Organic boron-metal crown ether heteronuclear catalyst and preparation method and application thereof

Abstract

The invention discloses an organic boron-metal crown ether heteronuclear catalyst, the catalyst having a boron-containing Lewis acid center and a metal Lewis acid center, and having a compound structure shown in Formula I: each X represents each Y represents the invention also discloses a preparation method of the above-mentioned organic boron-metal crown ether heteronuclear catalyst and its application in the preparation of polymer materials and small molecules. The catalyst has the advantages of simple preparation, high yield, small dosage, low cost, etc.; when used, it has the advantages of easy weighing, high catalytic activity, controllable reaction, etc.

Description

Technical Field

[0001] The invention relates to the field of catalyst synthesis, and in particular to the development and application of an organic boron-metal crown ether heteronuclear catalyst which can be used for preparing high molecular weight and organic small molecule fine chemicals. Background Art

[0002] Multi-metal synergistic catalysis is widely present in biological enzyme catalytic reactions, such as tyrosinase, superoxide dismutase, urease, phosphohydrolase, etc. Inspired by enzyme catalysis, chemists have synthesized a large number of multi-metal center catalysts and successfully applied them to chemical reactions such as aldol condensation [J.Am.Chem.Soc.2000,122, 12003–12004], olefin polymerization [J.Am.Chem.Soc.2014,136,10460–10469], hydrolysis kinetic resolution of alkylene oxides [J.Am.Chem.Soc.2007,129,1105–1112], copolymerization of alkylene oxides and carbon dioxide [J.Am.Chem.Soc.2010,132,14367–14369], and cycloaddition of alkylene oxides and carbon dioxide [Angew.Chem.Int.Ed.2015,54,134–138]. Thanks to the synergistic effect of multiple catalytic centers within the molecule, multi-nuclear metal catalysts often exhibit performance superior to that of corresponding mono-nuclear metal catalysts. Among them, heteronuclear metal catalysts have aroused widespread research interest among chemists due to the special synergistic effects exhibited by different metal centers [Angew.Chem.Int.Ed.2018,57,2492–2496; Nat. Chem.2020,12,372-380].

[0003] Since organoboranes have empty p orbitals, they exhibit Lewis acidity in catalytic reactions. Organoboranes, especially trialkylboranes and triarylboranes, are widely used in the synthesis of polymer materials. Typical representatives include polypolar monomers [Angew.Chem.Int.Ed.2018,57, 9430–9433], polycarbonates [J.Am.Chem.Soc.2016,138,11117–11120; CN 107849233 A; US 2018 / 0118884 A1], polyethers [Macromolecules 2018,51,8286–8297] and sulfur-containing polymers [CN 106866952 A; Macromolecules 2018,51,3126–3134]. In order to further improve the catalytic activity of alkyl boron, we designed a bifunctional catalytic system that integrates the activation center (alkyl boron) and the initiation center (quaternary ammonium salt) in the same molecule [PCT / CN2019 / 103919]. This catalytic system has shown superior catalytic performance to the two-component system in the preparation of polycarbonates [J.Am.Chem.Soc.2020,142,12245-12255], polyethers [Angew. Chem.,Int.Ed.2020,59,16910–16917], cyclic carbonates [DOI:10.1002 / anie.202010651], etc. Summary of the invention

[0004] The purpose of the present invention is to provide an organic boron-metal crown ether heteronuclear catalyst in view of the deficiencies in the prior art, which has the advantages of simple preparation, high yield, small dosage, low cost and the like; when used as a catalyst, it has the advantages of easy weighing, high catalytic activity, controllable reaction and the like.

[0005] An organic boron-metal crown ether heteronuclear catalyst, the catalyst having a boron-containing Lewis acid center and a metal Lewis acid center, and having a compound structure shown in Formula I:

[0006]

[0007] Wherein, when h=1, m and n are independently selected from integers of 1-50; when h≥2, each m and n are independently selected from integers of 0-50, each n and m are independent, each m may be the same or different, each n may be the same or different, each n cannot be 0 at the same time, and each m cannot be 0 at the same time;

[0008] R' and R" are independently selected from hydrogen, halogen and the following groups which are unsubstituted or substituted: C1-C 30 Aliphatic carbon chain, C6-C 30 Aromatic groups, C3-C 30Heterocyclic groups, C5-C 30 A heteroaromatic group, or a group containing one or more of O, S, N, Si, P, and Se atoms; wherein the substituent is selected from one or more of a halogen atom, a branched or straight-chain aliphatic group having 1 to 20 carbon atoms, an aromatic group having 6 to 30 carbon atoms, and a heteroaromatic group having 5 to 30 carbon atoms;

