WO2023011383A1

WO2023011383A1 - Copolymer, and preparation method therefor and use thereof

Info

Publication number: WO2023011383A1
Application number: PCT/CN2022/109300
Authority: WO
Inventors: 简忠保; 张燚鑫; 崔磊; 邹海良; 陈辰; 季鹤源
Original assignee: 华为技术有限公司
Priority date: 2021-07-31
Filing date: 2022-07-30
Publication date: 2023-02-09
Also published as: CN115677879A

Abstract

Provided in the embodiments of the present application is a catalyst for preparing a cyclic olefin copolymer, which catalyst comprises a main catalyst as shown in formula (1-a). D is a bridging group, and Q is a metal center; R₅, R₆, R₇ and R₈ independently comprise a hydrogen atom, a hydrocarbyl or a silicon-containing substituent, with the silicon-containing substituent being linked to the carbon atom corresponding to the substituted position by means of a silicon atom; R_a and R_b are a carbon-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group; at least one of R₅, R₆, R₇ and R₈ is a silicon-containing substituent, and/or at least one of R_a and R_b is a silicon-containing group; and R₉, R₁₃, R₁₄ and R₁₈ independently comprise a hydrogen atom, a hydrocarbyl or a hydrocarbyloxy. By using this catalyst, a low-molecular-weight cyclic olefin copolymer can be prepared without the additional introduction of a molecular weight regulator such as hydrogen or propylene, and the cyclic olefin copolymer also has a moderate glass transition temperature.

Description

A kind of copolymer and its preparation method and application

This application requires submission to the China Patent Office on July 31, 2021, the application number is 202110879346.3, and the application name is "catalyst for the preparation of cycloolefin copolymer, preparation method of cycloolefin copolymer, cycloolefin copolymer and its application". priority of the patent application, the entire content of which is incorporated in this application by reference.

technical field

The embodiments of the present application relate to the technical field of preparation of engineering plastics, in particular to a catalyst for the preparation of cycloolefin copolymers, a preparation method of cycloolefin copolymers, cycloolefin copolymers and applications thereof.

Background technique

Cycloolefin polymers are a class of thermoplastic engineering plastics with high added value, due to their excellent optical transparency, heat resistance, chemical stability, melt fluidity, moisture barrier, dimensional stability and low dielectric constant, etc. Performance, has been widely used in various electronic products, automotive headlights, glasses, medical food packaging materials and other fields.

There are two main ways to synthesize cyclic olefin polymers: one method is the chain addition copolymerization of ethylene or α-olefin (referring to a single olefin with a double bond at the end of the molecular chain) and norbornene cycloolefin monomer (As shown in the chemical reaction formula (1), m and n represent the degree of polymerization), the polymer prepared by this method is also called cycloolefin copolymer (Cyclic Olefin Copolymer, COC); another method is norbornene Ring-opening metathesis polymerization (ROMP) of isocyclic olefin monomers and subsequent hydrogenation (as shown in chemical reaction formula (2), n represents the degree of polymerization), and the resulting polymer is also called cycloolefin homopolymer ( Cyclic Olefin Polymer, COP).

The molecular weight and glass transition temperature (Glass transition temperature, T _g ) of cycloolefin polymers are two key performance indicators in the process of synthesis, processing and practical application. Molecular weight significantly affects the mechanical and processability of cycloolefin polymers. When the molecular weight of the cycloolefin polymer is relatively high (for example, the weight average molecular weight is greater than 100,000), the melt flow index (Melt Flow Rate, MFR) is very low, and processing is difficult. When the T _g of the cycloolefin polymer is too high, it will cause difficulty in processing or injection molding of the cycloolefin polymer; when the T _g is too low, the use environment and conditions of the cycloolefin polymer will be limited. Therefore, for the practical application of COC, it is necessary to find an effective method to prepare cycloolefin copolymers with low molecular weight (weight average molecular weight less than or equal to 150,000) and moderate T _g (110°C-180°C).

Contents of the invention

In view of this, the embodiment of the present application provides a catalyst for the preparation of cycloolefin copolymers, which can be used to prepare low molecular weight (weight average molecular weight less than or equal to 150,000) without additional introduction of molecular weight regulators such as hydrogen or propylene. Cyclic olefin copolymer, while ensuring that the cyclic olefin copolymer has a moderate glass transition temperature (110°C-180°C).

In the first aspect, the embodiment of the present application provides a catalyst for the preparation of cycloolefin copolymers, the catalyst includes a main catalyst with a structural formula as shown in formula (1-a):

In formula (1-a), D is a bridging group, and Q is a metal center;

R ₅ , R ₆ , R ₇ , and R ₈ independently include a hydrogen atom, a hydrocarbon group or a silicon-containing substituent, and the silicon-containing substituent is connected to the carbon atom at the corresponding substitution position through a silicon atom;

R _a and R _b are carbon-containing groups, silicon-containing groups, germanium-containing groups or tin-containing groups;

At least one of said R ₅ , R ₆ , R ₇ , R ₈ is a silicon-containing substituent, and/or at least one of said R _a , R _b is a silicon-containing group;

R ₉ , R ₁₃ , R ₁₄ , and R ₁₈ independently include a hydrogen atom, a hydrocarbon group or a hydrocarbon oxy group.

The catalyst for the preparation of cycloolefin copolymers provided by the embodiments of the present application includes the main catalyst shown in formula (1-a), the main catalyst is a cyclopentadiene fluorene bridged transition metal catalyst, and the cyclopentadiene of the main catalyst is Silicon-containing heteroatom groups are introduced into the alkenyl or fluorenyl groups. During the copolymerization of ethylene, α-olefins and cycloolefin monomers, the metal center of the main catalyst and the silicon atoms introduced into the cyclopentadienyl or fluorenyl groups A synergistic effect can be produced, which can promote the chain transfer in the polymerization process and improve the insertion rate of cycloolefin monomers, so that a low molecular weight ( A cycloolefin copolymer with a weight average molecular weight less than or equal to 150,000) and a moderate glass transition temperature. The obtained cyclic olefin copolymer has a low melt flow index due to its low molecular weight, good processing performance, and can avoid the problem that the glass transition temperature is too high to be difficult to process and difficult to injection molding due to the moderate glass transition temperature, and at the same time Moderate glass transition temperature can have better heat resistance, making cycloolefin copolymers suitable for various application scenarios.

In the embodiment of the present application, the metal center Q is represented by -M ¹ (R ₁ R ₂ )-, the M ¹ represents scandium, titanium, vanadium, zirconium, hafnium, niobium or tantalum, and the R ₁ and R ₂ independently include a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aryloxy group, an aralkyl group, an alkaryl group or an aralkenyl group.

In the embodiment of the present application, the bridging group D is represented as -X(R ₃ R ₄ )-, the X represents carbon or silicon, and the R ₃ and R ₄ independently include a hydrogen atom or a hydrocarbon group.

In the embodiments of the present application, the R _a is represented as -M ² (R ₁₀ R ₁₁ R ₁₂ ), the R _b is represented as -M ³ (R ₁₅ R ₁₆ R ₁₇ ), and M ² and M ³ independently represent Carbon, silicon, germanium or tin, R ₁₀ , R ₁₁ , R ₁₂ , R ₁₅ , R ₁₆ , R ₁₇ independently include alkyl, alkoxy, alkenyl, aryl, aryloxy, aralkyl, alkane Aryl or aralkenyl.

In one embodiment of the present application, the specific structural formula of the main catalyst shown in formula (1-a) is shown in formula (1-b):

In some embodiments of the present application, at least one of R ₅ , R ₆ , R ₇ , and R ₈ is a silicon-containing substituent, Ra _and R _b are not silicon-containing groups, Ra _and R _b are carbon-containing groups, The germanium-containing group or the tin-containing group, ie M ² , M ³ independently include carbon, germanium or tin. In other embodiments of the present application, at least one of R _a and R _b is a silicon-containing group, that is, one or both of M ² and M ³ is silicon, and R ₅ , R ₆ , R ₇ , and R ₈ are not groups containing silicon. Silicon substituent, R ₅ , R ₆ , R ₇ , R ₈ are hydrogen atoms or hydrocarbon groups. In other embodiments of the present application, at least one of R _a and R _b is a silicon-containing group, that is, one or both of M ² and M ³ is silicon, and at least one of R ₅ , R ₆ , R ₇ , and R ₈ One is a silicon-containing substituent.

In some embodiments of the present application, at least one of R ₆ and R ₇ is a silicon-containing substituent, and/or at least one of R _a and R _b is a silicon-containing group. The silicon-containing substituent is located at the 3-position and 4-position of cyclopentadiene, which is farther away from the metal center ^M1 than the 2-position and 5-position. M ¹ forms a weak coordination to promote chain transfer, reduce the molecular weight of the polymer, and avoid affecting the polymerization activity of the catalyst due to strong coordination.

In the embodiment of the present application, the number of carbon atoms of the hydrocarbon group and the silicon-containing substituent in R ₅ , R ₆ , R ₇ , and R ₈ is less than or equal to 6.

In the embodiments of the present application, the number of carbon atoms of R ₁₀ , R ₁₁ , R ₁₂ , R ₁₅ , R ₁₆ , and R ₁₇ is less than or equal to 10.

In the embodiment of the present application, the catalyst for the preparation of cycloolefin copolymers also includes a co-catalyst, and the co-catalyst includes but is not limited to one of methyl aluminoxane, modified methyl aluminoxane, and organoboron compound or more. In the embodiment of the present application, the organoboron compound includes tris(pentafluorophenyl)boron, triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl) base) one or more of borates. The use of methylalumoxane, modified methylalumoxane and organic boron compound as cocatalysts is beneficial to ensure the copolymerization reaction activity of cycloolefin copolymer preparation.

In the embodiment of the present application, the molar ratio of the main catalyst represented by the formula (1-a) to the co-catalyst is 1: (10-10000).

In the embodiment of the present application, the catalytic activity of the catalyst is higher than 10 ⁶ g·mol ^-1 ·h ^-1 . The main catalyst represented by the formula (1-a) of the present application has high catalytic activity when used in the preparation of cycloolefin copolymers.

In the embodiment of the present application, the main catalyst and the co-catalyst may be supported on a carrier. The carrier may be, for example, silicon oxide, aluminum oxide, titanium oxide, or the like.

In the second aspect, the embodiment of the present application provides a method for preparing a cycloolefin copolymer, comprising:

In the presence of the catalyst for preparing the cycloolefin copolymer described in the first aspect, the cycloolefin monomer is copolymerized with ethylene or α-olefin to obtain the cycloolefin copolymer.

In the embodiment of the present application, the reaction system of the copolymerization includes an inert solvent, and the inert solvent includes one or more of linear alkanes, cyclic hydrocarbons and aromatic compounds.

In the embodiment of the present application, the dosage of the procatalyst represented by the formula (1-a) in the reaction system of the copolymerization is 0.001mmol/L-10mmol/L.

In the implementation manner of the present application, the amount of the cycloolefin monomer in the reaction system of the copolymerization is 0.01 mol/L-10 mol/L.

In the embodiment of the present application, the molar ratio of the cycloolefin monomer to the main catalyst in the copolymerization reaction system is 500-500000. The main catalyst of the present application can adapt to a relatively wide range of cycloolefin monomer usage, and has high catalytic activity.

In the embodiment of the present application, the temperature of the copolymerization reaction is 50°C-120°C; the time of the copolymerization reaction is 2min-10min. The preparation method of the cyclic olefin copolymer of the present application requires low copolymerization reaction temperature, short time and high efficiency.

