A trifunctional organic catalyst, its preparation method and application

Abstract

The present invention discloses a trifunctional organic catalyst which simultaneously has the following three structures in the molecule: thiourea or urea, onium salt, and organoboron; the arrangement of the trifunctional catalyst can be thiourea or urea - onium salt - organoboron, or onium salt - thiourea or urea - organoboron; as shown in formula (I) or (II) respectively. The present invention also discloses a preparation method of the trifunctional organic catalyst and its application in the preparation of organic small molecules and macromolecular polymers. The trifunctional catalyst provided by the present invention introduces a highly active Lewis acidic center based on boron, and at the same time introduces a hydrogen bond donor active center of a thiourea or urea structure. The two cooperate to activate cyclic monomers, resulting in higher catalytic efficiency, yield, and product selectivity.

Description

Technical Field

[0001] The present invention relates to the field of catalysis, and particularly to the development and application of a trifunctional organic catalyst that can be used for the preparation of organic small molecule fine chemicals and polymer materials. Background Art

[0002] In the past few decades, organocatalysis has received extensive attention in small molecule synthesis and polymer construction. Compared with relatively complex metal catalysts, organocatalysts have the advantages of simple synthesis, high economic efficiency, and low biological toxicity. Nevertheless, the activities and product selectivities of most currently developed organocatalysts still cannot be compared with those of metal-organic complexes. Therefore, the development of highly efficient organocatalysts is of practical significance and challenge.

[0003] Currently, some hydrogen bond-based organocatalysts, including thiourea (or urea), N-heterocyclic carbene (NHC), frustrated Lewis pair (FLP), polyphenol, fluoroalcohol, silanediol with a cocatalyst, and ionic liquid (ILs), etc., have been widely studied. In particular, hydrogen bond donors such as thiourea or urea can effectively activate nucleophilic monomers, so they have relatively high catalytic activity, and they also have the advantages of relatively simple preparation, easy structural modulation, low catalyst toxicity, and compliance with the sustainable development strategy.

[0004] In recent years, the research group of Guangpeng Wu has developed a series of metal-free organoboron catalytic systems that can be modularly designed, simply synthesized, produced in kilogram scale, highly active, and widely applicable to substrates [CN 110938087 B]. Since organoboron has an empty p orbital, it has a Lewis acidic center similar to that of a metal, and is very suitable for catalyzing the polymerization of nucleophilic monomers. In addition, the bifunctional design further improves the catalytic effect of the catalyst due to the synergistic effect. Therefore, such catalysts have shown catalytic effects comparable to or even exceeding those of metal catalysts in small molecule synthesis and polymer construction [Angew.Chem.Int.Ed.2020,59,1691; Angew.Chem.Int.Ed.2020,59,23291; J.Am.Chem.Soc.2020,142,12245; Angew.Chem.Int.Ed.2021,60,19253].

[0005] However, for some monomers with low activity, the bifunctional catalyst may have problems of insufficient active centers and insufficient activation ability. If different electrophilic centers, such as highly efficient hydrogen bond donors such as thiourea (or urea), are introduced into the bifunctional catalyst, the synergistic effect can be better exerted to activate the monomers, thereby obtaining higher catalytic efficiency. Summary of the Invention

[0006] The present invention provides a trifunctional organic catalyst and a preparation method thereof. The preparation method is simple and has a high yield. The present invention also provides the application of the trifunctional organic catalyst in the preparation of fine chemicals with high added value.

[0007] The technical solution provided by the present invention is as follows:

[0008] A trifunctional organic catalyst, which simultaneously has the following three structures in the catalyst molecule: thiourea or urea, onium salt, and organoboron; the arrangement of the trifunctional catalyst can be thiourea or urea - onium salt - organoboron, or onium salt - thiourea or urea - organoboron;

[0009] The structural formulas of the trifunctional organic catalyst are respectively shown as formula (I) or (II). Formula (I) is thiourea or urea - onium salt - organoboron, and formula (II) is onium salt - thiourea or urea - organoboron:

[0010]

[0011] X = O or S atom; A = N or P atom; n, m are positive integers selected from 1 - 10;

[0012] Among them, B is a boron atom, X is O or S atom, and A is N or P atom;

[0013] m is preferably 1 or 2, and n is preferably 1 or 2;

[0014] L1, L2, L3, L4 are linking groups. In formula (I), L1 links the two structures of thiourea or urea and onium salt; L2 links onium salt and organoboron;

[0015] In formula (II), L3 links the two structures of thiourea or urea and onium salt; L4 links the two structures of thiourea or urea and organoboron;

[0016] L1, L2, L3, L4 are each independently selected from the following groups that are unsubstituted or have substituent A: C1 - C 18 alkyl, C3 - C 18 cycloalkyl, C3 - C 18 alkenyl, C3 - C 18 alkynyl, C6 - C 18 aryl, C3 - C 18 heterocyclic group or C5 - C 18 heteroaryl, or the above groups containing O, S, N, Si, P atoms;

[0017] The substituent A is selected from halogen atoms, C1 - C 10 alkyl, C1 - C 10 alkoxy, C3 - C 10 cycloalkyl, C6 - C 18 aryl, C5 - C 18one or more of heteroaryl groups;

[0018] When being a linking group, the alkyl group refers to an alkylene group or a sub-alkylene group, and the cycloalkyl group refers to a cycloalkyl group having more than 2 bonding positions;

[0019] R1 and R6 are each independently selected from the following groups which are unsubstituted or have substituent B: C1-C 18 alkyl group, C3-C 18 cycloalkyl group, C3-C 18 alkenyl group, C3-C 18 alkynyl group, C6-C 18 aryl group, C3-C 18 heterocyclic group or C5-C 18 heteroaryl group, or the above groups containing O, S, N, Si, P atoms;

[0020] The substituent B is selected from one or more of halogen atoms, C1-C 10 alkyl group, C1-C 10 alkoxy group, C3-C 10 cycloalkyl group, C6-C 18 aryl group, C5-C 18 heteroaryl groups;

[0021] R2 and R3 are each independently selected from the following groups which are unsubstituted or have substituent C: C1-C 18 alkyl group, C3-C 18 cycloalkyl group, C3-C 18 alkenyl group, C3-C 18 alkynyl group, C6-C 18 aryl group, C3-C 18 heterocyclic group or C5-C 18 heteroaryl group, or the above groups containing O, S, N, Si, P atoms;

[0022] The substituent C is selected from one or more of halogen atoms, C1-C 10 alkyl group, C1-C 10 alkoxy group, C3-C 10 cycloalkyl group, C6-C 18 aryl group, C5-C 18 heteroaryl groups;

[0023] Or R2 and R3 can be connected to form a ring, and combine with A atom to form an A-containing heterocycle which is unsubstituted or has substituent C;

[0024] Or in formula (I), R2 and R3 can also each independently be formula C or formula D; formula C is a thiourea or urea structure, and formula D is an organoboron structure;

[0025]

[0026] represents a linking key;

[0027] In Formula C and Formula D, the definition of L1' is the same as that of L1, and the definition of L2' is the same as that of L2; L1' and L1 may be the same or different, preferably L1' and L1 are the same; L2' and L2 may be the same or different, preferably L2' and L2 are the same;

[0028] m' and n' are each independently an integer from 1 to 10, preferably 1 or 2;

[0029] The definition of R1' is the same as that of R1, and R1' and R1 may be the same or different, preferably R1' and R1 are the same;

[0030] The definition of R4' is the same as that of R4, and R4' and R4 may be the same or different, preferably R4' and R4 are the same;

[0031] The definition of R5' is the same as that of R5, and R5' and R5 may be the same or different, preferably R5' and R5 are the same;

[0032] Further, in Formula (I), R2 is Formula C or the following groups which are unsubstituted or have substituent C: C1-C 18 alkyl, C3-C 18 cycloalkyl, C3-C 18 alkenyl, C3-C 18 alkynyl, C6-C 18 aryl, C3-C 18 heterocyclic group or C5-C 18 heteroaryl, or is the above groups containing O, S, N, Si, P atoms;

[0033] In Formula (I), R3 is Formula D or or the following groups which are unsubstituted or have substituent C: C1-C 18 alkyl, C3-C 18 cycloalkyl, C3-C 18 alkenyl, C3-C 18 alkynyl, C6-C 18 aryl, C3-C 18 heterocyclic group or C5-C 18 heteroaryl, or is the above groups containing O, S, N, Si, P atoms;

[0034] R4 and R5 are each independently selected from the following groups which are unsubstituted or have substituent D: C1-C 18 alkyl, C3-C 18 cycloalkyl, C3-C 18 alkenyl, C3-C 18 alkynyl, C6-C18 Aryl, C3-C 18 Heterocyclic group or C5-C 18 Heteroaryl, or the above groups containing O, S, N, Si, P atoms;

[0035] The substituent D is selected from a halogen atom, C1-C 10 Alkyl, C1-C 10 Alkoxy, C3-C 10 Cycloalkyl, C6-C 18 Aryl, C5-C 18 One or more of heteroaryl;

[0036] Or R4 and R5 can be connected to form a ring, and combined with the B atom to form an unsubstituted or substituted boron-containing cyclic group with substituent D;

[0037] Y Is a negative ion, selected from F – , Cl–, Br–, I–, NO3–, CH3COO–, CCl3COO–, CF3COO–, ClO4 – , BF4 – , BPh4 – , N3 – , OH – , p-toluate, p-toluenesulfonate, o-nitrophenolate, p-nitrophenolate, m-nitrophenolate, 2,4-dinitrophenolate, 3,5-dinitrophenolate, 2,4,6-trinitrophenolate, 3,5-dichlorophenolate, carbonate, hydrogencarbonate, 3,5-difluorophenolate, 3,5-bis(trifluoromethyl)phenolate or pentafluorophenolate anion.

[0038] Furthermore, preferably R1 is the following group which is unsubstituted or has substituent B: C1-C 10 Alkyl, C3-C 10 Cycloalkyl, C6-C 10 Aryl, or the above groups containing O, S, N, Si, P atoms; The substituent B is preferably one or more of a halogen atom, C1-C 10 Alkyl, C1-C 10 Alkoxy, C6-C 10 Aryl; More preferably, R1 is an unsubstituted or substituted C6-C 10 Aryl, and the C6-C 10 Aryl is preferably phenyl or naphthyl, and the substituent B on the C6-C 10 Aryl is a halogen atom, C1-C 10 Alkyl, C1-C 10 Alkoxy or trifluoromethyl;

[0039] Further, in formula (II), preferably, each of R2 and R3 is independently an unsubstituted group or a group having substituent C selected from the following groups: C1-C 10 alkyl, C3-C 10 cycloalkyl, C6-C 10 aryl, or a group containing O, S, N, Si, or P atoms selected from the above groups; the substituent C is preferably one or more selected from halogen atoms, C1-C 10 alkyl, C1-C 10 alkoxy, C6-C 10 aryl;

[0040] In formula (I), R2 is preferably a group of formula C or an unsubstituted group or a group having substituent C selected from the following groups: C1-C 10 alkyl, C3-C 10 cycloalkyl, C6-C 10 aryl, or a group containing O, S, N, Si, or P atoms selected from the above groups; the substituent C is preferably one or more selected from halogen atoms, C1-C 10 alkyl, C1-C 10 alkoxy, C6-C 10 aryl;

[0041] In formula (I), R3 is preferably a group of formula D or an unsubstituted group or a group having substituent C selected from the following groups: C1-C 10 alkyl, C3-C 10 cycloalkyl, C6-C 10 aryl, or a group containing O, S, N, Si, or P atoms selected from the above groups; the substituent C is preferably one or more selected from halogen atoms, C1-C 10 alkyl, C1-C 10 alkoxy, C6-C 10 aryl;

[0042] In formula (I) or formula (II), alternatively, R2 and R3 are linked to form a ring, and in combination with the A atom, form an A-containing heterocycloalkyl or A-containing heteroaryl having 4 to 6 carbon atoms, which is unsubstituted or has substituent C; the substituent C is preferably one or more selected from halogen atoms, C1-C 10 alkyl, C1-C 10 alkoxy;

[0043] The A-containing heterocycloalkyl having 4 to 6 carbon atoms is preferably piperidinyl or pyrrolyl; the A-containing heteroaryl having 4 to 6 carbon atoms is preferably pyridinyl;

[0044] Further, preferably, R6 is C1-C 10 alkyl, C3-C 10 cycloalkyl or C6-C 10 aryl; more preferably C1-C10 alkyl or C6-C 10 aryl;

[0045] Further, preferably, each of R4 and R5 is independently an unsubstituted group or a group having a substituent D selected from the following: C1-C 10 alkyl, C3-C 10 cycloalkyl, C6-C 10 aryl, or a group containing O, S, N, Si, or P atoms selected from the above; the substituent D is preferably a halogen atom, C1-C 10 alkyl, C1-C 10 alkoxy, C6-C 10 aryl; one or more of the above;

[0046] or R4 and R5 are connected to form a ring, and combined with a B atom to form a boron-containing cyclic group that is unsubstituted or has a substituent D;

[0047] More preferably, each of R4 and R5 is independently C1-C 10 alkyl, cyclohexyl, phenyl, or pentafluorophenyl; or R4 and R5 are connected to form a ring, and combined with a B atom to form the following boron-containing cyclic groups that are unsubstituted or have a substituent D: 9-borabicyclo[3.3.1]nonane, 7-borabicyclo[2.2.1]heptane, pinacolborane, dioxaborolane, borolane, borinane; the substituent D on the boron-containing cyclic group is preferably C1-C 10 alkyl;

[0048] Further, preferably, each of L1, L2, L3, and L4 is independently selected from an unsubstituted group or a group having a substituent A selected from the following: C1-C 12 alkylene, C3-C 10 cycloalkyl, or a group containing O, S, N, Si, or P atoms selected from the above; the substituent A is a halogen atom, C1-C 10 alkyl, C1-C 10 alkoxy; one or more of the above;

[0049] Even more preferably, L1 is C1-C 12 alkylene or cyclohexylene, and cyclohexylene has a chiral structure;

[0050] More preferably, each of L2, L3, and L4 is independently C1-C 12 alkylene.

[0051] More preferably, in the trifunctional catalyst, in formula (I), the onium salt is selected from one of the following structures:

[0052]

[0053] Represents a connecting bond;

[0054] When the onium salt is pyridine, L1 can be 0;

[0055] Among them, R c Is a substituent on the pyridine ring, R c Is 0 or one or more of a halogen atom, a C1-C 10 Alkyl group, a C1-C 10 Alkoxy group;

[0056] In formula (II), the onium salt is more preferably one of the following structures:

[0057]

[0058] Preferably, in the trifunctional organic catalyst, the organoboron R4R5B- is selected from one of the following structures:

[0059]

[0060] In the trifunctional organic catalyst, at least one of the linking groups L1, L2, L3, and L4 can be chiral. At this time, the chiral trifunctional organic catalyst can be used for chiral catalysis.

[0061] The trifunctional organic catalyst provided by the present invention is more preferably one of the following structures:

[0062]

[0063] The present invention also provides a preparation method of the trifunctional organic catalyst. The method is as follows: React a raw material containing at least one unsaturated double bond or triple bond: the thiourea or urea-onium salt shown in formula E, or the onium salt-thiourea or urea shown in formula F, with the R4R5B-H raw material by hydroboration reaction. After stirring at room temperature for 1 to 500 hours, remove impurities and organic solvents to obtain the thiourea or urea-onium salt-organoboron shown in formula (I), or the onium salt-thiourea or urea-organoboron shown in formula (II) respectively.

[0064]

[0065] In formula E or F, Represents a double bond or a triple bond.

[0066] In formula E, —L2— is obtained through hydroboration reaction,

[0067] In formula F, —L4— is obtained through hydroboration reaction.

[0068] Is as defined above.

[0069] Furthermore, the thiourea or urea-onium salt-organic boron shown in formula (I) can be prepared according to the following reaction formula:

[0070]

[0071] Taking the preparation methods of catalysts Cat.1 to Cat.3 as examples below, the preparation reaction formula of Cat.1 is shown as follows:

[0072]

[0073] Cat.1 has a structure of thiourea-onium salt-organic boron, which is obtained by the hydroboration reaction of the prepared thiourea-onium salt (T-1) containing double bonds with a hydroborating reagent (B-1).

[0074] The preparation reaction formula of Cat.2 is shown as follows:

[0075]

[0076] Cat.2 has a structure of onium salt-thiourea-organic boron, which is obtained by the reaction of the prepared onium salt-thiourea (T-2) containing double bonds with a hydroborating reagent (B-2).

[0077] The preparation reaction formula of Cat.3 is shown as follows:

[0078]

[0079] Cat.3 has a structure of thiourea-onium salt-organic boron, which is obtained by the reaction of the prepared two thiourea-onium salts (T-3) containing two double bonds with a hydroborating reagent (B-3).

[0080] The present invention also provides the application of the described trifunctional organic catalyst in the preparation of organic small molecules or macromolecular polymers.

