A binaphthol salph ligand, salph catalyst and preparation method and application in ring-opening polymerization

Abstract

The application discloses a binaphthol Salph ligand, a Salph catalyst and a preparation method and application thereof in ring-opening polymerization, belongs to the technical field of catalysts, and first proposes a binaphthol Salph ligand and a Salph catalyst, enriches the types of the Salph ligand and the Salph catalyst, widens the application field of the Salph ligand and the Salph catalyst, and further relates to a polymerization reaction system containing the Salph catalyst, and a method for preparing P(Me-DBO) with different regularity by selectively ring-opening polymerizing racemic Me-DBO by using the polymerization reaction system containing the Salph catalyst. This is the first report on the Salph ligand and the Salph catalyst for selectively ring-opening polymerizing an axially chiral monomer to obtain an axially chiral polymer.

Description

Technical Field

[0001] This invention belongs to the field of catalyst design, specifically relating to a binaphol Salph ligand, a method for preparing Salph catalyst, and its application in the stereoselective ring-opening polymerization of racemic lactone Me-DBO to prepare isotactic P (Me-DBO). Background Technology

[0002] Since their inception, polymer materials have brought great convenience to people's lives due to their low price and superior performance, and their production has increased year by year. By 2021, global plastic production had exceeded 390 million tons. However, most plastics have short lifespans and are difficult to degrade, causing enormous pollution to the environment. At the same time, most plastics are derived from petroleum resources, and their disposal also results in a huge waste of resources.

[0003] To address this problem, we designed a Me-DBO monomer, whose polymer exhibits superior properties, T g With a melting point as high as 110℃, and through stereopolymerization of optically pure polymers with different configurations, crystallinity is significantly enhanced, reaching over 300℃, making them highly promising for applications in high-temperature resistant and other specialty polymer materials. Furthermore, the monomers can be recovered through thermal degradation and reused for polymerization, avoiding environmental pollution and resource waste. However, the optically pure monomer Me-DBO requires chiral resolution with quinine, which is difficult and costly, limiting its application. Stereoselective ring-opening polymerization of racemic lactone monomer Me-DBO to prepare isotactic polymers can significantly reduce costs and promote industrial application; the key lies in catalyst design. We first tried rare-earth metal complexes of Salph ligand L1 and Salen ligands L2 and L3 as catalysts, as reported in the literature, but neither yielded polymers with high isotactic regularity. Using L1 only yielded syndiotactic polymers, while L2 and L3 yielded atactic polymers. More importantly, the polymers obtained with these ligands were all amorphous and could not crystallize, greatly limiting their application range. Summary of the Invention

[0004] To address the aforementioned shortcomings, the present invention aims to provide a binaphrol Salph ligand, a Salph catalyst, and a preparation method thereof, as well as their application in ring-opening polymerization. It also relates to a polymerization reaction system containing a Salph catalyst, and a method for selectively ring-opening polymerization of racemic Me-DBO to prepare P(Me-DBO) of different degrees of regularity using this Salph catalyst-containing polymerization reaction system, achieving a stereoselectivity greater than 0.98. This is the first time a catalyst has been designed for the selective ring-opening polymerization of axially chiral monomers. Furthermore, the present invention is the first to propose a binaphrol Salph ligand and a Salph catalyst, enriching the types of Salph ligands and catalysts and broadening their application fields.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] This invention provides a class of binaphthol ligands, the general structural formula of which is shown below:

[0007]

[0008] Wherein, R is hydrogen, alkyl, cycloalkyl, alkoxy, aryl, halogen, heteroaryl, substituted alkyl, substituted alkoxy, substituted aryl or substituted heteroaryl.

[0009] Furthermore, R represents hydrogen, C1 ~ C 10 Alkyl, C3-C6 cycloalkyl, C1-C 10 Alkyl group, C6 ~ C 14 Aryl, halogen, 5-6 quinone heteroaryl, substituted C1-C 10 Alkyl, substituted C1~C 10 Alkyl group, by one or more R a Replacement C6 ~C 14 aryl, with one or more R a Substituted 5-6 aryl groups.

[0010] Further, R can be hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl, furanyl, pyridyl, biphenyl, 2-phenylbiphenyl, triphenylmethyl, isopropylphenyl, benzyl, adamantyl, C1-C3 perfluoroalkoxy, C1-C3 perfluoroalkyl, arylmethylene, heteroarylmethylene, arylmethimethylene, or heteroarylmethimethylene.

[0011] Furthermore, the naphthol Salph ligand is either a racemic mixture or an optically pure isomer.

[0012] Furthermore, the structural formula of the binaph ligand is shown below:

[0013]

[0014] The R group can be modified, and the general formula is written as:

[0015] or or

[0016] R can have the following structures, for example:

[0017]

[0018] Where rac represents racemic, and R and S represent optically pure.

[0019] This invention also provides a method for preparing the above-mentioned naphthol Salph ligand, comprising: performing a ketamine condensation reaction between a salicylaldehyde compound and phenylenediamine in ethanol, and separating and purifying the reaction product after the reaction is completed to obtain the ligand.

[0020] The general structural formula of salicylaldehyde compounds is shown below:

[0021]

[0022] R is hydrogen, alkyl, cycloalkyl, alkoxy, aryl, halogen, heteroaryl, substituted alkyl, substituted alkoxy, substituted aryl, or substituted heteroaryl.

