阅读说明：本技术 一种环烯烃共聚物及其制备方法和应用 (Cycloolefin copolymer and preparation method and application thereof ) 是由 施英 张文泉 汪相宇 黄佳斯 于 2019-11-15 设计创作，主要内容包括：本发明涉及一种环烯烃共聚物及其制备方法和应用,所述环烯烃共聚物包括至少一个结构单元(A)和至少一个结构单元(B),本发明将这两种结构单元组合,使得到的环烯烃共聚物为非结晶型聚合物,与普通的环烯烃共聚物相比,玻璃化转变温度及热变形温度调控范围宽,具有优异的耐热性,且聚合物透光性优异,同时具有适宜的吸水率和力学性能,原料易得；本发明通过开环易位聚合反应以及加氢反应制备得到所述环烯烃共聚物,通过控制反应各个条件,从而获得满足实际应用要求的耐温型光学材料。(The invention relates to a cycloolefin copolymer and its preparation method and application, the said cycloolefin copolymer includes at least one constitutional unit (A) and at least one constitutional unit (B), the invention makes the cycloolefin copolymer obtained be amorphous polymer by combining these two constitutional units, compared with ordinary cycloolefin copolymer, glass transition temperature and thermal deformation temperature control range are wide, have excellent heat resistance, and the light transmittance of polymer is excellent, have appropriate water absorption and mechanical property at the same time, the raw materials are apt; the invention prepares the cycloolefin copolymer through ring-opening metathesis polymerization reaction and hydrogenation reaction, and obtains the temperature-resistant optical material meeting the actual application requirement by controlling each reaction condition.)

1. A cycloolefin copolymer, characterized in that the cycloolefin copolymer comprises at least one structural unit (a) and at least one structural unit (B);

the R is ₁、R ₂、R ₃、R ₄、R ₅Each independently selected from hydrogen or methyl;

m and k are each independently 0 or 1;

the dashed line marks represent the connecting bonds between the building blocks.

2. The cycloolefin copolymer according to claim 1, characterized in that the total number of structural units in the cycloolefin copolymer is n ₀The number of the structural units (A) is n ₁The number of the structural units (B) is n ₂N is said n ₀、n ₁、n ₂The following conditions are satisfied: n is more than or equal to 0.6 ₁/n ₀≤0.9，0.1≤n ₂/n ₀≤0.4。

3. A method for preparing a cycloolefin copolymer according to claim 1 or 2, characterized in that the preparation method comprises the following steps:

(1) subjecting a cycloolefin monomer to a ring-opening metathesis polymerization reaction to obtain a cycloolefin ring-opening polymer containing a structural unit (C) and a structural unit (D);

dashed line markers represent connecting bonds between structural units;

the cycloolefin monomer includes a monomer A

The R is ₁、R ₂、R ₃、R ₄、R ₅Each independently selected from hydrogen or methyl;

m and k are each independently 0 or 1;

(2) and carrying out hydrogenation reaction on the cyclic olefin ring-opening polymer to obtain the cyclic olefin copolymer.

4. The method according to claim 3, wherein in step (1), the monomer A specifically includes any one or at least two combinations of the following compounds represented by I-1 to I-6:

preferably, in the step (1), the monomer B specifically includes any one or at least two combinations of the following compounds represented by II-1 to II-16:

5. the preparation method according to claim 3 or 4, wherein the reaction system of the ring-opening metathesis polymerization of the step (1) further comprises a solvent, a chain transfer agent and a catalyst 1;

preferably, the solvent comprises any one or a combination of at least two of benzene, toluene, xylene, n-hexane and cyclohexane;

preferably, the mass of the cycloolefin monomer accounts for 5-50% of the mass of the solvent, and preferably 5-20%;

preferably, the chain transfer agent comprises α -olefinic compounds, preferably any one or a combination of at least two of 1-pentene, 1-hexene, 1-heptene and 1-octene;

preferably, the molar ratio of the chain transfer agent to the cycloolefin monomer is 1 (100-1000);

preferably, the catalyst 1 comprises Grubbs 1 ^st、Grubbs 2 ^ndAnd Hoveyda-Grubbs, or a combination of at least two thereof;

preferably, the mass ratio of the catalyst 1 to the cycloolefin monomer is 1 (10) ⁴～10 ⁵)；