[0081] Further, the method of the application is as follows: in the presence of a trifunctional organic catalyst, one or more cyclic monomers are bulk polymerized to obtain a macromolecular polymer in the presence or absence of a macromolecular chain transfer agent; or one or more cyclic monomers react with one or more of carbon dioxide, carbon disulfide, carbonyl sulfide or carbon monoxide to obtain an organic small molecule compound or a macromolecular polymer; the cyclic monomers include alkylene oxides, thioalkylene oxides, cyclic acid anhydrides or lactones; the macromolecular polymers are aliphatic polycarbonates obtained by catalyzing the copolymerization of carbon dioxide and alkylene oxides, polyethers obtained by catalyzing the ring-opening polymerization of alkylene oxides, polythiocarbonates obtained by catalyzing the ring-opening copolymerization of carbon dioxide and thioalkylene oxides, polythioethers obtained by catalyzing the ring-opening of cyclic thioethers, polyesters obtained by catalyzing the copolymerization of alkylene oxides and cyclic acid anhydrides, polythiocarbonates obtained by catalyzing the copolymerization of carbonyl sulfide and alkylene oxides or polyesters obtained by catalyzing the ring-opening polymerization of lactones, polyesters obtained by catalyzing the ring-opening of O-carboxyanhydrides, and polypeptides obtained by catalyzing the polymerization of N-carboxyanhydrides;

[0082] The organic small molecule compounds are cyclic carbonates obtained by catalyzing the reaction of carbon dioxide or carbon disulfide with alkylene oxides or thioalkylene oxides, cyclic lactones obtained by catalyzing the reaction of carbon monoxide with alkylene oxides, and cyclic thiocarbonates obtained by catalyzing the copolymerization of carbonyl sulfide with alkylene oxides or thioalkylene oxides.

[0083] The cyclic monomers include alkylene oxides, thioalkylene oxides, cyclic acid anhydrides or lactones, and are selected from one of the following structures:

[0084]

[0085] wherein, R6 to R 21 are each independently selected from H, halogen, C1-C with or without substituents and with or without O, S, N, Si, P atoms 30 alkyl, C3-C 30 cycloalkyl, C2-C 30 alkenyl, C2-C 30 alkynyl, C6-C 30 aryl, C3-C 30 heterocyclic group or C5-C 30 heteroaryl; the substituents are selected from one or more of halogen atoms, branched or straight-chain hydrocarbon groups having 1 to 20 carbon atoms, branched or straight-chain alkoxy groups having 1 to 20 carbon atoms, branched or straight-chain cycloalkyl groups having 3 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and heteroaryl groups having 5 to 20 carbon atoms; wherein, each R6 and R7, R8 and R9, R 10 and R 11 , R 12 and R 13 , R 14 and R 15 , R16 and R 17 、R 19 and R 20 、R 21 and R 22 may form a bond or a ring between them.

[0086] Preferably, the cyclic monomer includes, but is not limited to, one of the following structures:

[0087]

[0088]

[0089]

[0090] When the trifunctional organic catalytic system is applied, it can also be loaded on an inorganic carrier or an organic carrier and used as a heterogeneous catalyst.

[0091] The trifunctional organic catalyst provided by the present invention has the advantages of being easy to weigh, high catalytic activity, controllable reaction, etc. when used as a catalyst. The catalytic efficiency and yield can be regulated by changing the catalyst concentration, reactant concentration, reaction time, reaction temperature, etc. The preparation method provided by the present invention is simple, with a high yield, less dosage and low cost. The trifunctional organic catalyst provided by the present invention can effectively synthesize macromolecular polycarbonates, polyethers, polyesters, polysulfides, polythiocarbonates, polythioesters, etc., and can also be effectively used for the preparation of high-value-added fine chemicals such as cyclic carbonates and thio cyclic carbonate lactones.

[0092] Compared with the bifunctional catalyst of the prior art, the trifunctional catalyst provided by the present invention introduces a highly active Lewis acidic center based on boron, and at the same time introduces a hydrogen bond donor active center with a thiourea or urea structure. The two cooperate to activate the cyclic monomer, resulting in higher catalytic efficiency, yield and product selectivity. Detailed implementation mode

[0093] The technical solutions of the present invention will be described below through specific examples, but the protection scope of the present invention is not limited thereto.

[0094] Structure and number of the catalysts used

[0095]

[0096]

[0097] The preparation method of the catalyst is as follows:

[0098] Example 1: Preparation of Cat.1

[0099] 8.8 g (0.1 mol) of N,N-dimethylethylenediamine and 13.5 g of phenyl isothiocyanate (0.1 mol) were stirred at room temperature for 24 h. Then, 14.9 g of 5-bromo-1-pentene and 100 ml of acetonitrile were added, and the mixture was refluxed for 24 h to obtain the catalyst precursor T-1. After purification of T-1 by column chromatography, 0.1 mol of T-1 and 0.1 mol of B-1 were dissolved in 30 ml of anhydrous tetrahydrofuran in a glove box and refluxed for 24 h. After further removal of the solvent by rotary evaporation, Cat.1 was obtained.

[0100]

[0101] Example 2: Preparation of Cat.2

[0102] 8.8 g (0.1 mol) of N,N-dimethylpropylenediamine and 9.9 g of allyl isothiocyanate (0.1 mol) were stirred at room temperature for 24 h. Then, 14.4 g of methyl iodide, 13.8 g of potassium carbonate and 100 ml of acetonitrile were added, and the mixture was refluxed for 24 h to obtain the catalyst precursor T-2. After purification of T-2 by column chromatography, 0.1 mol of T-2 and 0.1 mol of B-2 were dissolved in 30 ml of anhydrous tetrahydrofuran in a glove box and refluxed for 24 h. After further removal of the solvent by rotary evaporation, Cat.2 was obtained.

[0103]

[0104] Example 3: Preparation of Cat.3

[0105] 9.7 g (0.1 mol) of diallylamine, 23.8 g of N-Boc-3-bromopropylamine (0.2 mol) and 13.8 g of potassium carbonate were dissolved in 100 ml of acetonitrile and refluxed for 24 h. After cooling, filtration and removal of the solvent by rotary evaporation, the desired quaternary ammonium salt was obtained. 0.1 mol of the quaternary ammonium salt and 0.2 mol of trifluoroacetic acid were stirred at room temperature for 2 h, and then 0.2 mol of phenyl isothiocyanate was added to obtain the desired catalyst precursor T-3. After purification of T-3 by column chromatography, 0.1 mol of T-3 and 0.1 mol of B-3 were dissolved in 30 ml of anhydrous tetrahydrofuran in a glove box and refluxed for 24 h. After further removal of the solvent by rotary evaporation, Cat.3 was obtained.

