressure-resistant bottle is sealed and taken out, the reaction temperature is controlled at-20-45℃, the reaction time is controlled at 1-120min, and the polyether is obtained.

[0060] The epoxy monomer is preferably propylene oxide, CAT1 and CAT2 are used as the catalysts respectively, and the initiator is selected from ammonium salt; the molar ratio of the propylene oxide, the catalyst and the ammonium salt is any value within the range of 200:1:0.5-10000:1:0.5, for example, it can be 200:1:0.5, 500:1:0.5, 1000:1:0.5, 3000:1:0.5, 5000:1:0.5 or 10000:1:0.5, etc.

[0061] The reaction temperature is any value within the range of-20-45℃, for example, it can be-20℃, -10℃, -5℃, 0℃, 10℃, 20℃, 30℃, 40℃ or 45℃, etc.; the reaction time is any value within the range of 1-120min, for example, it can be 1min, 5min, 10min, 20min, 30min, 60min, 80min, 90min, 100min or 120min, etc.

[0062] The molecular weight of the obtained polyether is within the range of 17200-1079300g / mol, the molecular weight distribution is within the range of 1.14-1.17.

[0063] Further, the catalyst is applied to the reaction of polymerization to obtain the polycarbonate, which comprises the following steps:

[0064] In a glove box, the catalyst is weighed into a pre-flame dried pressure-resistant bottle with a magnet, the molar ratio of the epoxy monomer, the catalyst and the initiator is 200:1:0.5-10000:1:0.5, the pressure-resistant bottle is sealed and taken out, the reaction temperature is controlled at-20-45℃, the reaction time is controlled at 1-120min, and the polyether is obtained.

[0065] The epoxy monomer is selected from phenyl glycidyl ether, CAT1 and CAT2 are used as the catalysts respectively, and the initiator is selected from ammonium salt; the molar ratio of the phenyl glycidyl ether, the catalyst and the ammonium salt is any value within the range of 500:2:1-5000:2:1, for example, it can be 500:2:1, 500:4:1, 1000:2:1 or 5000:2:1, etc.

[0066] The reaction pressure is any value within the range of 1.5-2.5 MPa, for example, it can be 1.5 MPa, 2 MPa, 2.2 MPa, 2.5 MPa, etc.; the reaction temperature is any value within the range of 40-80℃, for example, it can be 40℃, 50℃, 60℃, 70℃ or 80℃, etc.; the reaction time is any value within the range of 1.25-12 h, for example, it can be 1.25 h, 1.5 h, 2 h, 3 h, 5 h, 7 h, 9 h, 10 h, 12 h, etc.

[0067] The molecular weight of the obtained polyester is within the range of 20700-59400 g / mol, and the molecular weight distribution is within the range of 1.18-1.21. The molecular weight of the obtained polyester is within the range of 20700-59400 g / mol, and the molecular weight distribution is within the range of 1.18-1.21.

[0068] Further, the catalyst is applied to the reaction of polymerization to obtain the polyester, which comprises the following steps:

[0069] (3) In the glove box, the catalyst is weighed into a pre-flame dried pressure-resistant bottle with a magnet, the molar ratio of the epoxy monomer, the cyclic anhydride, the catalyst and the initiator is 400:200:2:1-1000:500:2:1, the pressure-resistant bottle is sealed and taken out, the reaction temperature is controlled within the range of 60-130℃, and the reaction time is controlled within the range of 0.25-0.75 h, to obtain the polyester.

[0070] The epoxy monomer is selected from the group consisting of cyclohexene oxide, the initiator is selected from the group consisting of ammonium salt, the cyclic anhydride is preferably phthalic anhydride, CAT1 and CAT2 are respectively used as the catalyst, and the molar ratio of the cyclohexene oxide, the phthalic anhydride, the catalyst and the ammonium salt is any value within the range of 400:200:2:1-1000:500:2:1, for example, it can be 400:200:2:1 or 1000:500:2:1, etc.

[0071] The reaction temperature is any value within the range of 60-130℃, for example, it can be 60℃, 80℃, 90℃, 100℃, 120℃ or 130℃, etc.; the reaction time is any value within the range of 0.25-0.75 h, for example, it can be 0.25 h, 0.3 h, 0.4 h, 0.5 h, 0.6 h or 0.75 h, etc.

[0072] The molecular weight of the obtained polyester is within the range of 20700-59400 g / mol, and the molecular weight distribution is within the range of 1.18-1.21. The molecular weight of the obtained polyester is within the range of 20700-59400 g / mol, and the molecular weight distribution is within the range of 1.18-1.21.

[0073] Further, the present application further provides that the polymer polynuclear boron organic catalyst is used for the alternating copolymerization or random, gradient, block copolymerization of the epoxy monomer and the aldehyde monomer; the structure of the aldehyde monomer includes but is not limited to the following structures:

[0074]

[0075] Advantages of the present application:

[0076] (1) The polymer polynuclear boron organic catalyst provided by the present application has the advantages of high activity, simple preparation method and low cost. The catalyst can control the types of polymerization substrates and polymers by adjusting the reaction conditions, the catalytic system, the substrate, etc. Due to the synergistic effect of the polynuclear boron center, polyether, polyester, polycarbonate and other polymers can be efficiently prepared, which greatly expands the types of organic catalysts and polymers.

[0077] (2) The polymer polynuclear boron organic catalyst provided by the present application can be used for the synthesis of small organic molecules or polymers, and can be used for loading, which is beneficial to the removal, recycling and reuse of the catalyst. BRIEF DESCRIPTION OF DRAWINGS

[0078] Figure 1 Preparation of catalyst precursor 1a 1 H NMR;

[0079] Figure 2 Preparation of catalyst precursor 1c 1 H NMR;

[0080] Figure 3 Preparation of polymer polynuclear boron organic catalyst CAT1 1 H NMR;

[0081] Figure 4 Preparation of polymer polynuclear boron organic catalyst CAT1 11 B NMR. DETAILED DESCRIPTION

[0082] The technical solutions in the embodiments of the present application will be described clearly and completely below in combination with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0083] In order to further understand the present application, the present application will be further described in combination with the drawings and embodiments.

