A cycloolefin polymer containing a thiophene group, and a method for preparing and use thereof

Abstract

The application discloses a cycloolefin polymer containing a thiophene group and a preparation method and application thereof, the cycloolefin polymer contains a thiophene structure, and a structural formula of the cycloolefin polymer is as follows: the cycloolefin polymer is a transparent resin with an amorphous structure at normal temperature, the glass transition temperature can be adjusted through the proportion of x and y, and the adjustment range is 120 DEG C-180 DEG C. Compared with a traditional cycloolefin polymer with a carbon-hydrogen structure, the cycloolefin polymer has higher heat resistance, meanwhile, the introduction of the thiophene structure can increase the refractive index of the material to 1.57, meanwhile, the light transmittance of the material reaches 91%, and the cycloolefin polymer can be widely applied in the field of transparent optical materials, such as optical lenses, polarizing films and the like.

Description

Technical Field

[0001] This invention belongs to the field of polyolefins, specifically relating to a cycloolefin polymerization containing thiophene groups, as well as a method for preparing the cycloolefin polymer and its applications. Background Technology

[0002] Cyclic olefin polymers (COPs) are transparent polymers obtained by the ring-opening metathesis polymerization (ROMP) of cyclic olefin monomers, followed by hydrogenation. The cyclic groups and ethyl groups in the polymer backbone are alternately distributed, and the cyclic structure hinders the aggregation and crystallization of ethyl groups. Therefore, they possess excellent transparency and other superior optical properties. Furthermore, these materials exhibit low dielectric properties, good biocompatibility, high heat resistance, and resistance to chemical corrosion, making them widely used in optics, electronic components, and biomedicine.

[0003] Heat resistance and refractive index are key performance indicators for COP (carbon-based plastic). During high-temperature injection molding, poor heat resistance can lead to dimensional changes in the COP, affecting dimensional accuracy and reducing yield. Conversely, a higher refractive index in COP can reduce the thinness of optical lenses. However, due to limitations imposed by hydrocarbon structures, the refractive index of commercially available COP is generally below 1.54, thus restricting its application scenarios.

[0004] Therefore, improving the heat resistance and refractive index of COP can greatly expand its application range, and providing COP with good heat resistance and high refractive index is also an important research direction at present. Summary of the Invention

[0005] In view of the problems of the prior art, the present invention provides a cyclic olefin polymer and its preparation method. The COP provided by the present invention not only has good heat resistance, but also has a higher refractive index. Its glass transition temperature can be adjusted from 120℃ to 180℃, and its refractive index reaches 1.57.

[0006] Another object of the present invention is to provide applications of such cyclic olefin polymers.

[0007] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:

[0008] A cycloolefin polymer containing a thiophene group has the general formula structure of the following formula (I):

[0009]

[0010] R1 and R2 are independently selected from H, aryl, and alkyl. The aryl group is, for example, any one of phenyl, xylene, trimethylbenzene, ethylbenzene, and diethylbenzene. The alkyl group is, for example, a C1 to C10 alkyl group, such as methyl, ethyl, propyl, butyl, isopropyl, pentyl, hexyl, isopentyl, heptyl, etc. m is a natural number from 0 to 5, for example 0, 1, 2, 3, 4, 5, preferably 1 to 3. x and y are selected from integers from 10 to 500, for example 10, 15, 20, 30, 40, 50, 75, 80, 90, 100, 125, 150, 180, 200, 250, 300, 350, 400, 450, 500, etc., preferably 150 to 200.

[0011] In another aspect of the present invention, a method for preparing the aforementioned cycloolefin polymer containing a thiophene group includes the following steps:

[0012] (1) Polymerization: The solvent, thiophene cyclic olefins and alkane cyclic olefins are added to the reactor in sequence. Then the reactor temperature and stirring are adjusted to the set values. After the reactor temperature reaches the experimental set temperature T1, the catalyst solution is added to the reactor and the reaction is carried out for the set time t1.