[0106]

[0107] Example 4: Preparation of Cat.4

[0108] Similar to the preparation process of Cat.3, 0.1 mol of diallylbutylamine, 0.1 mol of N-Boc-bromopropylamine and 0.1 mol of potassium carbonate were dissolved in 100 ml of acetonitrile, and the mixture was refluxed for 24 h. After cooling, filtering and removing the solvent by rotary evaporation, the required quaternary ammonium salt was obtained. 0.1 mol of the quaternary ammonium salt and 0.2 mol of trifluoroacetic acid were stirred at room temperature for 2 h, and then 0.2 mol of phenyl isothiocyanate was added to obtain the required catalyst precursor T-3. After purifying T-3 by column chromatography, 0.1 mol of T-3 and 0.1 mol of B-2 were taken in a glove box and dissolved in 30 ml of anhydrous tetrahydrofuran, and the mixture was refluxed for 24 h. After further removing the solvent by rotary evaporation, Cat.4 was obtained.

[0109] Examples 5 - 9: Preparation of Cat.5a - Cat.9a

[0110] Similar to the preparation process of Cat.1, 0.1 mol of N,N-dimethylethylenediamine (2-tert-butyl-3-aminomethylpyridine, 3-aminopyridine, 2-chloro-3-aminomethylpyridine) and 0.1 mol of phenyl isothiocyanate (3,5-bis(trifluoromethyl)phenyl isothiocyanate) were stirred at room temperature for 24 h, then 0.1 mol of allyl bromide (5-bromo-1-pentene, 7-bromo-1-heptene, 9-bromo-1-nonene) and 100 ml of acetonitrile were added, and the mixture was refluxed for 24 h to obtain the catalyst precursor. After purifying the catalyst precursor by column chromatography, 0.1 mol of the catalyst precursor and 0.1 mol of the corresponding borane (9-borabicyclo(3,3,1)-nonane, cycloheptaborane) were taken in a glove box and dissolved in 30 ml of anhydrous tetrahydrofuran, and the mixture was refluxed for 24 h. After further removing the solvent by rotary evaporation, Cat.5a - Cat.9a were obtained.

[0111] Examples 10 - 12: Preparation of Cat.10a - Cat.12a

[0112] Similar to the preparation process of Cat.2, 0.1 mol of N,N-diphenylpropanediamine and 0.1 mol of allyl isothiocyanate (propargyl isothiocyanate, allyl isocyanate) were stirred at room temperature for 24 h, then 0.1 mol of methyl iodide, 0.1 mol of potassium carbonate and 100 ml of acetonitrile were added, and the mixture was refluxed for 24 h to obtain the catalyst precursor. After purifying the catalyst precursor by column chromatography, 0.1 mol of the catalyst precursor and 0.1 mol of the corresponding borane (cyclohexaborane, diethylborane, 3,5-dimethylcyclohexaborane) were taken in a glove box and dissolved in 30 ml of anhydrous tetrahydrofuran, and the mixture was refluxed for 24 h. After further removing the solvent by rotary evaporation, Cat.5a - Cat.8a were obtained.

[0113] Example 13: Preparation of Cat.13a

[0114] Similar to the preparation process of Cat.1, 0.1 mol of N,N-dimethylethylenediamine and 0.1 mol of phenyl isothiocyanate were stirred at room temperature for 24 h, then 0.1 mol of 7-bromo-1-heptene and 100 ml of acetonitrile were added, and after reflux reaction for 24 h, a catalyst precursor was obtained. After purifying the catalyst precursor by column chromatography, 0.1 mol of the catalyst precursor and 0.1 mol of the corresponding borane (9-borabicyclo[3.3.1]nonane, cycloheptaborane) were dissolved in 30 ml of anhydrous tetrahydrofuran and refluxed for 24 h in a glove box. After cooling to room temperature, 0.1 mol of silver tetrafluoroborate was added, and after stirring for 1 h, the solid was filtered off, and the solvent was removed by rotary evaporation to obtain catalyst Cat.13a.

[0115] Example 14: Preparation of Cat.14a

[0116] Similar to the preparation process of Cat.2, 0.1 mol of (3-aminopropyl)diphenylphosphine and 0.1 mol of allyl isocyanate were stirred at room temperature for 24 h, then 0.1 mol of bromobenzene, 0.1 mol of potassium carbonate and 100 ml of acetonitrile were added, and after reflux reaction for 24 h, a catalyst precursor was obtained. After purifying the catalyst precursor by column chromatography, 0.1 mol of the catalyst precursor and 0.1 mol of cyclohexylborane were dissolved in 30 ml of anhydrous tetrahydrofuran and refluxed for 24 h in a glove box. After further removing the solvent by rotary evaporation, Cat.14a was obtained.

[0117] Example 15 - 21: Preparation of Cat.15a - Cat.21a

[0118] Similar to the preparation process of Cat.1, 0.1 mol of dibutylaminoethylphosphine (N,N-dimethylethylenediamine, N,N-dimethylcyclohexanediamine, N-cyclohexylcyclohexanediamine, 3-aminopyridine) and 0.1 mol of naphthyl isothiocyanate (3,5-bis(trifluoromethyl)phenyl isothiocyanate) were stirred at room temperature for 24 h, then 0.1 mol of 6-bromo-1-hexene (8-bromo-1-octene, 9-bromo-1-nonene, 5-bromo-1-pentene) and 100 ml of acetonitrile were added, and after reflux reaction for 24 h, a catalyst precursor was obtained. After purifying the catalyst precursor by column chromatography, 0.1 mol of the catalyst precursor and 0.1 mol of the corresponding borane (9-borabicyclo[3.3.1]nonane, dimethylborane, diphenylborane, bis(pentafluorophenyl)borane) were dissolved in 30 ml of anhydrous tetrahydrofuran and refluxed for 24 h in a glove box. Particularly, for Cat.15a, after the reaction solution cooled to room temperature after 24 h, 1 mol of sodium bicarbonate still needed to be added and stirred for one hour. After further removing the solvent by rotary evaporation, Cat.15a - Cat.21a were obtained.