[0009] Each X represents B is a boron atom; each R1, R2, R3 may be the same or different, and is independently selected from H, or the following groups which are unsubstituted or substituted: C1-C 30 Aliphatic groups, C6-C 30 Aromatic, C3-C 30 Heterocyclic group, C5-C 30 wherein the substituent is selected from one or more of halogen atoms, branched or linear aliphatic groups having 1 to 20 carbon atoms, aromatic groups having 6 to 30 carbon atoms, and heteroaromatic groups having 5 to 30 carbon atoms; and R1, R2 or R3 in X may bond to each other to form a ring.

[0010] Each Y represents

[0011]

[0012] Wherein, each Z is independently selected from O, S, Se elements or NR groups, N is nitrogen element, R is H, or the following groups which are unsubstituted or have a substituent: C1-C 30 Aliphatic groups, C6-C 30 Aromatic, C3-C 30 Heterocyclic group, C5-C 30 One or more of heteroaromatic groups, or the group containing one or more of O, S, N, Si, P atoms; wherein the substituent is selected from one or more of halogen atoms, branched or straight-chain aliphatic groups having 1 to 20 carbon atoms, aromatic groups having 6 to 30 carbon atoms, and heteroaromatic groups having 5 to 30 carbon atoms;

[0013] 20 ≥ j ≥ 0;

[0014] Each M i+ It represents a metal cation with a charge of i, which is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Ag, Cu, Ni, Hg, Pd, Y, Zr, and La metal cations.

[0015] Each A (i / g)- Indicates metal M i+ Balanced negative ions; each A(i / g)- Independently selected from One or more of sulfonate, perchlorate, chlorate, phosphate, carboxylate, carbonate, alkoxide, phenoloxide, sulfate, and nitrate. g represents the counter ion A (i / g)- to maintain charge balance.

[0016] Each R4-R7 may be the same or different and is independently selected from the following groups which are unsubstituted or substituted: independently selected from H, or the following groups which are unsubstituted or substituted: C1-C 30 Aliphatic groups, C6-C 30 Aromatic, C3-C 30 Heterocyclic group, C5-C 30 One or more of heteroaromatic groups, or the group containing one or more of O, S, N, Si, and P atoms; wherein the substituent is selected from one or more of halogen atoms, branched or straight-chain aliphatic groups having 1 to 20 carbon atoms, aromatic groups having 6 to 30 carbon atoms, and heteroaromatic groups having 5 to 30 carbon atoms; R4 and R5 cannot be C0 alkyl groups at the same time; any two or more groups among R4-R7 can be connected by covalent bonds to form a ring.

[0017] Each X can be directly connected to one or more groups of R4 to R9 of a certain Y, or to one or more groups of R1 to R3 of another X, through any one or more groups of R1 to R3 of X, to form a star structure or a branch structure, and then connected to Y; multiple Xs can be connected in this way to form a linear or ring structure, and then connected to Y; or a mixed structure of the above two can be used.

[0018] Each Y can be directly connected to one or more groups of R1, R2, or R3 of a certain X, or to one or more groups of R4 to R7 of another Y, through any one or more groups of R4 to R7 of Y, to form a star or branch structure and then connected to X; multiple Ys can be connected in this way to form a linear or ring structure and then connected to X; or a mixed structure of the above two can be used.

[0019] Preferably, the organoboron-metal crown ether heteronuclear catalyst is selected from the following structures:

[0020]

[0021] Among them, multiple Y can be connected to X through the same R1, R2 or R3, or through different R1, R2, R3. For example, YXY has the following two connection modes:

[0022]

[0023] Similarly, multiple Xs can be connected to Y through the same group among R4 to R9, or several different groups among R4 to R9; multiple Ys can be connected to Y through the same group among R4 to R9, or several different groups among R4 to R9; multiple Xs can be connected to X through the same R1, R2 or R3, or through different R1, R2, R3.

[0024] k is any integer from 1 to 500;

[0025] Preferably, R1, R2 or R3 of X in the organoboron-metal crown ether heteronuclear catalyst do not form a bond with each other to form a ring, and R1, R2 or R3 are each independently represented by any one or more of the following:

[0026]

[0027] And the R1 or R2 or R3 can bond with each other to form a ring, and R1+R2 can also represent the following structure:

[0028]

[0029] R1+R2+R3 can represent the following structure:

[0030] denoted as the attachment site;

[0031] Preferably, the structural unit in Y of the organoboron-metal crown ether heteronuclear catalyst is Can be independently selected from one or more combinations of the following structures:

[0032]

[0033]

[0034] Indicated as a linking site.

