Preparation method of cycloolefin copolymer and prepared cycloolefin copolymer

Abstract

The invention discloses a preparation method of a cycloolefin copolymer and the prepared cycloolefin copolymer. The preparation method comprises the following steps: carrying out a copolymerization reaction on an alpha olefin monomer and a cycloolefin monomer under the action of a phosphine-nitrogen ligand-containing mono-cycloolefin complex catalyst and a cocatalyst to obtain a cycloolefin copolymer, wherein the mono-cyclopentadienyl complex catalyst has a structure as shown in a formula (1); according to the invention, copolymerization of the alpha-olefin monomer and the cycloolefin monomer is catalyzed by the mono-cyclopentadienyl complex containing the phosphine-nitrogen ligand, so that the alpha-olefin monomer and cycloolefin copolymer with high cycloolefin content can be prepared.

Description

Technical Field

[0001] This invention relates to the field of cyclic olefin copolymerization technology, specifically to a method for preparing cyclic olefin copolymers and the resulting cyclic olefin copolymers. Background Technology

[0002] Cycloolefin copolymers, as a high-value-added engineering material, possess excellent optical properties, including high transparency, low birefringence, good heat resistance, chemical stability, low moisture absorption, and high barrier properties. They are widely used in optical thin films, camera lenses, and other fields. Furthermore, in addition to their high transparency, cycloolefin copolymers are not easily broken, have good sterilization adaptability (EO, γ-ray, steam sterilization), excellent chemical stability, acid and alkali resistance, and low protein adsorption, making them suitable for medical packaging applications such as vials and pre-filled syringes for vaccines and biological agents. Against the backdrop of a continuously expanding pharmaceutical market, the biological agent market is also experiencing sustained growth. Pre-filled syringes are gradually replacing traditional glass ampoules, vials, and ordinary syringes, indicating a vast future market potential.

[0003] Cyclic olefin copolymers are typically non-crystalline, transparent resins obtained by copolymerizing ethylene and norbornene (bicyclohepten). Catalyst systems used to prepare cyclic olefin copolymers mainly fall into three categories: pre-transition metallocerocatalysts, pre-transition metal non-cerocerocatalysts, and post-transition metal catalysts. Post-transition metal catalysts exhibit lower activity than metallocene catalysts for the copolymerization of olefins and cyclic olefins. For cyclic olefin monomers containing polar functional groups or double bond side groups, the activity of metallocene catalysts decreases, resulting in copolymers with low cyclic olefin content. In metallocene catalysts, one cyclopentadienyl ligand is replaced by another ligand. Mono-metallocene catalysts containing only one cyclopentadienyl ligand are also used in cyclic olefin copolymers, but the insertion rate of the cyclic olefin monomer is insufficient. Summary of the Invention

[0004] The purpose of this invention is to overcome the problem of low cyclic olefin content in the prior art, and to provide a method for preparing cyclic olefin copolymers and the obtained cyclic olefin copolymers. By using a monocerone complex containing phosphine nitrogen ligands to catalyze the copolymerization of α-olefin monomers and cyclic olefin monomers, α-olefin monomers and cyclic olefin copolymers with high cyclic olefin content can be prepared.

[0005] To achieve the above objectives, a first aspect of the present invention provides a method for preparing a cyclic olefin copolymer, the method comprising:

[0006] α-olefin monomers and cyclic olefin monomers are copolymerized in the presence of a monocyclic complex catalyst containing phosphine nitrogen ligands and a co-catalyst to obtain cyclic olefin copolymers; wherein the monocyclic complex catalyst has the structure shown in formula (1);

[0007]

[0008] In equation (1),

[0009] R 1 R 2 and R 3 Each independently chooses H and C. 1-20 hydrocarbon group, C 1-20 The group consisting of alkoxy groups and halogens;

[0010] R1 and R2 are each independently chosen from H and C. 1-4 hydrocarbon group, C 6-12 aryl and C 1-4 hydrocarbon group substituted C 7-16 A group consisting of aryl groups;

[0011] m is 1, 2, or 3;

[0012] Mt is a Group IVB metallic element;

[0013] Cp* is a cyclopentadienyl group containing an electron-donating substituent;

[0014] X is an atom or group bonded to the Mt element, and X is selected from C. 1-10 It is at least one group in the group consisting of a hydrocarbon group and a halogen; n is an integer and satisfies the Mt bond valence.

[0015] A second aspect of the present invention provides a cyclic olefin copolymer prepared by the preparation method described in the first aspect above, wherein the molar content of the cyclic olefin copolymer is 50-65%.

[0016] The beneficial technical effects achieved by the present invention through the above technical solution are as follows:

[0017] The method for preparing cyclic olefin copolymers provided by this invention uses a monocyclic complex catalyst containing phosphine nitrogen ligands and a co-catalyst as catalysts for copolymerization. By introducing the electronic effects of P and N ligands, the active center of the catalyst can be stably formed. The large-volume substituents can play a directional role, which is conducive to the insertion of cyclic olefin monomers. The cyclic olefin monomers can form a small number of blocks, which increases the glass transition temperature, improves the catalytic activity, and yields a copolymer with high molecular weight and high cyclic olefin binding content. Attached Figure Description

[0018] Figure 1 It is the copolymer obtained in Example 1. 13 C10 NMR spectrum. Detailed Implementation

[0019] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0020] The first aspect of this invention provides a method for preparing a cyclic olefin copolymer, the method comprising:

[0021] α-olefin monomers and cyclic olefin monomers are copolymerized in the presence of a monocyclic complex catalyst containing phosphine nitrogen ligands and a co-catalyst to obtain cyclic olefin copolymers; wherein the monocyclic complex catalyst has the structure shown in formula (1);