Preferably, the ring-opening metathesis polymerization of step (1) is terminated by a chain terminator;

preferably, the chain terminator comprises ethyl vinyl ether;

preferably, the molar ratio of the chain terminator to the cycloolefin monomer is 1 (1000 to 10000);

preferably, in step (1), the ring-opening metathesis polymerization is carried out under the protection of nitrogen;

preferably, step (1) specifically comprises: mixing a cyclic olefin monomer, a solvent and a chain transfer agent, stirring for the first time, then adding a catalyst 1, stirring for the second time, adding a chain terminator, and stirring for the third time to obtain a cyclic olefin ring-opening polymer reaction solution;

preferably, in the step (1), the temperature is controlled to be 0-30 ℃ while the first stirring is carried out;

preferably, in the step (1), the catalyst 1 is dissolved in a solvent and then is dropwise added into a reaction system;

preferably, in the step (1), the temperature is controlled to be less than or equal to 35 ℃ in the process of adding the catalyst 1;

preferably, in the step (1), the time for the second stirring is 0.5-2 h;

preferably, in the step (1), the third stirring time is 10-30 min;

preferably, step (1) specifically comprises: vacuumizing a reaction bottle, introducing nitrogen to replace air, adding a cycloolefin monomer, a solvent and a chain transfer agent under the protection of nitrogen, stirring for the first time, controlling the temperature to be 0-30 ℃, dissolving a catalyst 1 in the solvent, dropwise adding the catalyst into a reaction system at the temperature of less than or equal to 35 ℃, stirring for the second time for 0.5-2 hours after dropwise adding is finished, adding a chain terminating agent, and stirring for the third time for 10-30 minutes to obtain a cycloolefin ring-opening polymer reaction solution.

6. The preparation method according to any one of claims 3 to 5, wherein in the step (2), the reaction system of the hydrogenation reaction further comprises a catalyst 2;

preferably, the catalyst 2 comprises a homogeneous catalyst;

preferably, the homogeneous catalyst comprises RuHCl (CO) (PPh) ₃) ₃And/or Rh (PPh) ₃) ₃Cl；

Preferably, the Rh (PPh) ₃) ₃Cl and PPh ₃Used in combination, preferably PPh ₃Is added in an amount of Rh (PPh) ₃) ₃1-5 times of Cl in mass;

preferably, the adding amount of the catalyst 2 is 0.05-0.5% of the mass of the cycloolefin monomer;

preferably, in the step (2), the hydrogenation reaction is carried out in a high-pressure reaction kettle;

preferably, the high-pressure reaction kettle is pressurized to 5-10 MPa;

preferably, in the step (2), the temperature of the hydrogenation reaction is 80-140 ℃;

preferably, the step (2) specifically comprises: adding a catalyst 2 into the cycloolefin ring-opening polymer reaction liquid obtained in the step (1), uniformly stirring, putting into a high-pressure reaction kettle, replacing air in the kettle with nitrogen, pressurizing to 5-10 MPa with hydrogen, stirring for the fourth time, heating to 80-140 ℃, reacting until the pressure in the kettle is constant, stopping heating, cooling to room temperature, releasing pressure, and discharging to obtain a cycloolefin copolymer solution.

7. The production method according to any one of claims 3 to 6, wherein step (3) is performed after step (2): mixing the cycloolefin copolymer solution obtained in the step (2) with a water-soluble extractant solution, stirring and heating for the fifth time, adding a peroxide aqueous solution, stirring for the sixth time, reacting at a constant temperature, cooling, and keeping a cycloolefin copolymer solution phase;

preferably, in the step (3), the target temperature of the temperature rise is 80-110 ℃;

preferably, in the step (3), the constant-temperature reaction time is 0.5-2 h;

preferably, in the step (3), the water-soluble extractant comprises any one or a combination of at least two of formic acid, acetic acid, ethylenediamine, propylenediamine, monoethanolamine, diethanolamine and triethanolamine, preferably triethanolamine;

preferably, in the step (3), the mass concentration of the water-soluble extractant in the water-soluble extractant solution is 2-20%;