[0013] (2) Hydrogenation: Add hydrogenation catalyst to the reactor and heat it to the set temperature T2. Then, introduce hydrogen gas to the set value P. This is considered the start of the reaction. The reaction ends when the set time t2 is reached. After the reaction ends, cool the reactor to room temperature and release the pressure inside the reactor to atmospheric pressure. Inject the reaction solution into a large amount of ethanol to precipitate the polymer. Place the polymer in an oven and dry it to constant weight.

[0014] The reaction equations for the above polymerization and hydrogenation reactions are shown below:

[0015]

[0016] In step (1), the catalyst for polymerization is any one of Grubbs-type Ru-based catalyst or Schrock-type W or Mo-based catalyst, such as Grubbs first generation, Grubbs second generation, and Grubbs third generation catalysts, with Grubbs second generation catalyst being preferred.

[0017] Specifically, the catalyst concentration is 0.1-1 μmol / L, for example, 0.1 μmol / L, 0.2 μmol / L, 0.25 μmol / L, 0.5 μmol / L, 0.8 μmol / L, 1 μmol / L, etc., preferably 0.2-0.6 μmol / L. The catalyst concentration refers to the molar concentration of the catalyst added to the reaction vessel relative to the total volume of the reaction system, including the solvent, thiophene cyclic olefins, alkane cyclic olefins, and the catalyst solution.

[0018] In this invention, the thiophene cyclic olefins are obtained by reacting thiophene with cyclopentene, and the synthetic reaction equation is shown below:

[0019]

[0020] The reaction of thiophene and cyclopentene can refer to the existing Diels-Alder addition reaction technology. The monomers are mixed in proportion and then heated directly. After heating, the target monomer is obtained by distillation. There are no particular limitations in this invention.

[0021] Specifically, the reaction temperature is 100–250°C, such as 120°C, 150°C, 170°C, 190°C, 200°C, 230°C, etc., preferably 180–220°C; the reaction time is 0.5–10 h, such as 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, etc., preferably 1–5 h; the molar ratio of cyclopentene to thiophene in the above reaction is 1.0–1.5, such as 1.1, 1.2, 1.3, 1.4, 1.5, etc., preferably 1.01–1.1.

[0022] In this invention, the alkane-type cycloolefin structure is as follows:

[0023]

[0024] R1 and R2 are independently selected from H, aryl, and alkyl. The aryl group is, for example, any one of phenyl, xylene, trimethylbenzene, ethylbenzene, and diethylbenzene. The alkyl group is, for example, a C1 to C10 alkyl group, such as methyl, ethyl, propyl, butyl, isopropyl, pentyl, hexyl, isopentyl, heptyl, etc. m is a natural number from 0 to 5, for example 0, 1, 2, 3, 4, 5, preferably 1 to 3.

[0025] In step (1), the total concentration of the thiophene cyclic olefins and alkane cyclic olefin monomers is 0.5-5 mol / L, for example, 0.5 mol / L, 1 mol / L, 1.5 mol / L, 2 mol / L, 2.5 mol / L, 3 mol / L, 4 mol / L, 5 mol / L, etc., preferably 1-4 mol / L. In the polymerization reaction, the molar ratio of the thiophene cyclic olefins and alkane cyclic olefin monomers is usually 0.1-5, for example, 0.2, 0.5, 1, 2, 3, 4, 5, etc., preferably 0.2-2. The total concentration of the thiophene cyclic olefins and alkane cyclic olefin monomers refers to the total molar concentration of the thiophene cyclic olefins and alkane cyclic olefin monomers added to the reactor in the entire reaction system, based on the total volume of the solvent, thiophene cyclic olefins, alkane cyclic olefins, and catalyst solution.

[0026] In step (1), the polymerization temperature T1 is 10-200℃, such as 10℃, 20℃, 30℃, 40℃, 50℃, 80℃, 100℃, 120℃, 140℃, 150℃, 170℃, 180℃, 190℃, etc., preferably 70-130℃; the polymerization time t1 is 1-60min, such as 2min, 3min, 4min, 5min, 8min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 59min, etc., preferably 5-30min.