[0084] Preparation of catalyst precursor 1a

[0085] Example 1

[0086] Poly(4-vinylphenol) (550 mg, 4.58 mmol) and allyl bromide (4 ml, 45.8 mmol) were dissolved in acetonitrile (10 mL) and finally anhydrous potassium carbonate (4.19 g, 30.3 mmol) was added and heated at 67 °C for 12 h. After recovering the room temperature, it was left to stand, filtered with a fritted funnel with celite, the residue was washed three times with dichloromethane (10 mL*3) and then the filtrate was evaporated to dryness, washed twice with pentane (10 mL*2) and dried under vacuum at room temperature for 12 h to obtain the pure product. Figure 1 The hydrogen spectrum of the catalyst precursor 1a obtained is shown.

[0087] Example 2

[0088] Poly(4-vinylphenol) (550 mg, 4.58 mmol) and allyl bromide (6 ml, 68.7 mmol) were dissolved in acetonitrile (10 mL) and finally anhydrous potassium carbonate (4.81 g, 34.8 mmol) was added and heated at 60 °C for 14 h. After recovering the room temperature, it was left to stand, filtered with a fritted funnel with celite, the residue was washed three times with dichloromethane (10 mL*3) and then the filtrate was evaporated to dryness, washed twice with pentane (10 mL*2) and dried under vacuum at room temperature for 10 h to obtain the pure product.

[0089] Example 3

[0090] Poly(4-vinylphenol) (550 mg, 4.58 mmol) and allyl bromide (8 ml, 91.6 mmol) were dissolved in acetonitrile (10 mL) and finally anhydrous potassium carbonate (6.01 g, 43.5 mmol) was added and heated at 70 °C for 10 h. After recovering the room temperature, it was left to stand, filtered with a fritted funnel with celite, the residue was washed three times with dichloromethane (10 mL*3) and then the filtrate was evaporated to dryness, washed twice with pentane (10 mL*2) and dried under vacuum at room temperature for 14 h to obtain the pure product.

[0091] Preparation of catalyst precursor 1b

[0092] Example 4

[0093] Poly(4-vinylphenol) (550 mg, 4.58 mmol) and 4-bromo-1-butene (4.6 ml, 45.8 mmol) were dissolved in acetonitrile (10 mL) and finally anhydrous potassium carbonate (4.19 g, 30.3 mmol) was added and heated at 67 °C for 12 h. After recovering the room temperature, it was left to stand, filtered with a fritted funnel with celite, the residue was washed three times with dichloromethane (10 mL*3) and then the filtrate was evaporated to dryness, washed twice with pentane (10 mL*2) and dried under vacuum at room temperature for 12 h to obtain the pure product.

[0094] Example 5

[0095] Poly(4-vinylphenol) (550 mg, 4.58 mmol) and 4-bromo-1-butene (6.9 ml, 68.7 mmol) were dissolved in acetonitrile (10 mL) and finally anhydrous potassium carbonate (4.81 g, 34.8 mmol) was added and heated at 60 °C for 14 h. After recovering the room temperature, it was left to stand, filtered with a fritted funnel with celite, the residue was washed three times with dichloromethane (10 mL*3) and then the filtrate was evaporated to dryness, washed twice with pentane (10 mL*2), dried under vacuum at room temperature for 11 h to obtain the pure product.

[0096] Example 6

[0097] Poly(4-vinylphenol) (550 mg, 4.58 mmol) and 4-bromo-1-butene (9.2 ml, 91.6 mmol) were dissolved in acetonitrile (10 mL) and finally anhydrous potassium carbonate (6.01 g, 43.5 mmol) was added and heated at 70 °C for 10 h. After recovering the room temperature, it was left to stand, filtered with a fritted funnel with celite, the residue was washed three times with dichloromethane (10 mL*3) and then the filtrate was evaporated to dryness, washed twice with pentane (10 mL*2), dried under vacuum at room temperature for 14 h to obtain the pure product.

[0098] Preparation of catalyst precursor 1c

[0099] Example 7

[0100] Poly(4-vinylphenol) (550 mg, 4.58 mmol) and 5-bromo-1-pentene (5.4 ml, 45.8 mmol) were dissolved in acetonitrile (10 mL) and finally anhydrous potassium carbonate (4.19 g, 30.3 mmol) was added and heated at 67 °C for 12 h. After recovering the room temperature, it was left to stand, filtered with a fritted funnel with celite, the residue was washed three times with dichloromethane (10 mL*3) and then the filtrate was evaporated to dryness, washed twice with pentane (10 mL*2), dried under vacuum at room temperature for 12 h to obtain the pure product. As shown in Figure 1, the hydrogen spectrum of the catalyst precursor 1c prepared. Figure 2

[0101] Example 8

[0102] ​Poly(4-vinylphenol) (550 mg, 4.58 mmol) and 5-bromo-l-pentene (8.1 ml, 68.7 mmol) were dissolved in acetonitrile (10 mL) and finally anhydrous potassium carbonate (4.81 g, 34.8 mmol) was added and heated at 60 °C for 14 h. After recovering room temperature, the mixture was left to stand and filtered through a fritted funnel with celite, the residue was washed four times with dichloromethane (10 mL*4) and the filtrate was then rotary evaporated and washed three times with pentane (10 mL*3) and dried under vacuum at room temperature for 10 h to obtain the pure product.