In the embodiment of the present application, the structural formula of the cycloolefin monomer is shown in formula (2):

In formula (2), R ₁₉ is a hydrocarbon group or a hydrocarbon silicon group; R ₂₀ and R ₂₁ independently include a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an ester group, a carbonic acid group Ester group, cyano group, amino group, thiol group, atoms or atomic groups that can replace the above groups;

R ₂₂ and R ₂₃ independently include hydrogen atom, halogen atom, alkyl group, alkoxyl group, aryl group, aryloxyl group, hydroxyl group, ester group, carbonate group, cyano group, amino group, thiol group, and can replace the above-mentioned An atom or an atomic group of a group, or _R22 and _R23 are connected to form a group with a ring structure;

z is a positive integer.

In the embodiment of the present application, the α-olefin may be propylene, 1-butene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene or 2-ethyl-1-butene.

In the embodiment of the present application, the copolymerization reaction system does not contain a molecular weight regulator. The molecular weight regulator is, for example, hydrogen, propylene, or the like. The addition of molecular weight regulator not only makes the preparation process more complicated, but also affects the polymerization itself. For example, the introduction of hydrogen will reduce the activity of the catalyst system, and the introduction of propylene will introduce propylene molecules into the polymer, affecting the structure of the cycloolefin copolymer.

The preparation method of the cyclic olefin copolymer provided in the examples of the present application, by using the catalyst provided in the first aspect of the examples of the present application, does not need to introduce additional molecular weight regulators such as hydrogen or propylene, and can be prepared with low molecular weight and moderate vitrification. Cyclic olefin copolymers with a transition temperature to meet the processing performance and heat resistance requirements of various optical products such as optical lenses, display materials and packaging materials. This preparation method not only greatly simplifies the preparation route of cycloolefin copolymer materials, but also significantly improves the polymerization activity and energy and economic benefits, and opens up a new path for large-scale production of cycloolefin copolymer materials.

In the third aspect, the embodiment of the present application provides a cycloolefin copolymer prepared according to the preparation method described in the second aspect, the structural formula of the cycloolefin copolymer is shown in formula (3):

In formula (3), R ₁₉ is a hydrocarbon group or a hydrocarbon silicon group; R ₂₀ and R ₂₁ independently include a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an ester group, a carbonic acid group Ester group, cyano group, amino group, thiol group, atoms or atomic groups that can replace the above groups;

R ₂₂ , R ₂₃ , R ₂₄ , and R ₂₅ independently include hydrogen atom, halogen atom, alkyl, alkoxy, aryl, aryloxy, hydroxyl, ester, carbonate, cyano, amino, sulfur Alcohol groups, atoms or atomic groups that can replace the above groups, or _R22 and _R23 are connected to form a group with a ring structure, and _R24 and _R25 are connected to form a group with a ring structure;

x and y represent the polymerization degree, both x and y are positive numbers, 1<x:y<3, and z is a positive integer.

In the embodiment of the present application, the weight average molecular weight of the cycloolefin copolymer is in the range of 5000 to 150000 (g/mol); the molecular weight distribution index is in the range of 1.5 to 3.0.

In the embodiment of the present application, the insertion rate of the cycloolefin monomer of the cycloolefin copolymer is in the range of 20%-60%; the glass transition temperature of the cycloolefin copolymer is in the range of 110°C to 180°C.

In the embodiment of the present application, the visible light transmittance of the molded product of the cycloolefin copolymer is greater than 90%.

In the fourth aspect, the embodiment of the present application provides a composition comprising the cycloolefin copolymer described in the third aspect of the embodiment of the present application, or the cycloolefin copolymer prepared by the preparation method described in the second aspect.

In the embodiment of the present application, the composition also includes additives, and the additives include fillers, dyes, antioxidants, light stabilizers, ultraviolet absorbers, plasticizers, flame retardants, antistatic agents, and release agents. one or more.

In the fifth aspect, the embodiment of the present application provides an optical product, the optical product includes the cycloolefin copolymer described in the third aspect of the embodiment of the application, or the cycloolefin copolymer prepared by the preparation method described in the second aspect things.

In the embodiments of the present application, the optical product includes an optical lens, an optical film, an optical disc, a light guide plate or a display panel. The optical lenses include spectacle lenses, camera lenses, sensor lenses, illumination lenses, and imaging lenses.

The embodiment of the present application also provides a device, including the optical product described in the fifth aspect of the embodiment of the present application.

The embodiment of the present application also provides an electronic device, including a main body of the electronic device and a camera module assembled on the main body of the electronic device, the camera module includes a lens lens, and the lens lens adopts the ring described in the third aspect Olefin copolymer, or the preparation of the composition described in the fourth aspect.

Description of drawings

FIG. 1 is a schematic structural diagram of a device 100 provided in an embodiment of the present application;

Figure 2 is the hydrogen nuclear magnetic resonance spectrum ( ¹ H Nuclear Magnetic Resonance Spectroscopy, ¹ H NMR) of catalyst A in Example 1 of the present application;

Figure 3 is the carbon nuclear magnetic resonance spectrum ( ¹³ C Nuclear Magnetic Resonance Spectroscopy, ¹³ C NMR) of catalyst A in Example 1 of the present application;

Fig. 4 is the proton nuclear magnetic resonance spectrum of cycloolefin monomer in the embodiment 1 of the present application;

Fig. 5 is the carbon nuclear magnetic resonance spectrum of the cycloolefin monomer of embodiment 1 of the present application;

Fig. 6 is the proton nuclear magnetic resonance spectrum of cycloolefin copolymer in the embodiment 1 of the present application;

Fig. 7 is the carbon nuclear magnetic resonance spectrum of the cyclic olefin copolymer of the embodiment 1 of the present application;

Fig. 8 is the DSC (Differential Scanning Calorimetry, differential scanning calorimetry) curve of the cyclic olefin copolymer of the embodiment 1 of the present application;

Fig. 9 is the visible light transmittance test curve of the cycloolefin copolymer of Example 1 of the present application;

Fig. 10 is the DSC curve of the cyclic olefin copolymer of the application embodiment 2;

Fig. 11 is the DSC curve of the cyclic olefin copolymer of the application embodiment 3;

Fig. 12 is the DSC curve of the cyclic olefin copolymer of the application embodiment 4;

Figure 13 is the DSC curve of the cycloolefin copolymer of Example 5 of the present application.

Detailed ways

The embodiments of the present application will be described below with reference to the drawings in the embodiments of the present application.

The molecular weight and glass transition temperature of cyclic olefin copolymer COC are two key performance indicators. The molecular weight affects the processing performance, and the glass transition temperature affects the processing performance and the use environment and conditions. At present, metallocene catalysts are usually used for the preparation of cycloolefin copolymers. However, cycloolefin copolymers directly prepared by existing metallocene catalysts usually have a molecular weight of 200,000 or more, low melt flow index, difficult processing, and low commercial value. In order to obtain cycloolefin copolymers with low molecular weight, the existing traditional method is to additionally introduce molecular weight regulators such as hydrogen and propylene in the preparation process, and the additional introduction of molecular weight regulators may reduce the catalytic activity of the catalyst, and may also cause cycloolefin copolymerization The introduction of a molecular weight regulator into the compound will affect the structure of the cycloolefin copolymer, and the additional introduction of a molecular weight regulator will also complicate the preparation process. In addition, in the process of copolymerizing ethylene or α-olefin with cycloolefin monomer, the glass transition temperature of cycloolefin copolymer COC can be adjusted by adjusting the insertion rate of cycloolefin monomer in the copolymer.

In order to obtain a cyclic olefin copolymer COC with a lower molecular weight and a suitable glass transition temperature, the embodiment of the present application provides a catalyst for the preparation of a cyclic olefin copolymer, which can be used without additional introduction of molecular weight modifiers such as hydrogen or propylene Next, it is used to directly prepare cycloolefin copolymers with low molecular weight and moderate glass transition temperature, the catalyst includes a structural formula such as the main catalyst shown in formula (1-a):

In formula (1-a), D is a bridging group, and Q is a metal center;

In the catalyst for the preparation of cycloolefin copolymers provided in the examples of the present application, the main catalyst represented by formula (1-a) is a cyclopentadiene fluorene bridged transition metal catalyst, and the cyclopentadiene fluorene bridged transition metal catalyst The 2-position or 7-position of the cyclopentadienyl or fluorenyl group in the cyclopentadienyl or fluorenyl group is introduced with a silicon-containing heteroatom group. In the process of copolymerization of ethylene or α-olefin and cycloolefin monomer, the metal center ^M of the main catalyst and The silicon atom introduced on the cyclopentadienyl or fluorenyl has a synergistic effect, which can promote the chain transfer in the polymerization process and increase the insertion rate of the cycloolefin monomer, so that it can be used without additional molecular weight regulators such as hydrogen or propylene. Cycloolefin copolymers with low molecular weight and moderate glass transition temperature are obtained. Specifically, the silicon atom introduced on the cyclopentadienyl or fluorenyl has a weak coordination with the metal center M ¹ empty orbital, and competes with the coordination between the alkene-metal center M ¹ , thus promoting the chain Transfer, reduce the molecular weight of the polymer so that the cycloolefin copolymer has a low molecular weight; at the same time, through this competition, it increases the difficulty of coordination between ethylene or α-olefin and the metal center ^M1 , and improves the insertion rate of the cycloolefin monomer, thereby It plays the role of adjusting the glass transition temperature, so that the cycloolefin copolymer has a moderate glass transition temperature, which is suitable for various application scenarios. The catalyst for the preparation of cycloolefin copolymers in the examples of the present application can make the preparation of low molecular weight cycloolefin copolymers easier and more efficient, greatly simplify the polymerization process and polymerization equipment, and facilitate the large-scale production of low molecular weight cycloolefin copolymers. At the same time, other properties of the cycloolefin polymer, such as optical properties, thermal properties, and mechanical properties, can reach the level of low-molecular-weight COC materials prepared by traditional methods, so that they can also adapt to the application scenarios of COC materials prepared by traditional methods.

In the embodiments of the present application, the R _a is represented as -M ² (R ₁₀ R ₁₁ R ₁₂ ), the R _b is represented as -M ³ (R ₁₅ R ₁₆ R ₁₇ ), and M ² and M ³ independently represent Carbon, silicon, germanium or tin, R ₁₀ , R ₁₁ , R ₁₂ , R ₁₅ , R ₁₆ , R ₁₇ independently include alkyl, alkoxy, alkenyl, aryl, aryloxy, aralkyl, alkane Aryl or aralkenyl. R _a is connected to the carbon atom at the corresponding position on the fluorene ring through ^M2 , and R _b is connected to the carbon atom at the corresponding position on the fluorene ring through ^M3 .

In the embodiment of the ^present application, the main catalyst represented by the formula (1-b) is a type of bridging double transition metallocene compound, and M is a metal center, representing scandium, titanium, vanadium, zirconium, hafnium, niobium or tantalum, etc. Early transition metal, R1 _and _R2 are connected to metal center ^M1 , _R1 and _R2 independently include hydrogen atom, halogen atom, alkyl, alkoxy, alkenyl, aryl, aryloxy, aralkyl , alkaryl or aralkenyl. Cyclopentadiene and fluorene are connected through a bridging group -X(R ₃ R ₄ )-, and cyclopentadiene and fluorene are coordinated with the metal center M ¹ . X represents carbon or silicon, _R3 and _R4 independently include a hydrogen atom or a hydrocarbon group, and the hydrocarbon group can be an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkaryl group or an aralkenyl group. Specifically, the hydrocarbon group may be an alkyl group, alkenyl group, aryl group, aralkyl group, alkaryl group or aralkenyl group with carbon atoms less than or equal to 10 (ie, carbon number 1-10). In some embodiments of the present application, R ₃ and R ₄ may also be connected to form a ring structure.

