WO2024007505A1

WO2024007505A1 - Cycloolefin polymer film with optical anisotropy and preparation method therefor

Info

Publication number: WO2024007505A1
Application number: PCT/CN2022/131835
Authority: WO
Inventors: 张衡臣; 钟毅; 黄明礼; 刘阳; 左洪亮; 苑仁旭; 于明泉
Original assignee: 广东新华粤石化集团股份公司
Priority date: 2022-07-04
Filing date: 2022-11-15
Publication date: 2024-01-11
Also published as: CN115073664A; CN115073664B

Abstract

The present invention discloses a cycloolefin polymer film with optical anisotropy and a preparation method therefor, and aims to provide a cycloolefin polymer film having optical anisotropy, a stable molecular weight, a relatively narrow molecular weight distribution and a stable heat resistance (Tg), and a preparation method therefor. The method is stable in terms of process, convenient and rapid, can effectively improve the production efficiency of the product, and is beneficial to large-batch industrial production. The technical solution thereof comprises the following successive steps: 1) dissolving a catalyst, a catalyst modifier and a cocatalyst in a solvent in a high-purity nitrogen atmosphere to obtain a stable catalyst solution; 2) adding the catalyst solution prepared in step 1) to a solvent, respectively pumping different cycloolefin monomers at a feeding rate of 1-30 mL/min, and reacting same at 60-70°C for 1.5-2.5 h to obtain a cycloolefin polymer; and 3) adding a hydrogenation catalyst to the cycloolefin polymer in step 2), reacting same in a hydrogen atmosphere at 190-230°C for 5-7 h, and performing precipitating, washing and drying to obtain a saturated cycloolefin polymer. The present invention belongs to the field of new chemical materials.

Description

A kind of optically anisotropic cycloolefin polymer film and preparation method thereof

Technical field

The present invention belongs to the field of new chemical materials and relates to the technical field of cyclic olefin polymer synthesis. More specifically, it relates to a cyclic olefin polymer film with optical anisotropy. The present invention also relates to a preparation method and application of the polymer film.

Background technique

As an important application field of C5 resources, cyclic olefin polymer (COP) materials have many excellent properties, such as high light transmittance (91%), few impurities, low water absorption, low birefringence, and high heat resistance ( T _g is 140-170 ^℃ ), high modulus, small dielectric constant, and scratch resistance. COP is different from traditional polyolefin materials. It is an amorphous and transparent polyolefin material. It has been widely used in many fields such as optical materials such as LCD screens, lenses, and vaccine bottles. It has better toughness and lower impurities than PMMA and PC optical materials currently commonly used in the field of mobile phone lenses. It is also lighter in weight and lower in manufacturing cost than borosilicate glass vaccine bottles. therefore. Cyclic olefin polymer is a new type of special plastic material with high added value.

For the cyclic olefin polymer lens industry chain, polarizers are an important high-end component. Because polarizers can filter out most of the reflected light, making photos show better colors, they are currently widely used in camera lenses. For mobile phone lenses, the current supply is far from meeting the demand.

In recent years, with the rapid development of the mobile phone industry, the demand for mobile phone lenses has also become higher and higher. According to statistics, the proportion of smartphones equipped with two or more lenses increased from nearly 20% in 2017 to 86% in 2020. In this regard, the number of lenses shipped, which was only 3.7 billion in 2018, will double to 8 billion by 2025.

According to reports in patents CN 108885292A and CN 112703435A, currently cyclic olefin polymer polarizers are prepared from oriented films obtained through a complex stretching process. This process requires high post-processing of the polymer, and the final product is prone to produce more Defects and unstable processes greatly increase the cost. In addition, cyclic olefin polymer polarizers have extremely high requirements for light transmittance. This complex process may introduce more impurities during the operation, which also affects the optical performance stability of the product.

Contents of the invention

In view of the above problems, the first object of the present invention is to provide an optically anisotropic cycloolefin polymer film with stable molecular weight and narrow molecular weight distribution, and stable heat resistance (Tg).