[0103] Example 9

[0104] Poly(4-vinylphenol) (550 mg, 4.58 mmol) and 5-bromo-l-pentene (10.8 ml, 91.6 mmol) were dissolved in acetonitrile (10 mL) and finally anhydrous potassium carbonate (6.01 g, 43.5 mmol) was added and heated at 70 °C for 10 h. After recovering room temperature, the mixture was left to stand and filtered through a fritted funnel with celite, the residue was washed five times with dichloromethane (10 mL*5) and the filtrate was then rotary evaporated and washed twice with pentane (10 mL*2) and dried under vacuum at room temperature for 14 h to obtain the pure product.

[0105] Preparation of catalyst precursor 2a

[0106] Example 10

[0107] Styrene (4.4 ml, 38.4 mmol) and 1,3-cyclohexadiene (0.41 ml, 4.3 mmol) were dissolved in cyclohexane (25 mL) and finally sec-butyllithium (1.4 M in cyclohexane, 0.17 ml, 0.24 mmol) was added and stirred at room temperature for 3 h and then quenched with a small amount of methanol. The colourless mixture was then precipitated in methanol twice and the copolymer was recovered by filtration. The product was dried under high vacuum overnight to obtain a fine white powder.

[0108] Example 11

[0109] Styrene (4.4 ml, 38.4 mmol) and 1,3-cyclohexadiene (0.73 ml, 7.68 mmol) were dissolved in cyclohexane (25 mL) and finally sec-butyllithium (1.4 M in cyclohexane, 0.44 ml, 0.61 mmol) was added and stirred at room temperature for 2.5 h and then quenched with a small amount of methanol. The colourless mixture was then precipitated in methanol three times and the copolymer was recovered by filtration. The product was dried under high vacuum overnight to obtain a fine white powder.

[0110] Example 12

[0111] Styrene (4.4 mL, 38.4 mmol) and 1,3-cyclohexadiene (0.24 mL, 2.56 mmol) were dissolved in cyclohexane (25 mL), and then sec-butyllithium (1.4 M cyclohexane solution, 0.09 mL, 0.12 mmol) was added. The mixture was stirred at room temperature for 3.5 h, and then quenched with a small amount of methanol. The colorless mixture was then precipitated twice in methanol, and the copolymer was recovered by filtration. The product was dried overnight under high vacuum to obtain a fine white powder.

[0112] Preparation of polymeric polynuclear boron organocatalyst CAT1

[0113] Example 13

[0114] Polymer polynuclear boron organocatalysts were prepared using 1,9-boron bicyclic [3.3.1]nonane (9-BBN) as the catalyst precursor. The specific procedures are as follows:

[0115] In a glove box, catalyst precursor 1 (175 mg, 1.09 mmol) was added to a pre-dried solvent storage bottle equipped with a magnetic stirrer, followed by tetrahydrofuran (3 mL), and then dropwise addition of 9-boronbicyclo[3.3.1]nonane (9-BBN) (0.5 M inTHF) (2.3 mL, 1.15 mmol). The mixture was heated at 40 °C for 24 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 was dried under vacuum at room temperature for 12 h.

[0116] like Figure 3 The image shows the proton NMR spectrum of the prepared polymer polynuclear boron organocatalyst CAT1; as shown... Figure 4 The image shows the boron spectrum of the prepared polymer polynuclear boron organocatalyst CAT1.

[0117] Example 14

[0118] In a glove box, catalyst precursor 1 (175 mg, 1.09 mmol) was added to a pre-dried solvent storage bottle equipped with a magnetic stirrer, followed by tetrahydrofuran (3 mL), and then dropwise addition of 9-boronbicyclo[3.3.1]nonane (9-BBN) (0.5 M inTHF) (4.6 mL, 2.18 mmol). The mixture was heated at 25 °C for 26 h. The reaction mixture was concentrated under vacuum to obtain a crude solid product, which was further purified by washing twice with pentane. The white solid product was dried under vacuum at room temperature for 10 h.

[0119] Example 15

[0120] In a glove box, catalyst precursor 1 (175 mg, 1.09 mmol) was added to a pre-dried solvent storage vial with a stirring magnet, tetrahydrofuran (3 mL) was added, then 9-borabicyclo[3.3.1]nonane (9-BBN) (0.5 M in THF) (6.9 mL, 3.27 mmol) was added dropwise and heated at 80 °C for 22 h. The reaction mixture was concentrated in vacuo to obtain a crude solid product which was further purified by washing with pentane four times. The white solid product was dried in vacuo at room temperature for 14 h.

[0121] Preparation of the polymeric polynuclear boron organocatalyst CAT2

[0122] Example 16

[0123] The polymeric polynuclear boron organocatalyst was prepared using catalyst precursor 2, 9-borabicyclo[3.3.1]nonane (9-BBN), according to the following procedure:

[0124] In a glove box, catalyst precursor 2 (184 mg, 1 mmol) was added to a pre-dried solvent storage vial with a stirring magnet, tetrahydrofuran (3 mL) was added, then 9-borabicyclo[3.3.1]nonane (9-BBN) (0.5 M in THF) (2.1 mL, 1.05 mmol) was added dropwise and heated at 40 °C for 24 h. The reaction mixture was concentrated in vacuo to obtain a crude solid product which was further purified by washing with pentane three times. The white solid product was dried in vacuo at room temperature for 12 h.

[0125] Example 17

[0126] In a glove box, catalyst precursor 2 (184 mg, 1 mmol) was added to a pre-dried solvent storage vial with a stirring magnet, tetrahydrofuran (3 mL) was added, then 9-borabicyclo[3.3.1]nonane (9-BBN) (0.5 M in THF) (4.8 mL, 2.4 mmol) was added dropwise and heated at 60 °C for 26 h. The reaction mixture was concentrated in vacuo to obtain a crude solid product which was further purified by washing with pentane three times. The white solid product was dried in vacuo at room temperature for 10 h.