preferably, in the step (3), the addition amount of the water-soluble extractant solution is 25-100% of the mass of the cycloolefin copolymer solution obtained in the step (2);

preferably, in the step (3), the peroxide comprises an organic peroxide compound and/or an inorganic peroxide, preferably any one or a combination of at least two of hydrogen peroxide, peroxyacetic acid and ammonium persulfate, preferably hydrogen peroxide;

preferably, in the step (3), the mass concentration of the peroxide in the peroxide aqueous solution is 5-30%;

preferably, in the step (3), the addition amount of the peroxide aqueous solution is 25-100% of the mass of the cycloolefin copolymer solution obtained in the step (2);

preferably, the step (3) specifically comprises the following steps:

adding a water-soluble extractant solution into the cycloolefin copolymer solution obtained in the step (2), stirring for the fifth time, heating to 80-110 ℃, adding a peroxide aqueous solution, stirring for the sixth time, reacting at a constant temperature for 0.5-2 h, cooling, and keeping a cycloolefin copolymer solution phase;

preferably, step (4) is performed after step (3): adding a precipitator into the cycloolefin copolymer solution phase obtained in the step (3) for precipitation, filtering, collecting a solid phase, washing and drying to obtain the cycloolefin copolymer;

preferably, the precipitating agent comprises any one or a combination of at least two of isopropanol, methanol, ethanol and acetone.

8. The preparation method according to any one of claims 3 to 7, characterized by specifically comprising the steps of:

(1) vacuumizing a reaction bottle, introducing nitrogen to replace air, adding a cycloolefin monomer, a solvent and a chain transfer agent under the protection of nitrogen, stirring for the first time, controlling the temperature to be 0-30 ℃, dissolving a catalyst 1 in the solvent, dropwise adding the catalyst into a reaction system at the temperature of less than or equal to 35 ℃, stirring for the second time for 0.5-2 hours after dropwise adding is finished, adding a chain terminating agent, and stirring for the third time for 10-30 minutes to obtain a cycloolefin ring-opening polymer reaction solution;

(2) adding a catalyst 2 into the cycloolefin ring-opening polymer reaction liquid, stirring uniformly, putting into a high-pressure reaction kettle, replacing air in the kettle with nitrogen, pressurizing to 5-10 MPa with hydrogen, stirring for the fourth time, heating to 80-140 ℃, reacting until the pressure in the kettle is constant, stopping heating, cooling to room temperature, relieving pressure, and discharging to obtain a cycloolefin copolymer solution;

(3) adding a water-soluble extractant solution into the cycloolefin copolymer solution, stirring for the fifth time, heating to 80-110 ℃, adding a peroxide aqueous solution, stirring for the sixth time, reacting at a constant temperature for 0.5-2 h, cooling, and keeping a cycloolefin copolymer solution phase;

(4) and adding a precipitator into the cycloolefin copolymer solution phase for precipitation, filtering, collecting a solid phase, washing and drying to obtain the cycloolefin copolymer.

9. A polymeric optical material obtained by molding the cycloolefin copolymer according to claim 1 or 2.

10. Use of the polymeric optical material according to claim 9 in an optical device;

preferably, the optical device comprises a lens or a liquid crystal display screen;

preferably, the polymer optical material is applied to a light guide plate or a polarizing film of an optical device.

Technical Field

The invention relates to the technical field of optical materials, in particular to a cycloolefin copolymer and a preparation method and application thereof.

Background

With the development of electronics and display technologies towards high speed, high density, ultra-thin and high integration, the requirements on the properties of the polymer optical material, such as heat resistance, high temperature dimensional stability, water and oxygen resistance, are higher and higher, so researchers in the field pay attention to the research of colorless transparent high temperature resistant polymer optical materials.

Among them, cycloolefin copolymers have high transparency, low birefringence, high refractive index of light, chemical resistance, excellent heat resistance, melt flowability, dimensional stability, and the like, and are widely used for manufacturing various optical, information, electric, medical materials, and the like.