[0022]

[0023] In equation (1),

[0024] R 1 R 2 and R 3 Each independently chooses H and C. 1-20 hydrocarbon group, C 1-20 The group consisting of alkoxy groups and halogens;

[0025] R1 and R2 are each independently chosen from H and C. 1-4 hydrocarbon group, C 6-12 aryl and C 1-4 hydrocarbon group substituted C 7-16 A group consisting of aryl groups;

[0026] m is 1, 2, or 3;

[0027] Mt is a Group IVB metallic element;

[0028] Cp* is a cyclopentadienyl group containing an electron-donating substituent;

[0029] X is an atom or group bonded to the Mt element, and X is selected from C. 1-10 It is at least one group in the group consisting of a hydrocarbon group and a halogen; n is an integer and satisfies the Mt bond valence.

[0030] According to some embodiments of the present invention, all n X's are halogens.

[0031] According to other embodiments of the present invention, all n X's are C's. 1-10 Hydrocarbon group.

[0032] According to some other embodiments of the present invention, one X is C1-10 The hydrocarbon group and the remaining (n-1) X groups are halogens.

[0033] In some embodiments of the present invention, Cp* is pentamethylcyclopentadienyl.

[0034] In this invention, the halogens include fluorine, chlorine, bromine, and iodine.

[0035] In this invention, R 1 R 2 and R 3 They can be the same or different, but R is preferred. 2 and R 3 same.

[0036] In this invention, the n X's can be the same or different.

[0037] In this invention, C 1-20 The hydrocarbon group refers to a hydrocarbon group with a total number of carbon atoms of 1-20, such as C1, C2, C3, C4, C5, C6, C7, C8, C9, ...1, C1, C1, C1, C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 Or C 20 Hydrocarbon groups. For example, C 1-20 The hydrocarbon group can be C 1-20 alkyl or C 2-20 The alkenyl group.

[0038] In this invention, C 1-20 The alkoxy group refers to an alkoxy group with a total number of carbon atoms of 1-20, such as C1, C2, C3, C4, C5, C6, C7, C8, C9, ...1, C1, C1, 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 Or C 20 alkoxy groups.

[0039] In this invention, C 1-4 The hydrocarbon group refers to a hydrocarbon group with a total number of carbon atoms of 1-4, such as a C1, C2, C3, or C4 hydrocarbon group. For example, it can be a C1, C2, C3, or C4 hydrocarbon group. 1-4 alkyl or C 2-4 The alkenyl group.

[0040] In this invention, C 6-12 The aryl group refers to an aryl group with a total number of carbon atoms of 6-12, such as phenyl, naphthyl, or biphenyl.

[0041] In this invention, C 1-4 C with hydrocarbon substitution 7-16 An aryl group refers to an aryl group with a total number of 7-16 carbon atoms, and at least one H atom on the aryl group is bonded to a carbon atom. 1-4 Hydrocarbon group substitution, for example, can be a hydrocarbon group composed of C 1-4 The alkyl group is substituted with phenyl, naphthyl, biphenyl, anthracene, or phenanthrene. For example, it can be composed of C 1-4 alkyl and / or C 2-4 alkenyl-substituted C 7-16 Aryl groups.

[0042] In this invention, the Group IVB metal element is Ti, Zr, or Hf.

[0043] In some embodiments of the present invention, in formula (1),

[0044] R 1 R 2 and R 3 Each independently chooses H and C. 1-16 hydrocarbon group, C 1-16 The group consisting of alkoxy groups and halogens;

[0045] R1 and R2 are each independently chosen from H and C. 1-4 hydrocarbon group, C 6-10 aryl and C 1-4 hydrocarbon group substituted C 7-14 A group consisting of aryl groups;

[0046] Mt represents titanium, zirconium, or hafnium;

[0047] X chooses freely C 1-8 It consists of at least one group from the group consisting of hydrocarbon groups, fluorine, chlorine, bromine and iodine.

[0048] In some preferred embodiments of the present invention, in formula (1),

[0049] R 1 R 2 and R 3 Each independently chooses H and C. 1-10 hydrocarbon group, C 1-10 The group consisting of alkoxy groups and halogens;

[0050] R1 and R2 are each independently selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl, naphthyl, and C substituted with at least one of the following substituents: methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl. 7-14 A group consisting of aryl groups;

[0051] Mt represents titanium, zirconium, or hafnium;

[0052] X is selected from at least one group from the group consisting of methyl, ethyl, n-propyl, isopropyl, cyclopentadienyl, fluorine, chlorine, bromine, and iodine.

[0053] According to some embodiments of the present invention, all n X's are chlorine.

[0054] According to other embodiments of the present invention, all n X's are methyl groups.

[0055] According to some other embodiments of the present invention, one X is methyl and the remaining (n-1) X are chlorine.

[0056] In some preferred embodiments of the present invention, in formula (1),

[0057] R 1 R 2 and R 3 Each independently chooses H and C. 1-6 alkyl, C 1-6 The group consisting of alkoxy groups and halogens;

[0058] R1 and R2 are each independently selected from phenyl, naphthyl, and C, which are substituted with at least one of the following substituents: methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl. 7-14 At least one group in the aryl group;

[0059] Mt represents titanium, zirconium, or hafnium.

[0060] In this invention, m is 1, 2 or 3.

[0061] In this invention, n is 2.

[0062] The method for preparing cyclic olefin copolymers provided by this invention uses a monocyclic complex catalyst containing phosphine nitrogen ligands and a co-catalyst as catalysts for copolymerization. By introducing the electronic effects of P and N ligands, the active center of the catalyst can be stably formed. The large-volume substituents can play a directional role, which is conducive to the insertion of cyclic olefin monomers. The cyclic olefin monomers can form a small number of blocks, which increases the glass transition temperature, improves the catalytic activity, and yields a copolymer with high molecular weight and high cyclic olefin content.

[0063] This invention also provides a method for preparing the aforementioned monoceramic complex catalyst containing phosphine nitrogen ligands, the method comprising:

[0064] 1) In the presence of an organic solvent, the compound with the structure shown in formula (11) is reacted with n-butyllithium to obtain a first intermediate;

[0065] 2) The first intermediate is reacted with the compound with the structure shown in formula (12) in a second reaction to obtain the second intermediate;

[0066] 3) The second intermediate is reacted with trimethylazidosilane in a third reaction to obtain a third intermediate having the structure shown in formula (13);

[0067] 4) The third intermediate is reacted with the compound with the structure shown in formula (14) in a fourth reaction to obtain the fourth intermediate with the structure shown in formula (15);

[0068] 5) Combine the fourth intermediate with Cp*MtX (n+1) The fifth reaction is carried out to obtain the fifth intermediate;

[0069] 6) The fifth intermediate is reacted with a Grignard reagent in a sixth reaction to obtain a metal compound having the structure shown in formula (1);

[0070]

[0071] Among them, equations (11), (12), (13), (14), and (15) Cp*MtX (n+1) The definition of the substituent in formula (1) is the same as that in the first aspect mentioned above, and X1 in formula (12) is a halogen.

[0072] In this invention, the first compound obtained from the first reaction in step 1) is a lithium salt. The lithium salt can be directly introduced into step 2) for the second reaction, or it can be separated and purified before being introduced into step 2) for the second reaction. This invention does not particularly limit the separation and purification steps, and those skilled in the art can use conventional methods in the art, such as recrystallization and column chromatography, to perform separation and purification.

[0073] In some embodiments of the present invention, compounds with the structure shown in formula (11) are used in combination with n-butyllithium, compounds with the structure shown in formula (12), trimethylazidosilane, compounds with the structure shown in formula (14), and Cp*MtX. (n+1) The molar ratio of the reagent to the Grignard reagent is 1:1-2:1-2:1-4:2-10:1-2:1-5; for example, 1:1.2:1:2:6:1:2, 1:1:1:2:5:1:3, 1:2:2:4:8:2:4, and any value within the range of any two values.

[0074] In some embodiments of the present invention, the molar ratio of the second compound to trimethylazidosilane is 1:(0.8-2).

[0075] In some embodiments of the present invention, in step 1), the organic solvent is selected from at least one of toluene, hexane, pentane, benzene, xylene, dichloromethane, trichloromethane, tetrachloromethane, and tetrahydrofuran.

[0076] In some embodiments of the present invention, in step 5), Cp*MtX (n+1) Preferred Cp*MtCl 3， If Mt is Ti, Zr, or Hf, then Cp*MtCl3 is Cp*TiCl3, Cp*ZrCl3, or Cp*HfCl3.

[0077] In some embodiments of the present invention, in step 6), the Grignard reagent is selected from at least one of methyl magnesium bromide, ethyl magnesium bromide, isopropyl magnesium bromide, and phenyl magnesium bromide.

[0078] In some embodiments of the present invention, the conditions for the first reaction include: a reaction temperature of -100°C to 100°C and a reaction time of 0.5-2 hours.

[0079] In some embodiments of the present invention, the conditions for the second reaction include: a reaction temperature of -100°C to 40°C and a reaction time of 0.5-3 hours.

[0080] In some embodiments of the present invention, the conditions for the third reaction include: a reaction temperature of 50-200°C and a reaction time of 1-20 h.

[0081] In some embodiments of the present invention, the conditions for the fourth reaction include: a reaction temperature of 50-200°C and a reaction time of 2-30 h.

[0082] In some embodiments of the present invention, the conditions for the fifth reaction include: a reaction temperature of 50-200°C and a reaction time of 2-30 h.

[0083] In some embodiments of the present invention, the conditions for the sixth reaction include: a reaction temperature of 50-200°C and a reaction time of 2-30 h.

[0084] The preparation method described above may further include necessary post-processing steps. Those skilled in the art can use various steps conventionally used in the art to perform post-processing to purify the crude products from each step. For example, the post-processing steps may include solvent removal, washing, and drying.

[0085] In this invention, a monocyclic complex catalyst containing phosphine nitrogen ligands and a co-catalyst are used as catalysts for copolymerization. By introducing the electronic effects of P and N ligands, the active center of the catalyst can be stably formed. The large-volume substituents can play a directional role, which is conducive to the insertion of cyclic olefin monomers. The cyclic olefin monomers can form a small number of blocks, which increases the glass transition temperature and improves the catalytic activity, resulting in copolymers with high molecular weight and high cyclic olefin binding content.

[0086] In some embodiments of the invention, the cocatalyst comprises an aluminum-containing compound and optionally an organoboron compound.

[0087] In some preferred embodiments of the present invention, the co-catalyst comprises an aluminum-containing compound, wherein the molar ratio of the monocrole complex catalyst, calculated as metal element, to the aluminum-containing compound, calculated as aluminum element, is 1:(0.1-3000), preferably 1:(10-200).

[0088] In some preferred embodiments of the present invention, the co-catalyst comprises a mixture of an aluminum-containing compound and an organoboron compound, wherein the molar ratio of the monocrole complex catalyst, the aluminum-containing compound, and the organoboron compound, calculated as metal elements, is 1:(10-500):(1-5), preferably 1:(10-200):(1-5).

[0089] In some preferred embodiments of the present invention, the aluminum-containing compound is a mixture of alkylaluminum compounds and alkylaluminoxane compounds or an alkylaluminoxane compound.

[0090] Preferably, in the mixture of the alkylaluminum compound and the alkylaluminoxane compound, the molar ratio of the alkylaluminum compound (calculated as aluminum) to the alkylaluminoxane compound (calculated as aluminum) is 1:(10-500); more preferably, it is 1:(25-300).

[0091] Preferably, the alkylaluminoxane compound has the structure shown in formula (3).

[0092]

[0093] In equation (3), R 31 It is at least one group selected from methyl, ethyl, n-propyl, isopropyl, primary butyl, secondary butyl, and tert-butyl; t is an integer from 5 to 30. More preferably, in R 31 It is at least one group selected from methyl, ethyl, n-propyl, isopropyl, and tert-butyl. More preferably, in formula (3), R... 31 It is at least one group selected from methyl, ethyl, and isopropyl. Preferably, the alkylaluminoxane compound is methylaluminoxane (MAO) and / or isobutylaluminoxane, that is, R31 It is methyl or isobutyl.

[0094] In some preferred embodiments of the present invention, the alkylaluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride, dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride, and dihexylaluminum hydride. Preferably, the alkylaluminum compound is triisobutylaluminum.

[0095] In some embodiments of the present invention, the organoboron compound is selected from at least one of tris(pentafluorophenyl)boron (B(C6F5)3), N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate ([HNMe2Ph][B(C6F5)4]), and triphenylcarbamonite tetra(pentafluorophenyl)borate ([Ph3C][B(C6F5)4]).

[0096] In addition to the catalyst and co-catalyst, this invention may also contain other necessary additives, as long as these additives do not affect the catalytic effect of the composition. For example, it may contain an impurity remover.

[0097] In some embodiments of the present invention, the α-olefin monomer is ethylene and / or α-olefin.

[0098] In some preferred embodiments of the present invention, the α-olefin is selected from at least one of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 4-methyl-1-pentene.

[0099] In some embodiments of the present invention, the cyclic olefin monomer is selected from at least one of cyclopentene, cyclohexene, norbornene, 1-methylnorbornene, 5-methylnorbornene, dicyclopentadiene, 5-methylene-2-norbornene, and 5-ethylidene-2-norbornene; preferably selected from at least one of norbornene, dicyclopentadiene, 5-methylene-2-norbornene, and 5-ethylidene-2-norbornene.

[0100] In some embodiments of the present invention, the concentration of the cyclic olefin monomer in the copolymerization reaction system is 0.01-10 mol / L.

[0101] In some embodiments of the present invention, the partial pressure of the α-olefin monomer in the copolymerization reaction system is 0.5-5 MPa.

[0102] In some embodiments of the present invention, the concentration of the monoclonal complex catalyst in the copolymerization reaction system is 1 × 10⁻⁶.-8 -1×10 -5 mol / L.

[0103] In some embodiments of the present invention, the molar ratio of the cyclic olefin monomer to the monocyclic complex catalyst is 1.5 × 10⁻⁶. 5 -5×10 5 :1.

[0104] In some embodiments of the present invention, the copolymerization reaction conditions include: a reaction temperature of 40-120°C and a reaction time of 10-60 min. Preferably, the copolymerization reaction conditions include: a reaction temperature of 60-120°C and a reaction time of 10-60 min. All pressures mentioned in this invention are gauge pressures.

[0105] The copolymerization reaction of the present invention can be carried out by solution polymerization or bulk polymerization. The polymerization reaction of the present invention can be a solution polymerization reaction. It will be apparent to those skilled in the art that the solvent used should be liquid under homopolymerization conditions and should not participate in the polymerization reaction or react with the resulting polymer; that is, the solvent should be inert. Such solvents are obvious to those skilled in the art of polymerization and can be easily selected. Nevertheless, for the purposes of the present invention, specific examples of the organic solvent may be one or more of benzene, toluene, ethylbenzene, xylene, pentane, n-hexane, heptane, octane, and cyclohexane, preferably n-hexane, octane, or heptane, and more preferably n-hexane as the solvent in the homopolymerization reaction of the present invention. For the polymerization reaction of the present invention, the amount of solvent used results in a polymer concentration in the range of 5-30% by weight, preferably 8-10% by weight.

[0106] According to the present invention, the above-mentioned polymerization process is preferably carried out under an inert atmosphere, such as one or more of nitrogen, helium, argon, etc., to provide such an inert atmosphere.

[0107] In the polymerization reaction of this invention, a terminator can be used to terminate the polymerization reaction after it is completed. The terminator used for this step is conventional to those skilled in the art. Commonly used terminators include deionized water, alcohols, acids, etc. In this invention, the preferred terminator is one or more of isopropanol, methanol, water, etc.

[0108] The method of this invention is simple to operate and has a low catalyst cost.

[0109] The second aspect of the present invention provides a cyclic olefin copolymer prepared by the preparation method described in the first aspect above, wherein the molar content of the cyclic olefin copolymer is 45-70%, preferably 50-65%.

[0110] The cyclic olefin copolymers of the present invention are copolymers of α-olefins and cyclic olefins with high cyclic olefin content. The cyclic olefin copolymers prepared by the aforementioned preparation method of the present invention have high molecular weight and high cyclic olefin binding content, and the catalysts can achieve high catalytic efficiency.

[0111] In some embodiments of the present invention, the weight-average molecular weight of the cyclic olefin copolymer is 20,000 to 200,000, preferably 50,000 to 200,000; and the molecular weight distribution index is 1.9 to 2.5, preferably 1.9 to 2.3.

[0112] The present invention will be described in detail below through examples.

[0113] Unless otherwise specified, all raw materials used in the following preparation examples, embodiments and comparative examples are commercially available.

[0114] The number-average molecular weight Mn, weight-average molecular weight Mw, and molecular weight distribution index (PDI = Mw / Mn) of the polymers described below were determined by Waters 150 gel permeation chromatography (GPC) at 135 °C using 1,2,4-trichlorobenzene as the mobile phase.

[0115] Cycloolefin content: Measured using a Bruker 600MHz nuclear magnetic resonance spectrometer with deuterated chloroform as solvent at room temperature.

[0116] Polymerization activity (also known as catalytic efficiency) refers to the mass of polymer obtained per unit molar amount of Mt, expressed in g / (mol·Mt·h). For example, if Mt is Ti, the corresponding unit is g / (mol·Ti·h).

[0117]

[0118]

[0119] Among them, R 1 It is methyl, R 2 It is isopropyl, R 3 The group is isopropyl, m=2, R1 is phenyl, R2 is phenyl, Mt is Ti, X is methyl, n=2.

[0120] Preparation Example 1

[0121] The preparation method of the ligand with the structure shown in formula (A1) includes the following steps:

[0122] 1) Dissolve diphenylphosphine chloride (28.4 mmol) in 20 mL of toluene, and slowly add a hexane solution (18.6 mL) of n-butyllithium (29.8 mmol) dropwise at -78 °C using liquid nitrogen. React for 2 h, then raise the temperature to 25 °C;

[0123] 2) Weigh 4-bromobutane-2-one (4.29 g, 28.4 mmol), dissolve it in 100 mL of anhydrous diethyl ether, and react it with the lithium salt solution prepared in 1) at -78 °C for 2 h. Then, slowly heat the solution to 25 °C and continue the reaction for 12 h. After separation and purification, 5.09 g of a white solid, i.e., the ligand with the structure shown in formula (A1), is obtained. The yield is 67%.

[0124] Preparation Example 2

[0125] The preparation method of the ligand with the structure shown in formula (A2) includes the following steps:

[0126] Trimethylsilane N3SiMe3 (0.015 mol) was slowly added to 20 mL of a toluene solution containing 5 mmol of the ligand with the structure shown in formula (A1) obtained in Preparation Example 1. The reaction mixture was heated under reflux for 12 h. When the solvent and excess TMSN3 were removed by vacuum, a white crystalline solid was obtained, namely the ligand with the structure shown in (A2). The yield was 95%.

[0127] Preparation Example 3

[0128] The preparation method of the ligand with the structure shown in formula (A3) includes the following steps:

[0129] Di-o-isopropylaniline (0.015 mol) was slowly added to 20 mL of a toluene solution containing 5 mmol of the ligand with the structure shown in formula (A2) obtained in Preparation Example 2. The reaction mixture was heated under reflux for 12 h. After removing the solvent by vacuum, a white crystalline solid was obtained, namely the ligand with the structure shown in formula (A3). The yield was 85%.

[0130] Preparation Example 4

[0131] The preparation method of catalyst 1A includes the following steps:

[0132] The ligand (1 mmol) with the structure shown in formula (A3) obtained in Preparation Example 3 was dissolved in 15 mL of toluene, stirred until homogeneous, and slowly added dropwise to 5 mL of a toluene solution containing cyclopentadiene titanium trichloride (2 mmol). The mixture was heated to 110 °C and reacted for 12 h, then cooled to 25 °C, and 0.81 g of a yellow powder was obtained. This compound has the structure shown in formula (1A), wherein R... 1 It is methyl, R 2 It is isopropyl, R 3The product is isopropyl, m=2, R1 is phenyl, R2 is phenyl, Mt is Ti, X is chlorine, n=2; at room temperature, the obtained yellow powder (0.8 mmol) was dissolved in 10 mL of diethyl ether, and a solution of methyl magnesium bromide (3.1 mmol) in diethyl ether was added dropwise with stirring. The reaction was carried out at room temperature for 12 h, the solvent was removed under reduced pressure, the product was washed three times with pentane, and dried under vacuum to obtain 0.4 g of the product, namely catalyst 1A with the structure shown in formula (1A), wherein R 1 It is methyl, R 2 It is isopropyl, R 3 The derivative is isopropyl, m=2, R1 is phenyl, R2 is phenyl, Mt is Ti, X is methyl, n=2. The yield is 89%.

[0133] Preparation Example 5

[0134] Ligand B3 was prepared according to the method of Preparation Examples 1-3. The difference is that, unlike the ligand with the structure shown in formula (A3), R in B3... 1 It is methyl, R 2 It is isopropyl, R 3 The ligand B3 (1 mmol) is isopropyl, m = 2, R1 is isopropyl, and R2 isopropyl. The prepared ligand B3 is then dissolved in 10 mL of toluene, stirred until homogeneous, and slowly added dropwise to 5 mL of a toluene solution containing cyclopentadiene titanium trichloride (2 mmol). The mixture is heated to 100 °C and reacted for 15 h. The mixture is then cooled to 25 °C, and a yellow powder is obtained. The obtained yellow powder (0.8 mmol) is dissolved in 10 mL of diethyl ether, and a solution of methyl magnesium bromide (3.1 mmol) in diethyl ether is added dropwise with stirring. The mixture is reacted at room temperature for 12 h. The solvent is removed under reduced pressure, and the product is washed three times with pentane and dried under vacuum to obtain catalyst 1B. Unlike catalyst 1A, which has the structure shown in formula (1A), catalyst 1B contains R... 1 It is methyl, R 2 It is isopropyl, R 3 The group is isopropyl, m=2, R1 is isopropyl, R2 isopropyl, Mt is titanium, X is methyl, n=2.

