WO2022151797A1

WO2022151797A1 - Method for catalytically preparing vinyl ether polymer

Info

Publication number: WO2022151797A1
Application number: PCT/CN2021/127059
Authority: WO
Inventors: 廖赛虎; 张勋
Original assignee: 福州大学
Priority date: 2021-01-12
Filing date: 2021-10-28
Publication date: 2022-07-21
Also published as: CN113527556A; CN113527556B

Abstract

A method for preparing a high tacticity vinyl ether polymer by means of catalytic polymerization, which relates to the technical field of polymer preparation. By means of the method for catalytically preparing a high tacticity vinyl ether polymer, a cationic polymerization reaction is carried out on one or more vinyl ether monomers under the action of a catalyst in a protective atmosphere to obtain the high tacticity vinyl ether polymer. By means of the method, polymerization is initiated by active cations generated by reacting imino phosphamide and vinyl isobutyl ether, and controllable polymerization can be achieved by the interaction of imino phosphamide anions with the active cations at the chain end, thereby providing a feasible method for preparing a vinyl ether polymer with controllable molecular weight distribution. The catalyst used in the method is an organic catalyst for efficiently preparing a high tacticity polymer, and the reaction system is simple and does not require an additional Lewis acid or alkali to be added, so that the method has many advantages such as being environmentally friendly and having easy operation.

Description

Method for catalyzing the preparation of vinyl ether polymers

technical field

The invention relates to the technical field of polymer preparation, in particular to a method for preparing vinyl ether polymers with high stereoregularity by catalytic polymerization.

Background technique

As a class of mass-produced and low-cost thermoplastic polymers, polyolefins have the advantages of low density, high tensile strength, excellent chemical stability, and easy processing and molding. To date, the total production of polyolefins accounts for 55% of the total global polymer production. However, such hydrocarbons are not well separated from other materials, thus greatly limiting their application in composites, surface coatings, adhesives, and other high-performance engineering fields. Due to these problems, research on polar thermoplastic polymers has been promoted in recent years. At present, the functional modification of polymers has not fundamentally changed the properties of polymers. It is known that there are two main methods for obtaining polar polyolefins: 1) copolymerization of α-olefin and other functional monomers, 2) commercially available Post-modification of polyolefins. For example, many commercial polymers have been prepared by copolymerizing ethylene with acetate vinyl ethers and acrylates by free radical polymerization. In order to counteract the differences in the polymerization rates of different monomers, the polymerization is usually carried out in ethylene at 1000-3000 atmospheres, Adopt an indeterminate, driven process approach. However, this method has poor control over the molecular weight, branching rate, and steric hindrance of polar groups in the prepared polymers, thus limiting the versatility and tunability of polymers. In addition, free-radical polymers cannot use alpha-olefins as monomers, which greatly limits the scope of materials. Achieving the long-standing goal of transition metal-catalyzed copolymerization of olefins with polar vinyl monomers was then hindered by catalyst poisoning due to the high oxophilicity of the early transition metals. Late transition metal catalysts are expected to achieve this goal due to their good functional group compatibility. Although considerable research has been devoted to this area, the most efficient palladium complexes of phosphine sulfonates are still relatively inactive and yield only moderately functionalized low molecular weight polymers. Late-stage functionalization of olefin polymers is also an important research area. The main commercial method is to homogenize the C-H bond of the polymer under the action of thermal decomposition of peroxide to generate carbon-containing free radicals, and maleic anhydride captures the generated free radicals to realize the functionalization of the polymer.

technical problem

Since such methods require stringent reaction conditions and substrate-controlled regioselectivity leading to unwanted side reactions, such as maleic anhydride-modified polypropylene polymer molecular weight and material lower than that of cross-linked polymer and polymer The degree of functionalization is inversely related. The currently used noble metal catalysts and expensive reaction reagents cannot achieve the purpose of industrialization. The limitation of these methods is that the introduction of polar groups can adversely affect the thermodynamic and mechanical properties of polymers and corresponding materials. Ideally, the polarity and mechanical properties of thermoplastic polymers are independent of each other, which provides an effective way to control the function of the polymer without changing the thermodynamic and mechanical properties of the polymer. Therefore, it is still necessary to develop a simple and efficient preparation of polyvinyl ethers with high stereoregularity.

technical solutions

In order to solve the above technical problems, the present invention provides a method for preparing vinyl ether polymers with high stereoregularity by catalytic polymerization. The method uses imino phosphoramide compounds to catalyze cationic polymerization of vinyl ether monomers to prepare vinyl ethers. Base ether polymer; this polymer has the characteristics of high stereoregularity, controllable molecular weight and narrow molecular weight distribution.

The present invention provides a kind of method for preparing high stereoregularity vinyl ether polymer by acid catalysis, which comprises the following steps:

In a protective atmosphere, one or more vinyl ether monomers are subjected to cationic polymerization under the action of a catalyst to obtain a vinyl ether polymer with high stereoregularity; the catalyst is selected from one of the following structural formulas or more:

In the above structure, R ^1a , R ^1b , R ^1c , R ^1d , R ^2a , R ^2b , R ^2c , R ^2d are independently selected from hydrogen, halo, cyano, cycloalkyl, heterocycloalkyl, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkyl substituted by one or more halogen atoms, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ alkyl O(C=O)-, C ₁ - C ₁₂ alkyl (C=O)O-, C ₁ ～C ₁₂ alkyl (C=O)-, C ₁ ～C ₁₂ alkyl (C=O)NH-, [C ₁ ～C ₁₂ alkyl ( C=O)] ₂ N-, silicon group, C ₆ -C ₂₀ aryl group substituted by one or more halogen atoms, C ₂ -C ₂₀ -containing heteroaryl group substituted by 1-3 heteroatoms; Rf independently selected from methanesulfonyl or halogen-substituted methanesulfonyl; the heteroatom is one or more of N, O, S.

Preferably, when R ^1a , R ^1b , R ^1c , R ^1d , R ^2a , R ^2b , R ^2c and R ^2d are independently C ₁ -C ₁₂ alkyl, the C ₁ -C ₁₂ alkyl is Linear, cyclic or branched C ₁ -C ₁₂ alkyl.

Preferably, the C ₁ -C ₁₂ alkyl group is selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, cyclopentyl , one of cyclohexyl, octyl and dodecyl.

Preferably, when R ^1a , R ^1b , R ^1c and R ^1d are independently C ₁ -C ₁₂ alkyl groups substituted by one or more halogen atoms, the halogen atom-substituted C ₁ -C ₁₂ alkyl groups are selected from One of trifluoromethyl, perfluorobutyl and perfluorooctyl.

Preferably, when R ^1a , R ^1b , R ^1c and R ^1d are independently C ₆ -C ₂₀ aryl groups substituted by one or more halogen atoms, C6 -C 20 aryl groups are selected from phenyl, naphthyl, bi One of phenyl, anthracenyl, phenanthryl, pyrenyl and perylene groups.

Preferably, when R ^1a , R ^1b , R ^1c and R ^1d are independently a C ₂ -C ₂₀ -containing heteroaryl substituted by 1-3 heteroatoms, the heteroaryl is selected from furan, thiophene, pyrrole , one of thiazole, imidazole, pyridine, pyrazine, pyrimidine and pyridazine.

Preferably, when R ^2a , R ^2b , R ^2c and R ^2d are independently halo, they are selected from bromine or iodine.

Preferably, Rf is independently selected from trifluoromethanesulfonyl, 3,5-ditrifluoromethylbenzenemethanesulfonyl, 5-fluorobenzenemethanesulfonyl, 2-perfluoronaphthylmethanesulfonyl, trifluoroethylsulfonyl One of acyl, perfluoro-n-butylmethanesulfonyl, perfluoro-n-hexylmethanesulfonyl and perfluoro-n-octylmethanesulfonyl.

Preferably, R ^1a , R ^1b , R ^1c , R ^1d are independently selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl base, cyclohexyl, trifluoromethyl, methoxy, ethoxy,

one of the.

Preferably, the catalyst is selected from one of the following structures

In the above technical solutions of the present invention, Tf is one of the specific forms of Rf, which is trifluoromethanesulfonyl.

In the above-mentioned technical scheme of the present invention,

The catalyst with binaphthyl skeleton has the same active center of bis-trifluoromethanesulfonyl phosphoramide, and there is a 2.4.6 triisopropylphenyl bulky sterically hindered substituent at the 6,6' position, which can adjust the space of the catalyst steric hindrance, so it can play the same catalytic activity and stereoselectivity.

Preferably, the catalyst is a chiral catalyst of (R) or (S) configuration.

Preferably, the vinyl ether monomer has at least one of the following structures:

Preferably, R ³ is C ₁ -C ₂₀ carbon alkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₂₀ alkyl substituted by one or more halogen atoms, cholesterol and its derivatives, C ₃ -C ₉ cycloalkyl group, C ₆ -C ₁₀ aryl group, C ₃ -C ₉ heterocycloalkyl group, C ₅ -C ₉ heterocyclic aryl group, substituted by one or more groups at the same time, the substituents are independently Selected from C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkyl simultaneously substituted by one or more halogens, C ₁ -C ₁₂ hydroxyalkyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ Aminoalkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₀ aryl, C ₃ -C ₉ heterocycloalkyl, C ₅ -C ₉ heteroaryl.

wherein R ^4a is C ₁ -C ₂₀ carbon alkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₂₀ alkyl substituted by one or more halogens, cholesterol and its derivatives, C ₃ -C ₉ Cycloalkyl, C ₆ -C ₁₀ aryl, C ₃ -C ₉ heterocycloalkyl, C ₅ -C ₉ heterocyclic aryl, substituted by one or more groups at the same time, the substituents are independently selected from C ₁ ～C ₁₂ alkyl, C ₁ ～C ₁₂ alkyl substituted by one or more halogens, C ₁ ～C ₁₂ hydroxyalkyl, C ₁ ～C ₁₂ alkoxy, C ₁ ～C ₁₂ aminoalkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₀ aryl, C ₃ -C ₉ heterocycloalkyl, C ₅ -C ₉ heterocyclic aryl, C ₅ -C substituted by one or more groups at the same time C ₉ heterocyclic aryl, wherein n has a value of 1 to 100.

Preferably, R ^5a , R ^5b , R ^5c , R ^5d and R ^5e are independently selected from C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkyl substituted by one or more halogens, C ₁ -C ₁₂ hydroxyalkyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ aminoalkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₀ aryl, C ₃ -C ₉ heterocycloalkyl, A C ₅ -C ₉ heterocyclic aryl group, or a C ₅ -C ₉ heterocyclic aryl group substituted by one or more groups at the same time.

wherein R ^6a , R ^6b , R ^6c and R ^6d are independently selected from C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkyl substituted by one or more halogens, C ₁ -C ₁₂ hydroxyalkyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ aminoalkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₀ aryl, C ₃ -C ₉ heterocycloalkyl, C ₅ -C ₉ Heterocyclic aryl, C ₅ -C ₉ heterocyclic aryl substituted by one or more groups at the same time.

wherein R ^7a , R ^7b , R ^7c and R ^7d are independently selected from C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkyl substituted by one or more halogens, C ₁ -C ₁₂ hydroxyalkyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ aminoalkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₀ aryl, C ₃ -C ₉ heterocycloalkyl, C ₅ -C ₉ heterocycloalkyl A cyclic aryl group, or a C ₅ -C ₉ heterocyclic aryl group substituted with one or more groups at the same time.

Preferably, the vinyl ether monomers are independently selected from one or more of the above structures, and a copolymer is obtained when two or more different vinyl ether monomers are polymerized.

Preferably, in the structural formula of the above vinyl ether monomer, n is 1 to 50, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 , 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41 , 42, 43, 44, 45, 46, 47, 48, 49 or 50.