[0035] The organoboron-metal crown ether heteronuclear catalyst preferably has the structure shown below:

[0036]

[0037] The above-mentioned organic metal-free catalyst can be prepared by the following method: a metal crown ether complex (W1) containing at least one unsaturated bond (carbon-carbon double bond or carbon-carbon triple bond) and a reaction raw material (W2) containing at least one boron-hydrogen bond are subjected to a boronization reaction of the carbon-carbon double bond (or triple bond) to obtain an organic boron-metal crown ether heteronuclear catalyst; it should be noted that this catalyst method includes but is not limited to this method;

[0038]

[0039] The specific process of this reaction is as follows: any reaction raw material W1 and any reaction raw material W2 are mixed under the protection of nitrogen or other inert gas, an organic solvent is added, and the reaction is carried out at -20 to 150°C with stirring for 1 to 500 hours for hydroboration reaction. After the reaction is completed, impurities and organic solvent are removed to obtain an organic metal-free catalyst. The organic solvent is selected from one or more of tetrahydrofuran, benzene, toluene, chloroform, hexane, ether, dichloromethane, ethyl acetate, dimethyl sulfoxide, carbon tetrachloride, 1,4-dioxane, and pyridine.

[0040] The anion of the organoboron-metal crown ether heteronuclear catalyst can be changed by anion replacement before or after the hydroboration reaction.

[0041] The present invention also provides the application of the organic boron-metal crown ether heteronuclear catalyst in preparing polymer materials and small molecules.

[0042] The application of the organic metal-free catalyst can be used for homopolymerization or copolymerization of one or more cyclic monomers (and specific gases) under contact with the organic metal-free catalyst to obtain polymer materials. The application of the organic metal-free catalyst in the preparation of polymer materials is that one or more cyclic monomers react with any one or more of carbon dioxide, carbon disulfide, carbon oxysulfide, carbon monoxide, isocyanate, isothiocyanate, and sulfur dioxide under contact with an organic boron-metal crown ether heteronuclear catalyst to obtain a catalytic product. For example: catalyzing the reaction of carbon disulfide (sulfide) with epoxy (sulfur) alkane to prepare cyclic carbonate, catalyzing the reaction of carbon monoxide with epoxy alkane to prepare cyclic lactone, catalyzing the copolymerization of carbon oxysulfide and epoxy (sulfur) alkane to prepare cyclic thiocarbonate, catalyzing the reaction of isocyanate with epoxy alkane to prepare polyurethane, catalyzing the reaction of isocyanate with epoxy alkane to prepare thiopolyurethane, catalyzing the reaction of isothiocyanate with epoxy (sulfur) alkane to prepare polydisulfide imine.

[0043] The cyclic monomer is selected from alkylene oxide or cyclosulfide, alkylene oxide, cyclosulfide, cyclic anhydride, cyclic lactone:

[0044]

[0045] The isocyanate and isothiocyanate are selected from the following structures:

[0046]

[0047] Wherein, R8 and R9 are selected from H, halogen, substituted, unsubstituted, C1-C2 with or without O, S, N, Si, P atoms. 30 Alkyl, C3-C 30 Cycloalkyl, C2-C 30 Alkenyl, C2-C 30 Alkynyl, C6-C30 Aromatic, C3-C 30 Heterocyclic or C5-C 30 One or more of heteroaromatic groups; the substituent is selected from halogen atoms, branched or straight-chain hydrocarbon groups with 1 to 20 carbon atoms, branched or straight-chain alkoxy groups with 1 to 20 carbon atoms, branched or straight-chain cycloalkyl groups with 3 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms, and heteroaromatic groups with 5 to 20 carbon atoms; wherein each R8 and R9 can form a bond or a ring.

[0048] Preferably, the cyclic small molecule can be selected from one or more of the following structures:

[0049]

[0050]

[0051]

[0052] One or more alcohol compounds, acid compounds, amine compounds, polyols, polycarboxylic acids, polyol acids, and water can be added to the polymerization reaction system as chain transfer agents to prepare corresponding polymer polyols, or one or more polymers with alcohol hydroxyl groups, phenolic hydroxyl groups, amino groups, and carboxyl groups can be added to the polymerization reaction system as macromolecular chain transfer agents to prepare corresponding block copolymers or graft copolymers.