[0023] Furthermore, R represents hydrogen, C1 ~ C 10 Alkyl, C3-C6 cycloalkyl, C1-C 10 Alkyl group, C6 ~ C 14 Aryl, halogen, 5-6 quinone heteroaryl, substituted C1-C 10 Alkyl, substituted C1~C 10 Alkyl group, by one or more R a Replacement C6 ~C 14 aryl, with one or more R a Substituted 5-6 aryl groups.

[0024] Further, R can be hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl, furanyl, pyridyl, biphenyl, 2-phenylbiphenyl, triphenylmethyl, isopropylphenyl, benzyl, adamantyl, C1-C3 perfluoroalkoxy, C1-C3 perfluoroalkyl, arylmethylene, heteroarylmethylene, arylmethimethylene, or heteroarylmethimethylene.

[0025] Furthermore, the specific process for preparing the binaph ligand is as follows: salicylaldehyde compounds, phenylenediamine, and solvent are added to the reaction apparatus and refluxed for 12-20 hours. After the reaction is completed, the reaction product is separated and purified to obtain the ligand. The molar ratio of phenylenediamine to salicylaldehyde is 1-2:2-5.

[0026] Furthermore, the reflux reaction time was 12 hours, and the molar ratio of phenylenediamine to salicylaldehyde was 1:2.

[0027] Furthermore, the solvent is methanol, ethanol, isopropanol, toluene, acetonitrile, or N,N-dimethylformamide, preferably ethanol.

[0028] The reaction structure of the preparation method of the naphthol Salph ligand in this invention is shown below:

[0029]

[0030] The present invention also provides a Salph catalyst, which uses the above-mentioned naphthol Salph ligand as a ligand.

[0031] Furthermore, the general structural formula of the above-mentioned Salph catalyst is as follows:

[0032]

[0033] Wherein, R is hydrogen, alkyl, cycloalkyl, alkoxy, aryl, halogen, heteroaryl, substituted alkyl, substituted alkoxy, substituted aryl or substituted heteroaryl.

[0034] Furthermore, R represents hydrogen, C1 ~ C 10 Alkyl, C3-C6 cycloalkyl, C1-C 10 Alkyl group, C6 ~ C 14 Aryl, halogen, 5-6 quinone heteroaryl, substituted C1-C 10 Alkyl, substituted C1~C 10 Alkyl group, by one or more R a Replacement C6 ~C 14 aryl, with one or more R a Substituted 5-6 aryl groups.

[0035] Further, R can be hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl, furanyl, pyridyl, biphenyl, 2-phenylbiphenyl, triphenylmethyl, isopropylphenyl, benzyl, adamantyl, C1-C3 perfluoroalkoxy, C1-C3 perfluoroalkyl, arylmethylene, heteroarylmethylene, arylmethimethylene, or heteroarylmethimethylene.

[0036] Further, M can be Zn, Co, Cr, Cu, Fe, Pd, Ni, Mn, Y, La, Ln, Sc, Yb, Al, Ru, Ti, etc., preferably Zn, Y, La, Al, Sc or Yb.

[0037] Further, X can be furanyl, -N(SiHMe2)2, -N(SiMe3)2, alkyl, alkoxy, aryl, phenolic, halogen, etc., preferably furanyl, -N(SiHMe2)2 or -N(SiMe3)2.

[0038] This invention also provides a method for preparing the above-mentioned Salph catalyst, comprising the following steps: reacting the above-mentioned naphthol Salph ligand with the metal reagent MX n Coordination was performed to obtain;

[0039]

[0040] Wherein, R is hydrogen, alkyl, cycloalkyl, alkoxy, aryl, halogen, heteroaryl, substituted alkyl, substituted alkoxy, substituted aryl or substituted heteroaryl.

[0041] Furthermore, the naphthol Salph ligand and the metal reagent MX n The molar ratio is 1 ~ 3:1 ~ 3, preferably 1:1.

[0042] Furthermore, R represents hydrogen, C1 ~ C 10 Alkyl, C3-C6 cycloalkyl, C1-C 10 Alkyl group, C6 ~ C 14 Aryl, halogen, 5-6 quinone heteroaryl, substituted C1-C 10 Alkyl, substituted C1~C 10 Alkyl group, by one or more R a Replacement C6 ~C 14 aryl, with one or more R a Substituted 5-6 aryl groups.

[0043] Further, R can be hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl, furanyl, pyridyl, biphenyl, 2-phenylbiphenyl, triphenylmethyl, isopropylphenyl, benzyl, adamantyl, C1-C3 perfluoroalkoxy, C1-C3 perfluoroalkyl, arylmethylene, heteroarylmethylene, arylmethimethylene, or heteroarylmethimethylene.

[0044] Furthermore, M can be Zn, Co, Cr, Cu, Fe, Pd, Ni, Mn, Y, La, Ln, Sc, Yb, Al, Ru, Ti, etc.

[0045] Furthermore, X can be furanyl, -N(SiHMe2)2, -N(SiMe3)2, alkyl, alkoxy, aryl, phenolic, halogen, etc.

[0046] Metal reagent MX in this invention n It can be prepared using existing technologies.

[0047] The present invention also provides a polymerization reaction system comprising the above-mentioned Salph catalyst and initiator.