[0027] The solvent in step (1) polymerization reaction is an alkane or a cycloalkane, preferably at least one of hexane, cyclohexane, or heptane.

[0028] In step (2), the hydrogenation catalyst is a homogeneous hydrogenation catalyst made of noble metals, such as nickel, rhodium, palladium, ruthenium, etc., preferably nickel acetylacetonate, palladium acetate, rhodium triphenylphosphine chloride, or ruthenium triphenylphosphine chloride. The concentration of the hydrogenation catalyst in the reactor is 0.5-10 μmol / ml, for example 0.1 μmol / ml, 0.2 μmol / ml, 0.25 μmol / ml, 0.5 μmol / ml, 0.8 μmol / ml, 1 μmol / ml, 1.1 μmol / ml, 1.3 μmol / ml, 1.5 μmol / ml, 1.75 μmol / ml, 1.8 μmol / ml, 1.9 μmol / ml, etc., preferably 1-4 μmol / ml.

[0029] In step (2), the hydrogenation temperature T2 is 80-200℃, such as 80℃, 100℃, 120℃, 140℃, 150℃, 170℃, 180℃, 190℃, etc., preferably 120-180℃; the hydrogenation reaction time t2 is 0.5-10h, such as 0.5h, 0.8h, 1h, 1.5h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, etc., preferably 1-3h; the hydrogenation pressure P is 0.5-10MPa, such as 0.5MPa, 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, 3.5MPa, 4MPa, 4.5MPa, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa, 10MPa, etc., preferably 2-5MPa.

[0030] In another aspect, the application of the cycloolefin polymer containing thiophene groups of the present invention or the cycloolefin polymer containing thiophene groups prepared by the method of the present invention in the field of optical materials, especially in optical lenses and polarizing films.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] This invention provides a cyclic olefin polymer containing a thiophene group. The glass transition temperature of the polymer can be controlled by combining cyclic olefin monomers, with a controllable range of 120℃-180℃. Compared with existing commercially available COP, the thiophene structure in the cyclic olefin polymer containing the thiophene group of this invention can increase the refractive index of the material to 1.57, thus this material has great application potential in the field of optics. Detailed Implementation

[0033] The following examples are provided to further illustrate the method of the present invention, but should not be construed as limiting.

[0034] Test method:

[0035] 1. The oxygen monomer content in the synthesized polypropylene was determined by hydrogen nuclear magnetic resonance spectroscopy using a Varian Inova-400 (FT, 400MHz, 1H; 100MHz, 13C) instrument, and the isotacticity was determined by carbon nuclear magnetic resonance spectroscopy.

[0036] 2. Number average molecular weight (Mn) and molecular weight distribution (PDI) were determined by gel permeation chromatography with THF as the mobile phase, narrow distribution polystyrene as the standard, temperature 25℃, and HT-GPC (Agilent PL-220).

[0037] 3. The glass transition temperature (Tg) was determined using a DSC-60A with a temperature gradient of 10℃ / min.

[0038] 4. The refractive index (nD) was determined using an Abbe refractometer according to the method of GB / T7962.4-2010. This invention measures the refractive index of the cyclic olefin polymer at 23°C and 589 nm, and the refractive index at 589 nm in the range of -10 to 50°C.

[0039] 5. The transmittance was measured using a turbidimeter according to the method in JIS-K-7361-1.

[0040] Catalyst preparation:

[0041] Weigh 8.23 ​​mg of Grubbs-1 catalyst and 78 g of cyclohexane into a 200 ml glass bottle in a glove box, stir well, and prepare a catalyst solution with a concentration of 0.1 μmol / ml.

[0042] Weigh 8.48 mg of Grubbs-2 catalyst and 78 g of cyclohexane into a 200 ml glass bottle in a glove box, stir well, and prepare a catalyst solution with a concentration of 0.1 μmol / ml.