[0119] Example 22 - 24: Preparation of Cat.22a - Cat.24a

[0120] Similar to the preparation process of Cat.2, 0.1 mol of (5-aminopentyl)diphenylphosphine (N,N-diethylpropylamine, 3-aminopropyldibutylphosphine) and 0.1 mol of heptyl isothiocyanate (allyl isothiocyanate, pentyl isocyanate) were stirred at room temperature for 24 h, then 0.1 mol of iodobenzene (iodoethane, iodobutane), 0.1 mol of potassium carbonate and 100 ml of acetonitrile were added, and after reflux reaction for 24 h, the catalyst precursor was obtained. After purifying the catalyst precursor by column chromatography, 0.1 mol of the catalyst precursor and 0.1 mol of the corresponding borane (dibutylborane, pinacolborane, 9-borabicyclo[3.3.1]nonane) were taken in a glove box and dissolved in 30 ml of anhydrous tetrahydrofuran, and reflux reaction was carried out for 24 h. After further removing the solvent by rotary evaporation, Cat.22a - Cat.24a were obtained.

[0121] Application Examples 1 - 26: Using Catalysts 1 - 24 to Catalyze the Ring-Opening of Epoxyalkanes to Produce Polyethers Epoxides and Abbreviations Used in the Examples:

[0122]

[0123] In a glove box, according to the catalyst types and dosages in Table 1, an appropriate amount of the catalyst was taken and added to a serum bottle, and alkoxyalkane (0.1 mol) was added, and the reaction was carried out at 0 °C for 6 h. The reaction solution was taken to measure nuclear magnetic resonance to characterize the conversion rate of the monomer and the selectivity of the product. After drying, the target polyether could be obtained. The polymer was characterized by GPC. The polymerization results and characterizations are shown in Table 1.

[0124] Table 1 Test Results of the Catalytic Products in Application Examples 1 - 26 a

[0125]

[0126] a M n , number-average molecular weight, measured by gel permeation chromatography; PDI, molecular weight distribution, measured by gel permeation chromatography. b The PO raw material is a racemic monomer, and the resulting product is a chiral polymer with an ee value > 90%. Due to the preference for a specific chirality, the conversion rate is at most about 50%. c The polyether selectivity of the product is 100%.

[0127] Application Examples 27 - 50: Using Catalysts 1 - 24 to Catalyze the Ring-Opening Reaction of Epoxyalkanes and Carbon Dioxide

[0128] Epoxides and Abbreviations Used in the Examples

[0129]

[0130] The catalysts prepared from Catalyst Cat.1 - 24 were added into an autoclave according to Table 2, and 35 mmol of alkylene oxide was added. Then, 0.1 - 4 MPa of CO2 was filled, and the reaction was carried out for 8 h under the given temperature conditions. During the reaction, terminal alkylene oxides such as PO, etc., are prone to form polycarbonates at low temperatures, while at high temperatures such as 100 °C and above, they are prone to polymer chain back - biting or degradation, generating cyclic carbonates; internal alkylene oxides, such as CHO, etc., generate polycarbonates both at low and high temperatures. After releasing carbon dioxide, the reaction solution was taken to measure nuclear magnetic resonance to characterize the conversion rate of the monomer. The catalytic results and characterizations are shown in Table 2.

[0131] Table 2 Test Results of Catalytic Products of Application Examples 27 - 52

[0132]

[0133]

[0134] a M n , number - average molecular weight, measured by gel permeation chromatography; PDI, molecular weight distribution, measured by gel permeation chromatography. b The CHO raw material is a meso monomer, and the resulting product is a chiral polymer with an ee value > 90%. Due to the preference for a specific chirality, the conversion rate is at most about 50%. c The product selectivity is 100%.

[0135] Application Examples 53 - 64: Catalytic Homopolymerization of Cyclic Lactones with Catalyst Cat.1 - 12

[0136]

[0137] In a glove box, according to Table 3, Catalyst Cat.1 - 12 was taken and added into a serum bottle, and cyclic lactone (0.01 mol) was added. Ethylene glycol or a small amount of PO (any amount from 1 - 1000 times the amount of the catalyst can be used, and the amount used in this example is an equivalent amount of PO) was added to generate an alkoxy - initiated ion to ring - open the lactone, and the reaction was carried out for 6 h at the set temperature. The reaction solution was taken to measure nuclear magnetic resonance to characterize the conversion rate of the monomer and the selectivity of the product. After drying, the target polyester can be obtained. The polymer was characterized by GPC. The polymerization results and characterizations are shown in Table 3.

[0138] Table 3 Test Results of Polymerization Products of Application Examples 53 - 64

[0139]

[0140] a M n , number - average molecular weight, measured by gel permeation chromatography; PDI, molecular weight distribution, measured by gel permeation chromatography. bThe product selectivity is 100%.

[0141] Application Examples 65 - 76: Copolymerization of epoxides and cyclic anhydrides catalyzed by catalyst Cat.13 - 24

[0142] Epoxides used in the examples and their abbreviations

[0143]

[0144] Cyclic anhydrides used in the examples and their abbreviations

[0145]

[0146] In a glove box, the catalysts Cat.1 - 12 were taken according to Table 4 and added into a serum bottle, and cyclic lactone (0.01 mol) was added. Ethylene glycol or a small amount of PO (any amount from 1 to 1000 times the amount of the catalyst is acceptable, and the amount used in this example is an equivalent amount of PO) was added to generate an alkoxy - initiating ion to ring - open the lactone, and the reaction was carried out at a specific temperature for 6 h. The reaction solution was taken to measure NMR to characterize the monomer conversion and the product selectivity. After drying, the target polyester could be obtained. The polymer was characterized by GPC. The polymerization results and characterizations are shown in Table 4.