[0053] Preferably, the chain transfer agent includes but is not limited to small molecule chain transfer agents (1-45) and macromolecular chain transfer agents (46-48):

[0054]

[0055]

[0056] in, It represents the main chain of the macromolecular chain transfer agent. The alcoholic hydroxyl group, phenolic hydroxyl group, amino group, carboxyl group, etc. shown in the formula do not represent the actual number of functional groups and can be any value between 1 and 50,000 in theory.

[0057] The application of the above-mentioned organoboron-metal crown ether heteronuclear catalyst in the preparation of polymer materials and fine chemicals includes loading it on an inorganic carrier or an organic carrier, even if the organic or inorganic carrier has two effective functional groups X and Y.

[0058] The organic boron-metal crown ether heteronuclear catalyst provided by the present invention can not only be used for the preparation of the above-mentioned polyethers, polyesters, polycarbonates, polythiocarbonates, polythioethers and other polymer materials, but can also effectively synthesize fine chemicals with high added value such as cyclic (thio) carbonates, lactones, polyurethanes, thiopolyurethanes, and polydisulfimines. It should be pointed out that when the catalyst is used in polymerization, the addition of other Lewis bases, Lewis acids or other cocatalysts also falls within the protection scope of this patent.

[0059] In view of the unique catalytic performance of heteronuclear metal catalysts, the present invention aims to design a type of boron-metal heteronuclear catalyst, which introduces the boron center and the metal center into the same molecule through supramolecular action. Because the acidity of alkyl boron can be conveniently regulated by changing the substituents on the boron atom, and different metal centers can be selectively introduced by adjusting the crown ether ring, the compatibility of the boron center and the metal center can be conveniently regulated, so as to show excellent metal-free dual center synergy. BRIEF DESCRIPTION OF THE DRAWINGS

[0060] Figure 1 The catalyst cat.1 prepared in Example 1 1 H NMR spectrum;

[0061] Figure 2 The alkylene oxide / carbon dioxide copolymer prepared in Application Example 2 1 H NMR spectrum;

[0062] Figure 3 This is the GPC chart of the alkylene oxide / carbon dioxide copolymer prepared in Application Example 2;

[0063] Figure 4 The cyclosulfide / isocyanate copolymer prepared in Example 68 1 H NMR spectrum;

[0064] Figure 5 This is the GPC chart of the cyclosulfide / isocyanate copolymer prepared in Application Example 68. DETAILED DESCRIPTION

[0065] The present invention is described below by means of specific embodiments:

[0066] Example 1: Synthesis of catalyst cat.1

[0067]

[0068] In a glove box, 0.1 mol of each raw material r1-1 (12.20 g) and r1-2 (34.25 g) were added to 100 ml of tetrahydrofuran, and reacted at 60°C with stirring for 24 h. The solvent was drained and washed with hexane to obtain the target product cat.1 with a yield of 95%. Cat.1 was further characterized by NMR. 1 H NMR spectrum is shown in Figure 1 .

[0069] Example 2: Synthesis of catalyst cat.2

[0070]

[0071] In a glove box, 0.1 mol of each raw material r2-1 (6.99 g) and r2-2 (62.06 g) were added to 100 ml of ether, stirred at room temperature for 6 h, the solvent was drained, and washed with hexane to obtain the target product cat.2 with a yield of 91%. Cat.2 was further characterized by NMR.

[0072] Example 3: Synthesis of catalyst cat.3

[0073]

[0074] In a glove box, 0.2 mol of raw material r3-1 (13.99 g) and 0.1 mol of raw material r3-2 (46.74 g) were added to 100 ml of tetrahydrofuran, stirred at room temperature for 6 h, the solvent was drained, and washed with hexane to obtain the target product cat.3 with a yield of 90%. Cat.3 was further characterized by NMR.

[0075] Example 4: Synthesis of catalyst cat.4

[0076]

[0077] In a glove box, 0.1 mol of each raw material r4-1 (4.19 g) and r4-2 (48.58 g) were added to 100 ml of chloroform, reacted at 55°C for 24 h, the solvent was drained, and washed with hexane to obtain the target product cat.4 with a yield of 93%. Cat.4 was further characterized by NMR.

[0078] Example 5: Synthesis of catalyst cat.5

[0079]

[0080] In a glove box, 0.2 mol of raw material r5-1 (13.99 g) and 0.1 mol of raw material r5-2 (65.21 g) were added to 100 ml of dichloromethane, stirred at 30°C for 12 h, the solvent was drained, and washed with hexane to obtain the target product cat.5 with a yield of 85%. Cat.5 was further characterized by NMR.