Preferably, R ³ is C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₂₀ alkyl substituted by one or more halogens, cholesterol and its derivatives, C ₃ -C ₉ Cycloalkyl, C ₆ -C ₁₀ aryl, C ₃ -C ₉ heterocycloalkyl, C ₅ -C ₉ heterocyclic aryl, substituted by one or more groups at the same time, the substituents are independently selected from halogen , cyano, amino, hydroxyl, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkyl substituted by one or more halogens, C ₁ -C ₁₂ hydroxyalkyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ aminoalkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₀ aryl, C ₃ -C ₉ heterocycloalkyl, C ₅ -C ₉ heterocyclic aryl. For example, R ³ can be a C ₁ -C ₁₂ alkyl group, R ³ can be a C ₂ -C ₅ alkyl group, and R ³ can also be a C ₁₂ -C ₁₄ alkyl group.

Preferably, when R ³ is a cholesterol group and its derivatives, it can be substituted by one or more groups at the same time, and the substituents are independently selected from halogen, cyano, amino, hydroxyl, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ hydroxyalkyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ aminoalkyl, C ₃ -C ₈ cycloalkyl substituted by one or more halogens , C ₆ -C ₁₀ aryl, C ₃ -C ₉ heterocyclic alkyl, C ₅ -C ₉ heterocyclic aryl.

Preferably, R ³ is a C ₃ -C ₈ cycloalkyl group, a C ₆ -C ₁₀ aryl group, a C ₃ -C ₉ heterocycloalkyl group, and a C ₅ -C ₉ heterocyclic aryl group.

Preferably, R ³ is C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₀ aryl, C ₃ -C ₉ heterocycloalkyl or C ₅ -C ₉ heterocycle simultaneously substituted by one or more groups Aryl, the substituents are independently selected from halo, cyano, amino, hydroxy.

Preferably, R ³ is C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ hydroxyalkyl, C ₁ -C ₁₂ alkoxy, C ₁ -C 12 aminoalkyl, C 1 -C 12 alkoxy, C 1 -C ₁₂ ₃ - _C8cycloalkyl , _C6 - _C10aryl , C3 _- _{C9heterocycloalkyl} , _C5 - _C9heteroaryl .

Preferably, R ^4a is a C ₁ -C ₂₀ alkyl group simultaneously substituted by one or more groups, and the substituents are independently selected from halo, cyano, amino, hydroxyl, and C ₁ -C ₁₂ alkyl.

Preferably, R ^4a is C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ hydroxyalkyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ aminoalkyl, C 1 -C 12 alkoxy, C ₃ -C ₈ cycloalkyl, C ₆ -C ₁₀ aryl, C ₃ -C ₉ heterocycloalkyl, C ₅ -C ₉ heteroaryl. For example, R ^4a can be a C ₁ -C ₁₂ alkyl group, R ^4a can be a C ₂ -C ₅ alkyl group, and R ^4a can be a C ₂ -C ₄ alkyl group.

Further, R ^4a is C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, one or more halogen-substituted C ₁ -C ₂₀ alkyl, cholesterol and its derivatives, C ₃ -C ₉ cycloalkane group, C ₆ -C ₁₀ aryl group, C ₃ -C ₉ heterocyclic alkyl group, C ₅ -C ₉ heterocyclic aryl group.

Preferably, R ^4a is

R ^4b is a C ₆ -C ₁₀ aryl group, or a C ₆ -C ₁₀ aryl group simultaneously substituted with one or more groups, and the substituents are independently selected from halogen, cyano, amino, hydroxyl, C ₁ - C ₁₂ alkyl, C ₁ -C ₁₂ alkyl simultaneously substituted by one or more halogens, C ₁ -C ₁₂ hydroxyalkyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ aminoalkyl, C ₃ - _C8cycloalkyl , _C6 - _C10aryl , C3 _- _{C9heterocycloalkyl} , _C5 - _C9heteroaryl .

Preferably, R ^5a , R ^5b , R ^5c , R ^5d , R ^5e are independently selected from hydrogen, halo or C ₁ -C ₁₂ alkyl.

Preferably, R ^6a , R ^6b , R ^6c and R ^6d are independently selected from hydrogen, halo or C ₁ -C ₁₂ alkyl. For example, R ^6a can be a C ₁ -C ₁₂ alkyl group, for example, R ^6a can be a methyl group, and R ^6b , R ^6c and R ^6d can also be hydrogen.

Wherein, R ^7a , R ^7b , R ^7c and R ^7d are independently selected from hydrogen, halogen or C ₁ -C ₁₂ alkyl.

Preferably, the vinyl ether monomer structure is one or more of the following structures at the same time:

Preferably, the molar ratio of the vinyl ether monomer to the catalyst is 100:(0.001-5).

More preferably, the polymerization reaction time is controlled to be 5 min to 4 h.

Further preferably, the polymerization time is 10min-120min; more preferably, the polymerization time is 10min-60min.

Preferably, the reaction temperature is -78 to 25°C, more preferably, the reaction temperature is -78 to 0°C.

Preferably, the reaction process is carried out in an organic solvent; further, the organic solvent is selected from one of toluene, ethane, ethyl chloride, propane, butane, pentane, n-hexane, ethyl acetate and dichloromethane or several.

Preferably, after the reaction is complete, the steps of dissolving the obtained polymer in dichloromethane, then precipitating in methanol, filtering and drying are included.

Further, the protective atmosphere is nitrogen or argon atmosphere.

The principle of the method of the present invention is as follows:

Imidinophosphoramide (Cat) reacts with vinyl isobutyl ether to generate active cations to initiate polymerization. Steric hindrance enables control of polymer stereoselectivity.

beneficial effect

1. The present invention provides a method for preparing high stereoregularity polyvinyl ether polymer by acid-catalyzed cationic polymerization with simple components. Under suitable solvent and temperature, using iminophosphoramide compound (Cat) catalyst for The preparation of vinyl ether polymers with controllable molecular weight distribution provides an effective method. The catalyst used in the method is an organic catalyst for efficiently preparing high stereoregularity polymers, the reaction system is simple and does not need to add additional Lewis acid or base, and has many advantages such as environmental friendliness and simple operation;

2. The method of the present invention can prepare polyisobutyl vinyl ether and other vinyl ether polymers with controllable molecular weight, narrow molecular weight distribution and high stereoregularity.