[0135] Preparation Example 6

[0136] Catalyst 1C was prepared according to the method of Preparation Examples 1-4. Unlike catalyst 1A, which has the structure shown in formula (1A), catalyst 1C contains R... 1 It is a phenyl group, R 2 It is isopropyl, R 3 Mt is methyl, m=3, R1 is tert-butyl, R2 is tert-butyl, Mt is zirconium, X is methyl, n=2.

[0137] Preparation Example 7

[0138] Catalyst 1D was prepared according to the method of Preparation Examples 1-4. Unlike catalyst 1A, which has the structure shown in formula (1A), catalyst 1D contains R... 1 It is a phenyl group, R 2 It is isopropyl, R 3 The group is isopropyl, m=2, R1 is tert-butyl, R2 is methyl, Mt is hafnium, X is methyl, and n=2.

[0139] Example 1

[0140] The 500 mL high-pressure reactor was evacuated three times with high-purity nitrogen. Under vacuum, 200 mL of toluene solution containing norbornene (10 mmol) and 5 mL of toluene solution containing methylaluminoxane (1 mmol) were added sequentially. Ethylene was then introduced to 0.5 MPa, and the mixture was stirred at room temperature (approximately 25 °C) for 10 min. Then, 5 mL of toluene solution containing catalyst 1A (5 μmol) prepared in Preparation Example 4 was added. The reaction was carried out at 40 °C for 15 min. The high-pressure reactor was then vented and the product was discharged. The reaction was terminated with an ethanol / HCl mixture (ethanol / HCl volume ratio of 9:1). The condensed product was washed with ethanol and dried under vacuum to constant weight, yielding 6.56 g of cyclic olefin copolymer.

[0141] like Figure 1 The image shows the cyclic olefin copolymer obtained in Example 1. 13 C NMR spectrum, from Figure 1 It can be seen that the cyclic olefin content in the cyclic olefin copolymer prepared in Example 1 is 55.8 mol%.

[0142] The copolymerization activity was tested to be 5.25 × 10⁻⁶. 6 The obtained copolymer, with a yield of g / (mol·Mt·h), contained 55.8 mol% cyclic olefins and had a molecular weight Mn of 4.65 × 10⁻⁶. 5 The molecular weight distribution index Mw / Mn is 2.24.

[0143] Example 2

[0144] The 500 mL high-pressure reactor was evacuated three times with high-purity nitrogen. Under vacuum, 200 mL of toluene solution containing norbornene (20 mmol) and 5 mL of toluene solution containing methylaluminoxane (2.5 mmol) were added sequentially. Ethylene was then introduced to 0.5 MPa, and the mixture was stirred at room temperature (approximately 25 °C) for 10 min. Then, 5 mL of toluene solution containing catalyst 1A (5 μmol) prepared in Preparation Example 4 was added. The reaction was carried out at 40 °C for 15 min. The high-pressure reactor was then vented and the product was discharged. The reaction was terminated with an ethanol / HCl mixture (ethanol / HCl volume ratio of 9:1). The condensed product was washed with ethanol and vacuum dried to constant weight to obtain 8.73 g of cyclic olefin copolymer.

[0145] The copolymerization activity was measured to be 6.98 × 10⁻⁶. 6 The obtained copolymer, with a yield of g / (mol·Mt·h), contained 55.3 mol% cyclic olefins and had a molecular weight Mn of 5.31 × 10⁻⁶ g / (mol·Mt·h). 5 The molecular weight distribution index Mw / Mn is 2.26.

[0146] Example 3

[0147] The 500 mL high-pressure reactor was evacuated three times with high-purity nitrogen. Under vacuum, 200 mL of toluene solution containing norbornene (20 mmol) and 5 mL of toluene solution containing methylaluminoxane (2.5 mmol) were added sequentially. Ethylene was then introduced to 0.5 MPa, and the mixture was stirred at room temperature (approximately 25 °C) for 10 min. Then, 5 mL of toluene solution containing catalyst 1A (5 μmol) prepared in Preparation Example 4 was added. The reaction was carried out at 60 °C for 15 min. The high-pressure reactor was then vented and the product was discharged. The reaction was terminated with an ethanol / HCl mixture (ethanol / HCl volume ratio of 9:1). The condensed product was washed with ethanol and dried under vacuum to constant weight, yielding 7.86 g of cyclic olefin copolymer.

[0148] The copolymerization activity was measured to be 6.29 × 10⁻⁶. 6 The obtained copolymer, with a cyclic olefin content of 48.2 mol·Mt·h and a molecular weight Mn of 5.9 × 10⁻⁶ g / (mol·Mt·h), has a molecular weight Mn of 5.9 × 10⁻⁶ g / (mol·Mt·h). 5 The molecular weight distribution index Mw / Mn is 2.23.

[0149] Example 4

[0150] The 500 mL high-pressure reactor was evacuated three times with high-purity nitrogen. Under vacuum, 200 mL of toluene solution containing norbornene (20 mmol) and 5 mL of toluene solution containing methylaluminoxane (2.5 mmol) were added sequentially. Ethylene was then introduced to 0.5 MPa, and the mixture was stirred at room temperature (approximately 25 °C) for 10 min. Then, 5 mL of toluene solution containing catalyst 1B (5 μmol) prepared in Preparation Example 5 was added. The reaction was carried out at 120 °C for 15 min. The high-pressure reactor was then vented and the product was discharged. The reaction was terminated with an ethanol / HCl mixture (ethanol / HCl volume ratio of 9:1). The condensed product was washed with ethanol and dried under vacuum to constant weight to obtain 7.5 g of cyclic olefin copolymer.