[0043] Weigh 8.85 mg of Grubbs-3 catalyst and 78 g of cyclohexane into a 200 ml glass bottle in a glove box, stir well, and prepare a catalyst solution with a concentration of 0.1 μmol / ml.

[0044] Example 1

[0045] Preparation of thiophene cyclic olefins: 88g of thiophene and 64g of cyclopentene were sequentially added to a 0.5L reactor. The reactor was evacuated and purged with nitrogen three times. The reactor was heated to 200°C and stirred for 2 hours. After the reaction, the product was cooled to room temperature and separated by vacuum distillation to obtain 140g of thiophene cyclic olefin M1.

[0046]

[0047] Synthesis of COP-1 containing thiophene structure: Before the experiment, the reactor was preheated to 150°C, and the vacuuming and nitrogen purging process was repeated three times. After the process, the reactor was cooled to room temperature. 16g of monomer M1, 17.3g of tetracyclododecene (TCD), 78g of hexane, and 0.84mg of hexene were weighed into a 500ml reactor in a glove box. The reactor temperature was then raised to 80°C, and stirring was started. After the pressure stabilized, 2ml of Grubbs-1 catalyst solution was injected into the reactor through the feed hopper. After 5 minutes of reaction, the heating was turned off, and 5ml of hexane solution containing 77.1mg of nickel acetylacetonate hydrogenation catalyst was added to the reactor. The reactor temperature was then raised to 150°C, and hydrogen gas was introduced. After the hydrogen pressure stabilized at 5MPa, stirring was started, marking the start of the hydrogenation reaction. After 2 hours of reaction, the pressure was released, the reactor was opened, and a large amount of ethanol solution was injected into the reaction solution for inactivation and precipitation treatment. The polymer precipitated in the ethanol. The polymer was removed from ethanol and dried in a vacuum dryer until a constant weight was obtained, yielding 34.1 g of COP-1. Its Mn content was determined to be 4.6 × 10⁻⁶. 4 g / mol, PDI is 3.5, Tg is 163℃, nD is 1.56, and transmittance is 91%.

[0048] Example 2

[0049] Synthesis of COP-2 containing thiophene structure: Before the experiment, the reactor was preheated to 150°C, and the vacuuming and nitrogen purging process was repeated three times. After the process, the reactor was cooled to room temperature. 22.8 g of monomer M1, 17.3 g of tetracyclododecene (TCD), 78 g of cyclohexane, and 2.61 mg of hexene were weighed into a 500 ml reactor in a glove box and added. The reactor temperature was then raised to 120°C, and stirring was started. After the pressure stabilized, 1.5 ml of Grubbs-2 catalyst solution was injected into the reactor through the feed hopper. After reacting for 10 minutes, heating was turned off, and 5 ml of a cyclohexane solution containing 25.7 mg of nickel acetylacetone hydrogenation catalyst was added to the reactor. The reactor temperature was then raised to 180°C, and hydrogen gas was introduced. Once the hydrogen pressure stabilized at 3 MPa, stirring was started, marking the start of the hydrogenation reaction. After one hour of reaction, the pressure was released, the reactor was opened, and a large amount of ethanol solution was injected into the reaction solution for inactivation and precipitation treatment, resulting in polymer precipitation in the ethanol. The polymer was removed from the ethanol and placed in a vacuum dryer until constant weight was obtained, yielding 42.7 g of COP-2. Its Mn content was determined to be 3.8 × 10⁻⁶. 4 g / mol, PDI is 3.7, Tg is 167℃, nD is 1.57, and transmittance is 91%.