Description of drawings

Fig. 1 is the GPC efflux curves (1A and 1B) of the polymers obtained under the condition that the molar ratio of [IBVE]:[Cat] is 200:1 and 200:0.2;

Fig. 2 shows the NMR (Fig. 2A) and carbon NMR (Fig. 2B) of the obtained polymer when the monomer is selected as IBVE.

BEST MODE FOR CARRYING OUT THE INVENTION

The above description is only an overview of the technical solution of the present invention. In order to understand the technical means of the present invention more clearly, and implement it according to the content of the description, the preferred embodiments of the present invention are described in detail below with the accompanying drawings.

Add the binaphthol derivative (S)-3,3'-bis(2,4,6-triisopropylphenyl)-1,1'-binaphthol (1 mmol) to a flame-dried Schlenk bottle, And dissolved in anhydrous dichloromethane (5mL), N-trifluoromethanesulfonimide phosphorus trichloride (1.1mmol) and N,N'-diisopropylethylamine (5mmol) were added successively under argon protection at room temperature The reaction was carried out for half an hour, then trifluoromethanesulfonimide (2 mmol) was added to continue the reaction at room temperature for half an hour, the filtrate was filtered to remove insolubles, and the filtrate was separated by column chromatography. After removing the solvent, the obtained solid was dissolved in dichloromethane and acidified with hydrochloric acid (3M). After removing the solvent under reduced pressure, the target product is obtained. The catalyst is (S)-3,3'-bis(2,4,6-triisopropylphenyl)-1,1'-binaphthalene-2,2'- Dinaphthyl-bis-trifluoromethanesulfonyl phosphoramide (Cat-4).

Embodiments of the present invention

The specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings and embodiments. The following examples are intended to illustrate the present invention, but not to limit the scope of the present invention.

In the following examples of the present invention, hydrogen nuclear magnetic spectrum ( ¹ H NMR), carbon spectrum ( ¹³ C NMR), fluorine spectrum ( ¹⁹ F NMR), and phosphorus spectrum ( ³¹ P NMR) were performed by Bruker 400MHz nuclear magnetic analyzer. Take CDCl ₃ or CD ₂ Cl ₂ as solvent and tetramethylsilane (TMS) as internal standard to dissolve and test; the relative molecular weight and molecular weight distribution of polymers are determined by Waters 1515 series gel permeation chromatograph (GPC), using Differential refractive index detector Waters 2414 gel column HR 4 THF (7.8×300mm) was connected in series, the molecular weight of the column was 10 ² -10 ⁶ g/mol, THF was used as the mobile phase, and the flow rate was 1.0mL/min. Measured at 40°C, molecular weights are calculated on Shodex polystyrene standards.

Catalyst synthesis method one

The binaphthol derivative (1 mmol) was added to a flame-dried Schlenk flask and dissolved in anhydrous dichloromethane (5 mL), followed by N-trifluoromethanesulfonimide phosphorus trichloride (1.1 mmol) and N,N '-Diisopropylethylamine (5mmol) was reacted under argon protection for half an hour at room temperature, then trifluoromethanesulfonimide (2mmol) was added to continue the reaction at room temperature for half an hour, and the insolubles were removed by filtration. The filtrate was separated by column chromatography to remove After the solvent, the obtained solid was dissolved in dichloromethane and acidified with hydrochloric acid (3M). The target product was obtained after the solvent was removed under reduced pressure.

Example 1

According to the above method 1, when the binaphthol derivative is (S)-3,3'-bis(phenyl)-1,1'-binaphthol, the prepared catalyst is (S)-3, 3'-Bis(phenyl)-1,1'-binaphthyl-2,2'-dinaphthyl-bis-trifluoromethanesulfonyl phosphoramide (Cat-1).

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.12 (s, 1H), 8.03 (d, J=8.3 Hz, 1H), 7.66 (d, J=7.7 Hz, 2H), 7.57 (t, J=7.6 Hz) ,1H),7.45-7.33(m,5H).

¹³ C NMR (101 MHz, CDCl ₃ ) δ 143.4, 143.3, 136.0, 133.5, 133.5, 132.1, 131.8, 131.8, 130.1, 128.7, 128.3, 128.1, 127.1, 127.0, 126.7, 122.4, 122.4.

¹⁹ F NMR (376MHz, CDCl ₃ ) δ-79.08.

³¹ P NMR (162MHz, CDCl ₃ ) δ-1.32.

Embodiment 2

According to the above method 1, when the binaphthol derivative is (S)-3,3'-bis(4-trifluoromethylphenyl)-1,1'-binaphthol, the prepared catalyst is (S)-3,3'-bis(4-trifluoromethylphenyl)-1,1'-binaphthyl-2,2'-dinaphthyl-bis-trifluoromethanesulfonyl phosphoramide (Cat- 2).

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.17 (s, 1H), 8.07 (d, J=8.3 Hz, 1H), 7.77 (q, J=8.3 Hz, 4H), 7.63 (t, J=7.1 Hz ,1H),7.42(s,2H).

¹³ C NMR (151MHz, CD ₂ Cl ₂ ) δ 142.6, 142.5, 139.2, 132.7, 132.3, 132.1, 131.8, 130.5, 130.3, 130.1, 129.9, 128.9, 127.8, 127.4, 127.0, 125.4, 122.2, 126.4. ,118.8(q,J=322.2Hz).

¹⁹ F NMR (376MHz, CDCl ₃ ) δ-62.65,-78.50.

³¹ P NMR (162MHz, CDCl ₃ ) δ-5.61.

Embodiment 3

According to the above method 1, when the binaphthol derivative is (S)-3,3'-bis(3,5-bistrifluoromethylphenyl)-1,1'-binaphthol, the The catalyst is (S)-3,3'-bis(3,5-bistrifluoromethylphenyl)-1,1'-binaphthyl-2,2'-dinaphthyl-bistrifluoromethanesulfonate Acyl phosphoramide (Cat-3).

