KR20110043088A - The norbornene polymer and the method for polymerization of it - Google Patents

Abstract

PURPOSE: A norbornene polymer is provided to ensure excellent thermal characteristic and optical property and to enable use as a base film of a substrate film for LCD, lens film, diffusion film, and phase difference film. CONSTITUTION: A norbornene polymer comprises a structure unit represented by chemical formula 1. In chemical formula 1, R1 and R2 are a C1~20 aliphatic, cycloaliphatic or aromatic hydrocarbon, an aliphatic hydrocarbon in which a main chain is composed of 1-20 carbons and oxygen, C1-20 halogen-substituted aliphatic, cycloaliphatic or aromatic hydrocarbon, or C1-20 silicone compound-substituted aliphatic, cycloaliphatic or aromatic hydrocarbon, or a structure in which they are connected.

Description

Norbornene polymer and its manufacturing method

The present invention relates to a cyclic olefin polymer (COP; