Process for the preparation of a catalyst and its use in the preparation of polar cyclic olefin polymers

Abstract

The present application relates to the technical field of olefin polymerization (IPC classification number is C08F210 / 02), and particularly relates to a preparation method of a catalyst and application of the catalyst in preparation of polar cyclic olefin polymers, the preparation method comprises the following steps: adding benzene series, pyridine, a nickel source and a ligand into a container, stirring and reacting at normal temperature, filtering after the reaction is completed, and freeze-drying the filtrate to obtain the catalyst, the weight ratio of the benzene series, the pyridine, the nickel source and the ligand is (0.1-0.4):(7-10):(0.7-1.0):(2.5-3.0). The prepared catalyst improves the polymerization activity on the basis of the prior art, the prepared polymer has high molecular weight and high comonomer insertion rate, the catalytic system has strong water and oxygen resistance, harsh material purification is not needed, oxygen and water are not needed to be removed in the polymerization process, and complex industrial equipment conditions are avoided.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of olefin polymerization (IPC classification number C08F210 / 02), in particular to a preparation method of a catalyst and application of the catalyst in preparation of a polar cyclic olefin polymer. BACKGROUND

[0002] Cyclic olefin copolymer (COC) has excellent optical performance, low dielectric constant, good barrier property, high purity and other advantages, and is valued in the fields of optics, packaging, medical treatment, electronic products and the like. Commercially available conventional cyclic olefin copolymers are mostly non-polar polymers, which have the disadvantages of poor adhesion, poor printing effect, insufficient compatibility with other polymer materials and the like. In the production of cyclic olefin polymers, the addition of polar groups to prepare cyclic olefin copolymers with polar groups is an effective method to solve the shortcomings of the current COC, improve the physical and chemical properties thereof and broaden the application range thereof.

[0003] In 1995, Brookhart discovered that a diimine-coordinated post-transition metal catalyst could catalyze the copolymerization of ethylene and polar monomers, in 2000, Grubbs discovered a salicylaldimine catalyst that could catalyze the copolymerization of ethylene and polar norbornene, and in 2002, Drent et al. discovered that a phosphine sulfonic acid-coordinated catalyst could catalyze the copolymerization of olefins and polar monomers, but the above catalysts have the defects of low polymerization activity, low molecular weight of the polymer and insufficient insertion rate of the comonomer, resulting in the cyclic olefin copolymer lacking the necessary physical properties and being limited in application.

[0004] Chinese patent CN114395063A discloses a cyclic olefin copolymer with polar groups and a preparation method, by introducing polar cyclic units, the compatibility and adhesion during use of the material can be promoted, by controlling the structure of the non-polar units and the polar units, high light transmittance can be ensured under different ethylene-based chain-like unit copolymers, high optical performance is provided, the glass transition temperature can be adjusted in a wide range, however, in some application scenarios with high requirements for the polarity of the copolymer, such as when printing the polymer on the surface of a film, the above technical solution shows poor compatibility with the film material, on the basis of this research, the present application further develops a new catalyst suitable for the system, which is dedicated to improving the adhesion of the polymer and the compatibility with other polymer materials. SUMMARY

[0005] The first aspect of the present application provides a preparation method of a catalyst, the preparation method comprising: adding a benzene series, pyridine, a nickel source and a ligand into a container, stirring the reaction at room temperature, filtering after the reaction is completed, and freeze-drying the filtrate to obtain the catalyst, the weight ratio of the benzene series, the pyridine, the nickel source and the ligand being (0.1-0.4):(7-10):(0.7-1.0):(2.5-3.0).

[0006] As a preferred embodiment, the weight ratio of the benzene series, pyridine, nickel source, ligand is (0.1-0.3):(7-9):(0.7-1.0):(2.6-3.0).

[0007] Further preferably, the weight ratio of the benzene series, pyridine, nickel source, ligand is 0.2:8:0.9:(2.6-3.0).

[0008] As a preferred embodiment, the benzene series includes at least one of benzene, toluene, ethylbenzene, xylene, mesitylene, styrene, phenol, aniline, chlorobenzene, nitrobenzene.

[0009] The present application selects benzene series as benzene source, preferably toluene.

[0010] As a preferred embodiment, the nickel source includes at least one of tetramethyl ethylenediamine dimethyl nickel (CAS 122905-76-4), bis((2-dimethylamino)phenyl)amine nickel (II) chloride (CAS: 1033772-47-2), (N,N'-propylalkene(2-pyrrolylmethylidene amine)) nickel (II) (CAS: 15158-90-4), 3-(anilino methyl)-1,3-benzoxazol-2-ketone nickel dithiocyanate (CAS: 82498-00-8).

[0011] Preferably, the nickel source is tetramethyl ethylenediamine dimethyl nickel.

[0012] Preferably, the preparation method of the catalyst includes: adding toluene, pyridine, tetramethyl ethylenediamine dimethyl nickel, ligand in a container, stirring at room temperature (25±1℃), gas release can be seen during the reaction, and the solution gradually turns yellow. No gas release is the end of the reaction, the system is filtered, and the filtrate is freeze-dried to obtain a yellow catalyst.

[0013] As a preferred embodiment, the ligand has any one of the structural formulas of formula (1)-formula (5), all of which are provided by Anjie Chemical Co., Ltd.

[0014]

[0015]

[0016] As a preferred embodiment, the yield of the catalyst is greater than 90%.

[0017] The catalyst obtained by the preparation method has a yield of greater than 90%, high reaction efficiency, and high polymerization activity, high polymer molecular weight, and high comonomer insertion rate in the polymerization of a cyclic olefin copolymer. In addition, a conventional cyclic olefin copolymer catalyst system is sensitive to water and oxygen, resulting in a complex water removal process during production and a decrease in the performance of the prepared copolymer. The catalyst and catalyst system of the present application have strong resistance to water and oxygen, do not require oxygen and water removal during polymerization, and do not require the use of an alkyl aluminum compound as a impurity remover.

[0018] The second aspect of the present application provides a catalyst obtained by the preparation method of the catalyst for preparing a polar cyclic olefin polymer, the preparation method of the cyclic olefin copolymer comprising: polymerizing a vinyl monomer A, a non-polar monomer B, and a polar monomer under the catalyst at 0-150°C and 0.01-10 MPa to obtain a cyclic olefin copolymer.

[0019] As a preferred embodiment, the molar percentage of the vinyl monomer A is 70-99 mol%, the molar percentage of the non-polar monomer B is 0-30 mol%, and the molar percentage of the polar monomer is 0-30 mol%, and the non-polar monomer B and the polar monomer are not 0 mol% at the same time.

[0020] The applicant found that the addition of each monomer in the above proportions has higher polymerization activity in the present catalyst system, and the prepared cyclic olefin copolymer has better compatibility with other polymers. Through data verification, it was found that the prepared polymer has a lower B monomer content and higher flexibility.

[0021] The structure of the vinyl monomer A is shown in formula (1):

[0022]

[0023] R1 is hydrogen, C1-C10 alkyl;

[0024] The structure of the non-polar monomer B is shown in formula (2):

[0025]

[0026] m is 0, 1, R2 is selected from hydrogen, C1-C10 alkyl, C6-C10 aryl, and R3 is selected from one or more of hydrogen, C1-C10 alkyl, and C6-C10 aryl.

[0027] As a preferred embodiment, the polar monomer is a mono-substituted polar monomer C and / or a di-substituted polar monomer D, and the sum of the molar percentages of the non-polar monomer B and the polar monomers C and D is 1-30 mol%.

[0028] The structure of the monosubstituted polar monomer C is shown in formula (3) as follows:

[0029]

[0030] n is 0 or 1, R4 is selected from one or more of halogen, hydroxyl, carboxyl, cyano, acetoxy, -R7OH, -COOR8, -OR9;

[0031] The structure of the disubstituted polar monomer D is shown in formula (4) as follows:

[0032]

[0033] p is 0 or 1, R 5 is selected from one or more of halogen, hydroxyl, carboxyl, cyano, acetoxy, -R 7 OH, -COOR 8 , -OR9, R6 is selected from one or more of halogen, hydroxyl, carboxyl, cyano, acetoxy, -R7OH, -COOR8, -OR9; R7 is C1-C6 alkyl, R8 is C1-C4 alkyl, and R9 is C1-C4 alkyl.c and d are respectively polar norbornene or tetracyclododecene with monofunctional or bifunctional groups and derivatives thereof, wherein R4, R5 and R6 in c and d can be listed as -F, -Cl, -Br, -COOH, -COOCH3, -OH, -CH3OH, -CH2CH2OH, -(CH2)4OH, -OCH3, -OCH2CH3, -OC(CH3)3, -OOCCH3, -CN.

[0034] As a preferred embodiment, the molecular weight of the cyclic olefin copolymer is 50000-500000.

[0035] Compared with the prior art, the present application has the following beneficial effects:

[0036] 1. The catalyst prepared in the present application improves the polymerization activity on the basis of the prior art, and the prepared polymer has high molecular weight and high comonomer insertion rate.

[0037] 2. The cyclic olefin copolymer prepared in the present application is suitable for application scenarios with high requirements for the polarity of the copolymer, and is particularly suitable for the printing field of film materials, has high printing coating viscosity, good adhesion, and good compatibility with film materials.

[0038] 3. The cyclic olefin copolymer prepared in the present application has low requirements for monomers, and can be prepared to have a low cyclic olefin unit content within a wide range of monomer ratios, which is convenient for process control in production.

[0039] 4. The catalytic system of the present application has strong resistance to water and oxygen, and does not need harsh material purification and oxygen and water removal during polymerization, thereby avoiding complex industrial equipment conditions.

[0040] 5. The preparation process of the present application is simple, and has low requirements for reaction conditions, and is suitable for industrial production. DETAILED DESCRIPTION

[0041] Example 1

[0042] The first aspect of the present embodiment provides a preparation method of a catalyst, which comprises: adding 200 mL of a benzene series, 8.0 g of pyridine, 0.9 g of a nickel source, and 2.9 g of a ligand into a container, stirring the reaction at room temperature (25±1℃), and stopping the reaction when no gas is released in the reaction system. After the reaction is completed, the reaction solution is filtered and freeze-dried to obtain 3.3 g of a yellow catalyst C-1 with a yield of 92%.

[0043] The benzene series is toluene, and the nickel source is tetramethylethylenediamine dimethyl nickel.

[0044] The structural formula of the ligand is

[0045] The structural formula of the prepared catalyst is

[0046] The second aspect of the present embodiment provides an application of a catalyst obtained by the preparation method of the catalyst in the preparation of a polar cyclic olefin polymer, and the preparation method of the cyclic olefin copolymer comprises:

[0047] S1. Under the protection of nitrogen, 42 mL of a 2.0 mol / L solution of a norbornene monomer (B) in toluene and 25 mL of a 1.0 mol / L solution of a 5-hydroxy-2-norbornene monomer (C) in toluene are added into a reaction kettle, and stirring is performed at 500 r / min, and 20 g of ethylene (A) is introduced;

[0048] S2. The pressure in the system is increased to 5 MPa, and the system is balanced at 70℃ for 30 minutes, 2 mL of a toluene solution containing 2 μmol of the catalyst C-1 is added, the temperature and pressure of the system are kept unchanged, and the polymerization reaction is performed for 0.5 hours, then the stirring is stopped, the temperature of the reaction kettle is reduced to room temperature (25±1℃), and the pressure is released;

[0049] S3. The reaction solution is added into anhydrous ethanol and stirred, the precipitated polymer is filtered, and dried in a vacuum oven at 80℃ until the weight is constant to obtain a cyclic olefin copolymer.

[0050] Example 2

[0051] The first aspect of the present embodiment provides a preparation method of a catalyst, which is the same as that of Example 1, except that

[0052] The structural formula of the ligand is

[0053] The structural formula of the prepared catalyst is 3.1 g of yellow catalyst C-2 was obtained with a yield of 96%.

[0054] The second aspect of this embodiment provides an application of a catalyst obtained by the catalyst preparation method in the preparation of a polar cycloolefin polymer. The preparation method of the cycloolefin copolymer is the same as that of Example 1, except that the added catalyst is catalyst C-2.

[0055] Example 3

[0056] The first aspect of this embodiment provides a method for preparing a catalyst. The preparation method is the same as that of Example 1, except that:

[0057] The structural formula of the ligand is

[0058] The structural formula of the prepared catalyst is 2.7 g of yellow catalyst C-3 was obtained with a yield of 94%.

[0059] The second aspect of this embodiment provides an application of a catalyst obtained by the catalyst preparation method in the preparation of a polar cycloolefin polymer. The preparation method of the cycloolefin copolymer is the same as that of Example 1, except that the added catalyst is catalyst C-3.

[0060] Example 4

[0061] The first aspect of this embodiment provides a method for preparing a catalyst, which is the same as that of Example 1, except that:

[0062] The structural formula of the ligand is

[0063] The structural formula of the prepared catalyst is 3.3 g of yellow catalyst C-4 was obtained with a yield of 94%.

[0064] The second aspect of this embodiment provides an application of a catalyst obtained by the catalyst preparation method in the preparation of a polar cycloolefin polymer. The preparation method of the cycloolefin copolymer is the same as that of Example 1, except that the added catalyst is catalyst C-4.

[0065] Example 5

[0066] The first aspect of this embodiment provides a method for preparing a catalyst. The preparation method is the same as that of Example 1, except that:

[0067] The structural formula of the ligand is

[0068] The structural formula of the prepared catalyst is Obtained 2.9 g of yellow catalyst C-5, the yield was 91%.

[0069] The second aspect of the embodiment provides an application of the catalyst obtained by the preparation method of the catalyst in preparing polar cyclic olefin polymers, and the preparation method of the cyclic olefin copolymer is the same as that in Embodiment 1, except that the catalyst added is catalyst C-5.

[0070] The product weight, glass transition temperature (Tg), melting point (Tm), B / C monomer content, elongation at break, polymerization activity, and polar group insertion rate of the cyclic olefin copolymers prepared in Examples 1-5 were tested, and the results are shown in Table 1.

[0071] Tg, Tm testing method: determined by differential scanning calorimeter (DSC), and the Tg and Tm are taken from the signal data in the second heating curve at a temperature rising and falling speed of 20 ℃ / min.

[0072] B, C monomer content testing method: calculated from the integral intensity ratio of the corresponding signal peaks in nuclear magnetic hydrogen spectrum (1H NMR).

[0073] Elongation at break testing method: determined by a universal tensile testing machine, and the testing method refers to the national standard GB / T 1040.3;

[0074] Polymerization activity testing method: polymer product weight g / (amount of catalyst substance mol*time h);

[0075] Polar group insertion rate (B / C molar content) testing method: calculated according to nuclear magnetic hydrogen spectrum;

[0076] Weight average molecular weight Mw and molecular weight distribution PDI: determined by high temperature gel chromatography (GPC);

[0077] Contact angle: surface contact angle tester.

[0078] Table 1

[0079]

[0080]

[0081] Example 6

[0082] The first aspect of the embodiment provides a preparation method of a catalyst, and the preparation method is the same as that in Embodiment 1.

[0083] The second aspect of the present embodiment provides an application of the catalyst obtained by the catalyst preparation method in the preparation of polar cyclic olefin polymers, the preparation method of the cyclic olefin copolymer being the same as that of Embodiment 1, except that 12 g of ethylene is added and the pressure is raised to 3.0 MPa.

[0084] Embodiment 7

[0085] The first aspect of the present embodiment provides a catalyst preparation method, which is the same as that of Embodiment 1.

[0086] The second aspect of the present embodiment provides an application of the catalyst obtained by the catalyst preparation method in the preparation of polar cyclic olefin polymers, the preparation method of the cyclic olefin copolymer being the same as that of Embodiment 1, except that 8 g of ethylene is added and the pressure is raised to 2.0 MPa.

[0087] Embodiment 8

[0088] The first aspect of the present embodiment provides a catalyst preparation method, which is the same as that of Embodiment 1.

[0089] The second aspect of the present embodiment provides an application of the catalyst obtained by the catalyst preparation method in the preparation of polar cyclic olefin polymers, the preparation method of the cyclic olefin copolymer being the same as that of Embodiment 1, except that 4 g of ethylene is added and the pressure is raised to 1.0 MPa.

[0090] Embodiment 9

[0091] The first aspect of the present embodiment provides a catalyst preparation method, which is the same as that of Embodiment 1.

[0092] The second aspect of the present embodiment provides an application of the catalyst obtained by the catalyst preparation method in the preparation of polar cyclic olefin polymers, the preparation method of the cyclic olefin copolymer being the same as that of Embodiment 1, except that a 2.0 mol / L 5-hydroxy-2-norbornene monomer (C) toluene solution is added.

[0093] 5-hydroxy-2-norbornene monomer (C)

[0094] Embodiment 10

[0095] The first aspect of the present embodiment provides a catalyst preparation method, which is the same as that of Embodiment 1.

[0096] The second aspect of the present embodiment provides an application of the catalyst obtained by the catalyst preparation method in the preparation of polar cyclic olefin polymers, the preparation method of the cyclic olefin copolymer being the same as that of Embodiment 1, except that a 1.0 mol / L norbornene monomer (B) toluene solution is added.

[0097] Example 11

[0098] The first aspect of the present embodiment provides a method for preparing a catalyst, which is the same as that of Example 1.

[0099] The second aspect of the present embodiment provides an application of the catalyst obtained from the method for preparing a catalyst, which is the same as that of Example 1, in preparing a polar cyclic olefin polymer, except that 10 mL of water is added at the same time as the 2.0 mol / L solution of norbornene monomer (B) in toluene and the 1.0 mol / L solution of 5-hydroxy-2-norbornene monomer (C) in toluene.

[0100] The product weight, glass transition temperature (Tg), melting point (Tm), and B, C monomer contents of the cyclic olefin copolymers prepared in Test Examples 6-11 were tested, and the results are shown in Table 2.

[0101] Table 2

[0102]

[0103] Example 12

[0104] The first aspect of the present embodiment provides a method for preparing a catalyst, which is the same as that of Example 1.

[0105] The second aspect of the present embodiment provides an application of the catalyst obtained from the method for preparing a catalyst, which is the same as that of Example 1, in preparing a polar cyclic olefin polymer, except that 5-methoxyl-2-norbornene is used instead of 5-hydroxy-2-norbornene.

[0106] 5-methoxyl-2-norbornene

[0107] Example 13

[0108] The first aspect of the present embodiment provides a method for preparing a catalyst, which is the same as that of Example 1.

[0109] The second aspect of the present embodiment provides an application of the catalyst obtained from the method for preparing a catalyst, which is the same as that of Example 1, in preparing a polar cyclic olefin polymer, except that 5-methoxyl-2-norbornene is used instead of 5-hydroxy-2-norbornene.

[0110] 5-methoxyl-2-norbornene

[0111] Example 14

[0112] The first aspect of this embodiment provides a method for preparing a catalyst, which is the same as that of Example 1.

[0113] The second aspect of this embodiment provides an application of a catalyst obtained by the catalyst preparation method in the preparation of a polar cycloolefin polymer. The preparation method of the cycloolefin copolymer is the same as that of Example 1, except that 9-hydroxytetracyclo-4-dodecene is used instead of 5-hydroxy-2-norbornene.

[0114] 9-Hydroxytetracyclo-4-dodecene

[0115] Example 15

[0116] The first aspect of this embodiment provides a method for preparing a catalyst, which is the same as that of Example 1.

[0117] The second aspect of this embodiment provides an application of a catalyst obtained by the catalyst preparation method in the preparation of a polar cycloolefin polymer. The preparation method of the cycloolefin copolymer is the same as that of Example 1, except that 5-methyl-2-norbornene is used instead of norbornene.

[0118] 5-Methyl-2-norbornene

[0119] Example 16

[0120] The first aspect of this embodiment provides a method for preparing a catalyst, which is the same as that of Example 1.

[0121] The second aspect of this embodiment provides an application of a catalyst obtained by the catalyst preparation method in the preparation of a polar cycloolefin polymer. The preparation method of the cycloolefin copolymer is the same as that of Example 1, except that tetracyclododecene is used instead of norbornene.

[0122] Tetracyclododecene

[0123] The product weight, glass transition temperature (Tg), melting point (Tm), and B / C monomer content of the cycloolefin copolymers prepared in Examples 1-5 were tested. The results are shown in Table 3.

[0124] Table 3

[0125]

[0126] Example 17

[0127] The first aspect of this embodiment provides a method for preparing a catalyst, which is the same as that of Example 1.

[0128] The second aspect of the present embodiment provides an application of the catalyst obtained by the preparation method of the catalyst in the preparation of polar cyclic olefin polymers, the preparation method of the cyclic olefin copolymer is the same as that of Embodiment 1, except that 30 mL of the monomer D, a toluene solution containing 0.5 mol / L of the monomer (D) is added, and R5 in the monomer (D) is -OCOCH3 and R6 is -OCOCH3.

[0129]

[0130] Embodiment 18

[0131] The first aspect of the present embodiment provides a preparation method of the catalyst, which is the same as that of Embodiment 1.

[0132] The second aspect of the present embodiment provides an application of the catalyst obtained by the preparation method of the catalyst in the preparation of polar cyclic olefin polymers, the preparation method of the cyclic olefin copolymer is the same as that of Embodiment 1, except that 30 mL of the monomer D, a toluene solution containing 0.5 mol / L of the monomer (D) is added, and R5 in the monomer (D) is -OCOCH3 and R6 is -OCOCH3.

[0133] Embodiment 19

[0134] The first aspect of the present embodiment provides a preparation method of the catalyst, which is the same as that of Embodiment 1.

[0135] The second aspect of the present embodiment provides an application of the catalyst obtained by the preparation method of the catalyst in the preparation of polar cyclic olefin polymers, the preparation method of the cyclic olefin copolymer is the same as that of Embodiment 1, except that 30 mL of the monomer D, a toluene solution containing 0.5 mol / L of the monomer (D) is added, and R5 in the monomer (D) is -COOCH3 and R6 is -COOCH3.

[0136]

[0137] Embodiment 20

[0138] The first aspect of the present embodiment provides a preparation method of the catalyst, which is the same as that of Embodiment 1.

[0139] The second aspect of the present embodiment provides an application of the catalyst obtained by the preparation method of the catalyst in the preparation of polar cyclic olefin polymers, the preparation method of the cyclic olefin copolymer is the same as that of Embodiment 1, except that 30 mL of the monomer D, a toluene solution containing 0.5 mol / L of the monomer (D) is added, and R5 in the monomer (D) is -CH2OH and R6 is -CH2OH.

[0140]

[0141] The product weight, glass transition temperature (Tg), B / C / D monomer content of the prepared cycloolefin copolymer in Examples 17-20 were tested, and the results are shown in Table 4.

[0142] Table 4

[0143]

[0144] Example 21

[0145] The first aspect of the present embodiment provides a method for preparing a catalyst, which is the same as that in Example 1.

[0146] The second aspect of the present embodiment provides an application of the catalyst prepared by the method for preparing a catalyst, which is the same as that in Example 1, in the preparation of a polar cycloolefin copolymer, except that liquid propylene is used to replace ethylene (A), and propylene is added to the reactor at a pressure of 3 MPa by a metering pump, with an addition amount of 50 g, and the pressure of the reactor is maintained by nitrogen.

[0147] Example 22

[0148] The first aspect of the present embodiment provides a method for preparing a catalyst, which is the same as that in Example 1.

[0149] The second aspect of the present embodiment provides an application of the catalyst prepared by the method for preparing a catalyst, which is the same as that in Example 1, in the preparation of a polar cycloolefin copolymer, except that liquid 1-butene is used to replace ethylene (A), and propylene is added to the reactor at a predetermined pressure by a metering pump, with an addition amount of 50 g, and the pressure of the reactor is maintained by nitrogen.

[0150] Example 23

[0151] The first aspect of the present embodiment provides a method for preparing a catalyst, which is the same as that in Example 1.

[0152] The second aspect of the present embodiment provides an application of the catalyst prepared by the method for preparing a catalyst, which is the same as that in Example 1, in the preparation of a polar cycloolefin copolymer, except that liquid 1-hexene is used to replace ethylene (A), and propylene is added to the reactor at a predetermined pressure by a metering pump, with an addition amount of 50 g, and the pressure of the reactor is maintained by nitrogen.

[0153] Example 24

[0154] The first aspect of the present embodiment provides a method for preparing a catalyst, which is the same as that in Example 1.

[0155] The second aspect of the present example provides the use of the catalyst obtained from the preparation method of the catalyst in the preparation of polar cyclic olefin polymers, the preparation method of the cyclic olefin copolymer being the same as that of Example 1, except that liquid 1-octene is used to replace ethylene (A), and propylene is added into the reactor at a predetermined pressure by a metering pump, the amount of addition being 50 g, and the pressure of the reactor is maintained by nitrogen.

[0156] The product weight, glass transition temperature (Tg) and B / C monomer content of the cyclic olefin copolymers prepared in Examples 21-24 were tested, and the results are shown in Table 5.

[0157] Table 5

[0158]

[0159]

[0160] Comparative Example 1

[0161] The first aspect of the present comparative example provides a preparation method of a catalyst, the specific embodiment being the same as that of Example 1.

[0162] The second aspect of the present comparative example provides the use of the catalyst obtained from the preparation method of the catalyst in the preparation of polar cyclic olefin polymers, the specific embodiment being the same as that of Example 1, except that no monomer C is added.

[0163] Comparative Example 2

[0164] The first aspect of the present comparative example provides a preparation method of a catalyst, the specific embodiment being the same as that of Example 1.

[0165] The second aspect of the present comparative example provides the use of the catalyst obtained from the preparation method of the catalyst in the preparation of polar cyclic olefin polymers, the specific embodiment being the same as that of Example 1, except that 10 mL of water is added.

[0166] Comparative Example 3

[0167] The first aspect of the present comparative example provides a preparation method of a catalyst, the specific embodiment being the same as that of Example 1, except that 200 mL of benzene, 8.0 g of pyridine, 0.9 g of a nickel source and 2.3 g of a ligand are added into the container, thereby obtaining 2.8 g of yellow catalyst D-1, the yield being 95%.

[0168] The structural formula of the ligand is

[0169] The structural formula of the prepared catalyst is

[0170] The first aspect of the present comparative example provides a method for preparing a catalyst, the specific implementation manner being the same as that of Comparative Example 3.

[0171] Comparative Example 4

[0172] The first aspect of the present comparative example provides a method for preparing a catalyst, the specific implementation manner being the same as that of Comparative Example 3.

[0173] The second aspect of the present comparative example provides an application of the catalyst obtained from the method for preparing the catalyst in preparing a polar cyclic olefin polymer, the specific implementation manner being the same as that of Comparative Example 3, except that 10 mL of water is added.

[0174] The test results of Comparative Examples 1-4 are shown in Table 6 below.