[0147] Table 4 Test results of the polymerization products of Application Examples 65 - 76

[0148]

[0149] a M n , number - average molecular weight, measured by gel permeation chromatography; PDI, molecular weight distribution, measured by gel permeation chromatography. b The CHO raw material is a meso monomer, and the resulting product is a chiral polymer with an ee value > 90%. Due to the preference for a specific chirality, the conversion rate is at most about 50%. c The product selectivity is 100%.

[0150] Application Examples 77 - 86: Ring - opening polymerization of cyclic thioethers to prepare polysulfides using catalysts Cat.1 - 10 Abbreviations of cyclic thioalkanes used in the examples

[0151]

[0152] In a glove box, an appropriate amount of trifunctional catalysts Cat.1 - 10 were taken according to Table 5 and added into a serum bottle, and cyclic thioalkane (0.1 mol) was added. The reaction was carried out at 0 °C for 6 h. The reaction solution was taken to measure NMR to characterize the monomer conversion and the product selectivity. After drying, the target polysulfide could be obtained. The polymer was characterized by GPC. The polymerization results and characterizations are shown in Table 5.

[0153] Table 5 Test results of the polymerization products of Application Examples 77 - 86a

[0154]

[0155] a M n , the number-average molecular weight, measured by gel permeation chromatography; PDI, molecular weight distribution, measured by gel permeation chromatography. b The product selectivity is 100%.

[0156] Application Examples 87 - 102: Using the trifunctional catalyst Cat.11 - 24 to catalyze the copolymerization of carbon dioxide and episulfide hydrocarbons to prepare polythiocarbonates; Cat.2 and Cat.4 prepare small molecule products;

[0157]

[0158] The episulfide hydrocarbons used in the examples are abbreviated as

[0159] Take the prepared catalyst according to Table 6 and add it to the autoclave, and add 35 mmol of episulfide hydrocarbon, charge 0.1 - 4 MPa CO2, and react for 8 h under the given temperature conditions. During the reaction, terminal episulfide hydrocarbons such as PS, etc., are prone to form polythiocarbonates at low temperatures, while at high temperatures such as 100 °C and above, they are prone to polymer chain backbiting or degradation, generating cyclic thiocarbonates; internal episulfide hydrocarbons, such as CHS, etc., generate polythiocarbonates at both low and high temperatures. After releasing carbon dioxide, take the reaction solution to measure NMR to characterize the monomer conversion rate. The catalytic results and characterizations are shown in Table 6.

[0160] Table 6 Test results of the catalytic products of Application Examples 87 - 102

[0161]

[0162]

[0163] a M n , the number-average molecular weight, measured by gel permeation chromatography; PDI, molecular weight distribution, measured by gel permeation chromatography. b The CHO raw material is a meso monomer, and the resulting product is a chiral polymer, with an ee value > 90%. Due to the preference for a specific chirality, the conversion rate is at most about 50%. c The product selectivity is 100%. Application Examples 103 - 107: Using the trifunctional catalyst Cat.1 - 5 to catalyze the ring-opening of O-carboxyanhydride to prepare polyesters. The O-carboxyanhydrides and their numbers used in the examples

[0164]

[0165] In the glove box, take the trifunctional catalysts Cat.1 - 5 according to Table 7 and add them into a serum bottle. Then add O - carboxylic anhydride (OCA) (0.01 mol), and add ethylene glycol or a small amount of PO (any amount from 1 to 1000 times the amount of the catalyst can be used, and the amount used in this example is an equivalent amount of PO) to generate alkoxy - initiating ions to ring - open the monomer. React at a specific temperature for 6 h. Take the reaction solution to measure NMR to characterize the conversion rate of the monomer and the selectivity of the product. After drying, the target polyester can be obtained. Characterize the polymer by GPC. The polymerization results and characterizations are shown in Table 7.

[0166] Table 7 Test results of the polymerization products of Application Examples 103 - 107 a

[0167]

[0168]

[0169] a M n , number - average molecular weight, measured by gel permeation chromatography; PDI, molecular weight distribution, measured by gel permeation chromatography. b The product selectivity is 100%.

[0170] Application Examples 108 - 112: Using trifunctional catalysts Cat.6 - 10 to catalyze N - carboxylic anhydride to prepare polypeptides The N - carboxylic anhydrides and their numbers used in the examples

[0171]

[0172] In the glove box, take the trifunctional catalysts Cat.6 - 10 according to Table 8 and add them into a serum bottle. Then add N - carboxylic anhydride (NCA) (0.01 mol), and add ethylene glycol or a small amount of PO (any amount from 1 to 1000 times the amount of the catalyst can be used, and the amount used in this example is an equivalent amount of PO) to generate alkoxy - initiating ions to ring - open the monomer. React at a specific temperature for 6 h. Take the reaction solution to measure NMR to characterize the conversion rate of the monomer and the selectivity of the product. After drying, the target polypeptide can be obtained. Characterize the polymer by GPC. The polymerization results and characterizations are shown in Table 10.

[0173] Table 8 Test results a of the polymerization products of Application Examples 108 - 112

[0174]

[0175] a M n , number - average molecular weight, measured by gel permeation chromatography; PDI, molecular weight distribution, measured by gel permeation chromatography. c The selectivity of the product is 100%.

[0176] The specific embodiments described above have elaborated in detail on the technical solution and beneficial effects of the present invention. It should be understood that the above is only the most preferred embodiment of the present invention and is not used to limit the present invention. Any modifications, supplements, equivalent replacements, etc. made within the principle scope of the present invention shall be included within the protection scope of the present invention.