[0081] Example 6: Synthesis of catalyst cat.6

[0082]

[0083] In a glove box, 0.1 mol of each raw material r6-1 (6.99 g) and r6-2 (64.32 g) were added to 100 ml of dichloromethane, stirred at room temperature for 48 h, the solvent was drained, and washed with hexane to obtain the target product cat.6 with a yield of 86%. Cat.6 was further characterized by NMR.

[0084] Example 7: Synthesis of catalyst cat.7

[0085]

[0086] In a glove box, 0.1 mol of raw material r7-1 (34.59 g) and 0.1 mol of r7-2 (38.48 g) were added to 100 ml of toluene and stirred at 60 °C for 24 h. The solvent was drained and washed with hexane to obtain the target product cat.7 with a yield of 91%. Cat.7 was further characterized by NMR.

[0087] Example 8: Synthesis of catalyst cat.8

[0088]

[0089] In a glove box, 0.01 mol of cat.7 (7.21 g) and 0.02 mol of raw material r8-1 (1.64 g) were added to 100 ml of dichloromethane and reacted at room temperature for 8 h. The precipitate was removed by filtration, the solvent was drained, and the mixture was washed with hexane to obtain the target product cat.8 with a yield of 95%. Cat.8 was further characterized by NMR.

[0090] Example 9: Synthesis of catalyst cat.9

[0091]

[0092] (1) In a glove box, 0.1 mol of raw material R9-1 (12.20 g) and 0.1 mol of R9-2 (57.84 g) were added to 100 ml of toluene, and the mixture was reacted at 60 °C for 36 h. The solvent was drained and washed with hexane to obtain the target product Cat.9 with a yield of 88%. Cat.9 was further characterized by NMR.

[0093] Example 10: Synthesis of catalyst cat.10

[0094]

[0095] (1) In a glove box, add 0.1 mol of raw material r10-1 (17.81 g) and 0.1 mol of r10-2 (52.30 g) to 100 ml of tetrahydrofuran and react at 55°C for 24 h to obtain the intermediate product r10-3;

[0096] (2) 0.1 mol of raw material r10-4 (6.99 g) was added to the above reaction solution, and the mixture was reacted at 55° C. for 12 h. The solvent was drained and washed with hexane to obtain the target product cat.10 with a yield of 78%. Cat.10 was further characterized by NMR.

[0097] Example 11: Synthesis of catalyst cat.11

[0098]

[0099] (1) In a glove box, 0.1 mol of raw material r11-1 (6.99 g) and 0.1 mol of raw material r11-2 (94.89 g) were added to 100 ml of toluene and reacted at 80°C for 8 h. The solvent was drained and washed with hexane to obtain the target product cat.11 with a yield of 89%. Cat.11 was further characterized by NMR.

[0100] Example 12: Synthesis of catalyst cat.12

[0101]

[0102] (1) In a glove box, 0.1 mol of raw material r12-1 (12.20 g) and 0.1 mol of raw material r12-2 (51.35 g) were added to 500 ml of tetrahydrofuran, reacted at 60° C. for 8 h, the solvent was drained, and washed with hexane to obtain the target product cat.8 with a yield of 95%. Cat.12 was further characterized by NMR.

[0103] The following alkylene oxides and their abbreviations are

[0104]

[0105] The following cyclosulfides and their abbreviations are

[0106]

[0107] The cyclic anhydrides and their abbreviations used below are

[0108]

[0109] The cyclic lactones and their abbreviations used below are

[0110]

[0111] Application Example 1-17: Copolymerization of alkylene oxide and carbon dioxide using catalysts Cat.1 to Cat.11

[0112]

[0113] In a glove box, the catalyst prepared in the example (0.01 mmol) was added to an autoclave, and 0.01 mol of alkylene oxide was added, 1.5 MPa of CO2 was introduced, and the reaction was carried out at a given temperature for 6 h. The carbon dioxide was then released, and the reaction liquid was measured by nuclear magnetic resonance to characterize the conversion rate of the monomer and the selectivity of the product (the proportion of polycarbonate, polyether, and cyclic carbonate). 1 H NMR spectrum is shown in Figure 2 , the GPC diagram of Application Example 2 is shown in Figure 3 .

[0114] Table 1 shows the test results of the polymer products of Application Examples 1 to 17.

[0115]

[0116]

[0117] a M n : Number average molecular weight, measured by gel permeation chromatography; b PDI: molecular weight distribution, measured by gel permeation chromatography; c The obtained product is a small molecule compound - cyclic carbonate.