There are two main ways of polymerizing cycloolefins: the present invention relates to a method for preparing a high-temperature resistant ethylene/norbornene copolymer (COC) by ring-opening metathesis polymerization and addition polymerization, wherein the COC is a classical addition polymer material, the performance of the copolymer is excellent, the currently available commercial COC products include APEL of the japan mitsui chemical company and TOPAS of the takoner company, but the COC material still has defects in some aspects, such as the increase of the glass transition temperature (Tg) of the COC material with the increase of the norbornene content, the high Tg COC material is fragile due to the excessive rigid norbornene structural units, and the COC material is difficult to achieve high temperature resistance due to the insufficient molecular volume of norbornene, and the transparency needs to be improved. In addition, cyclic olefin Copolymer (COP) is obtained by ring-opening metathesis polymerization and hydrogenation of norbornene-type monomers, and currently commercialized COP materials include ZEONEX of japan rapes corporation, and COP materials have characteristics of uniform polymer composition, excellent optical properties, and the like, but if the glass transition temperature of COP materials obtained by ring-opening metathesis polymerization of conventional norbornene-type monomers is lower than that of COC materials.

Due to the defects, most of the cycloolefin copolymers are difficult to be applied to meet the requirements of high-grade electronic devices, such as high-grade lenses, liquid crystal display screens and the like.

CN109134755A discloses a heat-resistant cycloolefin copolymer and a preparation method thereof, in particular to a norbornene derivative 5-ethylidene-2-norbornene, 1-hexene-and 1-octene-long-chain α olefin copolymer, the preparation method of the invention has the advantages of mild reaction conditions, short period, simple operation and the like, and the used catalyst Cpket has very good catalytic activity and thermal stability for the copolymerization reaction, and has great industrial application value and good application prospect.

CN106905483B discloses a cycloolefin copolymer, which is obtained by copolymerization of comonomers under the action of a metathesis polymerization catalyst, wherein the comonomers are cycloolefin and bismaleimide, and the glass transition temperature Tg of the obtained cycloolefin copolymer is higher than 144 ℃. The invention also discloses a preparation method of the cycloolefin copolymer, which can improve the heat resistance of the cycloolefin copolymer obtained by polymerization by adding bismaleimide with a specific structure into a cycloolefin monomer, and the copolymer can be prepared under a relatively mild condition, thereby reducing the production cost of the cycloolefin copolymer. However, the reaction raw materials of the invention have complex structures and are not easy to obtain, and the glass transition temperature of more than 144 ℃ can not meet the requirements of the existing high-grade electronic equipment, so that the heat resistance is required to be further improved, and the transparency is also required to be improved.

CN109593160A discloses a preparation method of cycloolefin copolymer, belonging to the field of organic materials, the preparation steps of the invention are that inert organic solvent, cycloolefin and ethylene are respectively added into a reactor under the conditions of 40-95 ℃ and 0.1-5.0MPa pressure; wherein the molar ratio of the cycloolefin to the ethylene is 1-50: 1; then adding or not adding a chain transfer agent; finally, adding a catalyst to carry out solution polymerization reaction for 0.1-10 h. The polymerization activity of the ethylene-cycloolefin copolymer prepared by the method is high, and the prepared ethylene-cycloolefin copolymer has lower molecular weight compared with ethylene-cycloolefin copolymers prepared by other catalyst systems. But the resulting polymer has poor heat resistance and transparency.

Therefore, there is a need in the art to develop a novel cycloolefin copolymer that is easily available in raw materials, simple to prepare, and has excellent heat resistance and transparency, so as to be suitable for various high-grade electronic display devices.

Disclosure of Invention

An object of the present invention is to provide a cycloolefin copolymer which is excellent in heat resistance and transparency, and which is easily available in raw materials and simple in preparation method.

In order to achieve the purpose, the invention adopts the following technical scheme:

the present invention provides a cycloolefin copolymer comprising at least one structural unit (a) and at least one structural unit (B);

the R is ₁、R ₂、R ₃、R ₄、R ₅Each independently selected from hydrogen or methyl;

m and k are each independently 0 or 1;

the dashed line marks represent the connecting bonds between the building blocks.

The invention provides a novel cycloolefin copolymer, which comprises a structural unit (A) and a structural unit (B), wherein the structural units with the two specific structures are combined to obtain the cycloolefin copolymer which is an amorphous polymer.