[0151] The copolymerization activity was measured to be 6.0 × 10⁻⁶. 6 The obtained copolymer, with a yield of g / (mol·Mt·h), contained 50.1 mol% cyclic olefins and had a molecular weight Mn of 4.67 × 10⁻⁶. 5 The molecular weight distribution index Mw / Mn is 2.31.

[0152] Example 5

[0153] The 500 mL high-pressure reactor was evacuated three times with high-purity nitrogen. Under vacuum, 200 mL of toluene solution containing norbornene (20 mmol), 0.2 mL of toluene solution containing methylaluminoxane (0.5 mmol), and 5 mL of toluene solution containing [CPh3][B(C6F5)4] compound (0.005 mmol) were added sequentially. Ethylene was then introduced to 0.5 MPa, and the mixture was stirred at room temperature (approximately 25 °C) for 10 min. Then, 5 mL of toluene solution containing catalyst 1B (5 μmol) prepared in Preparation Example 5 was added. The mixture was reacted at 40 °C for 15 min. The high-pressure reactor was then vented and the product was discharged. The reaction was terminated with an ethanol / HCl mixture (ethanol / HCl volume ratio of 9:1). The condensed product was washed with ethanol and dried under vacuum to constant weight to obtain 8.62 g of cyclic olefin copolymer.

[0154] The copolymerization activity was measured to be 6.9 × 10⁻⁶. 6 The obtained copolymer, with a cyclic olefin content of 48.1 mol·Mt·h and a molecular weight Mn of 6.71 × 10⁻⁶ g / (mol·Mt·h), yielded a copolymer with a molecular weight Mn of 6.71 × 10⁻⁶ g / (mol·Mt·h). 5 The molecular weight distribution index Mw / Mn is 2.25.

[0155] Example 6

[0156] The 500 mL high-pressure reactor was evacuated three times with high-purity nitrogen. Under vacuum, 200 mL of toluene solution containing norbornene (20 mmol), 0.2 mL of toluene solution containing methylaluminoxane (0.5 mmol), and 5 mL of toluene solution containing [CPh3][B(C6F5)4] compound (0.01 mmol) were added sequentially. Ethylene was then introduced to 0.5 MPa, and the mixture was stirred at room temperature (approximately 25 °C) for 10 min. Then, 5 mL of toluene solution containing catalyst 1C (5 μmol) prepared in Preparation Example 6 was added. The mixture was reacted at 40 °C for 15 min. The high-pressure reactor was then vented and the product was discharged. The reaction was terminated with an ethanol / HCl mixture (ethanol / HCl volume ratio of 9:1). The condensed product was washed with ethanol and dried under vacuum to constant weight to obtain 8.34 g of cyclic olefin copolymer.

[0157] The copolymerization activity was measured to be 6.67 × 10⁻⁶. 6 The obtained copolymer, with a yield of g / (mol·Mt·h), contained 52.1 mol% cyclic olefins and had a molecular weight Mn of 9.82 × 10⁻⁶ g / (mol·Mt·h). 5 The molecular weight distribution index Mw / Mn is 2.23.

[0158] Example 7

[0159] The 500 mL high-pressure reactor was evacuated three times with high-purity nitrogen. Under vacuum, 200 mL of toluene solution containing norbornene (30 mmol), 0.2 mL of toluene solution containing methylaluminoxane (0.75 mmol), and 5 mL of toluene solution containing [CPh3][B(C6F5)4] compound (0.005 mmol) were added sequentially. Ethylene was then introduced to 0.5 MPa, and the mixture was stirred at room temperature (approximately 25 °C) for 10 min. Then, 5 mL of toluene solution containing catalyst 1C (5 μmol) prepared in Preparation Example 6 was added. After reacting at 40 °C for 15 min, the high-pressure reactor was vented and the product was discharged. The reaction was terminated with an ethanol / HCl mixture (ethanol / HCl volume ratio of 9:1). The condensed product was washed with ethanol and dried under vacuum to constant weight to obtain 7.12 g of cyclic olefin copolymer.

[0160] The copolymerization activity was measured to be 5.7 × 10⁻⁶. 6 The obtained copolymer, with a yield of g / (mol·Mt·h), contained 64.7 mol% cyclic olefins and had a molecular weight Mn of 8.43 × 10⁻⁶. 5 The molecular weight distribution index Mw / Mn is 2.25.

[0161] Example 8

[0162] The 500 mL high-pressure reactor was evacuated three times with high-purity nitrogen. Under vacuum, 200 mL of toluene solution containing norbornene (30 mmol), 0.2 mL of toluene solution containing methylaluminoxane (0.75 mmol), and 5 mL of toluene solution containing [CPh3][B(C6F5)4] compound (0.005 mmol) were added sequentially. Ethylene was then introduced to 0.5 MPa, and the mixture was stirred at room temperature (approximately 25 °C) for 10 min. Then, 5 mL of toluene solution containing catalyst 1D (5 μmol) prepared in Preparation Example 7 was added. The mixture was reacted at 40 °C for 15 min. The high-pressure reactor was then vented and the product was discharged. The reaction was terminated with an ethanol / HCl mixture (ethanol / HCl volume ratio of 9:1). The condensed product was washed with ethanol and dried under vacuum to constant weight to obtain 7.52 g of cyclic olefin copolymer.

[0163] The copolymerization activity was measured to be 6.02 × 10⁻⁶. 6 The obtained copolymer, with a yield of g / (mol·Mt·h), contained 65.3 mol% cyclic olefins and had a molecular weight Mn of 10.3 × 10⁻⁶ g / (mol·Mt·h). 5 The molecular weight distribution index Mw / Mn is 2.36.