In the embodiment of the present application, in formula (1-b), when R ₁ and R ₂ are halogen atoms, the halogen atoms may be fluorine, chlorine, bromine or iodine. In the embodiments of the present application, the alkyl group may be a linear, branched or cyclic alkyl group. The alkyl group may be unsubstituted or substituted. Alkenyl groups may be straight chain or branched chain alkenyl groups. Alkenyl may be unsubstituted alkenyl or substituted alkenyl. The alkoxy group may be linear, branched or alkoxy having a cyclic structure. In the embodiments of the present application, the number of carbon atoms of the alkyl group, alkoxy group and alkenyl group may be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. Specifically, the alkyl group may be methyl, ethyl, propyl, butyl, etc., for example. In the embodiments of the present application, the aryl group may be a non-substituted aryl group or a substituted aryl group. The number of carbon atoms in the aryl, aryloxy, aralkyl, alkaryl, and aralkenyl groups may be 6, 7, 8, 9, or 10. In some embodiments of the present application, the bridging group -X(R ₃ R ₄ )- can be, for example but not limited to, methylene, ethylene, isopropylidene (-C(CH ₃ ) ₂ -), Benzhydrylene (-C(C ₆ H ₅ ) ₂ -), bistrimethylsilylmethylene (-C(Si(CH ₃ ) ₃ ) ₂ -), etc.

In the embodiment of the present application, in formula (1-b), R ₅ , R ₆ , R ₇ , and R ₈ may independently include a hydrogen atom, a hydrocarbon group, or a silicon-containing substituent. Specifically, the hydrocarbon group may be an alkyl group, alkenyl group, aryl group, aralkyl group, alkaryl group or aralkenyl group with carbon atoms less than or equal to 10 (ie, carbon number 1-10). The alkyl group may be linear, branched, or an alkyl group having a cyclic structure. The alkyl group may be unsubstituted or substituted. Alkenyl groups may be straight chain or branched chain alkenyl groups. Alkenyl may be unsubstituted alkenyl or substituted alkenyl. The number of carbon atoms in the alkyl and alkenyl groups may be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. Specifically, the alkyl group may be methyl, ethyl, propyl, butyl, etc., for example. In the embodiments of the present application, the aryl group may be a non-substituted aryl group or a substituted aryl group. The number of carbon atoms in the aryl, aralkyl, alkaryl, and aralkenyl groups may be 6, 7, 8, 9, or 10. R ₅ , R ₆ , R ₇ , and R ₈ correspond to the carbon atoms at the 2-, 3-, 4-, and 5-positions of cyclopentadiene, respectively. In the embodiment of the present application, when R ₅ , R ₆ , R ₇ or R ₈ is a silicon-containing substituent, the silicon-containing substituent and the carbon atom at the 2-, 3-, 4-, or 5-position of cyclopentadiene form carbon silicon Bond. In the embodiment of the present application, one of R ₅ , R ₆ , R ₇ and R ₈ may be a silicon-containing substituent, or two or three of R ₅ , R ₆ , R ₇ and R ₈ Or four of them are silicon-containing substituents. When some of R ₅ , R ₆ , R ₇ and R ₈ are silicon-containing substituents, the groups that are not silicon-containing substituents may be hydrogen atoms or hydrocarbon groups. When more than one of R ₅ , R ₆ , R ₇ and R ₈ is a silicon-containing substituent, they may be the same silicon-containing substituent or different silicon-containing substituents. When more than one of R ₅ , R ₆ , R ₇ and R ₈ is a hydrocarbon group, they may be the same hydrocarbon group or different hydrocarbon groups. The silicon-containing substituent is connected to the carbon atom at the corresponding substitution position through a silicon atom, that is, the silicon-containing substituent is connected to the carbon atom on the corresponding cyclopentadiene ring through a silicon atom, and the silicon-containing substituent can be expressed as -Si(R'R"R"'),R',R",R"' can be an alkyl group or an aryl group, that is, the silicon-containing substituent can be an alkylsilyl group or an arylsilyl group. Specifically, the alkylsilyl group can be trimethylsilyl group (that is, R', R", R"' is methyl group), triethylsilyl group (that is, R', R", R"' is ethyl group), etc. , the arylsilyl group can specifically be, for example, a triphenylsilyl group (that is, R', R", R"' are phenyl groups). In some embodiments of the present application, the silicon-containing substituent may be an alkylsilyl group with a total of 1-10 carbon atoms. In some embodiments, R ₅ , R ₆ , R ₇ , and R ₈ independently include a hydrocarbon group or a silicon-containing substituent with carbon atoms less than or equal to 6 (ie, C ₁ -C ₆ ). A hydrocarbon group or a silicon-containing substituent with a smaller number of carbon atoms can reduce the steric hindrance around the metal center M ¹ , which is beneficial to keep the catalytic activity of the catalyst at a high level.

The silicon-containing substituent introduced at the carbon position of cyclopentadiene can have a synergistic effect with the metal center ^M1 , promote the chain transfer during the polymerization process, increase the insertion rate of cycloolefin monomer, and make the cycloolefin copolymer have low molecular weight and moderate glass transition temperature. In some embodiments of the present application, at least one of R ₆ or R ₇ is a silicon-containing substituent. The substituents at the 3 and 4 positions of cyclopentadiene are farther away from the metal center ^M1 than those at the 2 and 5 positions. The introduction of silicon-containing substituents at the 3 and 4 positions of cyclopentadiene can not only achieve the same The metal center M ¹ forms weak coordination to promote chain transfer, reduce the molecular weight of the polymer, and avoid affecting the polymerization activity of the catalyst due to strong coordination. For example, in one embodiment, R ₆ is a silicon-containing substituent, and R ₅ , R ₇ and R ₈ are hydrogen or hydrocarbon groups. In another embodiment, R ₇ is a silicon-containing substituent, and R ₅ , R ₆ and R ₈ are hydrogen or hydrocarbon groups. In some embodiments, R ₆ and R ₇ are silicon-containing substituents, and R ₅ and R ₈ are hydrogen or hydrocarbyl.

In the embodiment of the present application, in formula (1-b), M ² represents carbon, silicon, germanium or tin, and M ³ represents carbon, silicon, germanium or tin. M ² and M ³ may be the same atom or different atoms. M ² or M ³ can have a synergistic effect with the metal center M ¹ to promote chain transfer during the polymerization process, increase the insertion rate of cycloolefin monomers, and play a role in adjusting the molecular weight and glass transition temperature, so that the cycloolefin copolymer It has low molecular weight and moderate glass transition temperature.

In order to make the procatalyst shown in formula (1-b) realize the effect of regulating molecular weight and regulating glass transition temperature in the cycloolefin copolymer preparation process, finally obtain the cycloolefin copolymer with low molecular weight and moderate glass transition temperature , in the embodiment of the present application, at least one of the substituents R ₅ , R ₆ , R ₇ , and R ₈ on the cyclopentadiene ring is a silicon-containing substituent, or the substitution of the 2- or 7-position of the fluorene ring At least one of the groups is a silicon-containing group, that is, at least one of M ² and M ³ is silicon. The distance between the 2-position and 7-position of the fluorene ring and the metal center ^M1 is moderate, and the synergistic coordination between the silicon-containing groups at the 2-position and 7-position and the metal center ^M1 is neither too strong nor too weak, so that there is It is beneficial to promote chain transfer through weak coordination and synergy, reduce the molecular weight of the polymer, and avoid affecting the polymerization activity of the catalyst due to strong coordination. When one or both of M ² and M ³ is silicon, R ₅ , R ₆ , R ₇ , and R ₈ are all hydrogen atoms or hydrocarbon groups, which is beneficial to ensure that the polymerization activity remains at a higher level and better balance The polymer has low molecular weight and polymerization activity, and can reduce the difficulty of catalyst preparation. When one or both of M ² and M ³ is silicon, at least one of R ₅ , R ₆ , R ₇ , and R ₈ is a silicon-containing group, and the coordination between silicon and the metal center M ¹ can facilitate Polymers with lower molecular weights were prepared.

In some embodiments of the present application, at least one of R ₅ , R ₆ , R ₇ and R ₈ is a silicon-containing substituent, and M ² and M ³ independently include carbon, germanium or tin. In other embodiments of the present application, R ₅ , R ₆ , R ₇ , and R ₈ independently include a hydrogen atom or a hydrocarbon group, and at least one of M ² and M ³ is silicon. In other embodiments of the present application, at least one of R ₅ , R ₆ , R ₇ and R ₈ is a silicon-containing substituent, and at least one of M ² and M ³ is silicon. In one embodiment, R ₅ , R ₆ , R ₇ , and R ₈ independently include a hydrogen atom or a hydrocarbon group, M ² and M ³ are silicon, and R ₉ , R ₁₃ , R ₁₄ , and R ₁₈ are hydrogen atoms, that is, a fluorene ring The upper 2 and 7 positions are silicon-containing groups, and the rest of the substituting positions are hydrogen atoms. The main catalyst of this embodiment can not only adjust the molecular weight and glass transition temperature of the copolymer through synergistic effect, but also has a simple structure and is easy to prepare.

In the embodiments of the present application, R ₁₀ , R ₁₁ , R ₁₂ , R ₁₅ , R ₁₆ , and R ₁₇ may independently include alkyl, alkoxy, alkenyl, aryl, aryloxy, aralkyl, alkaryl base or aralkenyl. Specifically, R ₁₀ , R ₁₁ , R ₁₂ , R ₁₅ , R ₁₆ , and R ₁₇ may independently include alkyl, alkoxy, alkenyl, aryl, aryloxy, Aralkyl, alkaryl or aralkenyl. In the embodiments of the present application, the alkyl group may be a linear, branched or cyclic alkyl group. The alkyl group may be unsubstituted or substituted. Alkenyl groups may be straight chain or branched chain alkenyl groups. Alkenyl may be unsubstituted alkenyl or substituted alkenyl. The alkoxy group may be linear, branched or alkoxy having a cyclic structure. In the embodiments of the present application, the number of carbon atoms of the alkyl group, alkoxy group and alkenyl group may be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. Specifically, the alkyl group may be methyl, ethyl, propyl, butyl, etc., for example. In the embodiments of the present application, the aryl group may be a non-substituted aryl group or a substituted aryl group. The number of carbon atoms in the aryl, aryloxy, aralkyl, alkaryl, and aralkenyl groups may be 6, 7, 8, 9, or 10.

In the embodiment of the present application, in formula (1-b), R ₉ , R ₁₃ , R ₁₄ , and R ₁₈ independently include a hydrogen atom, a hydrocarbyl group or a hydrocarbyloxy group. Specifically, the hydrocarbon group may be an alkyl group, alkenyl group, aryl group, aralkyl group, alkaryl group or aralkenyl group with carbon atoms less than or equal to 10 (ie, carbon number 1-10). The alkoxy group may be an alkoxy group or an aryloxy group with carbon atoms less than or equal to 10 (that is, the number of carbon atoms is 1-10). The alkyl group may be linear, branched, or an alkyl group having a cyclic structure. The alkyl group may be unsubstituted or substituted. Alkenyl groups may be straight chain or branched chain alkenyl groups. Alkenyl may be unsubstituted alkenyl or substituted alkenyl. The alkoxy group may be linear, branched or alkoxy having a cyclic structure. In the embodiments of the present application, the number of carbon atoms of the alkyl group, alkoxy group and alkenyl group may be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. Specifically, the alkyl group may be methyl, ethyl, propyl, butyl, etc., for example. In the embodiments of the present application, the aryl group may be a non-substituted aryl group or a substituted aryl group. The number of carbon atoms in the aryl, aryloxy, aralkyl, alkaryl, and aralkenyl groups may be 6, 7, 8, 9, or 10. In some embodiments of the present application, R ₉ , R ₁₃ , R ₁₄ , and R ₁₈ are all hydrogen atoms, that is, only the 2- and 7-position carbons on the fluorenyl group have substituents, so that the substitution structure on the fluorenyl group becomes It is simpler and simplifies the preparation process of the catalyst.