[0118] Application Example 18-27: Copolymerization of alkylene oxide and cyclic anhydride using catalysts Cat.6 to Cat.8

[0119]

[0120] In a glove box, the catalyst prepared in the example (0.01 mmol) was added to a Schulink bottle, and alkylene oxide (0.05 mol) and cyclic anhydride (0.01 mol) were added, and the reaction was carried out at 80°C for 6 h. The reaction solution was taken for NMR measurement to characterize the conversion rate of the monomer and the selectivity of the product. The NMR spectrum is shown in Figure 2 The polymer was precipitated from ethanol, dried, and then characterized by GPC. The characterization results of NMR and GPC are shown in Table 2.

[0121] Table 2 shows the test results of the polymer products of Application Examples 18 to 27.

[0122]

[0123]

[0124] a M n : Number average molecular weight, measured by gel permeation chromatography; b PDI: Molecular weight distribution, measured by gel permeation chromatography.

[0125] Application Example 28-34: Homopolymerization of alkylene oxide using catalysts cat.3 and cat.10

[0126]

[0127] In a glove box, the catalyst prepared in Example 3 or 10 (0.01 mmol) was added to a serum bottle, and alkylene oxide (0.1 mol) was added, and the reaction was carried out at room temperature for 2 hours. The reaction solution was taken for NMR to characterize the conversion rate of the monomer and the selectivity of the product. After drying, the target polyether was obtained. The polymer was characterized by GPC. The polymerization results and characterization are shown in Table 3.

[0128] Table 3 shows the test results of the polymer products of Application Examples 28 to 34.

[0129]

[0130] a M n : Number average molecular weight, measured by gel permeation chromatography; b PDI: Molecular weight distribution, measured by gel permeation chromatography.

[0131] Application Examples 35-41: Homopolymerization of Cyclic Lactones Using Catalysts Cat.7 and Cat.8

[0132]

[0133] In a glove box, take the catalyst prepared in Examples 7 to 8 (0.01 mmol, CH3COO- ) was added to a serum bottle, and cyclic lactone (0.01 mol) and 1 ml toluene were added, and the reaction was carried out at 80°C for 6 hours. The reaction solution was taken for NMR to characterize the conversion rate of the monomer and the selectivity of the product. The product was precipitated with petroleum ether and dried to obtain the target polyester. The polymer was characterized by GPC. The polymerization results and characterization are shown in Table 4.

[0134] Table 4 shows the test results of the polymer products of Application Examples 35 to 41.

[0135]

[0136] a M n : Number average molecular weight, measured by gel permeation chromatography; b PDI: Molecular weight distribution, measured by gel permeation chromatography.

[0137] Application Examples 42-46: Using Catalysts Cat.1 to Cat.3 and Cat.8 to Catalyze Cyclosulfane / Carbon Dioxide Copolymerization

[0138]

[0139] In a glove box, the catalyst prepared in the example (0.01 mmol) was added to an autoclave, and 0.01 mol of the corresponding cyclosulfide was added, 1.5 MPa of CO2 was introduced, and the reaction was carried out at 80°C for 2 h. Carbon dioxide was then released, and the reaction liquid was measured by nuclear magnetic resonance to characterize the conversion rate of the monomer and the selectivity of the product (the proportion of polythiocarbonate, polythioether, and cyclic thiocarbonate). The polymerization results and characterization are shown in Table 5.

[0140] Table 5 shows the test results of the polymer products of Application Examples 42 to 46.

[0141]

[0142] a M n : Number average molecular weight, measured by gel permeation chromatography; b PDI: molecular weight distribution, measured by gel permeation chromatography; c The obtained product is a small molecule compound - cyclic thiocarbonate.

[0143] Application Examples 47-50: Using Catalysts Cat.1 to Cat.3 and Cat.8 to Catalyze the Copolymerization of Alkylene Oxide / Carbon Oxysulfide

[0144]

[0145] In a glove box, the catalyst prepared in the example (0.01 mmol) was added to an autoclave, and 0.01 mol of the corresponding alkylene oxide was added, 1.5 MPa of CO2 was introduced, and the reaction was carried out at 80°C for 2 h. Carbon oxysulfide was then released, and the reaction liquid was measured by nuclear magnetic resonance to characterize the conversion rate of the monomer and the selectivity of the product (the proportion of polythiocarbonate, polyether, and cyclic thiocarbonate). The polymerization results and characterization are shown in Table 6.

[0146] Table 6 shows the test results of the polymer products of Application Examples 47 to 50.