¹ H NMR (400 MHz, CD ₂ Cl ₂ ) δ 8.25 (s, 2H), 8.17 (d, J=1.6 Hz, 4H), 8.14 (dd, J=8.4, 1.1 Hz, 2H), 8.00 (d, J=1.8Hz, 2H), 7.68 (ddd, J=8.1, 6.4, 1.4Hz, 2H), 7.52–7.41 (m, 4H).

¹³ C NMR(126MHz,CD ₂ Cl ₂ )δ142.38,142.29,137.66,132.83,132.25,132.16,131.90,131.64,131.37,130.43,130.41,130.28,130.25,128.97,128.15,127.54,126.90,126.51,124.34,122.36 ,122.34,122.21,122.18,122.15,122.12,122.09,120.01,119.96,117.47.

¹⁹ F NMR (371 MHz, CD ₂ Cl ₂ ) δ–63.4 (12F),–76.2 (6F).

³¹ P NMR (203MHz, CD ₂ Cl ₂ )δ–3.7.

Embodiment 4

According to the above method 1, when the binaphthol derivative is (S)-3,3'-bis(2,4,6-triisopropylphenyl)-1,1'-binaphthol, the The obtained catalyst is (S)-3,3'-bis(2,4,6-triisopropylphenyl)-1,1'-binaphthyl-2,2'-dinaphthyl-bistrifluoro Methylsulfonyl phosphoramide (Cat-4).

¹ H NMR (400 MHz, CD ₂ Cl ₂ ) δ 7.98-7.95 (m, 2H), 7.92 (s, 2H), 7.53 (ddd, J=8.0, 6.7, 1.0 Hz, 2H), 7.30 (ddd, J =8.3,6.8,1.3Hz,2H),7.18(d,J=1.8Hz,2H),7.12–7.06(m,4H),2.95(hept,J=6.8Hz,2H),2.87(hept,J= 6.5Hz, 2H), 2.58 (hept, J=6.8Hz, 2H), 1.29 (dd, J=6.9, 1.2Hz, 12H), 1.25 (t, J=6.8Hz, 12H), 1.11 (d, J= 6.8Hz,6H),0.89(d,J=6.8Hz,6H).

¹³ C NMR(126MHz,CD ₂ Cl ₂ )δ149.04,147.53,147.42,145.15,145.07,133.20,132.47,131.21,131.16,131.12,130.77,128.20,126.68,126.65,126.10,121.14,121.12,121.10,120.35,34.38 ,30.90,30.80,26.37,24.72,23.75,23.66,22.94,21.82,19.05,18.96.

¹⁹ F NMR (371 MHz, CD ₂ Cl ₂ ) δ–79.4.

³¹ P NMR (203MHz, CD ₂ Cl ₂ )δ–1.7.

Embodiment 5

According to the above method 1, when the binaphthol derivative is (S)-3,3'-bis(2-naphthyl)-1,1'-binaphthol, the prepared catalyst is (S)- 3,3'-Bis(2-naphthyl)-1,1'-binaphthyl-2,2'-dinaphthyl-bis-trifluoromethanesulfonyl phosphoramide (Cat-5).

¹ H NMR (400MHz, CDCl ₃ ) δ 8.26(s, 1H), 8.16(s, 1H), 8.08(d, J=8.3Hz, 1H), 7.97-7.81(m, 3H), 7.77(d, J=8.5Hz, 1H), 7.62 (t, J=7.6Hz, 1H), 7.54–7.38 (m, 4H).

¹³ C NMR (151 MHz, CD ₂ Cl ₂ ) δ 143.0, 142.9, 133.3, 133.2, 133.2, 133.0, 132.8, 132.7, 132.5, 131.9, 129.6, 128.8, 128.3, 128.0, 127.6, 127.5, 127.4, 127.2, 127.2. ,118.8(q,J=321.6Hz).

¹⁹ F NMR (376MHz, CDCl ₃ ) δ-78.57.

³¹ P NMR (162MHz, CDCl ₃ ) δ-3.46.

Catalyst synthesis method two

The binaphthol derivative (1 mmol) was added to a flame-dried Schlenk bottle and dissolved in toluene (5 mL), followed by N-trifluoromethanesulfonimide phosphorus trichloride (1.1 mmol) and N,N'-diiso Propylethylamine (5mmol) was reacted under argon protection for half an hour at room temperature, and then hexamethylsilazane (1mmol) was added to continue the reaction at room temperature for half an hour, then the temperature was raised to 120 ° C and reacted for 2 days, and the reaction was quenched with dilute hydrochloric acid , filtered to remove insolubles, and the filtrate was separated by column chromatography. After removing the solvent, the solid obtained was dissolved in dichloromethane and acidified with hydrochloric acid (3M). The target product was obtained after the solvent was removed under reduced pressure.

Embodiment 6

According to the above method 2, when the binaphthol derivative is (S)-3,3'-bis(phenyl)-1,1'-binaphthol, the prepared catalyst is (S,S)- 3,3'-Diphenyl-[1,1'-Binaphthalene]-2,2'-Dinaphthalene-N'-P,P-Dinaphthyloxy-N-(trifluoromethanesulfonyl)imino Bisphosphonimide (Cat-6).

¹ H NMR (400 MHz, CD ₂ Cl ₂ ) δ 8.14-8.12 (m, 4H), 8.06 (d, J=8.2 Hz, 2H), 7.83 (t, J=7.4 Hz, 2H), 7.68-7.57 ( m, 6H), 7.45–7.29 (m, 16H), 7.21–7.18 (m, 2H), 7.00 (t, J=7.5Hz, 4H), 6.48 (d, J=7.7Hz, 4H).

¹⁹ F NMR (376MHz, CD ₂ Cl ₂ ) δ-78.55.

³¹ P NMR (162Hz, CD ₂ Cl ₂ ) δ-16.76.