[0048] Furthermore, the initiator includes alkyl alcohols, alkyl thiols, benzyl alcohols, or benzyl thiols, etc.

[0049] This invention also provides its application in the selective ring-opening polymerization of racemic Me-DBO using the above-mentioned polymerization reaction system to prepare P(Me-DBO) with different degrees of regularity. The method is characterized by the following steps: adding racemic Me-DBO, Salph catalyst, initiator, and solvent to a reaction apparatus, reacting at 20-45°C for 6-44 hours, and separating and purifying the reaction product to obtain the desired product; wherein the molar ratio of racemic Me-DBO, Salph catalyst, and initiator is 100-10000:1-5:1-5;

[0050] Furthermore, the solvent is a conventional organic solvent or a mixed solvent, such as dichloromethane, dimethyl sulfoxide, tetrahydrofuran, N-methylpyrrolidone, N,N-dimethylformamide, toluene, a mixed solvent of dichloromethane and n-hexane, etc., preferably toluene, dichloromethane and a mixed solvent of dichloromethane and n-hexane.

[0051] The reaction structures used in this invention to achieve selective ring-opening polymerization of racemic Me-DBO to prepare P(Me-DBO) with different degrees of regularity are shown below:

[0052]

[0053] The preparation method of this invention yields P(Me-DBO) with high regularity, which can form stereocomposite polymers; the resulting isotactic polymer P m > 0.98; where, within this field, P r Representatives have the same selectivity, P m Represents isomorphic selectivity; regardless of the regularity of the polymer, there exists a definition: P r +P m It is always equal to 1; P r =1 represents a perfect isomorphism, P m =1 is a perfect isomorphic structure.

[0054] It should be noted that, in this invention, the term "substitution" refers to the substitution of hydrogen atoms and / or carbon atoms within the basic structure by hydroxyl groups and / or functional groups, and / or heteroatoms or heteroatom-containing groups. Therefore, the term hydroxyl group includes heteroatom-containing groups. For the purposes of this document, a heteroatom is defined as any atom other than carbon and hydrogen. For example, methylcyclopentadiene (Cp) is a Cp group substituted with a methyl group (which is the basic structure), also referred to as a methyl functional group; ethanol is an ethyl group substituted with a –OH functional group (which is the basic structure); and pyridine is a phenyl group in the basic structure of a benzene ring where the carbon atom is substituted with a nitrogen atom.

[0055] For the purposes of this document, when a group is listed, it indicates the basic structure of that group (group type) and all other groups formed by the substitutions described above. The listed alkyl groups, etc., include all isomers, including cyclic isomers as desired; for example, butyl includes n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, and cyclobutyl (and analog-substituted cyclopropyl); pentyl includes n-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, and neopentyl (and analog-substituted cyclobutyl and cyclopropyl). Cyclic compounds with substituents include all isomer forms; for example, methylphenyl will include o-methylphenyl, m-methylphenyl, and p-methylphenyl; dimethylphenyl will include 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diphenylmethyl, 3,4-dimethylphenyl, and 3,5-dimethylphenyl.

[0056] In summary, the present invention has the following advantages:

[0057] This invention presents for the first time a binaphthol Salph ligand and a Salph catalyst, and its preparation method is simple and easy to operate, enriching the types of Salph ligands and catalysts. Furthermore, the binaphthol Salph ligand and Salph catalyst are used for the selective ring-opening polymerization of racemic Me-DBO. The P(Me-DBO) obtained by the preparation method of this invention exhibits high regularity. The resulting isotactic polymer P... m > 0.98, effectively solving the problem of low regularity of P(Me-DBO) prepared by selective ring-opening polymerization of Me-DBO. This is the first stereoselective ring-opening polymerization of axially chiral monomers, which solves the problem of poor selectivity of existing ligands for axially chiral monomers. Attached Figure Description

[0058] Figure 1 The naphthol Salph ligand (R)-2a prepared in Example 1 of this invention nuclear magnetic resonance spectrum ( 1 H NMR).

[0059] Figure 2 The naphthol Salph ligand (R)-2a prepared in Example 1 of this invention nuclear magnetic resonance spectrum ( 13 (C NMR).

[0060] Figure 3 The naphthol Salph ligand (R)-2b prepared in Example 2 of this invention nuclear magnetic resonance spectrum ( 1 H NMR).

[0061] Figure 4 The naphthol Salph ligand (R)-2b prepared in Example 2 of this invention nuclear magnetic resonance spectrum ( 13 (C NMR).

[0062] Figure 5 The naphthol Salph ligand (S)-2b prepared in Example 2 of this invention nuclear magnetic resonance spectrum ( 1 H NMR).

[0063] Figure 6 The naphthol Salph ligand (S)-2b prepared in Example 2 of this invention nuclear magnetic resonance spectrum ( 13 (C NMR).

[0064] Figure 7 The Salph catalyst (R)-3a prepared in Example 4 of this invention nuclear magnetic resonance spectrum ( 1 H NMR).

[0065] Figure 8 The Salph catalyst (R)-3a prepared in Example 4 of this invention nuclear magnetic resonance spectrum ( 13 (C NMR).

[0066] Figure 9 The Salph catalyst (R)-3b prepared in Example 4 of this invention nuclear magnetic resonance spectrum ( 1 H NMR).

[0067] Figure 10 The Salph catalyst (R)-3b prepared in Example 4 of this invention nuclear magnetic resonance spectrum ( 13 (C NMR).