[0050] Example 3

[0051] Synthesis of COP-3 containing thiophene structure: Before the experiment, the reactor was preheated to 150°C, and the vacuuming and nitrogen purging process was repeated three times. After the process, the reactor was cooled to room temperature. 7.6 g of monomer M1, 17.3 g of tetracyclododecene (TCD), 78 g of heptane, and 1.74 mg of hexene were weighed into a 500 ml reactor in a glove box and added. The reactor temperature was then raised to 100°C, and stirring was started. After the pressure stabilized, 1 ml of Grubbs-3 catalyst solution was injected into the reactor through the feed hopper. After reacting for 10 minutes, the heating was turned off, and 5 ml of hydrogenation catalyst solution containing 44.8 mg of palladium ethyl acetate was added to the reactor. The reactor temperature was then raised to 160°C, and hydrogen gas was introduced. After the hydrogen pressure stabilized at 4.5 MPa, stirring was started, marking the start of the hydrogenation reaction. After reacting for 2 hours, the pressure was released, the reactor was opened, and a large amount of ethanol solution was injected into the reaction solution for inactivation and precipitation treatment. The polymer precipitated in the ethanol. The polymer was removed from ethanol and dried in a vacuum dryer until constant weight was obtained, yielding 26.6 g of COP-3. Its Mn was 4.2 × 10⁴ g / mol, PDI was 3.4, Tg was 160℃, nD was 1.55, and transmittance was 90%.

[0052] Example 4

[0053]

[0054] Synthesis of COP-4 containing thiophene structure: Before the experiment, the reactor was preheated to 150°C, and the vacuuming and nitrogen purging process was repeated three times. After the process, the reactor was cooled to room temperature. 16g of monomer M1, 24.4g of hexadecimale (HCD), 78g of cyclohexane, and 1.74mg of hexene were weighed into a 500ml reactor in a glove box and added. The reactor temperature was then raised to 60°C, and stirring was started. After the pressure stabilized, 1.5ml of Grubbs-2 catalyst solution was injected into the reactor through the feed hopper. After 20 minutes of reaction, the heating was turned off, and 5ml of cyclohexane solution containing 185mg of triphenylphosphine rhodium chloride hydrogenation catalyst was added to the reactor. The reactor temperature was then raised to 170°C, and hydrogen gas was introduced. After the hydrogen pressure stabilized at 4MPa, stirring was started, marking the start of the hydrogenation reaction. After 1 hour of reaction, the pressure was released, the reactor was opened, and a large amount of ethanol solution was injected into the reaction solution for inactivation and precipitation treatment. The polymer precipitated in the ethanol. The polymer was removed from ethanol and dried in a vacuum dryer until a constant weight was obtained, yielding 42.1 g of COP-4. Its Mn content was determined to be 4.1 × 10⁻⁶. 4 The light transmittance is 91%, with a g / mol concentration, a PDI of 3.3, a Tg of 165℃, an nD of 1.56, and a transmittance of 91%.

[0055] Example 5

[0056]

[0057] Synthesis of COP-5 containing thiophene structure: Before the experiment, the reactor was preheated to 150°C, and the vacuuming and nitrogen purging process was repeated three times. After the process, the reactor was cooled to room temperature. 16g of monomer M1, 20.3g of dimethyltetracyclododecene (TCD-2), 78g of cyclohexane, and 1.74mg of hexene were weighed into a 500ml reactor in a glove box and added. The reactor temperature was then raised to 80°C, and stirring was started. After the pressure stabilized, 3ml of Grubbs-2 catalyst solution was injected into the reactor through the feed hopper. After 20 minutes of reaction, heating was turned off, and 5 ml of cyclohexane solution containing 147 mg of triphenylphosphine ruthenium chloride hydrogenation catalyst was added to the reactor. The reactor temperature was then raised to 140°C, and hydrogen gas was introduced. Once the hydrogen pressure stabilized at 5 MPa, stirring was started, marking the start of the hydrogenation reaction. After 3 hours of reaction, the pressure was released, the reactor was opened, and a large amount of ethanol solution was injected into the reaction solution for inactivation and precipitation treatment, resulting in polymer precipitation in the ethanol. The polymer was removed from the ethanol and placed in a vacuum dryer until constant weight was obtained, yielding 37.2 g of COP-5. Its Mn content was determined to be 4.5 × 10⁻⁶. 4 g / mol, PDI is 3.5, Tg is 165℃, nD is 1.56, and transmittance is 92%.