[0147]

[0148] a M n : Number average molecular weight, measured by gel permeation chromatography; b PDI: molecular weight distribution, measured by gel permeation chromatography; c The obtained product is a small molecule compound - cyclic thiocarbonate.

[0149] Application Examples 51-54: Using catalysts cat.1 to cat.3 and cat.8 to catalyze the copolymerization of cyclosulfide / carbon disulfide

[0150]

[0151] In a glove box, the catalyst prepared in the example (0.01 mmol) was added to an autoclave, and 0.01 mol of the corresponding cyclosulfide was added, and 0.01 mol of CS2 was added, and the reaction was carried out at 80°C for 2 h. The reaction solution was taken for NMR to characterize the conversion rate of the monomer and the selectivity of the product (the proportion of polythiocarbonate, polythioether, and cyclic thiocarbonate). The polymerization results and characterization are shown in Table 7.

[0152] Table 7 shows the test results of the polymer products of Application Examples 51 to 54.

[0153]

[0154] a M n : Number average molecular weight, measured by gel permeation chromatography; b PDI: molecular weight distribution, measured by gel permeation chromatography; c The obtained product is a small molecule compound - cyclic thiocarbonate.

[0155] Application Examples 55-58: Catalytic copolymerization of alkylene oxide / carbon disulfide using catalysts cat.1 to cat.3 and cat.8

[0156]

[0157] In a glove box, the catalyst prepared in the example (0.01 mmol) was added to an autoclave, and 0.01 mol of the corresponding cyclosulfide was added, and 0.01 mol of CS2 was added, and the reaction was carried out at 80°C for 2 h. The reaction solution was taken for NMR to characterize the conversion rate of the monomer and the selectivity of the product (the proportion of polythiocarbonate, polyether, and cyclic thiocarbonate). The polymerization results and characterization are shown in Table 8.

[0158] Table 8 shows the test results of the polymer products of Application Examples 55 to 58.

[0159]

[0160] a M n : Number average molecular weight, measured by gel permeation chromatography; b PDI: molecular weight distribution, measured by gel permeation chromatography; c The resulting product is a small molecule compound - cyclic thiocarbonate

[0161] Application Examples 59-62: Using catalysts cat.1 to cat.3 and cat.8 to catalyze the copolymerization of cyclosulfide / carbonyl sulfide

[0162]

[0163] In a glove box, the catalyst prepared in the example (0.01 mmol) was added to an autoclave, and 0.01 mol of the corresponding cyclosulfide was added, 1.5 MPa of COS was charged, and the reaction was carried out at 80°C for 2 h. COS was then released, and the reaction liquid was measured by NMR to characterize the conversion rate of the monomer and the selectivity of the product (the proportion of polythiocarbonate, polythioether, and cyclic thiocarbonate). The polymerization results and characterization are shown in Table 9.

[0164] Table 9 shows the test results of the polymer products of Application Examples 59 to 62.

[0165]

[0166] a M n : Number average molecular weight, measured by gel permeation chromatography; b PDI: molecular weight distribution, measured by gel permeation chromatography; c The obtained product is a small molecule compound - cyclic thiocarbonate.

[0167] Application Example 63-64: Catalytic copolymerization of alkylene oxide / carbon monoxide using catalyst cat.12

[0168]

[0169] In a glove box, the catalyst prepared in the example (0.01 mmol) was added to an autoclave, and 0.01 mol of the corresponding alkylene oxide was added, 1.5 MPa of CO was charged, and the reaction was carried out at 80°C for 2 h. CO was then released, and the reaction liquid was measured by NMR to characterize the conversion rate of the monomer and the selectivity of the product (the proportion of polyester, polyether and lactone). The polymerization results and characterization are shown in Table 10.

[0170] Table 10 shows the test results of the polymer products of Application Examples 63 to 67.

[0171]

[0172] a M n : Number average molecular weight, measured by gel permeation chromatography; b PDI: Molecular weight distribution, measured by gel permeation chromatography.

[0173] Application Example 65: Propylene oxide / phenyl isocyanate copolymerization catalyzed by catalyst cat.1

[0174]

[0175] In a glove box, the catalyst prepared in the example (0.01 mmol) was added to an autoclave, and 0.01 mol of propylene oxide and 0.01 mol of phenyl isocyanate were added, and the mixture was reacted at 25° C. for 3 h. The polymer was precipitated in ethanol and dried to obtain a copolymer.