[0068] Figure 11The Salph catalyst (S)-3b prepared in Example 4 of this invention nuclear magnetic resonance spectrum ( 1 H NMR).

[0069] Figure 12 The Salph catalyst (S)-3b prepared in Example 4 of this invention nuclear magnetic resonance spectrum ( 13 (C NMR).

[0070] Figure 13 The Salph catalyst (R)-3c prepared in Example 4 of this invention nuclear magnetic resonance spectrum ( 1 H NMR).

[0071] Figure 14 The Salph catalyst (R)-3d prepared in Example 4 of this invention nuclear magnetic resonance spectrum ( 1 H NMR).

[0072] Figure 15 The Salph catalyst (R)-3e prepared in Example 4 of this invention nuclear magnetic resonance spectrum ( 1 H NMR).

[0073] Figure 16 The Salph catalyst (R)-3f prepared in Example 4 of this invention nuclear magnetic resonance spectrum ( 1 H NMR).

[0074] Figure 17 The nuclear magnetic resonance spectrum of the polyester prepared in Example 5 of this invention is shown below. 1 H NMR).

[0075] Figure 18 The nuclear magnetic resonance spectrum of the polyester prepared in Example 5 of this invention is shown below. 13 (C NMR).

[0076] Figure 19 The nuclear magnetic resonance spectrum of the polyester prepared in Example 6 of this invention is shown below. 1 H NMR).

[0077] Figure 20 The nuclear magnetic resonance spectrum of the polyester prepared in Example 6 of this invention is shown below. 13 (C NMR).

[0078] Figure 21 The nuclear magnetic resonance spectrum of the polyester prepared in Example 7 of this invention is shown below.1 H NMR).

[0079] Figure 22 The nuclear magnetic resonance spectrum of the polyester prepared in Example 7 of this invention is shown below. 13 (C NMR). Detailed Implementation

[0080] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are only for explaining the invention and are not intended to limit the invention; that is, the described embodiments are merely some embodiments of the invention, and not all embodiments.

[0081] Therefore, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0082] Example 1

[0083] This example provides a method for preparing the associated naphthol Salph ligand, and the reaction route is shown below:

[0084]

[0085] The specific steps are as follows: Phenylenediamine (46 mg, 0.42 mmol, 1.05 equivalents), (R)-1a (300 mg, 0.80 mmol, 2 equivalents), and anhydrous ethanol (4 mL) were added to a side-necked flask. The mixture was heated under reflux for 20 h. After the reaction was complete, the mixture was cooled to room temperature and filtered using a frit-core glass funnel. The filter cake was washed with methanol, and the resulting yellow solid was dried in a vacuum oven to obtain the naphthol Salph ligand (R)-2a (306 mg, 89% yield). Its structure was characterized using a 400 MHz nuclear magnetic resonance instrument with CDCl3 as a reagent. (See [link to relevant documentation]). Figure 1 , 2 .

[0086] Example 2

[0087] This example provides a method for preparing the naphthol Salph ligand, which differs from Example 1 only in that the salicylaldehyde compound is...

[0088]

[0089] The corresponding naphthol Salph ligand obtained is

[0090]

[0091] The remaining steps and parameters are the same. Its structure was characterized using CDCl3 at 400 MHz NMR; see [link to relevant documentation]. Figure 3-6 .

[0092] Example 3

[0093] This example provides a method for synthesizing the metallic reagent Y[N(SiHMe2)2]3(THF)2, specifically including the following steps: In a glove box, LiN(SiHMe2)2 (859.3 mg, 6.2 mmol) was slowly added to a hexane suspension (17 mL) of YCl3(THF)3 (970.7 mg, 2.4 mmol), and the reaction was carried out at room temperature for 12 hours. The white solid was obtained by filtration, washed with frozen hexane, and the solvent was removed by vacuum. The obtained white solid was recrystallized twice in n-pentane to obtain the metallic reagent Y[N(SiHMe2)2]3(THF)2 (yield: 82%, 2.07 g).

[0094] Other metal reagents used in this invention, such as ytterbium (Yb) reagent, zinc (Zn) reagent, or lanthanum (La) reagent, can be prepared by referring to the above process.

[0095] The specific process is as follows:

[0096] The synthesis of ytterbium (Yb) reagent is as follows:

[0097] In a glove box, 30 mL of a 1 mol / L hexane solution of LiNSiMe3 was added to a 12 mL tetrahydrofuran suspension of YbCl3 (1.95 g, 10 mmol). The mixture was refluxed overnight, the solvent was removed under vacuum, 30 mL of toluene was added, and the solid was heated to dissolve it. The supernatant was collected by filtration and recrystallized at room temperature to give the product Yb[N(SiMe3)2](μ-Cl)Li(THF)3 (yield: 63%, 5.21 g).

[0098] The synthesis of zinc (Zn) reagent is as follows:

[0099] In a glove box, 20 mL of a 2 mol / L NaNSiMe3 hexane solution was added to a 12 mL suspension of ZnCl2 (1.34 g, 10 mmol) tetrahydrofuran. The mixture was refluxed at 50 °C for 5 hours. The filtrate was collected by filtration, the solvent was removed under vacuum, and the product Zn[N(TMS)2]2 (yield: 38%, 4.4 g) was obtained by vacuum distillation.