The cycloolefin copolymer provided by the present invention needs to contain both the structural unit (A) and the structural unit (B), wherein only one structural unit (A) may be contained, or two or more structural units (A) may be contained, and the structural units (B) are the same. Ester bonds and alicyclic groups in the structural unit (B) provide more rigid groups for the polymer, namely, the polymer is endowed with higher glass transition temperature and heat distortion temperature, but if the content of the structural unit (B) is too high, the polymer becomes brittle, so that the ratio of the two structural units is controlled within a proper range by matching with the structural unit (A), and the excellent heat resistance is endowed to the polymer, and simultaneously, the mechanical property and other properties of the polymer can be ensured not to be influenced.

Preferably, the total number of structural units in the cycloolefin copolymer is n ₀The number of the structural units (A) is n ₁The number of the structural units (B) is n ₂N is said n ₀、n ₁、n ₂The following conditions are satisfied: n is more than or equal to 0.6 ₁/n ₀≤0.9，E.g., 0.61, 0.63, 0.65, 0.66, 0.68, 0.7, 0.72, 0.75, 0.8, 0.82, 0.85, 0.88, etc., 0.1. ltoreq. n ₂/n ₀0.4, e.g., 0.12, 0.15, 0.18, 0.2, 0.22, 0.25, 0.28, 0.3, 0.32, 0.35, 0.38, etc.

The second object of the present invention is to provide a method for preparing a cycloolefin copolymer according to the first object, which comprises the steps of:

(1) subjecting a cycloolefin monomer to a ring-opening metathesis polymerization reaction to obtain a cycloolefin ring-opening polymer containing a structural unit (C) and a structural unit (D);

dashed line markers represent connecting bonds between structural units; each structural unit of the cycloolefin ring-opening polymer is connected by a double bond, and the position marked by a dotted line can be understood as a half double bond, and when the position is connected with a half double bond of another structural unit, a double bond is formed;

the cycloolefin monomer includes a monomer A

And a monomer B

The R is ₁、R ₂、R ₃、R ₄、R ₅Each independently selected from hydrogen or methyl;

m and k are each independently 0 or 1;

(2) and carrying out hydrogenation reaction on the cyclic olefin ring-opening polymer under the action of hydrogen to obtain the cyclic olefin copolymer.

The invention takes the norbornene type or dimethylocta-hydrogen naphthalene type based cycloolefin monomer A and the norbornyl ester type or dimethylocta-hydrogen naphthalene type based cycloolefin monomer B as the starting raw materials, can realize the ring-opening metathesis copolymerization reaction under the action of a proper catalyst, and a large amount of double bonds are reserved on the main chain of the prepared copolymer, and the existence of the double bonds can cause the copolymer to be not resistant to yellowing and heat, so that the unsaturated double bonds need to be converted into saturated carbon-carbon bonds through further hydrogenation reaction, thereby obtaining the cycloolefin copolymer with excellent heat resistance.

With respect to the cycloolefin in the present invention

The synthesis can be carried out commercially or according to the prior art, which can be exemplified by the synthesis method of cyclic olefin monomers disclosed in CN104262074A, by a person skilled in the art.

Cyclic olefins in the invention

Can be synthesized by a Diels-Alder reaction, and the reaction formula is shown as follows:

preferably, in the step (1), the monomer A specifically comprises any one or at least two combinations of the following compounds represented by I-1 to I-6:

preferably, in the step (1), the monomer B specifically includes any one or at least two combinations of the following compounds represented by II-1 to II-16:

preferably, the reaction system of the ring-opening metathesis polymerization in the step (1) further comprises a solvent, a chain transfer agent and a catalyst 1.

Preferably, the solvent includes any one or a combination of at least two of benzene, toluene, xylene, n-hexane, and cyclohexane.

Preferably, the mass of the cycloolefin monomer is 5 to 50% of the mass of the solvent, for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, etc., preferably 5 to 20%.

The preferred cycloolefin monomer accounts for 5-50% of the solvent by mass, because the monomer concentration is too low, the production efficiency is too low, the monomer concentration is too high, the solution viscosity is too high after ring-opening metathesis polymerization reaction, gelation is easy to occur, and difficulty is caused to hydrogenation reaction.