In some embodiments of the present application, the catalyst for the preparation of cycloolefin copolymers includes the main catalyst represented by formula (1-a), and also includes a co-catalyst, and the co-catalyst can include methyl aluminoxane (MAO), modified methyl One or more of aluminoxane (MMAO) and organoboron compounds. Among them, the organoboron compound may include tris(pentafluorophenyl) boron, triphenylcarbenium tetrakis(pentafluorophenyl) borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate One or more of salt. The co-catalyst is beneficial to enhance the activity of the main catalyst. Compared with methylalumoxane (MAO), the use of modified methylalumoxane (MMAO) as a cocatalyst can help reduce the amount of cycloolefin monomer. The use of methylalumoxane, modified methylalumoxane and organic boron compound as cocatalysts is beneficial to ensure the copolymerization reaction activity of cycloolefin copolymer preparation.

In the embodiment of the present application, the catalyst for the preparation of cycloolefin copolymers includes a main catalyst and a cocatalyst shown in formula (1-a), the more the cocatalyst is used, the lower the molecular weight of the cycloolefin polymer, and the higher the glass transition temperature , considering the molecular weight and glass transition temperature of the cycloolefin polymer, in this application, the molar ratio of the main catalyst to the co-catalyst can be 1: (10-10000). In some embodiments, the molar ratio of the main catalyst to the co-catalyst may be 1:(100-5000). In some embodiments, the molar ratio of the main catalyst to the co-catalyst may be 1:(500-4000).

In the embodiment of the present application, the catalyst for the preparation of cyclic olefin copolymers is used to prepare cyclic olefin copolymers, and has high catalytic activity, specifically, the catalytic activity is higher than 1×10 ⁶ g·mol ^-1 ·h ^-1 . In some embodiments, the catalytic activity is higher than 1×10 ⁷ g·mol ^-1 ·h ^-1 . The main catalyst represented by the formula (1-a) of the present application has high catalytic reaction activity when used in the preparation of cycloolefin copolymer, and the catalytic reaction activity is high, which is beneficial to improve the reaction speed and conversion rate of the copolymerization reaction.

The compound shown in the above-mentioned formula (1-b) of the embodiment of the present application can be prepared in the following manner:

Preparation of -X(R ₃ R ₄ )-bridged cyclopentadiene fluorene ligand, after lithiation of cyclopentadiene fluorene ligand with lithiation reagent, coordination reaction with M ¹ metal salt, the formula ( The compound shown in 1-b). The reaction process is shown in reaction formula (A).

The lithiation reagent can be, but is not limited to, n-butyllithium. The ^M1 metal salt may be a scandium salt, a titanium salt, a vanadium salt, a zirconium salt, a hafnium salt, a niobium salt or a tantalum salt. The lithiation process can be carried out under the conditions of anhydrous, oxygen-free and ice bath. Suction filtration is carried out after cyclopentadiene fluorene ligand lithiation, and the obtained product is moved into a glove box and added with an organic solvent and ^M1 metal salt, and stirred overnight for a coordination reaction. The organic solvent can be toluene, hexane, etc., which can dissolve the above product. solvent. The product obtained after the coordination reaction can be washed, extracted and recrystallized to obtain the final product.

Taking catalyst A as an example, the specific preparation process of catalyst A may include the following steps:

(1) Preparation of cyclopentadiene fluorene ligand:

Under anhydrous and oxygen-free conditions, at the reaction temperature of -78°C, add 2,7-dibromofluorene and anhydrous tetrahydrofuran into the reaction vessel, then add the hexane solution containing n-butyllithium drop by drop, and then drop by drop Add tetrahydrofuran solution containing trimethylchlorosilane (Me ₃ SiCl), and react overnight. Then, a hexane solution containing n-butyllithium and a tetrahydrofuran solution containing triphenylchlorosilane (Ph ₃ SiCl) were added dropwise again to react overnight. Subsequently, adding sodium hydroxide aqueous solution at room temperature for hydrolysis, extracting and separating the liquids with ether, and drying the organic phase with anhydrous magnesium sulfate to obtain 2,7-bis(triphenylsilyl)fluorene;

Under anhydrous and oxygen-free conditions, add the prepared 2,7-bis(triphenylsilyl)fluorene and anhydrous tetrahydrofuran into the reaction vessel, and add an equimolar amount of methyl lithium ether solution drop by drop at room temperature, React at room temperature overnight, then add dropwise anhydrous tetrahydrofuran solution dissolved in 6,6-dimethylfulvene, react overnight, add tetrabutylammonium chloride aqueous solution, stir, extract and separate the liquid, wash the aqueous phase with ether three times, After the organic phase is dried with anhydrous magnesium sulfate, it is dried and recrystallized to obtain a cyclopentadiene fluorene ligand precursor.

Under anhydrous and oxygen-free conditions, add the above-prepared cyclopentadiene fluorene ligand precursor and anhydrous tetrahydrofuran into the reaction vessel, add an equimolar amount of n-butyllithium hexane solution at -78°C, and then dropwise Trimethylchlorosilane (Me ₃ SiCl) was added dropwise, stirred overnight, the solvent was drained, and washed with hexane to obtain the cyclopentadiene fluorene ligand (ie, the catalyst A precursor).

The reaction process of the above steps can be referred to the reaction formula (1-1).

(2) Preparation of Catalyst A:

Under anhydrous and oxygen-free conditions, add cyclopentadiene fluorene ligand (catalyst A precursor) into the reaction vessel, add n-butyllithium under ice bath, remove the ice bath, react for 2-12 hours and pump Dry the solvent, move it into the glove box and add hexane, add zirconium tetrachloride under full stirring, and stir overnight. After overnight reaction, filter, wash the filter cake with hexane and dissolve in excess toluene, filter out the khaki-yellow insoluble matter, then concentrate the toluene solution, and recrystallize to obtain pink solid catalyst A. The reaction process of this step can be referred to reaction formula (1-2).

In the embodiment of the present application, the preparation of catalysts with other structures represented by formula (1-b) can refer to the preparation of catalyst A, which will not be described here.

The embodiment of the present application also provides a method for preparing a cycloolefin copolymer, using the catalyst for the preparation of the cycloolefin copolymer described in the embodiment of the present application, the preparation method comprising:

In the presence of the catalyst for preparing the cycloolefin copolymer, the cycloolefin monomer is copolymerized with ethylene or α-olefin to obtain the cycloolefin copolymer.

In the embodiment of the present application, the copolymerization reaction system includes an inert solvent, and the inert solvent includes one or more of linear alkanes, cyclic hydrocarbons and aromatic compounds. The straight-chain alkanes compound may specifically be straight-chain alkanes with 5-16 carbon atoms, such as pentane, hexane, heptane, octane and the like. Specifically, the cyclic hydrocarbon compound may be a cyclic hydrocarbon with 5-11 carbon atoms, such as cyclopentane, cyclohexane, and the like. Specifically, the aromatic hydrocarbon compound may be a liquid aromatic hydrocarbon with 6-20 carbon atoms, such as toluene.

In the embodiment of the present application, the dosage of the procatalyst represented by the formula (1-a) in the copolymerization reaction system is 0.001mmol/L-10mmol/L. In some embodiments, the dosage of the procatalyst represented by formula (1-a) in the copolymerization reaction system is 0.01mmol/L-1mmol/L. In some embodiments, the dosage of the procatalyst represented by formula (1-a) in the copolymerization reaction system is 0.01mmol/L-0.1mmol/L.

In the embodiment of the present application, the molar ratio of the main catalyst represented by formula (1-a) to the co-catalyst in the copolymerization reaction system may be 1: (10-10000). In some embodiments, the molar ratio of the main catalyst to the co-catalyst may be 1:(100-5000). In some embodiments, the molar ratio of the main catalyst to the co-catalyst may be 1:(500-4000).

In the embodiment of the present application, the amount of the cycloolefin monomer in the copolymerization reaction system may be 0.01 mol/L-10 mol/L. In some embodiments, the amount of the cycloolefin monomer in the copolymerization reaction system may be 0.01 mol/L-5 mol/L. In some embodiments, the amount of cycloolefin monomer used in the copolymerization reaction system may be 0.01 mol/L-1 mol/L.

In the embodiment of the present application, the molar ratio of the cycloolefin monomer to the main catalyst in the copolymerization reaction system is 500-500000. In some embodiments, the molar ratio of the cycloolefin monomer to the main catalyst in the copolymerization reaction system is 1,000-100,000. In some embodiments, the molar ratio of the cycloolefin monomer to the main catalyst in the copolymerization reaction system is 5,000-100,000. The main catalyst of the present application can adapt to a relatively wide range of cycloolefin monomer usage, and has high catalytic activity.

In the embodiment of the present application, the temperature of the copolymerization reaction may be 50°C-120°C; the time of the copolymerization reaction may be 2min-10min. In the present application, by using the above-mentioned catalyst for copolymerization, the reaction temperature is relatively mild and the time is short, so the polymerization process can be optimized. In some embodiments, the temperature of the copolymerization reaction may be 60°C-110°C. In some embodiments, the temperature of the copolymerization reaction may be 80°C-100°C. In some embodiments, the time of the copolymerization reaction may be 3 min-6 min.

In the embodiment of the present application, the structural formula of the cycloolefin monomer can be as shown in formula (2):

z is a positive integer.

In the embodiment of the present application, R ₁₉ is a hydrocarbyl group or a hydrocarbyl silicon group, and the hydrocarbyl group may be an alkylene group, an alkenylene group, an arylene group, an aralkylene group, an alkarylene group or an aralkenylene group. The number of carbon atoms in the hydrocarbon group may be less than or equal to 10 (ie, the number of carbon atoms is 1-10). Specifically, the number of carbon atoms of the alkylene group and the alkenylene group can be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. The number of carbon atoms in the arylene group, aralkylene group, alkarylene group, and aralkenylene group may be 6, 7, 8, 9, or 10. The hydrocarbyl silicon group may be an alkyl silicon group, an aryl silicon group. The number of carbon atoms in the hydrocarbyl silicon group may be less than or equal to 10 (that is, the number of carbon atoms is 1-10). In some embodiments, the hydrocarbylsilyl group can specifically be dimethylsilylene (-Si(CH ₃ ) ₂ -), diethylsilylene (-Si(C ₂ H ₅ ) ₂ -), diphenyl Siliconous group (-Si(C ₆ H ₅ ) ₂ -), etc.

In the embodiments of the present application, the atoms or atomic groups that can replace the above groups refer to hydrogen atoms, halogen atoms, alkyl groups, aryl groups, alkoxy groups, hydroxyl groups, ester groups, carbonate groups, cyano groups, amino groups, sulfur Atoms or atomic groups of alcohol groups may specifically, for example, be isotopic atoms of hydrogen atoms (deuterium, etc.), borane, metal ligands, and the like.

In the embodiments of the present application, among R ₂₀ , R ₂₁ , R ₂₂ and R ₂₃ , the halogen atom may be fluorine, chlorine, bromine or iodine. The alkyl group may be an alkyl group having 1 to 20 carbon atoms. In some embodiments, the number of carbon atoms in the alkyl group is 2-10; in other embodiments, the number of carbon atoms in the alkyl group is 8-20; in some other embodiments, the number of carbon atoms in the alkyl group is 8 -15. The alkyl group may be linear, branched, or an alkyl group having a cyclic structure. Specifically, the alkyl group may be methyl, ethyl, propyl, butyl, etc., for example. The alkyl group may be unsubstituted or substituted. In the embodiment of the present application, the aryl group may be an aromatic group with 6-20 carbon atoms, further, the aryl group may have 6-10 carbon atoms; further, the aryl group may have 7 carbon atoms -8. The aryl group may be a non-substituted aryl group or a substituted aryl group. In the embodiment of the present application, the number of carbon atoms in the alkoxy group may be 1-20. In some embodiments, the number of carbon atoms in the alkoxy group is 2-10; in other embodiments, the number of carbon atoms in the alkoxy group is 8-20; in some other embodiments, the number of carbon atoms in the alkoxy group is The number is 8-15. The alkoxy group may be linear, branched or alkoxy having a cyclic structure.