[0127] Example 18

[0128] In a glove box, catalyst precursor 2 (184 mg, 1 mmol) was added to a pre-dried solvent storage flask with a stirring magnet, THF (3 mL) was added, then 9-borabicyclo[3.3.1]nonane (9-BBN) (0.5 M in THF) (6 mL, 3 mmol) was added dropwise, and heated at 80 °C for 22 h. The reaction mixture was concentrated in vacuo to obtain a crude solid product, which was further purified by washing with pentane three times. The white solid product was dried in vacuo at room temperature for 14 h.

[0129] The following is an application example of the polymer polynuclear boron organic catalyst applied to a polymerization reaction.

[0130] Application Examples 1-12

[0131] Homopolymerization of alkylene oxide (PO) using CAT1 and CAT2

[0132]

[0133] In a glove box, PO, catalyst and ammonium salt were weighed into a pre-flame dried 10 mL pressure-resistant vial with a magnetic stirrer, the vial was sealed and taken out, and the reaction temperature was set to -20-45 °C, the molar ratio of PO to catalyst and ammonium salt was 200:1:0.5-10000:1:0.5, and the reaction time was controlled to be 1-120 min.

[0134] The specific operations of application examples 1-12 are as follows, and the key data is arranged in Table 1.

[0135] Application Example 1

[0136] In a glove box, CAT1 (n=92) (20 mg, 0.071 mmol), Bu4NC1 (9.9 mg, 0.036 mmol) and PO (0.995 ml, 14.2 mmol) were added to a pre-flame dried 10 mL pressure-resistant vial with a magnetic stirrer, and the reaction was carried out at 25 °C for 2 min. After the reaction was completed, the reaction was quenched, diluted with a small amount of dichloromethane, and part of the reaction solution was taken for detection. The number average molecular weight Mn was 17.2 kg / mol, and the molecular weight distribution was 1.15.

[0137] Application Example 2

[0138] In a glove box, a flame dried 10 mL pressure bottle vial was charged with CAT2 (n=92) (21.7 mg, 0.071 mmol), Bu4NCI (9.9 mg, 0.036 mmol) and PO (0.995 ml, 14.2 mmol), stirred at 25 °C for 2 min, quenched at the end of the reaction, diluted with a small amount of dichloromethane, and a portion of the reaction was taken for testing. The number average molecular weight Mnwas 16.8 kg / mol and the molecular weight distribution Mw / Mnwas 1.16, as determined by GPC. The number average molecular weight Mnwas 42.1 kg / mol and the molecular weight distribution Mw / Mnwas 1.14, as determined by GPC.

[0139] Application Example 3

[0140] In a glove box, a flame dried 10 mL pressure bottle vial was charged with CAT2 (n=92) (21.7 mg, 0.071 mmol), Bu4NCI (9.9 mg, 0.036 mmol) and PO (0.995 ml, 14.2 mmol), stirred at 25 °C for 2 min, quenched at the end of the reaction, diluted with a small amount of dichloromethane, and a portion of the reaction was taken for testing. The number average molecular weight Mnwas 16.8 kg / mol and the molecular weight distribution Mw / Mnwas 1.16, as determined by GPC. The number average molecular weight Mnwas 42.1 kg / mol and the molecular weight distribution Mw / Mnwas 1.14, as determined by GPC.

[0141] Application Example 4

[0142] In a glove box, a flame dried 10 mL pressure bottle vial was charged with CAT2 (n=92) (21.7 mg, 0.071 mmol), Bu4NCI (9.9 mg, 0.036 mmol) and PO (0.995 ml, 14.2 mmol), stirred at 25 °C for 2 min, quenched at the end of the reaction, diluted with a small amount of dichloromethane, and a portion of the reaction was taken for testing. The number average molecular weight Mnwas 16.8 kg / mol and the molecular weight distribution Mw / Mnwas 1.16, as determined by GPC. The number average molecular weight Mnwas 42.1 kg / mol and the molecular weight distribution Mw / Mnwas 1.14, as determined by GPC.

[0143] Application Example 5

[0144] In a glove box, a flame dried 10 mL pressure bottle vial was charged with CAT2 (n=92) (21.7 mg, 0.071 mmol), Bu4NCI (9.9 mg, 0.036 mmol) and PO (0.995 ml, 14.2 mmol), stirred at 25 °C for 2 min, quenched at the end of the reaction, diluted with a small amount of dichloromethane, and a portion of the reaction was taken for testing. The number average molecular weight Mnwas 16.8 kg / mol and the molecular weight distribution Mw / Mnwas 1.16, as determined by GPC. The number average molecular weight Mnwas 42.1 kg / mol and the molecular weight distribution Mw / Mnwas 1.14, as determined by GPC.

[0145] Application Example 6

[0146] In a glove box, a pre-flame dried 10 mL pressure bottle vial, already equipped with a magnetic stirrer, was charged with CAT2 (n=92) (21.7 mg, 0.071 mmol), Bu4NCI (9.9 mg, 0.036 mmol) and PO (4.97 ml, 71 mmol), and reacted at 25 °C for 8 min. After the reaction was completed, the reaction was quenched, diluted with a small amount of dichloromethane, and a portion of the reaction was taken for detection. The number average molecular weight Mn was 97.6 kg / mol, and the molecular weight distribution was 1.17.

[0147] Application Example 7

[0148] In a glove box, a pre-flame dried 50 mL pressure bottle vial, already equipped with a magnetic stirrer, was charged with CAT1 (n=92) (20 mg, 0.071 mmol), Bu4NCI (9.9 mg, 0.036 mmol) and PO (24.8 ml, 355 mmol), and reacted at 25 °C for 40 min. After the reaction was completed, the reaction was quenched, diluted with a small amount of dichloromethane, and a portion of the reaction was taken for detection. The number average molecular weight Mn was 520.9 kg / mol, and the molecular weight distribution was 1.14.