[0058] Example 6

[0059]

[0060] Synthesis of COP-6 containing thiophene structure: Before the experiment, the reactor was preheated to 150°C, and the vacuuming and nitrogen purging process was repeated three times. After the process, the reactor was cooled to room temperature. 16g of monomer M1, 25.5g of TCD-3, 78g of cyclohexane, and 0.87mg of hexene were weighed into a 500ml reactor in a glove box. The reactor temperature was then raised to 80°C, and stirring was started. After the pressure stabilized, 2ml of Grubbs-2 catalyst solution was injected into the reactor through the feed hopper. After 20 minutes of reaction, the heating was turned off, and 5ml of cyclohexane solution containing 147mg of nickel acetylacetonate hydrogenation catalyst was added to the reactor. The reactor temperature was then raised to 140°C, and hydrogen gas was introduced. After the hydrogen pressure stabilized at 5MPa, stirring was started, marking the start of the hydrogenation reaction. After 3 hours of reaction, the pressure was released, the reactor was opened, and a large amount of ethanol solution was injected into the reaction solution for inactivation and precipitation treatment. The polymer precipitated in the ethanol. The polymer was removed from ethanol and dried in a vacuum dryer until a constant weight was obtained, yielding 42.4 g of COP-6. Its Mn content was determined to be 4.4 × 10⁻⁶. 4 g / mol, PDI is 3.3, Tg is 164℃, nD is 1.56, and transmittance is 90%.

[0061] Comparative Example 1

[0062] Synthesis of COP-7 without thiophene structure: Before the experiment, the reactor was preheated to 150°C, and the vacuuming and nitrogen purging process was repeated three times. After the process, the reactor was cooled to room temperature. 32g TCD, 78g cyclohexane, and 0.84mg hexene were weighed into a 500ml reactor in a glove box. The reactor temperature was then raised to 80°C, and stirring was started. After the pressure stabilized, 1ml of Grubbs-2 catalyst solution was injected into the reactor through the feed hopper. After 5 minutes of reaction, heating was turned off, and 5ml of cyclohexane solution containing 90mg nickel acetylacetonate hydrogenation catalyst was added to the reactor. The reactor temperature was then raised to 140°C, and hydrogen gas was introduced. After the hydrogen pressure stabilized at 5MPa, stirring was started, marking the start of the hydrogenation reaction. After 3 hours of reaction, the pressure was released, the reactor was opened, and a large amount of ethanol solution was injected into the reaction solution for inactivation and precipitation treatment. The polymer precipitated in the ethanol. The polymer was removed from ethanol and dried in a vacuum dryer until a constant weight was obtained, yielding 32.8 g of COP-7. Its Mn content was determined to be 4.1 × 10⁻⁶. 4 g / mol, PDI is 3.4, Tg is 158℃, nD is 1.54, and transmittance is 90%.

[0063] Comparative Example 2

[0064] Synthesis of COP-8 without thiophene structure: Before the experiment, the reactor was preheated to 150°C, and the vacuuming and nitrogen purging process was repeated three times. After the process, the reactor was cooled to room temperature. 32g of TCD-2, 78g of cyclohexane, and 0.84mg of hexene were weighed into a 500ml reactor in a glove box. The reactor temperature was then raised to 80°C, and stirring was started. After the pressure stabilized, 1ml of Grubbs-2 catalyst solution was injected into the reactor through the feed hopper. After 5 minutes of reaction, the heating was turned off, and 5ml of cyclohexane solution containing 90mg of nickel acetylacetonate hydrogenation catalyst was added to the reactor. The reactor temperature was then raised to 180°C, and hydrogen gas was introduced. After the hydrogen pressure stabilized at 3MPa, stirring was started, marking the start of the hydrogenation reaction. After 1 hour of reaction, the pressure was released, the reactor was opened, and a large amount of ethanol solution was injected into the reaction solution for inactivation and precipitation treatment. The polymer precipitated in the ethanol. The polymer was removed from ethanol and dried in a vacuum dryer until a constant weight was obtained, yielding 32.8 g of COP-8. Its Mn content was determined to be 4.2 × 10⁻⁶. 4 g / mol, PDI is 3.4, Tg is 158℃, nD is 1.54, and transmittance is 90%.