In the embodiment of the present application, the ring structure formed by the connection of R ₂₂ and R ₂₃ can be a saturated or unsaturated carbocyclic ring, a saturated or unsaturated heterocyclic ring, and the heteroatoms in the heterocyclic ring can be nitrogen, sulfur, oxygen, boron, silicon wait. For example, the group connected to the ring structure formed by R ₂₂ and R ₂₃ may include hydrogen atom, halogen atom, alkyl group, aryl group, alkoxyl group, hydroxyl group, ester group, cyano group, amino group, thiol group , Atoms or atomic groups that may substitute for the above-mentioned groups.

In the implementation manner of the present application, z is a positive integer, specifically 1, 2, 3, 4, etc.

In the embodiments of the present application, the α-olefin refers to a monoolefin with a double bond at the end of the molecular chain, and the number of carbon atoms of the α-olefin may be 2-20. Specifically, the α-olefin may be propylene, 1-butene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-methyl- 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene or 2-ethyl-1-butene.

In the embodiment of the present application, no molecular weight regulator is included in the copolymerization reaction system. The method for preparing cycloolefin copolymers in the examples of the present application can achieve the effect of adjusting the molecular weight only through the catalyst for preparing cycloolefins provided in the examples of the present application, and obtain low molecular weight cycloolefin copolymers.

In the embodiment of the present application, taking the copolymerization reaction of cycloolefin monomer and ethylene as an example, the reaction process for preparing the cycloolefin copolymer can be shown in the reaction formula (1-3):

The preparation method of the cyclic olefin copolymer provided in the examples of the present application, by using the catalyst provided in the examples of the present application, does not need to introduce additional molecular weight regulators such as hydrogen or propylene, and can prepare and obtain low molecular weight and moderate glass transition temperature. Cycloolefin copolymers to meet the processing performance and heat resistance requirements of various optical products such as optical lenses, display materials and packaging materials, while other properties of cycloolefin copolymers such as optical properties, thermal properties and mechanical properties, etc. It maintains the same level as traditional low-molecular-weight cycloolefin copolymer materials, so the low-molecular-weight cycloolefin copolymer materials produced by this method can be applied to the application scenarios of traditional cycloolefin copolymer materials. This preparation method not only greatly simplifies the preparation route of cycloolefin copolymer materials, but also significantly improves the polymerization activity and energy and economic benefits, and opens up a new path for large-scale production of cycloolefin copolymer materials. The polymerization reaction of cyclic olefin monomers and α-olefins in the examples of the present application has relatively high activity. The experimental results show that the cyclic olefin copolymer prepared by the above-mentioned method in the embodiment of the present application has a moderate _Tg (110-180°C) and a relatively low molecular weight (≤150,000), and the insertion rate of the cyclic olefin monomer is between 20%- Between 60%, the molecular weight distribution index is between 1.5-3.0.

The embodiment of the present application also provides a cycloolefin copolymer prepared by the above method, the structural formula of which is shown in formula (3):

It can be understood that, in the embodiment of the present application, the cycloolefin polymer represented by formula (3), wherein R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ and R in the cycloolefin monomer represented by formula (2) ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , and R ₂₃ are selected in the same way, and will not be repeated here.

In the embodiments of the present application, in R ₂₄ and R ₂₅ , the halogen atom may be fluorine, chlorine, bromine or iodine. The alkyl group may be an alkyl group having 1 to 20 carbon atoms. In some embodiments, the number of carbon atoms in the alkyl group is 2-10; in other embodiments, the number of carbon atoms in the alkyl group is 8-20; in some other embodiments, the number of carbon atoms in the alkyl group is 8 -15. The alkyl group may be linear, branched, or an alkyl group having a cyclic structure. Specifically, the alkyl group may be methyl, ethyl, propyl, butyl, etc., for example. The alkyl group may be unsubstituted or substituted. In the embodiment of the present application, the aryl group can be an aromatic group with 6-20 carbon atoms, further, the aryl group can have 6-10 carbon atoms; further, the aryl group can have 7 carbon atoms -8. The aryl group may be a non-substituted aromatic group or a substituted aromatic group. In the embodiment of the present application, the number of carbon atoms in the alkoxy group may be 1-20. In some embodiments, the number of carbon atoms in the alkoxy group is 2-10; in other embodiments, the number of carbon atoms in the alkoxy group is 8-20; in some other embodiments, the number of carbon atoms in the alkoxy group is The number is 8-15. The alkoxy group may be linear, branched or alkoxy having a cyclic structure.

In the embodiment of the present application, the ring structure formed by the connection of R ₂₄ and R ₂₅ can be a saturated or unsaturated carbocyclic ring, a saturated or unsaturated heterocyclic ring, and the heteroatoms in the heterocyclic ring can be nitrogen, sulfur, oxygen, boron, silicon wait. For example, the group connected to the ring structure formed by R ₂₄ and R ₂₅ may include hydrogen atom, halogen atom, alkyl group, aryl group, alkoxy group, hydroxyl group, ester group, cyano group, amino group, thiol group , Atoms or atomic groups that may substitute for the above-mentioned groups.

In the implementation manner of the present application, z is a positive integer, specifically 1, 2, 3, 4, etc. The ratio of x and y may be such that 1.5<x:y<2.5.

In the embodiment of the present application, the weight average molecular weight of the cycloolefin copolymer is less than or equal to 150,000; the molecular weight distribution index is in the range of 1.5 to 3.0. In some embodiments, the weight average molecular weight of the cyclic olefin copolymer is in the range of 5,000 to 150,000; in some embodiments, the weight average molecular weight of the cyclic olefin copolymer is in the range of 10,000 to 120,000. In some embodiments, the cycloolefin copolymer has a weight average molecular weight in the range of 20,000 to 100,000. Cycloolefin copolymers have a relatively low weight-average molecular weight and better processability, which is conducive to improving commercial value. In some embodiments, the molecular weight distribution index is in the range of 1.7-2.4.

In some embodiments of the present application, the insertion rate of the cycloolefin monomer is between 20% and 60%; in some embodiments, the insertion rate of the cycloolefin monomer is between 20% and 50%; in some embodiments, the ring The insertion rate of olefin monomers is between 30% and 40%. A suitable cycloolefin monomer insertion rate can make the cycloolefin polymer have a suitable glass transition temperature. In some embodiments of the present application, the glass transition temperature of the cycloolefin copolymer is in the range of 110°C to 180°C. In some embodiments, the cycloolefin copolymer has a glass transition temperature in the range of 120°C to 160°C. In some embodiments, the cycloolefin copolymer has a glass transition temperature in the range of 130°C to 150°C. A glass transition temperature in the range of 120°C to 160°C can not only obtain excellent processing and forming properties, but also ensure that the copolymer products can be used under higher ambient temperature conditions, so as to better balance processing performance and use conditions.

In the embodiment of the present application, the visible light transmittance of the molded product of the cycloolefin copolymer is greater than 90%. The molded body can be a sheet-shaped molded body formed by hot pressing; it can also be a film-shaped molded body formed by coating; the thickness of the molded body can be in the range of 0.1mm-1mm.

In this application, "-" indicates a range, both endpoints are inclusive. For example, the amount of the main catalyst in the copolymerization reaction system is 0.001mmol/L-10mmol/L, which means that the amount of the main catalyst is any value within the range of 0.001mmol/L to 10mmol/L, including the endpoint value 0.001mmol/L and 10mmol/L.

The embodiment of the present application also provides a composition comprising the cycloolefin copolymer mentioned above in the embodiment of the present application. The composition can be used as an optical material.

In the embodiment of the present application, the composition also includes additives, which may include fillers, dyes, antioxidants, light stabilizers, ultraviolet absorbers, plasticizers, flame retardants, antistatic agents, and release agents. one or more. The composition may also include other polymers, which may be other cyclic olefin polymers different from the embodiments of the present application, or non-cyclic olefin polymers, and may be added in an appropriate amount according to needs. In the composition, the mass content of the cycloolefin polymer mentioned in the embodiment of the present application may be greater than or equal to 60%. In some embodiments, the mass content of the cycloolefin polymer mentioned above in the embodiments of the present application may be 60%, 70%, 80%, 90%, 95%, or 98%.

The embodiment of the present application also provides an optical product, which includes the cycloolefin copolymer mentioned above in the embodiment of the present application. The above cycloolefin copolymer or composition can be processed into optical articles by various known molding methods. The optical product can be partially processed by using the above-mentioned cycloolefin copolymer or composition, or can be processed by using the above-mentioned cycloolefin polymer or optical material as a whole.

In the embodiments of the present application, the optical product may specifically include an optical lens, an optical film, an optical disc, a light guide plate or a display panel.

In the embodiments of the present application, the optical lens may specifically include a spectacle lens, a camera lens, a sensor lens, an illumination lens, an imaging lens, and the like. Specifically, the camera lens can be a mobile phone camera lens, a notebook computer camera lens, a desktop camera lens, an automobile camera lens, and the like. Wherein, the spectacle lens may include myopia spectacle lens, presbyopic spectacle lens, sunglass lens, contact lens correction lens, goggle lens and the like. Wherein, the sensor lens may be a motion detector lens, a proximity sensor lens, an attitude control lens, an infrared sensor lens, and the like. Wherein, the lighting lens can be an indoor lighting lens, an outdoor lighting lens, a vehicle headlight lens, a vehicle fog light lens, a vehicle rear light lens, a vehicle running light lens, a vehicle fog light lens, a vehicle interior lens, a light emitting diode (LED ) lens or organic light emitting diode (OLED) lens, etc. Wherein, the imaging lens may be a scanner lens, a projector lens, a telescope lens, a microscope lens, a magnifying glass lens, and the like.

In the embodiments of the present application, the optical film may include a light guide film, a reflective film, an anti-reflection film, a diffusion film, a filter film, a polarizing film, a light splitting film, a phase film, and the like. The optical film can be used in the display field, the lighting field, and the like, for example, it can be used in a film for a liquid crystal substrate.

Referring to FIG. 1 , the embodiment of the present application further provides a device 100 including the above-mentioned optical product in the embodiment of the present application. The device 100 can be an electronic device, specifically, it can include mobile terminals, glasses, cameras, vehicles (such as automobiles, motorcycles, trains, etc.), lighting equipment (such as table lamps, ceiling lights, street lights, etc.), imaging devices (such as endoscopic mirrors, microscopes, telescopes, projectors, scanners, etc.), security equipment, etc. Wherein, the mobile terminal may specifically include various handheld devices with wireless communication functions (such as various mobile phones, tablet computers, mobile notebooks, netbooks), wearable devices (such as smart watches), or other processing devices connected to wireless modems, And various forms of user equipment (user equipment, UE), mobile station (mobile station, MS), terminal equipment (terminal device), etc. The device 100 includes a camera module 2, and the camera module 2 includes a camera lens, and the camera lens is prepared by using the above-mentioned cycloolefin copolymer in the embodiment of the present application. The device 100 also includes a camera protection cover 103 covering the lens of the camera.

In a specific embodiment of the present application, the device 100 is a mobile terminal, the mobile terminal includes a camera module, the camera module includes a camera lens, and the camera lens is prepared by using the above-mentioned cycloolefin copolymer in the embodiment of the present application.

In a specific embodiment of the present application, the device 100 is an endoscope, the endoscope includes a camera module, the camera module includes a camera lens, and the camera lens is prepared by using the above-mentioned cycloolefin copolymer in the embodiment of the present application.