[0176] Application Example 66: Propylene oxide / phenyl isothiocyanate copolymerization catalyzed by catalyst cat.1

[0177]

[0178] In a glove box, the catalyst prepared in the example (0.01 mmol) was added to an autoclave, and 0.01 mol of propylene oxide and 0.01 mol of phenyl isothiocyanate were added, and the mixture was reacted at 25° C. for 3 h. The polymer was precipitated in ethanol and dried to obtain a copolymer.

[0179] Application Example 67: Using catalyst cat.1 to catalyze the copolymerization of episulfide and phenyl isocyanate

[0180]

[0181] In a glove box, the catalyst prepared in the example (0.01 mmol) was added to an autoclave, and 0.01 mol of propylene sulfide and 0.01 mol of phenyl isocyanate were added, and the mixture was reacted at 25° C. for 3 h. The polymer was precipitated in ethanol and dried to obtain a copolymer.

[0182] Application Example 68: Copolymerization of propylene sulfide / phenyl isothiocyanate using catalyst cat.1

[0183]

[0184] In a glove box, the catalyst prepared in the example (0.01 mmol) was added to an autoclave, and 0.01 mol of propylene sulfide and 0.01 mol of phenyl isothiocyanate were added, and the mixture was reacted at 25°C for 3 h. The polymer was precipitated in ethanol, dried, and characterized by NMR and GPC. The NMR spectrum of the obtained copolymer is shown in Figure 4 The GPC spectrum of the obtained copolymer is shown in Figure 5 , with a number average molecular weight of 62.7 kg / mol and a polydispersity of 1.25.

Claims

1. An organic boron-metal crown ether heteronuclear catalyst, characterized in that: The catalyst has the structure shown below:

2. A method for preparing the organoboron-metal crown ether heteronuclear catalyst according to claim 1, characterized in that: The method comprises: obtaining an organic boron-metal crown ether heteronuclear catalyst by a hydroboration reaction of the carbon-carbon double bond or the carbon-carbon triple bond of a metal crown ether complex W1 containing at least one carbon-carbon double bond or carbon-carbon triple bond and a reaction raw material W2 containing at least one boron-hydrogen bond; wherein the anion of the organic boron-metal crown ether heteronuclear catalyst is changed by anion replacement before or after the hydroboration reaction.

3. Use of the organic boron-metal crown ether heteronuclear catalyst according to claim 1 in the preparation of polymer materials and small molecules, characterized in that: include: One or more cyclic monomers are copolymerized with one or more of carbon dioxide, carbon disulfide, and carbon oxysulfide in the presence of an organic boron-metal crown ether heteronuclear catalyst to obtain a polymer material; one or more cyclic alkylene oxides are copolymerized with one or more cyclic acid anhydrides; and one or more cyclic monomers are ring-opened homopolymerized or copolymerized; One or more cyclic monomers react with any one or more of carbon dioxide, carbon disulfide, carbon oxysulfide, carbon monoxide, isocyanate, isothiocyanate, and sulfur dioxide in the presence of an organic boron-metal crown ether heteronuclear catalyst to obtain a small molecule; The cyclic monomer is selected from alkylene oxides, alkylene sulfides, cyclic anhydrides or cyclic lactones, and has the structure: The isocyanate and isothiocyanate are selected from the following structures: Wherein, R8 is selected from halogen, substituted, unsubstituted, C1-C2 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 Aromatic, C3-C 30 One or more of the heterocyclic groups; R9 is selected from H, halogen, substituted, unsubstituted, C1-C2 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 Aromatic, C3-C 30 One or more of heterocyclic groups; 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, and heteroaromatic groups having 5 to 20 carbon atoms; When R8 and R9 are endocyclic substituents, they are substituent groups.

4. The use of the organoboron-metal crown ether heteronuclear catalyst according to claim 3 in the preparation of polymer materials and organic small molecules, characterized in that: One or more alcohol compounds, acid compounds, amine compounds, and water are added as chain transfer agents to prepare the corresponding polymer polyols, or one or more polymers with alcohol hydroxyl groups, phenolic hydroxyl groups, amino groups, and carboxyl groups are added to the polymerization reaction system as macromolecular chain transfer agents to prepare the corresponding block copolymers.

5. Use of the organoboron-metal crown ether heteronuclear catalyst according to claim 4 in the preparation of polymer materials and organic small molecules, characterized in that: One or more polyols and polycarboxylic acids are added as chain transfer agents to prepare the corresponding polymer polyols.

6. Use of the organic boron-metal crown ether heteronuclear catalyst according to claim 4 in the preparation of polymer materials and organic small molecules, characterized in that: One or more polyol acids are added as chain transfer agents to prepare the corresponding polymer polyols.

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