The second object of the present invention is to provide a method for preparing the above-mentioned optically anisotropic cyclic olefin polymer film, which is stable in process, convenient and fast, can effectively improve product production efficiency, and is conducive to large-scale industrial production.

To this end, the technical solution provided by the present invention is:

A method for preparing an optically anisotropic cyclic olefin polymer film, including the following steps:

1) Dissolve the catalyst, catalyst modifier, and cocatalyst in the solvent in a high-purity nitrogen atmosphere to obtain a stable catalyst solution;

The molar ratio of the catalyst, catalyst modifier and cocatalyst is: 1:0.5-10:10-100, preferably 1:1-5:30-80.

2) Add the catalyst solution prepared in step 1) into the solvent, then add different cycloolefin monomers at a feed rate of 1mL/min-30mL/min, and react at 60-70°C for 1.5-2.5 hours Cyclic olefin polymer is obtained;

The molar ratio of the cycloolefin monomer synthesis and the catalyst in step 1) is: 1:5*10 ^-5 -5*10 ^-4 , preferably 1:1-3*10 ^-4 .

3) Add a hydrogenation catalyst to the cycloolefin polymer described in step 2), react at 190-230°C in a hydrogen atmosphere for 5-7 hours, and obtain a saturated cycloolefin polymer after precipitation, washing and drying.

The molar ratio of the cyclic olefin polymer and the hydrogenation catalyst is: 1:1*10 ^-3 -1*10 ^-2 , preferably 1:2-5*10 ^-3 .

Further, the above-mentioned preparation method of the optically anisotropic cyclic olefin polymer film includes the following steps in sequence:

1) Place molybdenum pentachloride in a dehydrated Schlenk bottle in a glove box with a high-purity nitrogen atmosphere, dissolve it with the solvent cyclohexane, stir evenly with a magnet, add triethylaluminum, and finally add ligand 2 Tert-butyl activates cresol to obtain a stable catalyst solution;

The molar ratio of the triethylaluminum and molybdenum pentachloride is 10-100:1;

2) After the solvent is added to the dried reaction vessel, add the catalyst solution prepared in step 1), and finally add 0.2 mol of cyclic olefin monomer at a preset rate of 1mL/min-30mL/min using a plunger flow pump. Pour into the reaction system in sequence;

3) After reacting at 70°C for 2 hours, add the palladium/carbon hydrogenation catalyst, then adjust the reaction temperature to 210°C, and react in a hydrogen atmosphere for 6 hours;

4) Finally, filter the resulting polymer solution to remove the hydrogenation catalyst, add it to excess ethanol solution to obtain a white precipitate, wash it 3 times with ethanol solution of hydrochloric acid, and dry it in a vacuum drying oven at 80°C for 48 Hours, wait for constant weight.

Further, in the above-mentioned preparation method of optically anisotropic cycloolefin polymer film, the cycloolefin monomer is selected from cyclopentene, cyclopentadiene, dicyclopentadiene, tricyclopentadiene, One or more of cyclopentadiene polymer, norbornene, methylnorbornene, vinylnorbornene, tetracyclododecene, methyltetracyclododecene, and tricyclodecene.

Further, in the above-mentioned preparation method of optically anisotropic cycloolefin polymer film, the solvent is selected from n-hexane, cyclohexane, n-heptane, n-octane, benzene, toluene, xylene, chlorobenzene, ortho- One or more of dichlorobenzene, dichloromethane, chloroform, and carbon tetrachloride.

Further, in the above-mentioned preparation method of optically anisotropic cyclic olefin polymer film, the catalyst is selected from tantalum, molybdenum, tungsten, ruthenium and its tantalum chloride, molybdenum chloride, tungsten chloride, ruthenium chloride or tantalum One or more of oxychloride, molybdenum oxychloride, tungsten oxychloride, and ruthenium oxychloride.