Claims

1. A trifunctional organic catalyst, characterized in that The structural formulas of the trifunctional organic catalysts are shown in Formula (I) or (II) respectively. Formula (I) is thiourea or urea-onium salt-organic boron, and Formula (II) is onium salt-thiourea or urea-organic boron: Wherein, B is a boron atom, X is an O or S atom, and A is an N or P atom; m is 1 or 2, and n is 1 or 2; L1, L2, L3, and L4 are linking groups, and L1 is a C1-C 12 alkylene group or a cyclohexylene group, and the cyclohexylene group has a chiral structure; L2, L3, L4 are each independently a C1-C 12 alkylene group; In formula (I), the onium salt is selected from one of the following structures, or R2 is of formula C, and R3 is of formula D or C1-C 10 alkyl; Represents a connection key; When the onium salt is pyridine, L1 is 0 or C1-C 12 alkylene; Among them, R c is a substituent on the pyridine ring, and R c is one or more of H or a halogen atom, C1-C 10 alkyl; Formula C is a thiourea or urea structure, and Formula D is an organic boron structure; Represents a connection key; In Formula C and Formula D, the definition of L1’ is the same as L1, and the definition of L2’ is the same as L2; m’ and n’ are each independently 1 or 2; The definition of R1’ is the same as R1; The definition of R4’ is the same as R4; The definition of R5’ is the same as R5; In Formula (II), the onium salt is one of the following structures: In Formula (I) or (II), the organic boron R4R5B- is selected from one of the following structures: R1 is an unsubstituted or C6-C aromatic group having substituent B, 10 wherein the C6-C 10 aromatic group is phenyl or naphthyl, and the substituent B on the C6-C 10 aromatic group is a halogen atom, C1-C 10 alkyl, C1-C 10 alkoxy or trifluoromethyl; is an anion selected from F – , Cl – , Br – , I – , NO3 – , CH3COO – , CCl3COO – , CF3COO – , ClO4 – , BF4 – , BPh4 – , N3 – , OH – , p-toluate, p-toluenesulfonate, o-nitrophenolate, p-nitrophenolate, m-nitrophenolate, 2,4-dinitrophenolate, 3,5-dinitrophenolate, 2,4,6-trinitrophenolate, 3,5-dichlorophenolate, carbonate, hydrogencarbonate, 3,5-difluorophenolate, 3,5-bis(trifluoromethyl)phenolate or pentafluorophenolate anion.

2. The trifunctional organic catalyst according to claim 1, wherein The trifunctional organic catalyst has one of the following structures:

3. A method for preparing the trifunctional organic catalyst according to claim 1 or 2, characterized in that, The method is as follows: React the thiourea or urea-onium salt shown in Formula E, or the onium salt-thiourea or urea shown in Formula F, with the R4R5B-H raw material by hydroboration reaction. After stirring at room temperature for 1 to 500 hours, remove impurities and organic solvents to obtain the thiourea or urea-onium salt-organic boron shown in Formula (I), or the onium salt-thiourea or urea-organic boron shown in Formula (II) respectively; In Formula E or F, represents a double bond or a triple bond; In formula E, —L2— is obtained through a hydroboration reaction, In formula F, obtained through hydroboration reaction is —L4—; R1 to R6, L1 to 46, n, are defined as described in claim 1.

4. Use of the trifunctional organic catalyst according to claim 1 or 2 in the preparation of organic small molecule compounds and macromolecular polymers, characterized in that The method of the application is that in the presence of a trifunctional organic catalyst, one or more cyclic monomers are bulk polymerized to obtain a macromolecular polymer with or without a macromolecular chain transfer agent; or one or more cyclic monomers react with one or more of carbon dioxide, carbon disulfide, carbonyl sulfide or carbon monoxide to obtain an organic small molecule compound or a macromolecular polymer; the cyclic monomers include alkylene oxides, thioalkylene oxides, cyclic acid anhydrides or lactones; the macromolecular polymer is an aliphatic polycarbonate obtained by copolymerizing carbon dioxide and alkylene oxides, a polyether obtained by ring-opening polymerization of alkylene oxides, a polythiocarbonate obtained by ring-opening copolymerization of carbon dioxide and thioalkylene oxides, a polysulfide obtained by ring-opening of cyclic thioethers, a polyester obtained by copolymerizing alkylene oxides and cyclic acid anhydrides, a polythiocarbonate obtained by copolymerizing carbonyl sulfide and alkylene oxides or a polyester obtained by ring-opening polymerization of lactones, a polyester obtained by ring-opening of O-carboxyanhydrides, or a polypeptid obtained by polymerization of N-carboxyanhydrides; The organic small molecule compound is a cyclic carbonate obtained by catalyzing the reaction of carbon dioxide or carbon disulfide with alkylene oxides or thioalkylene oxides, a cyclic lactone obtained by catalyzing the reaction of carbon monoxide with alkylene oxides, or a cyclic thiocarbonate obtained by copolymerizing carbonyl sulfide with alkylene oxides or thioalkylene oxides.

5. The application according to claim 4, characterized in that, The cyclic monomers include alkylene oxides, thioalkylene oxides, cyclic acid anhydrides or lactones, and are selected from one of the following structures: Among them, R6 to R 21 are each independently selected from one or more of H, halogen, C1-C 30 alkyl with or without substituents and containing or not containing O, S, N, Si, P atoms, C3-C 30 cycloalkyl, C2-C 30 alkenyl, C2-C 30 alkynyl, C6-C 30 aryl, C3-C 30 heterocyclic group or C5-C 30 heteroaryl; the substituents are selected from one or more of halogen atoms, branched or straight-chain hydrocarbon groups having 1 to 20 carbon atoms, branched or straight-chain alkoxy groups having 1 to 20 carbon atoms, branched or straight-chain cycloalkyl groups having 3 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and heteroaryl groups having 5 to 20 carbon atoms; among them, each of R6 and R7, R8 and R9, R 10 and R 11 , R 12 and R 13 , R 14 and R 15 , R 16 and R 17 , R 19 and R 20 , R 21 and R 22 can form a bond or a ring.

6. The application according to claim 4, wherein In the trifunctional organic catalyst, at least one of the linking groups L1, L2, L3, and L4 has chirality, and the trifunctional organic catalyst with chirality is used for chiral catalysis.

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