[0100] The synthesis of lanthanum (La) reagents is as follows:

[0101] In a glove box, La[N(TMS)2]3 (3.1 g, 5 mmol) and tetrahydrofuran (3.6 g, 50 mmol) were added sequentially to 35 mL of toluene. The mixture was refluxed at 90 °C for 30 minutes, and the solvent was removed under vacuum to obtain the product La[N(SiHMe2)2]3(THF)2 (yield: 99%, 2.65 g).

[0102] The synthesis of metallic reagents (Sc) is as follows:

[0103] In the glove box, ScCl3(THF) 2-3 (1.03 g, 3.3 mmol) was dissolved in n-hexane (25 ml), and LiN(SiHMe2)2 (1.23 g, 8.8 mmol) was slowly added to the solution. The mixture was stirred at room temperature for 12 hours, the solvent was removed under vacuum, and the product Sc(N(SiHMe2)2)3(THF) was obtained by recrystallization with pentane (yield: 30%, 0.52 g).

[0104] Example 4

[0105] This case provides a method for preparing a Salph catalyst, which combines the naphthol Salph ligand (2a-b)L obtained in Examples 1-2 with the metal reagent MX obtained in Example 3. n The reaction involves coordination of (Y[N(SiHMe2)2]3(THF)2, Yb[N(SiMe3)2](μ-Cl)Li(THF)3, Zn[N(TMS)2]2, La[N(SiHMe2)2]3(THF)2, Sc(N(SiHMe2)2)3(THF) with the directly purchased metal reagent AlMe3. The reaction route is shown below:

[0106]

[0107] Representative catalysts are shown below:

[0108]

[0109] The specific process for preparing the above-mentioned Salph catalyst is as follows:

[0110] Yttrium (Y) reagent:

[0111] The specific steps are as follows: In a glove box, Y(N(SiHMe2)2)3(THF)2 (115 mg, 0.183 mmol, 1 equivalent) was dissolved in n-hexane (2.5 mL), and (R)-2a (150 mg, 0.183 mmol, 1 equivalent) was dissolved in toluene (1.5 mL) by heating. Then, the toluene solution of (R)-2a was added to the n-hexane solution of Y(N(SiHMe2)2)3(THF)2, and the mixture was stirred at room temperature for 63 h. After the reaction was completed, the solvent was dried under vacuum, and the crude product was washed with n-pentane to obtain a reddish-brown powder (R)-3a (93 mg, 46% yield). Its structure was characterized by a 400 MHz nuclear magnetic resonance instrument using C6D6 as a reagent. See [link to relevant documentation]. Figure 7 , 8 .

[0112] The specific steps are as follows: In a glove box, Y(N(SiHMe2)2)3(THF)2 (194 mg, 0.308 mmol, 1 equivalent) was dissolved in n-hexane (5 mL), and (R)-2b (300 mg, 0.308 mmol, 1 equivalent) was dissolved in toluene (3 mL) by heating. Then, the toluene solution of (R)-2b was added to the n-hexane solution of Y(N(SiHMe2)2)3(THF)2, and the mixture was stirred at room temperature for 63 h. After the reaction was completed, the solvent was dried, and the crude product was washed with n-pentane to obtain a reddish-brown powder (R)-3b (361 mg, 89% yield). Its structure was characterized by a 400 MHz nuclear magnetic resonance instrument using C6D6 as a reagent. See [link to relevant documentation]. Figure 9 , 10 .

[0113] Aluminum (Al) reagents:

[0114] The specific steps are as follows: In a glove box, (R)-2a (25.7 mg, 0.0313 mmol, 1 equivalent) was dissolved in toluene (2 mL), and a hexane solution of Al(CH3)3 (1.6 M, 20 μL, 1 equivalent) was added. The mixture was stirred at room temperature for 24 h. After the reaction was complete, the solvent was dried under vacuum, and the crude product was washed with n-pentane to obtain a red powder (R)-3c (20 mg, 74% yield). Its structure was characterized by nuclear magnetic resonance at 400 MHz using C6D6 as a reagent. See [link to relevant documentation]. Figure 13 .

[0115] In a glove box, (R)-2b (45 mg, 0.0462 mmol, 1 equivalent) was dissolved in toluene (2 mL). After cooling to room temperature, a hexane solution of Al(CH3)3 (1.6 M, 29 μL, 1 equivalent) was added, and the mixture was stirred at room temperature for 24 h. After the reaction was complete, the suspension was filtered, and the crude product was washed with n-pentane to obtain a red powder (R)-3d (30 mg, 64% yield). Its structure was characterized by NMR at 400 MHz using C6D6 as a reagent. See [link to relevant documentation]. Figure 14 .

[0116] Scandium (Sc) reagent

[0117] The specific steps are as follows: In a glove box, Sc(N(SiHMe2)2)3(THF) (19 mg, 0.0370 mmol, 1 equivalent) was dissolved in toluene (2 mL), and ligand (R)-2a (30 mg, 0.0370 mmol, 1 equivalent) was slowly added. The mixture was stirred at room temperature for 24 h. After the reaction was complete, the solvent was dried under vacuum, and the crude product was washed with n-hexane to obtain a brownish-green powder (R)-3e (30 mg, 77% yield). Its structure was characterized by a 400 MHz nuclear magnetic resonance instrument using C6D6 as a reagent. See [link to relevant documentation]. Figure 15 .