Further, in the above-mentioned preparation method of optically anisotropic cyclic olefin polymer film, the catalyst modifier is an alcohol compound, an alkylphenol compound, an ether compound, an acid compound, an acyl compound, or an ester compound. , one or more heterocyclic compounds.

Further, in the above-mentioned preparation method of optically anisotropic cyclic olefin polymer film, the alkylphenol compound is p-tert-butylphenol, di-tert-butylp-methylphenol, nonylphenol, or dodecylphenol. , one or more of biphenyldiol, naphthodiol, and binaphthol.

Further, in the above-mentioned preparation method of optically anisotropic cyclic olefin polymer film, the cocatalyst is an alkyl aluminum halide, preferably trimethylaluminum, triethylaluminum, diethyl aluminum monochloride, dichloromono-alkyl aluminum. One or more of ethyl aluminum, tri-n-butylaluminum, triisobutylaluminum, and tri-n-octyl aluminum.

Further, in the above-mentioned preparation method of the optically anisotropic cyclic olefin polymer film, the washing uses an ethanol solution in which hydrochloric acid is dropped, and the pH value is 3-6.

Further, in the above-mentioned method for producing an optically anisotropic cyclic olefin polymer film, the vacuum drying temperature is 80°C, the drying time is 48 hours, and the vacuum degree is -0.1MPa.

A cyclic olefin polymer film with optical anisotropy, prepared by the method mentioned above in the claims.

Compared with the prior art, the beneficial effects of the present invention are:

1) The technical solution provided by the present invention cleverly designs block copolymers to form a microphase separation structure, thereby naturally having optical anisotropy. The obtained cyclic olefin polymer material has a stable molecular weight and a narrow molecular weight distribution, and Its heat resistance (Tg) is stable; therefore, it can be used in the preparation of polarizers.

2) The preparation method of the optically anisotropic cyclic olefin polymer film of the present invention controls the nucleation size of different monomer molecular chains of the cyclic olefin polymer and has obvious microphase separation by regulating the feeding sequence of the cyclic olefin monomers. Phenomenon of block copolymer structure. The reaction process is stable, the polymerization conversion rate reaches more than 95%, and no polymerization gel is generated, which effectively solves the problem that monomers easily form gels during polymerization and affect the yield of polymerization reaction or product performance. The preparation method is convenient and rapid, improves product production efficiency, and is conducive to large-scale industrial production.

3) The nucleation size of each component of the optically anisotropic cyclic olefin polymer film prepared by the present invention is suitable, the microscopic separation phenomenon of the prepared block copolymer is obvious, the results are highly reproducible, and the optical anisotropy is excellent. .

Description of the drawings

Figure 1 is an SEM image of an optically anisotropic cyclic olefin polymer film.

Detailed ways

The present invention will be described in further detail below with reference to examples, but the implementation of the present invention is not limited thereto.

Example 1

The invention provides a cyclic olefin polymer film with optical anisotropy, which is prepared by the following method:

1) First, take 1*10 ^-4 mol of molybdenum pentachloride in a high-purity nitrogen atmosphere glove box and place it in a dehydrated Schlenk bottle. Dissolve it with 10 ml of solvent cyclohexane. After stirring evenly with a magnet, add triethyl Base aluminum 5*10 ^-3 mol, and finally add ligand 1*10 ^-4 mol di-tert-butyl p-cresol to activate to obtain a stable catalyst solution;

2) After adding 300ml of solvent into the dried 1L reaction vessel, add all the catalyst solution prepared in step 1) into it, and finally add the monomers 0.18mol tetracyclododecene and 0.02mol dicyclopentadiene at the preset rate 1mL/min was pumped into the reaction system sequentially using a plunger flow pump. After reacting at 70°C for 2 hours, add 5*10 ^-4 mol palladium/carbon hydrogenation catalyst, then adjust the reaction temperature to 210°C, and react in a hydrogen atmosphere for 6 hours. Finally, the resulting polymer solution was filtered to remove the hydrogenation catalyst, and then added to excess ethanol solution to obtain a white precipitate, which was washed three times with ethanol solution of hydrochloric acid and dried in a vacuum drying oven at 80°C for 48 hours. After constant weight, take it out for granulation. Using this particle, the above-mentioned performance test was carried out, and the results are shown in Figure 1 and Table 1.