Embodiment 7

According to the above method 2, when the binaphthol derivative is (S)-3,3'-bis(4-tert-butylphenyl)-1,1'-binaphthol, the prepared catalyst is ( S,S)-3,3'-bis(4-tert-butylphenyl)-[1,1'-binaphthyl]-2,2'-dinaphthyl-N'-P,P-dinaphthyloxy -N-(trifluoromethanesulfonyl)iminobisphosphonimide (Cat-7).

¹ H NMR (400 MHz, CD ₂ Cl ₂ ) δ 8.19 (s, 2H), 8.11 (dd, J=16.6, 8.3 Hz, 4H), 7.88-7.84 (m, 2H), 7.674-7.665 (m, 4H) ), 7.61(t, J＝6.8Hz, 2H), 7.41-7.39(m, 8H), 7.33-7.29(m, 6H), 7.03(d, J＝7.9Hz, 4H), 6.62(d, J＝ 7.9Hz, 4H), 1.33(s, 18H), 1.12(s, 18H).

¹⁹ F NMR (376MHz, CD ₂ Cl ₂ ) δ-78.53.

³¹ P NMR (162MHz, CD ₂ Cl ₂ ) δ-16.07.

Embodiment 8

According to the above method 2, when the binaphthol derivative is (S)-3,3'-bis(3,5-dimethylphenyl)-1,1'-binaphthol, the prepared catalyst is (S,S)-3,3'-bis(3,5-dimethylphenyl)-[1,1'-binaphthyl]-2,2'-dinaphthalene-N'-P,P- Dinaphthyloxy-N-(trifluoromethanesulfonyl)iminobisphosphonimide (Cat-8).

¹ H NMR (400 MHz, CD ₂ Cl ₂ ) δ 8.11 (s, 2H), 8.04 (d, J=8.2 Hz, 2H), 7.90-7.88 (m, 2H), 7.85-7.81 (m, 2H), 7.75–7.72 (m, 2H), 7.67–7.60 (m, 2H), 7.56 (t, J=7.4Hz, 2H), 7.34–7.31 (m, 2H), 7.28–7.26 (m, 2H), 6.97 ( d, J=17.4Hz, 4H), 6.89(s, 4H), 6.69(s, 2H), 6.49(s, 4H), 2.28(s, 12H), 2.02(s, 12H).

¹⁹ F NMR (376MHz, CD ₂ Cl ₂ ) δ-79.17.

³¹ P NMR (162MHz, CD ₂ Cl ₂ ) δ-17.93.

Embodiment 9

According to the above method 2, when the binaphthol derivative is (S)-3,3'-bis(3,5-diethylphenyl)-1,1'-binaphthol, the prepared catalyst is (S,S)-3,3'-bis(3,5-diethylphenyl)-[1,1'-binaphthyl]-2,2'-dinaphthalene-N'-P,P- Dinaphthyloxy-N-(trifluoromethanesulfonyl)iminobisphosphonimide (Cat-9).

¹ H NMR (400 MHz, CD ₂ Cl ₂ ) δ 8.10-8.04 (m, 4H), 7.92-7.90 (m, 2H), 7.83-7.80 (m, 2H), 7.71-7.69 (m, 2H), 7.64 –7.60(m,2H),7.55(t,J=7.3Hz,2H),7.32-7.30(m,2H),7.27-7.25(m,2H),7.01-6.99(m,4H),6.91(s) ,4H),6.65(s,2H),6.54(s,4H),2.59–2.50(m,8H),2.39–2.30(m,8H),1.23(t,J=7.6Hz,12H),1.01( t,J=7.6Hz,12H).

¹⁹ F NMR (376MHz, CD ₂ Cl ₂ ) δ-79.06.

³¹ P NMR (162MHz, CD ₂ Cl ₂ ) δ-17.27.

Embodiment ten

According to the above method 2, when the binaphthol derivative is (S)-3,3'-bis(3,5-bistrifluoromethylphenyl)-1,1'-binaphthol, the The catalyst is (S,S)-3,3'-bis(3,5-ditrifluoromethylphenyl)-[1,1'-binaphthyl]-2,2'-dinaphthalene-N'- P,P-Dinaphthyloxy-N-(trifluoromethanesulfonyl)iminobisphosphonimide (Cat-10).

¹ H NMR (400 MHz, CD ₂ Cl ₂ ) δ 8.11-8.08 (m, 4H), 7.95-7.89 (m, 4H), 7.84 (d, J=8.5 Hz, 4H), 7.77-7.70 (m, 8H) ), 7.61(t, J＝7.5Hz, 2H), 7.39-7.35(m, 6H), 7.20-7.17(m, 2H), 6.66(s, 2H).

¹⁹ F NMR (376MHz, CD ₂ Cl ₂ ) δ-60.78, -61.27, -77.86.

³¹ P NMR (162MHz, CD ₂ Cl ₂ ) δ-13.11.

Embodiment 11

According to the above method 2, when the binaphthol derivative is (S)-3,3'-bis(9,9-dimethylfluorenyl)-1,1'-binaphthol, the

The catalyst is (S,S)-3,3'-bis(9,9-dimethylfluorenyl)-[1,1'-binaphthyl]-2,2'-binaphthalene-N'-P, P-Dinaphthyloxy-N-(trifluoromethanesulfonyl)iminobisphosphonimide (Cat-11).

¹ H NMR (400 MHz, CD ₂ Cl ₂ ) δ 8.14-8.05 (m, 6H), 7.90-7.84 (m, 4H), 7.75-7.70 (m, 2H), 7.61 (d, J=7.3 Hz, 4H) ), 7.52 (s, 2H), 7.44–7.42 (m, 10H), 7.35–7.32 (m, 2H), 7.28–7.22 (m, 10H), 7.08 (s, 2H), 6.76 (d, J=7.4 Hz, 2H), 6.59(d, J＝7.8Hz, 2H), 6.38(d, J＝6.9Hz, 2H), 1.49(s, 6H), 1.41(s, 6H), 1.24(s, 6H), 1.16(s,6H).

¹⁹ F NMR (376MHz, CD ₂ Cl ₂ ) δ-78.66.