[0175] Table 6

[0176]

Claims

1. A method for preparing a catalyst, characterized in that: The preparation method comprises: adding 200 mL of a benzene series compound, 8.0 g of pyridine, 0.9 g of a nickel source, and 2.9 g of a ligand into a container, stirring and reacting at room temperature of 25±1°C, and completing the reaction when no gas is released in the reaction system. After the reaction is completed, filtering is performed, and the filtrate is freeze-dried to obtain 3.3 g of a yellow catalyst C-1; The benzene series compound is toluene, and the nickel source is tetramethylethylenediaminedimethylnickel; The structural formula of the ligand is The structural formula of the prepared catalyst is 2. A method for preparing a catalyst, characterized in that: The preparation method comprises: adding 200 mL of a benzene series compound, 8.0 g of pyridine, 0.9 g of a nickel source, and 2.9 g of a ligand into a container, stirring and reacting at room temperature of 25±1°C, and completing the reaction when no gas is released in the reaction system. After the reaction is completed, filtering is performed, and the filtrate is freeze-dried to obtain 3.1 g of a yellow catalyst C-2; The benzene series compound is toluene, and the nickel source is tetramethylethylenediaminedimethylnickel; The structural formula of the ligand is The structural formula of the prepared catalyst is 3. A method for preparing a catalyst, characterized in that: The preparation method comprises: adding 200 mL of a benzene series compound, 8.0 g of pyridine, 0.9 g of a nickel source, and 2.9 g of a ligand into a container, stirring and reacting at room temperature of 25±1°C, and completing the reaction when no gas is released in the reaction system. After the reaction is completed, filtering is performed, and the filtrate is freeze-dried to obtain 2.7 g of a yellow catalyst C-3; The benzene series compound is toluene, and the nickel source is tetramethylethylenediaminedimethylnickel; The structural formula of the ligand is The structural formula of the prepared catalyst is 4. A method for preparing a catalyst, characterized in that: The preparation method comprises: adding 200 mL of a benzene series compound, 8.0 g of pyridine, 0.9 g of a nickel source, and 2.9 g of a ligand into a container, stirring and reacting at room temperature of 25±1°C, and completing the reaction when no gas is released in the reaction system. After the reaction is completed, filtering is performed, and the filtrate is freeze-dried to obtain 3.3 g of a yellow catalyst C-4; The benzene series compound is toluene, and the nickel source is tetramethylethylenediaminedimethylnickel; The structural formula of the ligand is The structural formula of the prepared catalyst is 5. A method for preparing a catalyst, characterized in that: The preparation method comprises: adding 200 mL of a benzene series compound, 8.0 g of pyridine, 0.9 g of a nickel source, and 2.9 g of a ligand into a container, stirring and reacting at room temperature of 25±1°C, and completing the reaction when no gas is released in the reaction system. After the reaction is completed, filtering is performed, and the filtrate is freeze-dried to obtain 2.9 g of a yellow catalyst C-5; The benzene series compound is toluene, and the nickel source is tetramethylethylenediaminedimethylnickel; The structural formula of the ligand is The structural formula of the prepared catalyst is 6. Use of a catalyst obtained by the method for preparing a catalyst according to any one of claims 1 to 5 in the preparation of polar cycloolefin polymers, characterized in that: The preparation method of the cycloolefin copolymer comprises: polymerizing a vinyl monomer A, a non-polar monomer B and a polar monomer in the presence of the catalyst under the conditions of 0-150° C. and 0.01-10 MPa to obtain the cycloolefin copolymer.

7. The use according to claim 6, characterized in that The mole percentage of the vinyl monomer A is 70-99 mol%, the mole percentage of the non-polar monomer B is 0-30 mol%, the mole percentage of the polar monomer is 0-30 mol%, and the mole percentage of the non-polar monomer B and the polar monomer is 0 mol% when they are different.

8. The use according to claim 7, characterized in that The polar monomer is a monosubstituted polar monomer C and / or a disubstituted polar monomer D, and the sum of the molar percentages of the non-polar monomer B and the polar monomers C and D is 1-30 mol%.

9. The use according to claim 8, characterized in that The molecular weight of the cycloolefin copolymer is 50,000-500,000.

10. The use according to claim 9, characterized in that The contact angle of the cyclic olefin copolymer is 70-100°.

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