Example 2

2) After adding 300ml of solvent into the dried 1L reaction vessel, add all the catalyst solution prepared in step 1) into it, and finally add the monomers 0.18mol tetracyclododecene and 0.02mol dicyclopentadiene at the preset rate 30mL/min was pumped into the reaction system sequentially using a plunger flow pump. After reacting at 70°C for 2 hours, add 5*10 ^-4 mol palladium/carbon hydrogenation catalyst, then adjust the reaction temperature to 210°C, and react in a hydrogen atmosphere for 6 hours. Finally, the generated polymer solution was filtered to remove the hydrogenation catalyst, and then added to excess ethanol solution to obtain a white precipitate, which was washed three times in an ethanol solution of hydrochloric acid and dried in a vacuum drying oven at 80°C for 48 hours. After constant weight, take it out for granulation. Using this particle, the above-mentioned performance test was carried out, and the results are shown in Figure 1 and Table 1.

Example 3

2) After adding 300ml of solvent into the dried 1L reaction vessel, add all the catalyst solution prepared in step 1) into it, and finally add the monomers 0.02mol tetracyclododecene and 0.18mol dicyclopentadiene at the preset rate 1mL/min was pumped into the reaction system sequentially using a plunger flow pump. After reacting at 70°C for 2 hours, add 5*10 ^-4 mol palladium/carbon hydrogenation catalyst, then adjust the reaction temperature to 210°C, and react in a hydrogen atmosphere for 6 hours. Finally, the resulting polymer solution was filtered to remove the hydrogenation catalyst, and then added to excess ethanol solution to obtain a white precipitate, which was washed three times with ethanol solution of hydrochloric acid and dried in a vacuum drying oven at 80°C for 48 hours. After constant weight, take it out for granulation. Using this particle, the above-mentioned performance test was carried out, and the results are shown in Figure 1 and Table 1.

Example 4

2) After adding 300ml of solvent into the dried 1L reaction vessel, add all the catalyst solution prepared in step 1) into it, and finally add the monomers 0.1mol tetracyclododecene and 0.1mol dicyclopentadiene at the preset rate 1mL/min was pumped into the reaction system sequentially using a plunger flow pump. After reacting at 70°C for 2 hours, add 5*10 ^-4 mol palladium/carbon hydrogenation catalyst, then adjust the reaction temperature to 210°C, and react in a hydrogen atmosphere for 6 hours. Finally, the resulting polymer solution was filtered to remove the hydrogenation catalyst, and then added to excess ethanol solution to obtain a white precipitate, which was washed three times with ethanol solution of hydrochloric acid and dried in a vacuum drying oven at 80°C for 48 hours. After constant weight, take it out for granulation. Using this particle, the above-mentioned performance test was carried out, and the results are shown in Figure 1 and Table 1.

Example 5

2) After adding 300ml of solvent into the dried 1L reaction vessel, add all the catalyst solution prepared in step 1) into it, and finally add the monomers 0.18mol methyltetracyclododecene and 0.02mol tetracyclododecene according to the The preset rate is 1mL/min and is sequentially pumped into the reaction system using a plunger flow pump. After reacting at 70°C for 2 hours, add 5*10 ^-4 mol palladium/carbon hydrogenation catalyst, then adjust the reaction temperature to 210°C, and react in a hydrogen atmosphere for 6 hours. Finally, the resulting polymer solution was filtered to remove the hydrogenation catalyst, and then added to excess ethanol solution to obtain a white precipitate, which was washed three times with ethanol solution of hydrochloric acid and dried in a vacuum drying oven at 80°C for 48 hours. After constant weight, take it out for granulation. Using this particle, the above-mentioned performance test was carried out, and the results are shown in Figure 1 and Table 1.