Preferably, the chain transfer agent comprises α -olefinic compounds, preferably any one or a combination of at least two of 1-pentene, 1-hexene, 1-heptene and 1-octene.

Preferably, the molar ratio of the chain transfer agent to the cycloolefin monomer is 1 (100 to 1000), for example, 1:200, 1:300, 1:400, 1:500, 1:600, 1:700, 1:800, 1:900, and the like.

Preferably, the catalyst 1 comprises Grubbs 1 ^st、Grubbs 2 ^ndAnd Hoveyda-Grubbs, or a combination of at least two thereof.

The invention preferably uses the specific ruthenium catalyst to catalyze the ring-opening metathesis polymerization, the catalyst has high activity, low catalyst addition amount and high cycloolefin conversion rate, the catalytic hydrogenation reaction can be directly carried out without further treatment after the reaction, the optical-grade cycloolefin copolymer can be prepared by simple post-treatment, and the whole process is simple and easy to operate.

Preferably, the mass ratio of the catalyst 1 to the cycloolefin monomer is 1 (10) ⁴～10 ⁵) For example, 1:11000, 1:15000, 1:16000, 1:17000, 1:18000, 1:20000, 1:30000, 1:40000, 1:50000, 1:60000, 1:70000, 1:80000, 1:90000 and the like.

Preferably, the ring-opening metathesis polymerization of step (1) is terminated by a chain terminator.

Preferably, the chain terminator comprises ethyl vinyl ether.

Preferably, the molar ratio of the chain terminator to the cycloolefin monomer is 1 (1000 to 10000), for example 1:2000, 1:3000, 1:4000, 1:5000, 1:6000, 1:7000, 1:8000, 1:9000 and the like.

Preferably, in step (1), the ring-opening metathesis polymerization is carried out under nitrogen protection.

Preferably, step (1) specifically comprises: mixing a cyclic olefin monomer, a solvent and a chain transfer agent, stirring for the first time, then adding a catalyst 1, stirring for the second time, adding a chain terminator, and stirring for the third time to obtain a cyclic olefin ring-opening polymer reaction liquid.

Preferably, in the step (1), the temperature is controlled to be 0 to 30 ℃ while the first stirring is performed, for example, 1 ℃, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 28 ℃ and the like.

Preferably, in the step (1), the catalyst 1 is firstly dissolved in the solvent and then is added dropwise into the reaction system.

Preferably, in step (1), the temperature is controlled to be less than or equal to 35 ℃ during the addition of the catalyst 1, such as 15 ℃, 16 ℃, 17 ℃, 18 ℃, 19 ℃, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃ and the like.

Preferably, in the step (1), the time for the second stirring is 0.5-2 h, such as 0.6h, 0.7h, 0.8h, 0.9h, 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h and the like.

Preferably, in the step (1), the time for the third stirring is 10-30 min, such as 12min, 14min, 16min, 18min, 20min, 22min, 25min, 26min, 28min, 29min, and the like.

Preferably, step (1) specifically comprises: vacuumizing a reaction bottle, introducing nitrogen to replace air, adding a cycloolefin monomer, a solvent and a chain transfer agent under the protection of nitrogen, stirring for the first time, controlling the temperature to be 0-30 ℃, dissolving a catalyst 1 in the solvent, dropwise adding the catalyst into a reaction system at the temperature of less than or equal to 35 ℃, stirring for the second time for 0.5-2 hours after dropwise adding is finished, adding a chain terminating agent, and stirring for the third time for 10-30 minutes to obtain a cycloolefin ring-opening polymer reaction solution.

Preferably, in the step (2), the reaction system of the hydrogenation reaction further comprises a catalyst 2.

Preferably, the catalyst 2 comprises a homogeneous catalyst.

Preferably, the homogeneous catalyst comprises RuHCl (CO) (PPh) ₃) ₃And/or Rh (PPh) ₃) ₃Cl。

Preferably, the Rh (PPh) ₃) ₃Cl and PPh ₃Used in combination, preferably PPh ₃Is added in an amount of Rh (PPh) ₃) ₃1 to 5 times, for example, 2 times, 3 times, 4 times, etc., of Cl.

Preferably, the catalyst 2 is added in an amount of 0.05 to 0.5% by mass, for example, 0.06%, 0.08%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.48% and the like, based on the mass of the cycloolefin monomer.