[0149] Application Example 8

[0150] In a glove box, a pre-flame dried 50 mL pressure bottle vial, already equipped with a magnetic stirrer, was charged with CAT2 (n=92) (21.7 mg, 0.071 mmol), Bu4NCI (9.9 mg, 0.036 mmol) and PO (24.8 ml, 355 mmol), and reacted at 25 °C for 50 min. After the reaction was completed, the reaction was quenched, diluted with a small amount of dichloromethane, and a portion of the reaction was taken for detection. The number average molecular weight Mn was 507.6 kg / mol, and the molecular weight distribution was 1.16.

[0151] Application Example 9

[0152] In a glove box, a pre-flame dried 250 mL pressure bottle vial, already equipped with a magnetic stirrer, was charged with CAT1 (n=92) (20 mg, 0.071 mmol), Bu4NCI (9.9 mg, 0.036 mmol) and PO (49.7 ml, 710 mmol), and reacted at 25 °C for 90 min. After the reaction was completed, the reaction was quenched, diluted with a small amount of dichloromethane, and a portion of the reaction was taken for detection. The number average molecular weight Mn was 1099.6 kg / mol, and the molecular weight distribution was 1.14.

[0153] Application Example 10

[0154] In a glove box, a pre-flame dried 250 mL pressure bottle vial with a magnetic stirrer was charged with CAT2 (n=92) (21.7 mg, 0.071 mmol), Bu4NCI (9.9 mg, 0.036 mmol) and PO (49.7 ml, 710 mmol), and reacted at 25 °C for 110 min. After the reaction was completed, the reaction was quenched, diluted with a small amount of dichloromethane, and a portion of the reaction solution was taken for detection. The number average molecular weight Mn was 1079.3 kg / mol, and the molecular weight distribution was 1.17.

[0155] Application Example 11

[0156] In a glove box, a pre-flame dried 50 mL pressure bottle vial with a magnetic stirrer was charged with CAT1 (n=92) (20 mg, 0.071 mmol), benzoic acid tetrabutylammonium (13.1 mg, 0.036 mmol) and PO (14.9 ml, 213 mmol), and reacted at 25 °C for 20 min. After the reaction was completed, the reaction was quenched, diluted with a small amount of dichloromethane, and a portion of the reaction solution was taken for detection. The number average molecular weight Mn was 301.7 kg / mol, and the molecular weight distribution was 1.15.

[0157] Application Example 12

[0158] In a glove box, a pre-flame dried 50 mL pressure bottle vial with a magnetic stirrer was charged with CAT2 (n=92) (21.7 mg, 0.071 mmol), benzoic acid tetrabutylammonium (13.1 mg, 0.036 mmol) and PO (14.9 ml, 213 mmol), and reacted at 25 °C for 20 min. After the reaction was completed, the reaction was quenched, diluted with a small amount of dichloromethane, and a portion of the reaction solution was taken for detection. The number average molecular weight Mn was 298.6 kg / mol, and the molecular weight distribution was 1.17.

[0159] Table 1 Summary of key data of application examples 1-12

[0160]

[0161]

[0162] Application Examples 13-24

[0163] Copolymerization of alkylene oxide with CO2 catalyzed by CAT1 and CAT2

[0164]

[0165] A stainless steel autoclave with magnetic stirrer was placed in a 110 °C oven, after 2 hours, it was taken out while hot, sealed, vacuumed until the autoclave slowly dropped to room temperature, replaced with nitrogen three times and then used. Under nitrogen protection, a certain amount of catalyst was weighed into a dry and clean autoclave, a certain amount of PGE was added, stirred for 10 minutes until the catalyst was completely dissolved, then a certain pressure of CO2 (1.5-2.5 MPa) was filled into the autoclave. The reaction temperature was set to -40-80 °C, the molar ratio of ammonium salt to catalyst and PGE was 1:2:500-1:2:5000, the reaction time was controlled at 0.25 h-12 h, and the reaction was terminated. Slowly release the remaining CO2 at room temperature. A small amount of reaction product was taken out for 'H NMR and GPC analysis.

[0166] The specific operation of application examples 13-24 is as follows, and the key data is arranged in Table 2.

[0167] Application Example 13

[0168] In the glove box, CAT1 (n=92) (20 mg, 0.072 mmol), Bu4NCl (9.9 mg, 0.036 mmol), and PGE (2.4 ml, 18 mmol) were added to a 10 mL high-pressure reaction kettle with a magnetic stirrer in advance. The reaction kettle was taken out of the glove box, 15 bar pressure of carbon dioxide was filled in the outside, and the reaction was carried out at 60 °C for 2 h. After the reaction was completed, the reaction was quenched, and part of the reaction liquid was taken for detection. GPC measurement showed that the number average molecular weight Mn was 49.6 kg / mol, and the molecular weight distribution was 1.20.

[0169] Application Example 14

[0170] In the glove box, CAT1 (n=92) (20 mg, 0.072 mmol), Bu4NCl (9.9 mg, 0.036 mmol), and PGE (2.4 ml, 18 mmol) were added to a 10 mL high-pressure reaction kettle with a magnetic stirrer in advance. The reaction kettle was taken out of the glove box, 15 bar pressure of carbon dioxide was filled in the outside, and the reaction was carried out at 60 °C for 2 h. After the reaction was completed, the reaction was quenched, and part of the reaction liquid was taken for detection. GPC measurement showed that the number average molecular weight Mn was 49.6 kg / mol, and the molecular weight distribution was 1.18.