Example 6

2) After adding 300ml of solvent into the dried 1L reaction vessel, add all the catalyst solution prepared in step 1) into it, and finally add the monomers 0.1mol methyltetracyclododecene and 0.1mol tetracyclododecene according to the The preset rate is 1mL/min and is pumped into the reaction system sequentially using a plunger flow pump. After reacting at 70°C for 2 hours, add 5*10 ^-4 mol palladium/carbon hydrogenation catalyst, then adjust the reaction temperature to 210°C, and react in a hydrogen atmosphere for 6 hours. Finally, the resulting polymer solution was filtered to remove the hydrogenation catalyst, and then added to excess ethanol solution to obtain a white precipitate, which was washed three times with ethanol solution of hydrochloric acid and dried in a vacuum drying oven at 80°C for 48 hours. After constant weight, take it out for granulation. Using this particle, the above-mentioned performance test was carried out, and the results are shown in Figure 1 and Table 1.

Example 7

1) First, take 1*10 ^-4 mol of molybdenum pentachloride in a high-purity nitrogen atmosphere glove box and place it in a dehydrated Schlenk bottle. Dissolve it with 10ml of solvent cyclohexane. After stirring evenly with a magnet, add triethyl Base aluminum 5*10 ^-3 mol, and finally add ligand 1*10 ^-4 mol naphthalenediol for activation to obtain a stable catalyst solution;

Comparative example 1

As the monomers added to the reaction system in Example 1, they were no longer added separately but were replaced by a monomer mixture of 0.02 mol tetracyclododecene and 0.18 mol dicyclopentadiene. Except for this, granulation was carried out in the same manner as in Example 1, and the above-mentioned performance test was performed. The results are shown in Table 1.

Comparative example 2

As the catalytic system added to the reaction system in Example 1, the amount of catalyst modifier di-tert-butyl p-cresol used to activate the catalyst was changed from 1*10 ^-4 mol to 1*10 ^-5 mol. Except for this, granulation was carried out in the same manner as in Example 1, and the above-mentioned performance test was performed. The results are shown in Table 1.

Comparative example 3

As the catalytic system added to the reaction system in Example 1, the amount of catalyst modifier di-tert-butyl p-cresol used to activate the catalyst was changed from 1*10 ^-4 mol to 2*10 ^-3 mol. Except for this, granulation was carried out in the same manner as in Example 1, and the above-mentioned performance test was performed. The results are shown in Table 1.

Comparative example 4

As the catalytic system added to the reaction system in Example 1, the type of catalyst modifier used to activate the catalyst was changed from di-tert-butyl-p-cresol to diphenylamine. Except for this, granulation was carried out in the same manner as in Example 1, and the above-mentioned performance test was performed. The results are shown in Table 1.

Table 1: Cyclic olefin polymers prepared in Examples 1-10 and Comparative Example 1

The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, etc. may be made without departing from the spirit and principles of the present invention. All simplifications should be equivalent substitutions, and are all included in the protection scope of the present invention.

Claims

A method for preparing an optically anisotropic cyclic olefin polymer film, which is characterized in that it includes the following steps in sequence:

1) Under high-purity nitrogen atmosphere, dissolve the catalyst, catalyst modifier, and cocatalyst in the solvent to obtain a stable catalyst solution;

The molar ratio of the catalyst, catalyst modifier and cocatalyst is: 1:0.5-10:10-100, preferably 1:1-5:30-80.