[0118] In a glove box, Sc(N(SiHMe2)2)3(THF) (32 mg, 0.0616 mmol, 1 equivalent) was dissolved in toluene (3.7 mL), and ligand (R)-2b (60 mg, 0.0616 mmol, 1 equivalent) was slowly added. The mixture was stirred at room temperature for 24 h. After the reaction was complete, the solvent was dried under vacuum, and the crude product was washed with n-hexane to obtain a brownish-green powder (R)-3f (50 mg, 67% yield). Its structure was characterized by NMR at 400 MHz using C6D6 as a reagent. See [link to relevant documentation]. Figure 16 .

[0119] Example 5

[0120] This example provides a method for preparing P(Me-DBO) of different degrees of regularity by selective ring-opening polymerization of racemic Me-DBO using the Salph catalyst prepared in Example 4. The reaction route is shown below:

[0121]

[0122] Among them, the Salph catalyst is The initiator is 4-MeC6H4CH2OH, and the solvent is toluene.

[0123] The specific preparation steps of the above reaction route are as follows:

[0124] Monomers Me-DBO (100 mg, 0.42 mmol) and (R)-3b (1.3 mg, 1.05 μmol) were weighed into a 4 mL screw-cap sample vial. Toluene (210 μL) and a toluene solution of initiator 4-MeC6H4CH2OH (1.05 μmol) were added. The mixture was stirred at room temperature for 22 h. After the polymerization reaction reached equilibrium, the reaction was quenched with 0.2 mL of deuterated chloroform solution containing 1 wt.% benzoic acid. The solution was then added dropwise to methanol to allow the polymer to precipitate. The polymer was dissolved in CHCl3 and precipitated again from the methanol solution. This process was repeated once more to completely remove unreacted monomers. The polymer was dried in a vacuum oven at 60 °C until its weight no longer changed. The molecular weight of the polymer was analyzed by GPC to obtain M. n = 29.7 kg / mol, K = 1.14; the isotacticity of the polymer was characterized by NMR at 400 MHz using CDCl3 as a reagent, P m = 0.92, see Figure 17 , 18 .

[0125] Example 6

[0126] This example provides a method for preparing P(Me-DBO) of different degrees of regularity by selective ring-opening polymerization of racemic Me-DBO using the Salph catalyst prepared in Example 4. The reaction route is shown below:

[0127]

[0128] Among them, the Salph catalyst is The initiator is 4-MeC6H4CH2OH, and the solvent is dichloromethane.

[0129] The specific preparation steps of the above reaction route are as follows:

[0130] Monomers Me-DBO (100 mg, 0.42 mmol) and (R)-3b (1.3 mg, 1.05 μmol) were weighed into a 4 mL screw-cap sample vial. DCM (210 μL) and a DCM solution of initiator 4-MeC6H4CH2OH (1.05 μmol) were added. The mixture was stirred at room temperature for 12 h. After the polymerization reaction reached equilibrium, the reaction was quenched with 0.2 mL of deuterated chloroform solution containing 1 wt.% benzoic acid. The solution was then added dropwise to methanol to allow the polymer to precipitate. The polymer was dissolved in CHCl3 and precipitated again from the methanol solution. This process was repeated once more to completely remove unreacted monomers. The polymer was dried in a vacuum oven at 60 °C until its weight no longer changed. The molecular weight of the polymer was analyzed by GPC to obtain M. n= 11.0 kg / mol, K = 1.22; the isotacticity of the polymer was characterized by a 400 MHz nuclear magnetic resonance instrument using CDCl3 as a reagent, P m = 0.80, see Figure 19 , 20 .

[0131] Example 7

[0132] This example provides a method for preparing P(Me-DBO) of different degrees of regularity by selective ring-opening polymerization of racemic Me-DBO using the Salph catalyst prepared in Example 4. The reaction route is shown below:

[0133]

[0134] Among them, the Salph catalyst is The initiator is 4-MeC6H4CH2OH, and the solvent is a mixture of dichloromethane and n-hexane in equal volumes.

[0135] The specific preparation steps of the above reaction route are as follows:

[0136] Monomers Me-DBO (100 mg, 0.42 mmol) and (R)-3b (1.3 mg, 1.05 μmol) were weighed into 4 mL screw-cap sample vials. Equal volumes of a mixed solvent of DCM (105 μL) and n-hexane (105 μL) and a DCM solution of initiator 4-MeC6H4CH2OH (1.05 μmol) were added. After stirring at room temperature for 6 h, the reaction was quenched with 0.2 mL of deuterated chloroform solution containing 1 wt.% benzoic acid. The solution was then added dropwise to methanol to allow the polymer to precipitate. The polymer was dissolved in CHCl3 and precipitated again from the methanol solution. This process was repeated once more to completely remove unreacted monomers. The polymer was dried in a vacuum oven at 60 °C until its weight no longer changed. The molecular weight of the polymer was analyzed by GPC to obtain M. n = 16.2 kg / mol, K = 1.22; the isotacticity of the polymer was characterized by a 400 MHz nuclear magnetic resonance instrument using CDCl3 as a reagent, P m > 0.98, see Figure 21 , 22 .