In a specific embodiment of the present application, the device 100 is a vehicle, the vehicle includes a camera module, the camera module includes a camera lens, and the camera lens is prepared by using the above-mentioned cycloolefin copolymer in the embodiment of the present application.

In a specific embodiment of the present application, the device 100 is a security device, the security device includes a camera module, the camera module includes a camera lens, and the camera lens is prepared by using the above-mentioned cycloolefin copolymer in the embodiment of the application.

The embodiments of the present application will be further described below in terms of multiple embodiments.

Example 1

Catalyst preparation:

(1a) Under anhydrous and oxygen-free conditions, in a 100mL reaction vessel at a reaction temperature of -78°C, add 5mmol of 2,7-dibromofluorene and 50mL of anhydrous tetrahydrofuran, and add 10mmol of n-butyl lithium dropwise. Hexane solution, followed by dropwise addition of tetrahydrofuran solution containing 10 mmol trimethylchlorosilane (Me ₃ SiCl) to react overnight. Then, a hexane solution containing 10 mmol n-butyl lithium and a tetrahydrofuran solution containing 10 mmol triphenylchlorosilane (Ph ₃ SiCl) were added dropwise again to react overnight. Subsequently, 50 mL of 0.5 mol/L sodium hydroxide aqueous solution was added at room temperature for hydrolysis, extracted with ether and separated, and the organic phase was dried with anhydrous magnesium sulfate to obtain 2,7-bis(triphenylsilyl)fluorene.

(1b) Under anhydrous and oxygen-free conditions, in a 100mL reaction vessel, add 5mmol of the prepared 2,7-bis(triphenylsilyl)fluorene and 50mL of anhydrous tetrahydrofuran, and add an equimolar amount of Methyllithium ether solution (1.4mol/L), react overnight at room temperature, then add 20mL of anhydrous tetrahydrofuran solution with 5mmol 6,6-dimethylfulvene dropwise, react overnight, add 100mL tetrabutyl chloride Aqueous ammonium solution was stirred for 10 min, extracted and separated, the aqueous phase was washed three times with 50 mL of diethyl ether, the organic phase was dried with anhydrous magnesium sulfate, dried and recrystallized to obtain the cyclopentadiene fluorene ligand precursor.

(1c) Under anhydrous and oxygen-free conditions, in a 100mL reaction vessel, add 5mmol of the cyclopentadiene fluorene ligand precursor prepared above and 50mL of anhydrous tetrahydrofuran, and add an equimolar amount of n-butyllithium at -78°C Hexane solution, then 5 mL of trimethylchlorosilane (Me ₃ SiCl) was added dropwise, stirred overnight, the solvent was drained, and washed with hexane for 1-3 times to obtain the catalyst A precursor.

(1d) Under anhydrous and oxygen-free conditions, add 1g of catalyst A precursor to a 100mL reaction vessel, add 3.4mL of n-butyllithium at a reaction temperature of 0°C, slowly warm up to room temperature, react for 2-12 hours, and then drain Solvent, moved into the glove box and added hexane, and added 0.6 g of zirconium tetrachloride under thorough stirring, and stirred overnight. After overnight reaction, filter, wash the filter cake with hexane and dissolve in excess toluene, filter out the khaki-yellow insoluble matter, then concentrate the toluene solution, and recrystallize to obtain pink solid catalyst A. The pink solid catalyst A obtained in this embodiment is 0.3g, the yield is 19.7%, and the purity is 93.5%. Fig. 2 is the H NMR spectrum of catalyst A. Fig. 3 is the carbon nuclear magnetic resonance spectrum of catalyst A. The proton nuclear magnetic resonance spectrum of Fig. 2 and the carbon nuclear magnetic resonance spectrum of Fig. 3 show that catalyst A is successfully prepared.

Preparation of cycloolefin monomer: In a 220mL autoclave, add 78g of dicyclopentadiene, 110g of norbornene and a small amount of 2,6-dimethoxyphenol (BHT) sequentially, and heat the reaction at 220°C under a nitrogen atmosphere for 24 Hour, after the completion of the reaction, the temperature of the reaction system is down to room temperature, direct vacuum distillation, the previous cut is unreacted dicyclopentadiene, and then the cut is cycloolefin monomer target product, the reaction process is as reaction formula (1-4) shown. The cyclic olefin monomer obtained in this embodiment is 128g of colorless liquid, and the yield is 67%. Fig. 4 is the H NMR spectrum of the cyclic olefin monomer in this embodiment; C NMR spectrum. The proton nuclear magnetic resonance spectrum of Figure 4 and the carbon nuclear magnetic resonance spectrum of Figure 5 indicate that the cycloolefin monomer was successfully prepared.

Preparation of cyclic olefin copolymer: put a glass reactor containing 2.5 g of the above cyclic olefin monomer, 2.5 mL of MAO solution (1.5 mol/L, dissolved in toluene) and 45 mL of toluene into the ethylene pipeline, and replace it with nitrogen three times After the ethylene pipeline, open the ethylene gas and stir to make the toluene solution in the glass kettle saturated with ethylene, adjust the polymerization temperature to 90°C, add 2.0 mg of the catalyst A prepared in this example in 2 mL of toluene solution, adjust and maintain the ethylene pressure at 1 atmosphere, Polymerization was carried out for 5 minutes. After the polymerization is completed, pour the obtained reaction solution into 10% hydrochloric acid aqueous solution, separate the liquids after fully stirring, wash the organic layer with water twice again; fully stir the obtained organic layer with acetone to settle, add an appropriate amount of acetone after filtering Reflux for 2 hours. Finally, the polymer was filtered and washed three times with acetone. The product was placed in a vacuum oven and dried at 130°C for 18 hours to obtain a white cycloolefin copolymer material. The process of the polymerization reaction is shown in the reaction formula (1-5). Fig. 6 is the proton nuclear magnetic resonance spectrum of the cyclic olefin copolymer of the embodiment 1 of the present application; Fig. 7 is the carbon nuclear magnetic resonance spectrum of the cyclic olefin copolymer of the embodiment 1 of the present application. A) in Fig. 7 is an enlarged view of the dotted line area. The H NMR spectrum in Figure 6 and the C NMR spectrum in Figure 7 indicate that the cycloolefin polymer was successfully prepared.

The mass of the cycloolefin copolymer material prepared in this example is 2.4 g, and the polymerization activity of the catalyst is 1.4*10 ⁷ g mol ⁻¹ h ⁻¹ . The relative number average molecular weight that adopts high temperature gel chromatography to detect cycloolefin copolymer material is 26kg/mol (weight average molecular weight is 62.4kg/mol), molecular weight distribution index is 2.4 (molecular weight distribution index equals weight average molecular weight divided by number average molecular weight ). The obtained cycloolefin copolymer was detected by high-temperature carbon nuclear magnetic spectrum, and the results showed that the insertion rate of the cycloolefin monomer of the COC material prepared in this example was 33%, and the insertion rate=(y/(x+y))* 100%. Adopt differential scanning calorimetry (DSC) to detect the glass transition temperature of the cycloolefin copolymer obtained, Fig. 8 is the DSC curve of the cycloolefin copolymer of the embodiment 1 of the present application, the result shows that the cycloolefin copolymer prepared in this embodiment The glass transition temperature of the olefin copolymer is 141.02°C. It can also be seen from Figure 8 that there is no crystallization peak in the DSC curve. It is beneficial to avoid the formation of crystalline polyethylene segments. The cycloolefin copolymer of the embodiment of the present application is formed into a film or sheet sample with a thickness of 0.1mm-1mm. After testing, the visible light transmittance of the cycloolefin copolymer film or sheet sample prepared in this embodiment is greater than 90%. Fig. 9 is a test curve of the visible light transmittance of the cycloolefin copolymer of Example 1 of the present application.

Compared with the prior art, the embodiment of the present application does not require an external molecular weight regulator, and the preparation of low-molecular-weight cycloolefin copolymer materials can be directly realized by using catalyst A, while ensuring other excellent properties of the cycloolefin copolymer materials.

Example 2

The synthesis steps of catalyst and cycloolefin monomer are the same as in Example 1.

Preparation of cyclic olefin copolymer: put a glass reactor containing 3.5g of cyclic olefin monomer, 2.5mL of MAO (1.5mol/L, dissolved in toluene) and 45mL of toluene into the ethylene pipeline, and replace the ethylene pipeline with nitrogen three times Then turn on the ethylene gas and stir to make the toluene solution in the glass kettle saturated with ethylene, adjust the polymerization temperature to 90°C, add 2.0 mg of catalyst A in 2 mL of toluene solution, adjust and maintain the ethylene pressure at 1 atmosphere, and polymerize for 5 minutes. After the polymerization is completed, pour the obtained reaction solution into 10% hydrochloric acid aqueous solution, separate the liquids after fully stirring, wash the organic layer with water twice again; fully stir the obtained organic layer with acetone to settle, add an appropriate amount of acetone after filtering Reflux for 2 hours. Finally, the polymer was filtered and washed three times with acetone. The product was placed in a vacuum oven and dried at 130°C for 18 hours to obtain a white cycloolefin copolymer material.

The mass of the cycloolefin copolymer prepared in this example was 3.28 g, and the polymerization activity of the catalyst was 1.9*10 ⁷ g mol ⁻¹ h ⁻¹ . The relative number average molecular weight of the cycloolefin copolymer detected by high temperature gel chromatography was 58 kg/mol (the weight average molecular weight was 98.6 kg/mol), and the molecular weight distribution index was 1.7. The obtained cyclic olefin copolymer was detected by high-temperature carbon nuclear magnetic spectrum, and the result showed that the insertion rate of cyclic olefin monomer in the cyclic olefin copolymer material prepared in this embodiment was 38%. Adopt differential scanning calorimetry (DSC) to detect the glass transition temperature of the cycloolefin copolymer that obtains, and Fig. 10 is the DSC curve of the cycloolefin copolymer of the application embodiment 2, and the result shows, the glass transition temperature of cycloolefin copolymer The transition temperature is 141.43°C. After testing, the visible light transmittance of the cycloolefin copolymer prepared in this embodiment is greater than 90%.

Compared with Example 1, Example 2 increases the amount of cycloolefin monomers. It can be seen from Example 1 and Example 2 that the main catalyst of the embodiment of the application can be realized within a wide monomer concentration range. Low molecular weight, suitable for preparation of glass transition temperature COC.

Example 3

Cycloolefin copolymer preparation: a glass reactor containing 2.5g cycloolefin monomer, 2.6mL MMAO solution (8%wt, dissolved in heptane) and 45mL toluene was connected to the ethylene pipeline, and the ethylene was replaced three times with nitrogen After the pipeline, open the ethylene gas and stir to make the toluene solution in the glass kettle saturated with ethylene, adjust the polymerization temperature to 90°C, add 2.0 mg of catalyst A in 2 mL of toluene solution, adjust and maintain the ethylene pressure at 1 atmosphere, and polymerize for 5 minutes. After the polymerization is completed, pour the obtained reaction solution into 10% hydrochloric acid aqueous solution, separate the liquids after fully stirring, wash the organic layer with water twice again; fully stir the obtained organic layer with acetone to settle, add an appropriate amount of acetone after filtering Reflux for 2 hours. Finally, the polymer was filtered and washed three times with acetone. The product was placed in a vacuum drying oven and dried at 130° C. for 18 hours to obtain a white cycloolefin copolymer.

The mass of the cycloolefin copolymer prepared in this example was 2.97 g, and the polymerization activity of the catalyst was 1.8*10 ⁷ g mol ⁻¹ h ⁻¹ . The relative number average molecular weight of the cycloolefin copolymer material obtained in this example is 35 kg/mol (the weight average molecular weight is 84 kg/mol), and the molecular weight distribution index is 2.4. The obtained cyclic olefin copolymer was detected by high-temperature carbon NMR spectroscopy, and the result showed that the insertion rate of cyclic olefin monomer in the cyclic olefin copolymer material prepared in this embodiment was 30%. Adopt differential scanning calorimetry (DSC) to detect the glass transition temperature of the cyclic olefin copolymer obtained, Fig. 11 is the DSC curve of the cyclic olefin copolymer of the embodiment 3 of the present application, the result shows, the cyclic olefin copolymer prepared in this embodiment The glass transition temperature of the olefin copolymer is 129.81°C. After testing, the visible light transmittance of the cycloolefin copolymer prepared in this embodiment is greater than 90%.