³¹ P NMR (162MHz, CD ₂ Cl ₂ ) δ-17.15.

Embodiment 12

According to the above method 2, when the binaphthol derivative is (S)-3,3'-bis(2-naphthyl)-1,1'-binaphthol, the prepared catalyst is (S,S )-3,3'-bis(2-naphthyl)-[1,1'-binaphthyl]-2,2'-dinaphthyl-N'-P,P-dinaphthyloxy-N-(trifluoro Methylsulfonyl)iminobisphosphonimide (Cat-12).

¹ H NMR (400 MHz, CD ₂ Cl ₂ ) δ 8.19-8.08 (m, 6H), 7.99-7.91 (m, 4H), 7.83-7.75 (m, 4H), 7.65-7.56 (m, 8H), 7.51 –7.49(m,2H),7.45-7.42(m,4H),7.38-7.31(m,10H),7.25-7.19(m,6H),6.63(d,J=8.6Hz,2H),6.13(d , J=8.8Hz, 2H).

¹⁹ F NMR (376MHz, CD ₂ Cl ₂ ) δ-78.88.

³¹ P NMR (162MHz, CD ₂ Cl ₂ ) δ-17.08.

Embodiment thirteen

According to the above method 2, when the binaphthol derivative is (S)-3,3'-bis(biphenyl)-1,1'-binaphthol, the prepared catalyst is (S,S) -3,3'-bis(4-phenylphenyl)-[1,1'-binaphthyl]-2,2'-dinaphthalene-N'-P,P-dinaphthyloxy-N-(tri- Fluoromethanesulfonyl)iminobisphosphonimide (Cat-13).

¹ H NMR (400 MHz, CD ₂ Cl ₂ ) δ 8.19 (d, J=8.2 Hz, 2H), 8.16-8.07 (m, 4H), 7.87 (t, J=7.4 Hz, 2H), 7.79 (d, J=8.6Hz, 2H), 7.72-7.65(m, 2H), 7.62(t, J=7.4Hz, 2H), 7.54-7.32(m, 22H), 7.32-7.13(m, 16H), 6.66(d ,J=7.8Hz,4H).

¹⁹ F NMR (376MHz, CD ₂ Cl ₂ ) δ-78.58.

³¹ P NMR (162MHz, CD ₂ Cl ₂ ) δ-16.00.

Synthetic method of polymers

Take 15 20mL fully dried Schlenk reaction tubes and protect with argon. Add vinyl isobutyl ether (IBVE) and reaction solvent to 15 of them, and at the same time, add different catalysts (Cat) and polymerization solvent to another 15 dry Schlenk reaction tubes of 4 mL to dissolve, wherein, [IBVE]0: The molar ratio of [Cat]0 was 200:1, the volume of monomeric IBVE was 0.26 mL, and the volume of solvent was 5 mL. The reaction tube was placed in a low temperature reactor at a predetermined temperature (-78°C) for 15 minutes. Under argon protection, the catalyst solution was added to the monomer solution with a syringe to initiate polymerization. After the predetermined reaction time, cation exchange resin was added and stirred for 30 minutes to remove insoluble matter. The filtrate was decompressed to remove the solvent, and the residue was removed. A small amount of dichloromethane was added to dissolve and the obtained solution was added dropwise to a large amount of methanol for sedimentation, and the vinyl ether polymer was collected after suction filtration, and the obtained polymer was dried in a vacuum oven.

Effects of Different Catalysts on Polymerization Results

Using different catalysts, the effects of a series of catalysts on the polymerization results were investigated under the same experimental conditions.

Table 1 Influence of different catalysts on polymerization results

Table 1 shows the polymerization results of different catalysts under the above conditions. In Table 1, the calculation formula of theoretical molecular weight (Mn, theo) is as follows: [M]0/[Cat]0×conversion rate×M+M(Et2NH), That is, [monomer]0/[catalyst]0×conversion rate×monomer molar mass+terminal molar mass (Et2NH).

According to the results in Table 1, polymers with different regularity can be prepared when the catalyst in the present invention is used. When catalyst 4 is used as the catalyst, a polymer with high regularity can be obtained, and the m value of the polymer is 92%. Under the same reaction conditions, using the achiral catalyst bis-trifluoromethanesulfonimide (HNTf2) as the catalyst can only obtain polymers with low molecular weight and low regularity. Influence of Different Vinyl Ether Monomers on Polymerization Results

According to the experimental results obtained in Table 1, the best catalyst 4 was used as the catalyst, and the effects of a series of vinyl ether monomers on the polymerization results were investigated under the same experimental conditions.

Table 2 Polymerization results with different monomers

According to Table 2, it can be seen that polymers (m) with better regularity can be obtained for straight-chain vinyl ethyl ether, vinyl propyl ether and vinyl butyl ether, which proves that the best catalyst in the present invention has better The substrate adaptability and good application prospect. Fig. 2 shows the NMR (Fig. 2A) and carbon NMR (Fig. 2B) of the obtained polymer when the monomer is selected as IBVE.

The effect of different temperatures on polymerization results

Table 3 Polymerization results at different temperatures

According to the experimental results given in Table 3, it can be seen that the temperature of the polymerization reaction plays a crucial role in the regularity of the polymer. With the decrease of the reaction temperature, the dispersibility and regularity of the obtained polymer gradually increased, and the polymer with the highest regularity could be obtained when the reaction was carried out at -78°C.

Effects of different solvent concentrations on polymerization results

According to the experimental results obtained in Table 1, the best catalyst 4 was used as the catalyst, and the effects of a series of solvents on the polymerization results were investigated under the same experimental conditions; The effects of different solvent concentrations on the polymerization results were investigated.