[0171] Application Example 15

[0172] In a glove box, CAT1 (n=92) (20 mg, 0.072 mmol), Bu4NC1 (9.9 mg, 0.036 mmol), and PGE (24 ml, 180 mmol) were added to a pre-flame-dried 100 mL high-pressure reaction vessel equipped with a magnetic stirrer. The reaction vessel was removed from the glove box, and the vessel was charged with 15 bar of carbon dioxide at ambient temperature. The reaction was stirred at 60 °C for 12 h. The reaction was quenched, and a portion of the reaction was analyzed. The number average molecular weight (Mn) was 451.3 kg / mol, and the molecular weight distribution (Mw / Mn) was 1.20 by GPC.

[0173] Application Example 16

[0174] In a glove box, CAT1 (n=92) (20 mg, 0.072 mmol), Bu4NC1 (9.9 mg, 0.036 mmol), and PGE (24 ml, 180 mmol) were added to a pre-flame-dried 100 mL high-pressure reaction vessel equipped with a magnetic stirrer. The reaction vessel was removed from the glove box, and the vessel was charged with 15 bar of carbon dioxide at ambient temperature. The reaction was stirred at 60 °C for 12 h. The reaction was quenched, and a portion of the reaction was analyzed. The number average molecular weight (Mn) was 451.3 kg / mol, and the molecular weight distribution (Mw / Mn) was 1.20 by GPC.

[0175] Application Example 17

[0176] In a glove box, CAT1 (n=92) (20 mg, 0.072 mmol), Bu4NC1 (9.9 mg, 0.036 mmol), and PGE (24 ml, 180 mmol) were added to a pre-flame-dried 100 mL high-pressure reaction vessel equipped with a magnetic stirrer. The reaction vessel was removed from the glove box, and the vessel was charged with 15 bar of carbon dioxide at ambient temperature. The reaction was stirred at 60 °C for 12 h. The reaction was quenched, and a portion of the reaction was analyzed. The number average molecular weight (Mn) was 451.3 kg / mol, and the molecular weight distribution (Mw / Mn) was 1.20 by GPC.

[0177] Application Example 18

[0178] ​​​In a glove box, CAT2(n=92) (22.1 mg, 0.072 mmol), Bu4NCI (9.9 mg, 0.036 mmol), and PGE (2.4 ml, 18 mmol) were added to a 10 mL high pressure reaction vessel previously flame dried and equipped with a magnetic stirrer. The reaction vessel was removed from the glove box, charged with 15 bar of carbon dioxide and reacted at 60 °C for 2 h. The reaction was quenched and a sample was taken for analysis. GPC gave a number average molecular weight Mn of 47.1 kg / mol and a molecular weight distribution Mw / Mn of 1.22.

[0179] Application Example 19

[0180] In a glove box, CAT2(n=92) (22.1 mg, 0.072 mmol), Bu4NCI (9.9 mg, 0.036 mmol), and PGE (4.8 ml, 36 mmol) were added to a 10 mL high pressure reaction vessel previously flame dried and equipped with a magnetic stirrer. The reaction vessel was removed from the glove box, charged with 15 bar of carbon dioxide and reacted at 60 °C for 3 h. The reaction was quenched and a sample was taken for analysis. GPC gave a number average molecular weight Mn of 90.1 kg / mol and a molecular weight distribution Mw / Mn of 1.19.

[0181] Application Example 20

[0182] In a glove box, CAT2(n=92) (22.1 mg, 0.072 mmol), Bu4NCI (9.9 mg, 0.036 mmol), and PGE (24 ml, 180 mmol) were added to a 100 mL high pressure reaction vessel previously flame dried and equipped with a magnetic stirrer. The reaction vessel was removed from the glove box, charged with 15 bar of carbon dioxide and reacted at 60 °C for 12 h. The reaction was quenched and a sample was taken for analysis. GPC gave a number average molecular weight Mn of 445.9 kg / mol and a molecular weight distribution Mw / Mn of 1.21.

[0183] Application Example 21

[0184] ​​​In a glove box, a pre-flame dried 10 mL autoclave, which was already equipped with a magnetic stirrer, was charged with CAT2(n=92) (22.1 mg, 0.072 mmol), Bu4NCI (9.9 mg, 0.036 mmol), and PGE (2.4 ml, 18 mmol). The reactor was removed from the glove box, and the reactor was charged with 25 bar of carbon dioxide at 60 °C for 1.75 h. After the reaction was completed, the reaction was quenched, and a portion of the reaction solution was taken for testing. The number average molecular weight Mnwas 47.1 kg / mol, and the molecular weight distribution Mw / Mnwas 1.20, which were determined by GPC.

[0185] Application Example 22

[0186] In a glove box, a pre-flame dried 10 mL autoclave, which was already equipped with a magnetic stirrer, was charged with CAT2(n=92) (44.1 mg, 0.144 mmol), Bu4NCI (9.9 mg, 0.036 mmol), and PGE (2.4 ml, 18 mmol). The reactor was removed from the glove box, and the reactor was charged with 15 bar of carbon dioxide at 60 °C for 1.25 h. After the reaction was completed, the reaction was quenched, and a portion of the reaction solution was taken for testing. The number average molecular weight Mnwas 47.9 kg / mol, and the molecular weight distribution Mw / Mnwas 1.20, which were determined by GPC.

[0187] Application Example 23

[0188] In a glove box, a pre-flame dried 100 mL autoclave, which was already equipped with a magnetic stirrer, was charged with CAT1(n=92) (20 mg, 0.072 mmol), succinic acid tetrabutylammonium salt (12.9 mg, 0.036 mmol), and PGE (2.4 ml, 18 mmol). The reactor was removed from the glove box, and the reactor was charged with 15 bar of carbon dioxide at 60 °C for 1.5 h. After the reaction was completed, the reaction was quenched, and a portion of the reaction solution was taken for testing. The number average molecular weight Mnwas 51.2 kg / mol, and the molecular weight distribution Mw / Mnwas 1.19, which were determined by GPC.