[0065] Comparative Example 3

[0066] Synthesis of COP-9 without thiophene structure: Before the experiment, the reactor was preheated to 150°C, and the vacuuming and nitrogen purging process was repeated three times. After the process, the reactor was cooled to room temperature. 32g HCD, 78g cyclohexane, and 0.84mg hexene were weighed into a 500ml reactor in a glove box and added. The reactor temperature was then raised to 80°C, and stirring was started. After the pressure stabilized, 1ml of Grubbs-2 catalyst solution was injected into the reactor through the feed hopper. After 5 minutes of reaction, heating was turned off, and 5ml of cyclohexane solution containing 90mg nickel acetylacetone hydrogenation catalyst was added to the reactor. The reactor temperature was then raised to 180°C, and hydrogen gas was introduced. After the hydrogen pressure stabilized at 3MPa, stirring was started, marking the start of the hydrogenation reaction. After 1 hour of reaction, the pressure was released, the reactor was opened, and a large amount of ethanol solution was injected into the reaction solution for inactivation and precipitation treatment. The polymer precipitated in the ethanol. The polymer was removed from ethanol and dried in a vacuum dryer until a constant weight was obtained, yielding 32.8 g of COP-9. Its Mn content was determined to be 4.3 × 10⁻⁶. 4 g / mol, PDI is 3.4, Tg is 158℃, nD is 1.54, and transmittance is 90%.

[0067] Analysis of the comparative and example data shows that the thiophene structure can effectively improve the Tg and nD of COP. The Tg of COP without the thiophene structure is 158°C and the nD is 1.54. After introducing thiophene, the Tg can be increased to above 160°C, reaching a maximum of 167°C, and the nD can be increased to above 1.55, reaching a maximum of 1.57. Furthermore, analysis of Examples 1-6 shows that the higher the thiophene content, the more significant the improvement in Tg and nD.

Claims

1. A cyclic olefin polymer containing a thiophene group, characterized in that, It has the general formula structure of the following equation (I): R1 and R2 are independently selected from H, aryl, and alkyl, m is a natural number from 0 to 5, and x and y are integers from 10 to 500.

2. The cycloolefin polymer containing a thiophene group according to claim 1, characterized in that, m is a natural number from 1 to 3, and x and y are integers from 150 to 200.

3. The method for preparing the cycloolefin polymer containing a thiophene group as described in claim 1 or 2, characterized in that, Includes the following steps: (1) Polymerization: The solvent, thiophene cyclic olefins and alkane cyclic olefins are added to the reactor in sequence. Then the reactor temperature and stirring are adjusted to the set values. After the reactor temperature reaches the experimental set temperature T1, the catalyst solution is added to the reactor and the reaction is carried out until the set time t1. (2) Hydrogenation: Add hydrogenation catalyst to the reactor and heat it to the set temperature T2. Then, introduce hydrogen gas to the set value P. This is considered the start of the reaction. The reaction ends after the set time t2. After the reaction ends, cool the reactor to room temperature and reduce the pressure inside the reactor to atmospheric pressure. Inject the reaction solution into a large amount of ethanol to precipitate the polymer. Place the polymer in an oven and dry it to constant weight.

4. The preparation method according to claim 3, characterized in that, The catalyst used for polymerization in step (1) is either a Grubbs-type Ru catalyst or a Schrock-type W or Mo catalyst.

5. The preparation method according to claim 4, characterized in that, The catalyst used for polymerization in step (1) is any one of the first-generation Grubbs catalyst, second-generation Grubbs catalyst, or third-generation Grubbs catalyst.