[0137] Comparative Example 1

[0138] This example provides a method for preparing P(Me-DBO) of different degrees of regularity by selective ring-opening polymerization of racemic Me-DBO using the Salph catalyst prepared in Example 4. The only difference from Example 6 is the catalyst used:

[0139]

[0140] In this example, nuclear magnetic resonance (NMR) analysis of the obtained P(Me-DBO) showed a monomer conversion rate of 76%. The polymer's... 13 ¹³C NMR analysis showed that the polymer was a syndiotactic polymer, P. r The value was 0.81 (NMR spectrum). This comparative example demonstrates that introducing a chiral binaphthyl group into the Salph catalyst can significantly improve isotropic selectivity, proving the superiority of this invention.

[0141] The partial characterization data of the Salph ligands and Salph catalysts prepared in this invention are shown below:

[0142]

[0143] 1 H NMR (400 MHz, CDCl3, 25 °C): δ 12.54 (s, 2H), 8.76 (s, 2H), 7.80 (d, J = 9.0 Hz, 4H), 7.69 (d, J = 8.5 Hz, 2H), 7.60–7.52 (m, 2H), 7.43–7.28(m, 8H), 7.27–7.05 (m, 8H), 7.01 (d, J = 7.5 Hz, 4H), 6.95 (d, J = 8.2 Hz,2H), 6.63 (t, J = 7.4 Hz, 2H), 6.47 (t, J = 7.5 Hz, 4H). 13 C NMR (100 MHz, CDCl3, 25 °C): δ 163.3, 154.7, 142.2, 141.8, 140.7, 135.6, 134.8, 132.8,132.7, 130.9, 128.7, 128.6, 128.4, HRMS (ESI-TOF): m / z calculated for C 60 H 40 N₂O₂ [M + H] + 821.3090, found 821.3095.

[0144]

[0145] 1 H NMR (400 MHz, CDCl3, 25 °C): δ 12.79 (s, 2H), 8.74 (s, 2H), 7.80(s, 2H), 7.60–7.53 (m, 2H), 7.43 (t, J = 7.9 Hz, 4H), 7.36–7.00 (m, 30H),6.92–6.85 (m, 2H), 6.66 (d, J = 8.0 Hz, 4H). 13 C NMR (100 MHz, CDCl3, 25 °C):δ 163.2, 155.0, 142.7, 140.8, 140.5, 140.3, 137.7, 135.6, 134.7, 132.6,130.8, 129.1, 128.7, 128.3, 128.2, 128.1, 128.1, 127.5, 127.0, 126.6, 126.5,125.9, 125.8, 125.3, 124.9, 124.7, 123.0, 120.5, 120.4, 118.9. HRMS (ESI-TOF): m / z calculated for C 72 H 48 N2O2 [M + H] + 973.3716, found 973.3745.

[0146]

[0147] 1 H NMR (400 MHz, CDCl3, 25 °C): δ 12.80 (s, 2H), 8.77 (s, 2H), 7.83(s, 2H), 7.61–7.56 (m, 2H), 7.47–7.38 (m, 4H), 7.38–7.01 (m, 30H), 6.93–6.85(m, 2H), 6.66 (d, J = 7.9 Hz, 4H). 13C NMR (100 MHz, CDCl3, 25 °C): δ 163.2,155.0, 142.7, 140.8, 140.5, 140.2, 137.7, 135.6, 134.7, 132.6, 130.8, 129.1,128.7, 128.3, 128.3, 128.1, 128.1, 127.5, 127.0, 126.6, 126.6, 125.9, 125.9,125.3, 124.9, 124.7, 123.0, 120.5, 120.4, 118.9. HRMS (ESI-TOF): m / zcalculated for C 72 H 48 N2O2 [M + H] + 973.3716, found 973.3748.

[0148]

[0149] 1 H NMR (400 MHz, C6D6, 25 °C): δ 8.31 (s, 2H), 7.96–6.48 (m, 36H),4.83 (s, 1H), 4.65 (s, 1H), 2.59 (s, 4H), 0.63 (s, 4H), 0.23 – -0.22 (m,12H). 13 C NMR (100 MHz, C6D6, 25 °C): δ 166.7, 166.2 (N=C), 162.1, 161.0,146.0, 145.9, 142.9, 142.7, 141.4, 140.7, 139.6, 138.8, 138.7, 138.5, 135.4,135.0, 134.2, 133.9, 133.4, 133.4, 129.7, 129.4, 129.3, 127.2, 126.9, 126.8,126.6, 126.3, 126.2, 126.0, 125.7, 125.4, 125.2, 122.5, 122.4, 121.9, 119.2,119.2 (Ar), 69.2, 24.9(THF), 3.2, 3.0 (SiHMe2).

[0150]

[0151] 1 H NMR (400 MHz, C6D6, 25 °C): δ 8.38 (d, J = 22.3 Hz, 2H), 7.86–6.71(m, 44H), 4.89 (s, 1H), 4.66 (s, 1H), 2.65 (d, J = 7.2 Hz, 4H), 0.68 (s, 4H),0.21 – -0.14 (m, 12H). 13 C NMR (100 MHz, C6D6, 25 °C): δ 166.8, 166.2 (N=C),162.1, 161.2, 145.9, 145.8, 142.0, 141.8, 141.4, 141.2, 140.8, 140.2, 139.7,139.6, 139.1, 138.9, 138.7, 138.5, 135.4, 135.1, 134.2, 134.0, 133.5, 133.4,130.1, 129.8, 129.5, 129.4, 129.1, 128.8, 128.7, 127.1, 127.1, 127.0, 127.0,126.9, 126.4, 126.2, 126.1, 125.8, 125.5, 125.2 122.5, 122.4, 122.0, 119.3,119.2 (Ar), 69.3, 24.9 (THF), 3.3, 3.0 (SiHMe2). HRMS (ESI-TOF): m / zcalculated for C 80 H 68 N3O3Si2Y [M + H] + 1264.3936, found 1264.3853.