[0189] Application Example 24

[0190] ​​​In a glove box, CAT2 (n=92) (22.1 mg, 0.072 mmol), succinic acid tetrabutylammonium salt (12.9 mg, 0.036 mmol), and PGE (2.4 ml, 18 mmol) were added to a pre-flame dried 10 mL high pressure reaction vessel equipped with a magnetic stirrer. The reaction vessel was removed from the glove box, pressurized to 15 bar with carbon dioxide, and heated to 60 °C for 1.5 h. The reaction was quenched and a portion of the reaction was analyzed. The number average molecular weight Mnwas 50.6 kg / mol and the molecular weight distribution Mw / Mnwas 1.21 by GPC.

[0191] Table 2 Summary of key data for Examples 13-24

[0192]

[0193] Examples 25-32

[0194] Copolymerization of alkylene oxides with cyclic anhydrides using CAT1 and CAT2

[0195]

[0196] In a glove box, CAT2 (n=92) (22.1 mg, 0.072 mmol), succinic acid tetrabutylammonium salt (12.9 mg, 0.036 mmol), and PGE (2.4 ml, 18 mmol) were added to a pre-flame dried 10 mL high pressure reaction vessel equipped with a magnetic stirrer. The reaction vessel was removed from the glove box, pressurized to 15 bar with carbon dioxide, and heated to 60 °C for 1.5 h. The reaction was quenched and a portion of the reaction was analyzed. The number average molecular weight Mnwas 50.6 kg / mol and the molecular weight distribution Mw / Mnwas 1.21 by GPC.

[0197] Examples 25-32 were prepared as follows, and the key data are summarized in Table 3.

[0198] Example 25

[0199] In a glove box, CAT2 (n=92) (22.1 mg, 0.072 mmol), succinic acid tetrabutylammonium salt (12.9 mg, 0.036 mmol), and PGE (2.4 ml, 18 mmol) were added to a pre-flame dried 10 mL high pressure reaction vessel equipped with a magnetic stirrer. The reaction vessel was removed from the glove box, pressurized to 15 bar with carbon dioxide, and heated to 60 °C for 1.5 h. The reaction was quenched and a portion of the reaction was analyzed. The number average molecular weight Mnwas 50.6 kg / mol and the molecular weight distribution Mw / Mnwas 1.21 by GPC.

[0200] Example 26

[0201] ​​In a glove box, a flame-dried 10 mL pressure tube already equipped with a magnetic stirrer was charged with CAT1 (n=92) (20 mg, 0.072 mmol), Bu4NCI (9.9 mg, 0.036 mmol), PA (296 mg, 2 mmol) and CHO (0.4 ml, 4 mmol) successively. The pressure tube was taken out of the glove box and reacted at 130 °C for 0.25 h. After the reaction was completed, the reaction was quenched. After the polymer was purified, the number average molecular weight Mn was 24.3 kg / mol and the molecular weight distribution was 1.20.

[0202] Application Example 27

[0203] In a glove box, a flame-dried 50 mL pressure tube already equipped with a magnetic stirrer was charged with CAT1 (n=92) (20 mg, 0.072 mmol), Bu4NCI (9.9 mg, 0.036 mmol), PA (5.3 g, 36 mmol) and CHO (7.3 ml, 72 mmol) successively. The pressure tube was taken out of the glove box and reacted at 130 °C for 0.5 h. After the reaction was completed, the reaction was quenched. After the polymer was purified, the number average molecular weight Mn was 59.4 kg / mol and the molecular weight distribution was 1.20.

[0204] Application Example 28

[0205] In a glove box, a flame-dried 10 mL pressure tube already equipped with a magnetic stirrer was charged with CAT2 (n=92) (22.1 mg, 0.072 mmol), Bu4NCI (9.9 mg, 0.036 mmol), PA (296 mg, 2 mmol) and CHO (0.4 ml, 4 mmol) successively. The pressure tube was taken out of the glove box and reacted at 60 °C for 0.75 h. After the reaction was completed, the reaction was quenched. After the polymer was purified, the number average molecular weight Mn was 20.7 kg / mol and the molecular weight distribution was 1.20.

[0206] Application Example 29

[0207] In a glove box, a flame-dried 10 mL pressure tube already equipped with a magnetic stirrer was charged with CAT2(n=92) (22.1 mg, 0.072 mmol), Bu4NCI (9.9 mg, 0.036 mmol), PA (296 mg, 2 mmol) and CHO (0.4 ml, 4 mmol) successively. The pressure tube was taken out of the glove box and reacted at 130 °C for 0.25 h. After the reaction was completed, the reaction was quenched. After the polymer was purified, the number average molecular weight Mn was 25.1 kg / mol and the molecular weight distribution was 1.20.

[0208] Application Example 30

[0209] In a glove box, a flame-dried 50 mL pressure tube already equipped with a magnetic stirrer was charged with CAT2(n=92) (22.1 mg, 0.072 mmol), Bu4NCI (9.9 mg, 0.036 mmol), PA (5.3 g, 36 mmol) and CHO (7.3 ml, 72 mmol) successively. The pressure tube was taken out of the glove box and reacted at 130 °C for 0.5 h. After the reaction was completed, the reaction was quenched. After the polymer was purified, the number average molecular weight Mn was 55.4 kg / mol and the molecular weight distribution was 1.21.