Preferably, in the step (2), the hydrogenation reaction is carried out in a high-pressure reaction kettle.

Preferably, the high-pressure reactor is pressurized to 5 to 10MPa, such as 5.5MPa, 6MPa, 6.5MPa, 7MPa, 7.5MPa, 8MPa, 8.5MPa, 9MPa, 9.5MPa, and the like.

Preferably, in the step (2), the temperature of the hydrogenation reaction is 80 to 140 ℃, for example, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 135 ℃ and the like.

Preferably, the step (2) specifically comprises: adding a catalyst 2 into the cycloolefin ring-opening polymer reaction liquid obtained in the step (1), uniformly stirring, putting into a high-pressure reaction kettle, replacing air in the kettle with nitrogen, pressurizing to 5-10 MPa with hydrogen, stirring for the fourth time, heating to 80-140 ℃, reacting until the pressure in the kettle is constant, stopping heating, cooling to room temperature, releasing pressure, and discharging to obtain a cycloolefin copolymer solution.

Preferably, step (3) is performed after step (2): and (3) mixing the cycloolefin copolymer solution obtained in the step (2) with a water-soluble extractant solution, stirring and heating for the fifth time, adding a peroxide aqueous solution, stirring for the sixth time, reacting at a constant temperature, cooling, and keeping a cycloolefin copolymer solution phase.

The purpose of step (3) is to remove the catalyst, a system composed of a water-soluble extracting agent/peroxide participates in the removal reaction of the catalyst together, the effect is excellent, the removal rate can reach 99.0 percent at most, and the highest recovery rate of the noble metal and the best quality of the polymer product are realized.

Preferably, in the step (3), the target temperature for raising the temperature is 80 to 110 ℃, for example, 82 ℃, 85 ℃, 88 ℃, 90 ℃, 92 ℃, 95 ℃, 98 ℃, 100 ℃, 102 ℃, 105 ℃ and the like.

Preferably, in the step (3), the isothermal reaction time is 0.5-2 h, such as 0.6h, 0.7h, 0.8h, 1h, 1.2h, 1.5h, 1.8h, and the like.

Preferably, in the step (3), the water-soluble extractant includes any one or a combination of at least two of formic acid, acetic acid, ethylenediamine, propylenediamine, monoethanolamine, diethanolamine and triethanolamine, preferably triethanolamine.

Preferably, in the step (3), the mass concentration of the water-soluble extractant in the water-soluble extractant solution is 2-20%, for example, 3%, 4%, 5%, 8%, 10%, 12%, 14%, 16%, 18%, etc.

In the step (3), the amount of the water-soluble extractant solution added is preferably 25 to 100% by mass, for example, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or the like, based on the mass of the cycloolefin copolymer solution obtained in the step (2).

Preferably, in step (3), the peroxide comprises an organic peroxide and/or an inorganic peroxide, preferably any one or a combination of at least two of hydrogen peroxide, peroxyacetic acid and ammonium persulfate, preferably hydrogen peroxide.

Preferably, in the step (3), the mass concentration of the peroxide in the peroxide aqueous solution is 5 to 30%, for example, 6%, 8%, 10%, 12%, 15%, 16%, 18%, 20%, 22%, 25%, 28%, etc.

In the step (3), the amount of the aqueous peroxide solution is preferably 25 to 100% by mass, for example, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or the like, based on the mass of the cycloolefin copolymer solution obtained in the step (2).

Preferably, the step (3) specifically comprises the following steps:

and (3) adding a water-soluble extractant solution into the cycloolefin copolymer solution obtained in the step (2), stirring for the fifth time, heating to 80-110 ℃, adding a peroxide aqueous solution, stirring for the sixth time, reacting for 0.5-2 h at constant temperature, cooling, and keeping a cycloolefin copolymer solution phase.

Preferably, step (4) is performed after step (3): and (4) adding a precipitator into the cycloolefin copolymer solution phase obtained in the step (3) for precipitation, filtering, collecting a solid phase, washing and drying to obtain the cycloolefin copolymer.

Preferably, the precipitating agent comprises any one or a combination of at least two of isopropanol, methanol, ethanol and acetone.