[0152]

[0153] 1 H NMR (400 MHz, C6D6, 25 °C): δ 8.37 (d, J = 23.0 Hz, 2H), 7.87 –6.99 (m, 44H), 4.89 (s, 1H), 4.66 (s, 1H), 2.65 (q, J = 6.9 Hz, 4H), 0.69 (d,J = 6.1 Hz, 4H), 0.24 – -0.16 (m, 12H). 13C NMR (100 MHz, C6D6, 25 °C): δ166.8, 166.2 (N=C), 162.1, 161.2, 145.9, 145.8, 142.0, 141.8, 141.4, 141.2,140.8, 140.2, 139.7, 139.6, 139.1, 138.9, 138.7, 138.5, 135.4, 135.1, 134.2,134.0, 133.5, 133.4, 130.1, 129.8, 129.5, 129.4, 128.8, 128.7, 127.1, 127.1,127.0, 126.9, 126.4, 126.2, 126.1, 125.8, 125.5, 125.2, 122.5, 122.4, 122.0,119.3, 119.2 (Ar), 69.3, 25.0 (THF), 3.3, 3.0 (SiHMe2).

[0154] The above content is merely an example and illustration of the structure of the present invention. Any modifications or additions to the specific embodiments described, or substitutions made by those skilled in the art without creative effort, shall still fall within the scope of protection of this patent.

Claims

1. A binaphthol ligand, characterized in that, The general structural formula of the binaph ligand is shown below: ， Where R is hydrogen, C1 ~ C 10 Alkyl, C3-C6 cycloalkyl, C1-C 10 Alkyl group, C6 ~ C 14 Aryl, halogen or 5-6 quinone heteroaryl.

2. The naphthol Salph ligand as described in claim 1, characterized in that, R can be hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, tert-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclohexyl, furanyl, pyridyl, biphenyl, 2-phenylbiphenyl, triphenylmethyl, isopropylphenyl, benzyl, adamantyl, C1-C3 perfluoroalkoxy, C1-C3 perfluoroalkyl, arylmethylene, heteroarylmethylene, arylmethimethylene, or heteroarylmethimethylene.

3. The method for preparing the binaph ligand according to any one of claims 1-2, characterized in that, Includes the following steps: The product was prepared by reacting salicylaldehyde compounds with phenylenediamine in a ketamine condensation reaction, followed by separation and purification of the reaction product after the reaction was completed. The general structural formula of salicylaldehyde compounds is shown below: ， R represents hydrogen, C1 ~ C 10 Alkyl, C3-C6 cycloalkyl, C1-C 10 Alkyl group, C6 ~ C 14 Aryl, halogen, or 5-6 quinone heteroaryl; The structural formula of phenylenediamine is shown below: 。 4. A Salph catalyst, characterized in that, The Salph catalyst uses the naphthol Salph ligand as described in any one of claims 1-2 as a ligand; the structural formula of the Salph catalyst is shown below: ， Where R is hydrogen, C1~C 10 Alkyl, C3-C6 cycloalkyl, C1-C 10 Alkoxy, C6~C 14 Aryl, halogen, or 5-6 quinone heteroaryl; M is Y, Yb, Zn, Cr, Co, Al, Sc, or La; X can be furanyl, -N(SiHMe2)2, -N(SiMe3)2, alkyl, alkoxy, aryl, phenolic, or halogen. m is 1 or 2.

5. The method for preparing the Salph catalyst according to claim 4, characterized in that, The process includes the following steps: combining the naphthol Salph ligand as described in any one of claims 1-2 with the metal reagent MX. m Coordination was performed to obtain; ， Where R is hydrogen, C1 ~ C 10 Alkyl, C3-C6 cycloalkyl, C1-C 10 Alkyl group, C6 ~ C 14 Aryl, halogen, or 5-6 quinone heteroaryl; M is Y, Yb, Zn, Al, Sc, or La; X can be furanyl, -N(SiHMe2)2, -N(SiMe3)2, alkyl, alkoxy, aryl, phenolic, or halogen. m is 1 or 2.

6. A polymerization reaction system, characterized in that, It includes the Salph catalyst and initiator as described in claim 4; the initiator is an alkyl alcohol, alkyl thiol, benzyl alcohol, or benzyl thiol.

7. The application of the polymerization reaction system described in claim 6 in the selective ring-opening polymerization of racemic Me-DBO to prepare P(Me-DBO) of different degrees of regularity, characterized in that, Includes the following steps: Racemic Me-DBO, Salph catalyst, initiator, and solvent were added to a reaction apparatus and reacted at 20–45 °C for 6–44 h. The reaction product was then separated and purified to obtain the final product. The molar ratio of racemic Me-DBO, Salph catalyst, and initiator was 100–10000:1–5:1–5. The Me-DBO structure is shown below: 。

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