2) Add the catalyst solution prepared in step 1) into the solvent, then add different cycloolefin monomers at a feed rate of 1mL/min-30mL/min, and react at 60-70°C for 1.5-2.5 hours Cyclic olefin polymer is obtained;

The molar ratio of the cycloolefin monomer synthesis and the catalyst in step 1) is: 1:5*10 -5 -5*10 -4 ;

3) Add a hydrogenation catalyst to the cyclic olefin polymer described in step 2), react at 190-230°C in a hydrogen atmosphere for 5-7 hours, and obtain a saturated cyclic olefin polymer after precipitation, washing and drying;

The molar ratio of the cyclic olefin polymer and the hydrogenation catalyst is: 1:1*10 -3 -1*10 -2 .
The preparation method of optically anisotropic cyclic olefin polymer film according to claim 1, characterized in that it includes the following steps in sequence:

1) Place molybdenum pentachloride in a dehydrated Schlenk bottle in a glove box with a high-purity nitrogen atmosphere, dissolve it with the solvent cyclohexane, stir evenly with a magnet, add triethylaluminum, and finally add ligand 2 Tert-butyl activates cresol to obtain a stable catalyst solution;

The molar ratio of the triethylaluminum and molybdenum pentachloride is 10-100:1;

2) After the solvent is added to the dried reaction vessel, add the catalyst solution prepared in step 1), and finally add 0.2 mol of cyclic olefin monomer at a preset rate of 1mL/min-30mL/min using a plunger flow pump. Pour into the reaction system in sequence;

3) After reacting at 70°C for 2 hours, add the palladium/carbon hydrogenation catalyst, then adjust the reaction temperature to 210°C, and react in a hydrogen atmosphere for 6 hours;

4) Finally, filter the resulting polymer solution to remove the hydrogenation catalyst, add it to excess ethanol solution to obtain a white precipitate, wash it 3 times with ethanol solution of hydrochloric acid, and dry it in a vacuum drying oven at 80°C for 48 Hours, wait for constant weight.
The method for preparing an optically anisotropic cycloolefin polymer film according to claim 1, wherein the cycloolefin monomer is selected from the group consisting of cyclopentene, cyclopentadiene, dicyclopentadiene, and tricycloolefin. Polycyclopentadiene, cyclopentadiene multimer, norbornene, methylnorbornene, vinylnorbornene, tetracyclododecene, methyltetracyclododecene, tricyclodecene Kind or variety.
The method for preparing an optically anisotropic cyclic olefin polymer film according to claim 1, wherein the solvent is selected from the group consisting of n-hexane, cyclohexane, n-heptane, n-octane, benzene, toluene, dihydrogen, One or more of toluene, chlorobenzene, o-dichlorobenzene, methylene chloride, chloroform, and carbon tetrachloride.
The method for preparing an optically anisotropic cyclic olefin polymer film according to claim 1, wherein the catalyst is selected from the group consisting of tantalum, molybdenum, tungsten, ruthenium and tantalum chloride, molybdenum chloride, and tungsten chloride. , ruthenium chloride or tantalum oxychloride, molybdenum oxychloride, tungsten oxychloride, ruthenium oxychloride, one or more; the catalyst modifier is alcohol compounds, alkylphenol compounds, ethers One or more compounds, acid compounds, acyl compounds, ester compounds, and heterocyclic compounds.
The method for preparing an optically anisotropic cyclic olefin polymer film according to claim 1, wherein the alkylphenol compound is p-tert-butylphenol, di-tert-butylp-methylphenol, or nonylphenol. , one or more of dodecylphenol, biphenyldiphenol, naphthodiol, and binaphthylphenol.
The method for preparing an optically anisotropic cyclic olefin polymer film according to claim 1, wherein the cocatalyst is an alkyl aluminum halide, preferably trimethylaluminum, triethylaluminum, or diethyl chloride. One or more of basal aluminum, monoethylaluminum dichloride, tri-n-butylaluminum, triisobutylaluminum, and tri-n-octyl aluminum.
The method for preparing an optically anisotropic cyclic olefin polymer film according to claim 1, wherein the washing uses an ethanol solution in which hydrochloric acid is dropped, and the pH value is 3-6.
The method for preparing an optically anisotropic cyclic olefin polymer film according to claim 1, characterized in that the vacuum drying temperature is 80°C, the drying time is 48 hours, and the vacuum degree is -0.1MPa.
A cyclic olefin polymer film with optical anisotropy, characterized in that it is prepared by the method described in any one of claims 1 to 9.