6. The preparation method according to claim 5, characterized in that, The catalyst used for polymerization in step (1) is a second-generation Grubbs catalyst.

7. The preparation method according to claim 4, characterized in that, The concentration of the catalyst in the reactor is 0.1-1 µmol / L.

8. The preparation method according to claim 7, characterized in that, The concentration of the catalyst in the reactor is 0.2-0.6 µmol / L.

9. The preparation method according to claim 3, characterized in that, The thiophene-type cyclic olefins are obtained by heating a mixture of thiophene and cyclopentene. The reaction temperature is 100~250℃; and / or The reaction time is 0.5~10h; and / or The molar ratio of cyclopentene to thiophene is 1.0 to 1.

5.

10. The preparation method according to claim 9, characterized in that, The reaction temperature is 180~220℃; and / or The reaction time is 1-5 hours; and / or The molar ratio of cyclopentene to thiophene is 1.01 to 1.

1.

11. The preparation method according to claim 3, characterized in that, The alkane-type cyclic olefins have the general formula (II): R1 and R2 are independently selected from H, aryl, and alkyl, and m is a natural number from 0 to 5.

12. The preparation method according to claim 11, characterized in that, m is a natural number between 1 and 3.

13. The preparation method according to any one of claims 3-12, characterized in that, The total concentration of thiophene cyclic alkenes and alkane cyclic alkenes in step (1) is 0.5-5 mol / L.

14. The preparation method according to claim 13, characterized in that, The total concentration of thiophene cyclic alkenes and alkane cyclic alkenes in step (1) is 1-4 mol / L.

15. The preparation method according to claim 13, characterized in that, The molar ratio of the thiophene cyclic olefins and the alkane cyclic olefins is 0.1~5; and / or The polymerization temperature T1 is 10-200℃; and / or The polymerization time t1 is 1-60 min; and / or The solvent is at least one of alkanes and cycloalkanes.

16. The preparation method according to claim 15, characterized in that, The molar ratio of the thiophene cyclic olefins and the alkane cyclic olefins is 0.2~2; and / or The polymerization temperature T1 is 70-130℃; and / or The polymerization time t1 is 5-30 min; and / or The solvent is at least one of hexane, cyclohexane, and heptane.

17. The preparation method according to claim 3, characterized in that, The hydrogenation catalyst mentioned in step (2) is a noble metal homogeneous hydrogenation catalyst.

18. The preparation method according to claim 17, characterized in that, The hydrogenation catalyst mentioned in step (2) is at least one of nickel, rhodium, palladium or ruthenium.

19. The preparation method according to claim 18, characterized in that, The hydrogenation catalyst mentioned in step (2) is at least one of nickel acetylacetonate, palladium acetate, rhodium triphenylphosphine chloride, and ruthenium triphenylphosphine chloride.

20. The preparation method according to any one of claims 17-19, characterized in that, The concentration of the hydrogenation catalyst in the reactor is 0.5-10 µmol / ml.

21. The preparation method according to claim 20, characterized in that, The concentration of the hydrogenation catalyst in the reactor is 1-4 µmol / ml.

22. The preparation method according to claim 3, characterized in that, In step (2), the hydrogenation temperature T2 is 80-200℃; and / or The hydrogenation reaction time t2 is 0.5-10 h; and / or The hydrogenation pressure P is 0.5-10 MPa.

23. The preparation method according to claim 22, characterized in that, In step (2), the hydrogenation temperature T2 is 120-180℃; and / or The hydrogenation reaction time t2 is 1-3 h; and / or The hydrogenation pressure P is 2-5 MPa.

24. The application of the cycloolefin polymer containing a thiophene group as described in claim 1 or 2, or the cycloolefin polymer containing a thiophene group prepared by any one of claims 3-23, in the field of optical materials.

25. The application according to claim 24, characterized in that, Applications in optical lenses and polarizing films.

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