Compared with Example 1, Example 3 has changed the cocatalyst. From Example 1 and Example 3, it can be seen that using the catalyst A of the embodiment of the present application as the main catalyst, when using different cocatalysts, all can achieve low molecular weight, suitable for glass Preparation of transition temperature COC.

Example 4

Cycloolefin copolymer preparation: a glass reactor containing 3.5g cycloolefin monomer, 2.6mL of MMAO (8%wt heptane) and 45mL toluene was connected to the ethylene pipeline, and the ethylene pipeline was replaced with nitrogen for three times, and then the ethylene gas was opened And stir to make the toluene solution in the glass kettle saturated with ethylene, adjust the polymerization temperature to 90° C., add 1.2 mg of the catalyst prepared by the present invention in 2 mL of toluene solution, adjust and maintain the pressure of ethylene at one atmospheric pressure, and carry out the polymerization reaction for 5 minutes. After the polymerization is completed, pour the obtained reaction solution into 10% hydrochloric acid aqueous solution, separate the liquids after fully stirring, wash the organic layer with water twice again; fully stir the obtained organic layer with acetone to settle, add an appropriate amount of acetone after filtering Reflux for 2 hours. Finally, the polymer was filtered and washed three times with acetone. The product was placed in a vacuum oven and dried at 130°C for 18 hours to obtain a white cycloolefin copolymer material.

The mass of the cycloolefin copolymer prepared in this example was 1.96 g, and the polymerization activity of the catalyst was 1.2*10 ⁷ g mol ⁻¹ h ⁻¹ . The relative number average molecular weight of the cycloolefin copolymer material obtained in this example was detected by high temperature gel chromatography to be 26 kg/mol (the weight average molecular weight was 62.4 kg/mol), and the molecular weight distribution index was 2.4. The obtained cyclic olefin copolymer was detected by high-temperature carbon nuclear magnetic spectrum, and the insertion rate of the cyclic olefin monomer was 39%. Adopt differential scanning calorimetry (DSC) to detect the glass transition temperature of the cycloolefin copolymer that obtains, and Fig. 12 is the DSC curve of the cycloolefin copolymer of the embodiment 4 of the present application, the result shows, the cycloolefin copolymer prepared in this embodiment The glass transition temperature of the olefin copolymer material is 145.67°C. After testing, the visible light transmittance of the cycloolefin copolymer prepared in this embodiment is greater than 90%.

Compared with Example 1, Example 4 changed the amount of cocatalyst and cyclic olefin monomer, and the results showed that, by adopting the main catalyst of the embodiment of the application and changing the amount of cocatalyst and cyclic olefin monomer, low molecular weight, suitable for For the preparation of glass transition temperature COC, the main catalyst provided in the examples of the present application has a wide application range and good effect.

Example 5

Catalyst preparation:

(1a) Under anhydrous and oxygen-free conditions, in a 100mL reaction vessel at a reaction temperature of -78°C, add 5mmol of 2,7-dibromofluorene and 50mL of anhydrous tetrahydrofuran, and add 10mmol of n-butyl lithium dropwise. Hexane solution, followed by dropwise addition of tetrahydrofuran solution containing 10 mmol trimethylchlorosilane (Me ₃ SiCl) to react overnight. Then, a hexane solution containing 10 mmol of n-butyl lithium and a tetrahydrofuran solution containing 10 mmol of trimethylchlorosilane (Me ₃ SiCl) were added dropwise again to react overnight. Subsequently, 50 mL of 0.5 mol/L sodium hydroxide aqueous solution was added at room temperature for hydrolysis, extracted with ether and separated, and the organic phase was dried with anhydrous magnesium sulfate to obtain 2,7-bis(trimethylsilyl)fluorene.

(1b) to (1d) with embodiment 1.

The synthesis steps of cycloolefin monomer are the same as in Example 1.

Preparation of cyclic olefin copolymer: Connect a glass reactor containing 2.5g cyclic olefin monomer, 2.5mL of MAO (1.5mol/L toluene solution) and 45mL toluene into the ethylene pipeline, replace the ethylene pipeline with nitrogen three times and open it Ethylene gas and stirring make the toluene solution in the glass kettle saturated with ethylene, adjust the polymerization temperature to 90°C, add 1.3 mg of catalyst B in 2 mL of toluene solution, adjust and maintain the ethylene pressure at one atmosphere, and carry out the polymerization reaction for 5 minutes. After the polymerization is completed, pour the obtained reaction solution into 10% hydrochloric acid aqueous solution, separate the liquids after fully stirring, wash the organic layer with water twice again; fully stir the obtained organic layer with acetone to settle, add an appropriate amount of acetone after filtering Reflux for 2 hours. Finally, the polymer was filtered and washed three times with acetone. The product was placed in a vacuum oven and dried at 130°C for 18 hours to obtain a white cycloolefin copolymer material.

The mass of the cycloolefin copolymer prepared in this example was 1.99 g, and the polymerization activity of the catalyst was 1.2*10 ⁷ g mol ⁻¹ h ⁻¹ . The relative number average molecular weight of the cycloolefin copolymer material obtained in this example was detected by high temperature gel chromatography to be 35 kg/mol (the weight average molecular weight was 70 kg/mol), and the molecular weight distribution index was 2.0. The obtained cyclic olefin copolymer was detected by high-temperature carbon nuclear magnetic spectroscopy, and the insertion rate of the cyclic olefin monomer was 31%. Adopt differential scanning calorimetry (DSC) to detect the glass transition temperature of the cycloolefin copolymer that obtains, and Fig. 13 is the DSC curve of the cycloolefin copolymer of the embodiment 5 of the present application, and the result shows, the cycloolefin copolymer prepared in this embodiment The glass transition temperature of the olefin copolymer material is 131.51°C. After testing, the visible light transmittance of the cycloolefin copolymer prepared in this embodiment is greater than 90%.

Example 6

Catalyst preparation:

(1a) Under anhydrous and oxygen-free conditions, in a 100mL reaction vessel at a reaction temperature of -78°C, add 5mmol of 2,7-dibromofluorene and 50mL of anhydrous tetrahydrofuran, and add 10mmol of n-butyl lithium dropwise Hexane solution, followed by dropwise addition of tetrahydrofuran solution containing 10 mmol trimethylchlorosilane (Me ₃ SiCl) to react overnight. Then, a hexane solution containing 10 mmol n-butyl lithium and a tetrahydrofuran solution containing 10 mmol triethylchlorosilane (Et ₃ SiCl) were added dropwise again to react overnight. Subsequently, 50 mL of 0.5 mol/L sodium hydroxide aqueous solution was added at room temperature for hydrolysis, extracted with ether and separated, and the organic phase was dried with anhydrous magnesium sulfate to obtain 2,7-bis(triethylsilyl)fluorene.

(1b) to (1d) with embodiment 1.

The synthesis steps of cycloolefin monomer are the same as in Example 1.

Preparation of cyclic olefin copolymer: Connect a glass reactor containing 2.5g cyclic olefin monomer, 2.5mL of MAO (1.5mol/L toluene solution) and 45mL toluene into the ethylene pipeline, replace the ethylene pipeline with nitrogen three times and open it Ethylene gas and stirring make the toluene solution in the glass kettle saturated with ethylene, adjust the polymerization temperature to 90°C, add 1.5 mg of catalyst C in 2 mL of toluene solution, adjust and maintain the ethylene pressure at 1 atmospheric pressure, and polymerize for 5 minutes. After the polymerization is completed, pour the obtained reaction solution into 10% hydrochloric acid aqueous solution, separate the liquids after fully stirring, wash the organic layer with water twice again; fully stir the obtained organic layer with acetone to settle, add an appropriate amount of acetone after filtering Reflux for 2 hours. Finally, the polymer was filtered and washed three times with acetone. The product was placed in a vacuum oven and dried at 130°C for 18 hours to obtain a white cycloolefin copolymer material.

The mass of the cycloolefin copolymer prepared in this example was 0.62 g, and the polymerization activity of the catalyst was 3.7*10 ⁶ g mol ⁻¹ h ⁻¹ . The relative number average molecular weight of the cycloolefin copolymer material obtained in this example was detected by high temperature gel chromatography to be 44 kg/mol (the weight average molecular weight was 70.4 kg/mol), and the molecular weight distribution index was 1.6. The obtained cyclic olefin copolymer was detected by high-temperature carbon nuclear magnetic spectrum, and the insertion rate of the cyclic olefin monomer was 37%. The glass transition temperature of the obtained cycloolefin copolymer was detected by differential scanning calorimetry (DSC), and the results showed that the glass transition temperature of the cycloolefin copolymer material prepared in this example was 145.7°C. After testing, the visible light transmittance of the cycloolefin copolymer prepared in this embodiment is greater than 90%.

Example 7

Catalyst preparation:

The only difference from Example 1 is that step (1c) is not required, and the cyclopentadiene fluorene ligand precursor obtained in step (1b) is directly used as the catalyst D precursor to perform step (1d).

The synthesis steps of cycloolefin monomer are the same as in Example 1.

Preparation of cyclic olefin copolymer: Connect a glass reactor containing 2.5g cyclic olefin monomer, 2.5mL of MAO (1.5mol/L toluene solution) and 45mL toluene into the ethylene pipeline, replace the ethylene pipeline with nitrogen three times and open it Ethylene gas and stirring make the toluene solution in the glass kettle saturated with ethylene, adjust the polymerization temperature to 90°C, add 1.9 mg of catalyst D in 2 mL of toluene solution, adjust and maintain the ethylene pressure at one atmosphere, and carry out the polymerization reaction for 5 minutes. After the polymerization is completed, pour the obtained reaction liquid into 10% hydrochloric acid aqueous solution, separate the liquids after fully stirring, wash the organic layer with water twice again; fully stir the obtained organic layer with acetone to settle, add an appropriate amount of acetone after filtration Reflux for 2 hours. Finally, the polymer was filtered and washed three times with acetone. The product was placed in a vacuum oven and dried at 130°C for 18 hours to obtain a white COC material.

The mass of the cycloolefin copolymer prepared in this example was 1.3 g, and the polymerization activity of the catalyst was 7.8*10 ⁶ g mol ⁻¹ h ⁻¹ . The relative number average molecular weight of the cycloolefin copolymer material obtained in this example was detected by high temperature gel chromatography to be 11.3 kg/mol (the weight average molecular weight was 21.5 kg/mol), and the molecular weight distribution index was 1.9. The obtained cyclic olefin copolymer was detected by high-temperature carbon nuclear magnetic spectrum, and the insertion rate of the cyclic olefin monomer was 35%. The glass transition temperature of the obtained cycloolefin copolymer was detected by differential scanning calorimetry (DSC), and the results showed that the glass transition temperature of the cycloolefin copolymer material prepared in this example was 142°C. After testing, the visible light transmittance of the cycloolefin copolymer prepared in this embodiment is greater than 90%.

Comparative example 1

The cycloolefin copolymer was prepared by using the existing catalyst I (isopropylidene bridged cyclopentadiene fluorene zirconium dichloride).