Preferably, the preparation method specifically comprises the following steps:

(1) vacuumizing a reaction bottle, introducing nitrogen to replace air, adding a cycloolefin monomer, a solvent and a chain transfer agent under the protection of nitrogen, stirring for the first time, controlling the temperature to be 0-30 ℃, dissolving a catalyst 1 in the solvent, dropwise adding the catalyst into a reaction system at the temperature of less than or equal to 35 ℃, stirring for the second time for 0.5-2 hours after dropwise adding is finished, adding a chain terminating agent, and stirring for the third time for 10-30 minutes to obtain a cycloolefin ring-opening polymer reaction solution;

(2) adding a catalyst 2 into the cycloolefin ring-opening polymer reaction liquid, stirring uniformly, putting into a high-pressure reaction kettle, replacing air in the kettle with nitrogen, pressurizing to 5-10 MPa with hydrogen, stirring for the fourth time, heating to 80-140 ℃, reacting until the pressure in the kettle is constant, stopping heating, cooling to room temperature, relieving pressure, and discharging to obtain a cycloolefin copolymer solution;

(3) adding a water-soluble extractant solution into the cycloolefin copolymer solution, stirring for the fifth time, heating to 80-110 ℃, adding a peroxide aqueous solution, stirring for the sixth time, reacting at a constant temperature for 0.5-2 h, cooling, and keeping a cycloolefin copolymer solution phase;

(4) and adding a precipitator into the cycloolefin copolymer solution phase for precipitation, filtering, collecting a solid phase, washing and drying to obtain the cycloolefin copolymer.

It is a further object of the present invention to provide a polymer optical material obtained by processing (for example, forming a film) the cycloolefin copolymer described in one of the objects.

Preferably, the method for processing the cyclic olefin copolymer into the film comprises the following steps:

taking a certain amount of cycloolefin copolymer in a sample bottle, heating and dissolving in a solvent to prepare a solution with the mass concentration of 5-15%, pouring the solution onto a clean glass plate to form a film by tape casting, heating the solution in an oven at 80 ℃ for 4-6 h, volatilizing most of the solvent, heating the solution in a vacuum drying oven at 70 ℃ for 8-12 h, naturally cooling the solution to room temperature, placing the glass plate in deionized water, removing the film, and drying the film in the oven at 100 ℃ to prepare the heat-resistant cycloolefin copolymer optical film.

The fourth object of the present invention is to provide an application of the polymer optical material of the third object, and the polymer optical material is applied to an optical device.

Preferably, the optical device comprises a lens or a liquid crystal display.

Preferably, the polymer optical material is applied to a light guide plate or a polarizing film of an optical device.

Compared with the prior art, the invention has the following beneficial effects:

(1) the invention combines two structural units with specific structures, the obtained cycloolefin copolymer is an amorphous polymer, compared with the common cycloolefin copolymer, the regulation and control range of the glass transition temperature and the thermal deformation temperature is wide, the heat resistance is excellent, the light transmittance of the polymer is excellent, the polymer has proper water absorption and mechanical properties, the raw materials are easy to obtain, the glass transition temperature of the cycloolefin copolymer is 185-210 ℃, the thermal deformation temperature is 158-178 ℃, the light transmittance reaches 91%, the PDI is 1.75-2.30, and the molecular weight distribution is uniform;

(2) the invention takes the norbornene type or dimethylocta-hydrogen naphthalene type based cycloolefin monomer A and the norbornyl ester type or dimethylocta-hydrogen naphthalene type based cycloolefin monomer B as the starting raw materials, can realize the ring-opening metathesis copolymerization reaction under the action of a proper catalyst, and a large amount of double bonds are reserved on the main chain of the prepared copolymer, and the existence of the double bonds can cause the copolymer to be not resistant to yellowing and heat, so that the unsaturated double bonds need to be converted into saturated carbon-carbon bonds through further hydrogenation reaction, thereby obtaining the cycloolefin copolymer with excellent heat resistance.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

The proportions of the structural units in the cycloolefin copolymers obtained in the following examples and comparative examples are calculated on the basis of the charge of the monomers, n being for example in example 1 ₁/n ₀＝0.6，n ₂/n ₀＝0.4。