[0164] Comparative Example 1

[0165] The cyclic olefin copolymer was prepared according to the method of Example 1, except that 5 mL of toluene solution containing 5 μmol of catalyst 1A obtained in Preparation Example 4 was replaced with 5 mL of toluene solution containing rac-dimethylsilylbis(1-indenyl)zirconia (5 μmol), and 3.67 g of cyclic olefin copolymer was obtained.

[0166] The copolymerization activity was measured to be 2.02 × 10⁻⁶. 6 The obtained copolymer, with a cyclic olefin content of 25.3 mol·Mt·h and a molecular weight Mn of 3.5 × 10⁻⁶ g / (mol·Mt·h), has a molecular weight Mn of 3.5 × 10⁻⁶ g / (mol·Mt·h). 5 The molecular weight distribution index Mw / Mn is 2.2.

[0167] The results above show that, compared with the cyclic olefin copolymer prepared in Comparative Example 1, the cyclic olefin copolymers prepared using Examples 1-8 of the present invention have higher copolymerization activity, higher cyclic olefin content, and higher molecular weight.

[0168] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing a cyclic olefin copolymer, characterized in that, The preparation method includes: α-olefin monomers and cyclic olefin monomers are copolymerized in the presence of a monocyclic complex catalyst containing phosphine nitrogen ligands and a co-catalyst to obtain cyclic olefin copolymers; wherein the monocyclic complex catalyst has the structure shown in formula (1); In equation (1), R 1 R 2 and R 3 Each independently chooses H and C. 1-20 hydrocarbon group, C 1-20 The group consisting of alkoxy groups and halogens; R1 and R2 are each independently chosen from H and C. 1-4 hydrocarbon group, C 6-12 aryl and C 1-4 hydrocarbon group substituted C 7-16 A group consisting of aryl groups; m is 1, 2, or 3; Mt is a Group IVB metallic element; Cp* is a cyclopentadienyl group containing an electron-donating substituent; X is an atom or group bonded to the Mt element, and X is selected from C. 1-10 It is at least one group in the group consisting of a hydrocarbon group and a halogen; n is an integer and satisfies the Mt bond valence.

2. The preparation method according to claim 1, wherein, In equation (1), R 1 R 2 and R 3 Each independently chooses H and C. 1-16 hydrocarbon group, C 1-16 The group consisting of alkoxy groups and halogens; R1 and R2 are each independently chosen from H and C. 1-4 hydrocarbon group, C 6-10 aryl and C 1-4 hydrocarbon group substituted C 7-14 A group consisting of aryl groups; Mt represents titanium, zirconium, or hafnium; X chooses freely C 1-8 It consists of at least one group from the group consisting of hydrocarbon groups, fluorine, chlorine, bromine and iodine.

3. The preparation method according to claim 1 or 2, wherein, The cocatalyst includes aluminum-containing compounds and optionally organoboron compounds.

4. The preparation method according to claim 3, wherein, The co-catalyst comprises an aluminum-containing compound, and the molar ratio of the monocrole complex catalyst (calculated as metal element) to the aluminum-containing compound (calculated as aluminum element) is 1:(0.1-3000), preferably 1:(10-200).

5. The preparation method according to claim 3, wherein, The cocatalyst comprises a mixture of an aluminum-containing compound and an organoboron compound, wherein the molar ratio of the monocrole complex catalyst, the aluminum-containing compound, and the organoboron compound, calculated as metal elements, is 1:(10-500):(1-5), preferably 1:(10-200):(1-5).

6. The preparation method according to claim 3, wherein, The aluminum-containing compound is a mixture of alkylaluminum compounds and alkylaluminoxane compounds or an alkylaluminoxane compound; preferably, the alkylaluminoxane compound is methylaluminoxane and / or isobutylaluminoxane, and the alkylaluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride, dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride, and dihexylaluminum hydride.

7. The preparation method according to claim 3, wherein, The organoboron compound is selected from at least one of tris(pentafluorophenyl)boron, N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, and triphenylcarbamonium tetra(pentafluorophenyl)borate.

8. The preparation method according to any one of claims 1-7, wherein, The α-olefin monomer is ethylene and / or α-olefin; And / or, the cyclic olefin monomer is selected from at least one of cyclopentene, cyclohexene, norbornene, 1-methylnorbornene, 5-methylnorbornene, dicyclopentadiene, 5-methylene-2-norbornene, and 5-ethylidene-2-norbornene; And / or, in the copolymerization system, the concentration of the cyclic olefin monomer is 0.01-10 mol / L; And / or, in the copolymerization system, the partial pressure of the α-olefin monomer is 0.5-5 MPa.

9. The preparation method according to any one of claims 1-8, wherein, In the copolymerization system, the concentration of the monocerocene complex catalyst is 1 × 10⁻⁶. -8 -1×10 -5 mol / L; And / or, the molar ratio of the cyclic olefin monomer to the monoceramic complex catalyst is 1.5 × 10⁻⁶. 5 -5×10 5 :

1.

10. The preparation method according to any one of claims 1-9, wherein, The conditions for the copolymerization reaction include: a reaction temperature of 40-120℃ and a reaction time of 10-60 min.

11. A cyclic olefin copolymer prepared by the preparation method according to any one of claims 1-10; wherein, The cyclic olefin copolymer contains 45-70% molar content of cyclic olefins.

12. The cyclic olefin copolymer according to claim 11, wherein, The weight-average molecular weight of the cyclic olefin copolymer is 20,000 to 200,000, and the molecular weight distribution index is 1.9 to 2.5.

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