Table 4 Polymerization results with different solvents

According to the results in Table 4, it can be seen that the solvent and monomer concentration of the polymerization reaction can also affect the regularity of the obtained polymer. When non-polar toluene and n-hexane are used as solvents, highly regulated polymers can be obtained, and the m value of the polymer is up to 92%. The polar solvent is unfavorable to the regularity of the polymer. For example, when dichloromethane is used as the solvent, the regularity of the polymer is obviously reduced, and the m value of the polymer is only 80%. When a one-to-one mixture of toluene and hexane is used as the solvent, the regularity of the polymer is comparable to that when toluene is used as the solvent, but the molecular weight distribution of the polymer is narrowed. In addition, when the one-to-one mixture of dichloromethane and n-hexane is used as the solvent, the regularity of the polymer is still low. The concentration of the polymer reaction has also been proved to affect the regularity of the obtained polymer. It can be seen from the table that with the decrease of the reaction concentration, the regularity rate of the obtained polymer gradually increases. When the reaction concentration is 0.05mol/L, the obtained polymer The regularity is the highest, and the m value is up to 95%.

Effects of Different Catalyst Amounts on Polymerization Results

According to the experimental results obtained in Table 1, the best catalyst 4 was used as the catalyst, and the effects of different catalyst dosages on the polymerization results were investigated under the same experimental conditions. Figure 1 shows the GPC efflux curves (1A and 1B) of the polymers obtained at molar ratios of [IBVE]:[Cat] of 200:1 and 200:0.2.

Table 5 The effect of different catalyst dosages on the degree of polymerization

From the results in Table 5, it can be seen that polymers with different degrees of polymerization can be obtained by adjusting the ratio of monomer to catalyst, that is, changing the amount of catalyst used. Up to 160000g/mol.

Claims

A method for catalyzing the preparation of vinyl ether polymers, comprising the following steps: subjecting one or more vinyl ether monomers to a cationic polymerization reaction under the action of a catalyst to obtain vinyl ether polymers; it is characterized in that: The catalyst is selected from one or more of the following structural formulas:

In the above structure, R1a, R1b, R1c, R1d, R2a, R2b, R2c, R2d are independently selected from hydrogen, halo, cyano, cycloalkyl, heterocycloalkyl, C1-C12 alkyl, one or more C1-C12 alkyl, C1-C12 alkoxy, C1-C12 alkyl O(C=O)-, C1-C12 alkyl (C=O)O-, C1-C12 alkyl ( C=O)-, C1-C12 alkyl (C=O)NH-, [C1-C12 alkyl (C=O)]2N-, silicon group, C6-C20 aryl substituted by one or more halogen atoms base, C2-C20-containing heteroaryl substituted by 1-3 heteroatoms; Rf is methanesulfonyl or methanesulfonyl substituted by halogen atoms; the heteroatom is one or more of N, O, S kind.
The method for catalyzing the preparation of vinyl ether polymers according to claim 1, wherein when R1a, R1b, R1c, R1d, R2a, R2b, R2c, and R2d are independently C1-C12 alkyl groups, the The C1-C12 alkyl groups mentioned are straight-chain, cyclic or branched C1-C12 alkyl groups.
The method for catalyzing the preparation of vinyl ether polymers according to claim 2, wherein the C1-C12 alkyl groups are methyl, ethyl, propyl, isopropyl, n-butyl, secondary One of butyl, isobutyl, tert-butyl, pentyl, cyclopentyl, cyclohexyl, octyl, dodecyl.
The method for catalyzing the preparation of vinyl ether polymers according to claim 1, wherein when R1a, R1b, R1c, and R1d are independently C1-C12 alkyl groups substituted by one or more halogen atoms, the halogen The atom-substituted C1-C12 alkyl group is selected from one or more of trifluoromethyl, perfluorobutyl and perfluorooctyl.
The method for catalyzing the preparation of vinyl ether polymers according to claim 1, wherein when R1a, R1b, R1c and R1d are independently C6-C20 aryl groups substituted by one or more halogen atoms, C6- The C20 aryl group is selected from one or more of phenyl, naphthyl, biphenyl, anthracenyl, phenanthryl, pyrenyl, and perylene.
The method for catalyzing the preparation of vinyl ether polymers according to claim 1, wherein when R1a, R1b, R1c, and R1d are independently C2-C20-containing heteroaryl groups substituted by 1-3 heteroatoms, The heteroaryl group is selected from one or more of furan, thiophene, pyrrole, thiazole, imidazole, pyridine, pyrazine, pyrimidine and pyridazine.
The method for catalyzing the preparation of vinyl ether polymers according to claim 1, wherein when R2a, R2b, R2c and R2d are independently halogen, they are selected from bromine or iodine.
The method for catalyzing the preparation of vinyl ether polymers according to claim 1, wherein Rf is independently selected from trifluoromethanesulfonyl, 3,5-ditrifluoromethylbenzenemethanesulfonyl, 5-fluorobenzene One of methanesulfonyl, 2-perfluoronaphthylmethanesulfonyl, trifluoroethylsulfonyl, perfluoro-n-butylmethanesulfonyl, perfluoro-n-hexylmethanesulfonyl and perfluoro-n-octylmethanesulfonyl.
The method for catalyzing the preparation of vinyl ether polymers according to claim 1, wherein: R1a, R1b, R1c, R1d are independently selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, methyl, ethyl propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl, trifluoromethyl, methoxy, ethoxy,

one of the.
The method for catalyzing the preparation of vinyl ether polymers according to claim 1, wherein the catalyst is selected from one of the following structures
The method for catalyzing the preparation of vinyl ether polymers according to claim 1, wherein the molar ratio of the vinyl ether monomers to the catalyst is 100:(0.0001-5).
The method for catalyzing the preparation of vinyl ether polymers according to claim 1, wherein the polymerization reaction is carried out in an organic solvent, and the organic solvent is selected from the group consisting of toluene, ethane, ethyl chloride, propane, butane , one or more of pentane, n-hexane, cyclohexane, ethyl acetate and dichloromethane.
The method for catalyzing the preparation of vinyl ether polymers according to claim 1, wherein the polymerization reaction is carried out at a temperature of -78°C to 25°C.
The method for catalyzing the preparation of vinyl ether polymers according to claim 1, wherein the polymerization reaction is carried out under the protection of an inert gas.