Preparation of cyclic olefin copolymer: After connecting a glass reactor containing 4.5g of cyclic olefin monomer, 3.4mL of MAO (1.5mol/L toluene solution) and 45mL of toluene into the ethylene pipeline, and replacing the ethylene pipeline with nitrogen three times Turn on the ethylene gas and stir to make the toluene solution in the glass kettle saturated with ethylene, adjust the polymerization temperature to 50°C, add 0.9 mg of catalyst I in 2 mL of toluene solution under the condition of ethylene flow, adjust and keep the ethylene pressure at one atmospheric pressure, and perform the polymerization reaction 5 minutes. After the polymerization is completed, pour the obtained reaction solution into 10% hydrochloric acid aqueous solution, separate the liquids after fully stirring, wash the organic layer with water twice again; fully stir the obtained organic layer with acetone to settle, add an appropriate amount of acetone after filtering Reflux for two hours, and finally the polymer was filtered and washed three times with acetone. The product was placed in a vacuum oven and dried at 130°C for 18 hours to obtain a white cycloolefin copolymer.

The mass of the cycloolefin copolymer prepared in this comparative example was 1.78 g, and the polymerization activity of the catalyst was 1.1*10 ⁷ g mol ^-1 h ^-1 . The number-average molecular weight of the cyclic olefin copolymer measured by the same method as the above-mentioned embodiment is 124 kg/mol (the weight-average molecular weight is 248 kg/mol), and the molecular weight distribution index is 2.0. The insertion rate of cycloolefin monomer was 33%. The glass transition temperature of cycloolefin copolymer is 136.98°C.

Comparative example 2

Preparation of cyclic olefin copolymer: Connect a glass reactor containing 4.5g cyclic olefin monomer, 1.7mL of MAO (1.5M toluene solution) and 45mL toluene into the ethylene pipeline, replace the ethylene pipeline with nitrogen three times, and then open the ethylene gas And stir to make the toluene solution in the glass kettle saturated with ethylene, adjust the polymerization temperature to 90° C., add 0.9 mg of catalyst I in 2 mL of toluene solution under the condition of passing through ethylene, adjust and maintain the pressure of ethylene at 1 atmospheric pressure, and polymerize for 5 minutes. After the polymerization is completed, pour the obtained reaction liquid into 10% hydrochloric acid aqueous solution, separate the liquids after fully stirring, wash the organic layer with water twice again; fully stir the obtained organic layer with acetone to settle, add an appropriate amount of acetone after filtration Reflux for two hours, and finally the polymer was filtered and washed three times with acetone. The product was placed in a vacuum oven and dried at 130°C for 18 hours to obtain a white cycloolefin copolymer.

The mass of the cycloolefin copolymer prepared in this comparative example was 1.15 g, and the polymerization activity of the catalyst was 0.7*10 ⁷ g mol ^-1 h ^-1 . The number-average molecular weight of the cyclic olefin copolymer measured by the same method as the above-mentioned embodiment is 117 kg/mol (the weight-average molecular weight is 199 kg/mol), and the molecular weight distribution index is 1.7. The insertion rate of cycloolefin monomer was 35%. The glass transition temperature of cycloolefin copolymer is 141.24°C.

From Comparative Example 1 and Comparative Example 2, it can be seen that the catalyst 1 of Comparative Example 1 is used to prepare cycloolefin copolymers. Under different co-catalyst usage levels and polymerization temperatures, the weight average molecular weight of the cycloolefin copolymers produced is all much greater than 150kg/mol (ie 150,000), the molecular weight is relatively large. And embodiment 1-7 can obtain the cyclic olefin copolymer with smaller molecular weight less than 150,000 of weight average molecular weight by adopting the catalyst provided by the embodiment of the present application, this is mainly due to the main catalyst cyclopentadienyl or fluorenyl The silicon-containing group can produce weak coordination with the empty orbital of the metal center, and compete with the coordination between the olefin/metal center, thereby promoting chain transfer and reducing the molecular weight of the polymer; at the same time, through this competition, It increases the difficulty of coordination between the olefin and the metal center, improves the insertion rate of the cycloolefin monomer, and is beneficial to adjust the glass transition temperature of the cycloolefin copolymer.

Claims

A kind of cyclic olefin copolymer preparation catalyst is characterized in that, described catalyzer comprises structural formula such as the procatalyst shown in formula (1-a):

In formula (1-a), D is a bridging group, and Q is a metal center;

R 5 , R 6 , R 7 , and R 8 independently include a hydrogen atom, a hydrocarbon group or a silicon-containing substituent, and the silicon-containing substituent is connected to the carbon atom at the corresponding substitution position through a silicon atom;

R a and R b are carbon-containing groups, silicon-containing groups, germanium-containing groups or tin-containing groups;

At least one of said R 5 , R 6 , R 7 , R 8 is a silicon-containing substituent, and/or at least one of said R a , R b is a silicon-containing group;

R 9 , R 13 , R 14 , and R 18 independently include a hydrogen atom, a hydrocarbon group or a hydrocarbon oxy group.
The catalyst according to claim 1, characterized in that at least one of R 6 and R 7 is a silicon-containing substituent, and/or at least one of R a and R b is a silicon-containing group.
The catalyst according to claim 1 or 2, characterized in that the number of carbon atoms of the hydrocarbon groups and silicon-containing substituents in R 5 , R 6 , R 7 and R 8 is less than or equal to 6.
The catalyst according to any one of claims 1-3, wherein the metal center Q is represented by -M 1 (R 1 R 2 )-, and the M 1 represents scandium, titanium, vanadium, zirconium, hafnium , niobium or tantalum, and the R1 and R2 independently include a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aryloxy group, an aralkyl group, an alkaryl group or an aralkenyl group.
The catalyst according to any one of claims 1-4, wherein the bridging group D is represented as -X(R 3 R 4 )-, the X represents carbon or silicon, and the R 3 and R 4 independently includes a hydrogen atom or a hydrocarbon group.
The catalyst according to any one of claims 1-5, characterized in that, said Ra is represented by -M 2 (R 10 R 11 R 12 ), M 2 independently represents carbon, silicon, germanium or tin, and R 10 , R 11 , and R 12 independently include alkyl, alkoxy, alkenyl, aryl, aryloxy, aralkyl, alkaryl or aralkenyl.
The catalyst according to any one of claims 1-6, characterized in that, said R b represents -M 3 (R 15 R 16 R 17 ), M 3 independently represents carbon, silicon, germanium or tin, and R 15 , R 16 , and R 17 independently include alkyl, alkoxy, alkenyl, aryl, aryloxy, aralkyl, alkaryl or aralkenyl.
The catalyst according to claim 7, characterized in that the number of carbon atoms in the R 10 , R 11 , R 12 , R 15 , R 16 and R 17 is less than or equal to 10.
The catalyst according to any one of claims 1-8, characterized in that, the catalyst further comprises a co-catalyst, and the co-catalyst includes methyl aluminoxane, modified methyl aluminoxane, organoboron compound one or more of.
The catalyst according to claim 9, wherein the organoboron compound comprises tris(pentafluorophenyl) boron, triphenylcarbenium tetrakis(pentafluorophenyl) borate, N,N-dimethyl One or more of aniline tetrakis (pentafluorophenyl) borates.
The catalyst according to claim 9 or 10, characterized in that the molar ratio of the main catalyst to the co-catalyst is 1:(10-10000).
The catalyst according to any one of claims 1-11, characterized in that the catalytic activity of the catalyst is higher than 10 6 g·mol -1 ·h -1 .
A kind of preparation method of cyclic olefin copolymer is characterized in that, comprises:

In the presence of the cycloolefin copolymer preparation catalyst described in any one of claims 1-12, the cycloolefin monomer is copolymerized with ethylene or α-olefin to obtain the cycloolefin copolymer.
The preparation method according to claim 13, characterized in that, the reaction system of the copolymerization includes an inert solvent, and the inert solvent includes one or more of linear alkanes, cyclic hydrocarbons and aromatic compounds. Various.
The preparation method according to claim 13 or 14, characterized in that the amount of the main catalyst in the reaction system of the copolymerization is 0.001mmol/L-10mmol/L.
The preparation method according to any one of claims 13-15, characterized in that the amount of the cycloolefin monomer in the copolymerization reaction system is 0.01mol/L-10mol/L.
The preparation method according to any one of claims 13-16, characterized in that the molar ratio of the cycloolefin monomer to the main catalyst in the copolymerized reaction system is 500-500000.
The preparation method according to any one of claims 13-17, characterized in that, the temperature of the copolymerization reaction is 50°C-120°C; the time of the copolymerization reaction is 2min-10min.
According to the preparation method described in any one of claims 13-18, it is characterized in that the structural formula of the cycloolefin monomer is as shown in formula (2):

In formula (2), R 19 is a hydrocarbon group or a hydrocarbon silicon group; R 20 and R 21 independently include a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an ester group, a carbonic acid group Ester group, cyano group, amino group, thiol group, atoms or atomic groups that can replace the above groups;

R 22 and R 23 independently include hydrogen atom, halogen atom, alkyl group, alkoxyl group, aryl group, aryloxyl group, hydroxyl group, ester group, carbonate group, cyano group, amino group, thiol group, and can replace the above-mentioned An atom or an atomic group of a group, or R22 and R23 are connected to form a group with a ring structure;

z is a positive integer.
The preparation method according to any one of claims 13-19, characterized in that the copolymerization reaction system does not contain a molecular weight regulator.
A kind of cyclic olefin copolymer, it is characterized in that, described cyclic olefin copolymer is made according to the preparation method described in any one of claim 13-20, and the structural formula of described cyclic olefin copolymer is as shown in formula (3):

In formula (3), R 19 is a hydrocarbon group or a hydrocarbon silicon group; R 20 and R 21 independently include a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl group, an ester group, a carbonic acid group Ester group, cyano group, amino group, thiol group, atoms or atomic groups that can replace the above groups;

R 22 , R 23 , R 24 , and R 25 independently include hydrogen atom, halogen atom, alkyl, alkoxy, aryl, aryloxy, hydroxyl, ester, carbonate, cyano, amino, sulfur Alcohol groups, atoms or atomic groups that can replace the above groups, or R22 and R23 are connected to form a group with a ring structure, and R24 and R25 are connected to form a group with a ring structure;

x and y represent the polymerization degree, both x and y are positive numbers, 1<x:y<3, and z is a positive integer.
The cycloolefin copolymer according to claim 21, characterized in that, the weight average molecular weight of the cycloolefin copolymer is in the range of 5000 to 150000; the molecular weight distribution index is in the range of 1.5 to 3.0.
The cyclic olefin copolymer according to claim 21 or 22, characterized in that, the insertion rate of the cyclic olefin monomer of the cyclic olefin copolymer is in the range of 20%-60%; the vitrification of the cyclic olefin copolymer The transition temperature is in the range of 110°C to 180°C.
The cycloolefin copolymer according to any one of claims 21-23, characterized in that the visible light transmittance of the molded product of the cycloolefin copolymer is greater than 90%.
A composition, characterized in that it comprises the cyclic olefin copolymer according to any one of claims 21-24, or comprises the cyclic olefin copolymer prepared by the preparation method according to any one of claims 13-20 .
The composition according to claim 25, characterized in that, the composition also includes additives, and the additives include fillers, dyes, antioxidants, light stabilizers, ultraviolet absorbers, plasticizers, flame retardants, anti- One or more of electrostatic agent and release agent.
An optical product, characterized in that the optical product comprises the cycloolefin copolymer as described in any one of claims 21-24, or comprises the product prepared by the preparation method as described in any one of claims 13-20 Cycloolefin copolymers.
The optical product according to claim 27, wherein the optical product comprises an optical lens, an optical film, an optical disc, a light guide plate or a display panel.
An electronic device, characterized in that it includes an electronic device body and a camera module assembled on the electronic device body, the camera module includes a lens lens, and the lens lens adopts any one of claims 21-24 The cyclic olefin copolymer, or the preparation of the composition as claimed in claim 25 or 26.
A device characterized by comprising the optical article as claimed in claim 27 or 28.