[0210] Application Example 31

[0211] In a glove box, a flame-dried 10 mL pressure tube already equipped with a magnetic stirrer was charged with CAT2(n=92) (22.1 mg, 0.072 mmol), butane-1,4-dioic acid tetrabutylammonium salt (12.9 mg, 0.036 mmol), PA (296 mg, 2 mmol) and CHO (0.4 ml, 4 mmol) successively. The pressure tube was taken out of the glove box and reacted at 100 °C for 0.5 h. After the reaction was completed, the reaction was quenched. After the polymer was purified, the number average molecular weight Mn was 25.1 kg / mol and the molecular weight distribution was 1.19.

[0212] Application Example 32

[0213] In a glove box, a flame-dried 10 mL pressure bottle already equipped with a magnetic stirrer was charged with CAT2(n=92) (22.1 mg, 0.072 mmol), succinic acid tetrabutylammonium salt (12.9 mg, 0.036 mmol), PA (296 mg, 2 mmol) and CHO (0.4 ml, 4 mmol) in this order. The pressure bottle was removed from the glove box and reacted at 100 °C for 0.5 h. After the reaction was completed, the reaction was quenched. After the polymer was purified, the number average molecular weight Mn was 23.8 kg / mol and the molecular weight distribution was 1.18.

[0214] Table 3 Summary of key data for examples 25-32

[0215]

[0216] The above description is merely the preferred embodiments of the present application, and is not intended to limit the present application. Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that modifications, equivalent substitutions, improvements, etc. can be made to the technical solutions described in the foregoing embodiments, or some of the technical features can be replaced by equivalent features. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A polymeric polynuclear boron organocatalyst, characterized in that, Its structure is shown in Equation I or Equation II: (Formula I) (Formula II); Where n is an integer between 85 and 95, m is an integer between 85 and 95, x is an integer between 0 and 3, and y is an integer between 1 and 5; R 1 It is any one of hydrogen, methyl, ethyl, butyl, phenyl, or substituted phenyl; BR2 is selected from , , , or Any one of them.

2. The polymeric polynuclear boron organocatalyst according to claim 1, characterized in that, The n is 90, 91, or 92; the m is 90, 91, or 92.

3. The polymeric polynuclear boron organocatalyst according to claim 1, characterized in that, The catalyst comprises any one of the following structural formulas: CAT1 CAT2 CAT3 CAT4 CAT5 CAT6 CAT7 CAT8 CAT9 CAT10; Where m is an integer between 85 and 95; and n is an integer between 85 and 95.

4. The method for preparing the catalyst according to any one of claims 1-3, characterized in that, Includes the following steps: Tetrahydrofuran was added to the catalyst precursor, followed by the addition of a borohydride reagent. The mixture was heated at 25–80 °C for 22–26 h. The reaction mixture was concentrated under vacuum to obtain a crude product. The crude product was purified by washing with pentane 2–5 times and then dried under vacuum at room temperature for 10–14 h to obtain the catalyst. The borohydride reagent includes any one of 9-boronbicyclo[3.3.1]nonane, cyclopentylborane, cyclohexylborane, dicyclohexylborane, or 3-methylcyclopentylborane; The catalyst precursor is catalyst precursor 1 or catalyst precursor 2, wherein the molar ratio of catalyst precursor 1 to borohydride reagent is 1:(1.02~3), and the molar ratio of catalyst precursor 2 to borohydride reagent is 1:(1.02~3).

5. The preparation method according to claim 4, characterized in that, The catalyst precursor is a polymer with terminal olefin double bonds, and its chemical structural formula is as follows: or Catalyst precursor 1; Catalyst precursor 2; Where n is an integer between 85 and 95; m is an integer between 85 and 95; x is an integer between 0 and 3; y is an integer between 1 and 5; R is any one of hydrogen, methyl, ethyl, butyl, phenyl, or substituted phenyl.

6. The preparation method according to claim 5, characterized in that, The catalyst precursor is any one of catalyst precursor 1a, catalyst precursor 1b, catalyst precursor 1c, or catalyst precursor 2a: Catalyst precursor 1a, catalyst precursor 1b, catalyst precursor 1c, catalyst precursor 2a; Where n is an integer between 85 and 95; m is an integer between 85 and 95.

7. The preparation method according to claim 4, characterized in that, The preparation steps of the catalyst precursor 1 are as follows: The polymer of 4-vinylphenol monomers and haloolefins in a molar ratio of 1:(10~20) were dissolved in acetonitrile, anhydrous potassium carbonate was added, and the mixture was heated at 60~70℃ for 10~14 h. After standing at room temperature, the residue after filtration was washed 2~5 times with dichloromethane, evaporated to dryness, washed 1~3 times with pentane, and dried under vacuum at room temperature for 10~14 h to obtain catalyst precursor 1.

8. The preparation method according to claim 4, characterized in that, The preparation steps of the catalyst precursor 2 are as follows: Styrene monomers and conjugated diene monomers in a molar ratio of (5~15):1 were weighed and dissolved in cyclohexane. Sec-butyllithium was added and stirred at room temperature for 2.5~3.5 h. The mixture was then quenched with a small amount of methanol. The colorless mixture was precipitated in methanol 1~3 times. The product was recovered by filtration and dried under high vacuum overnight to obtain a fine white powder, which is catalyst precursor 2.

9. The use of the catalyst according to any one of claims 1-3 in the preparation of polymers by catalytic polymerization, characterized in that, The polymer is a polyether, polyester, or polycarbonate. The polyether is obtained by homopolymerization of epoxy monomers catalyzed by a catalyst. The polyester is obtained by copolymerization of epoxy monomers and cyclic anhydrides catalyzed by a catalyst. The polycarbonate is obtained by copolymerization of epoxy monomers and carbon dioxide catalyzed by a catalyst.

10. The use of the catalyst according to any one of claims 1-3 in the preparation of small organic molecules, characterized in that, The organic small molecule is a cyclic carbonate, which is obtained by coupling an epoxy monomer and carbon dioxide.

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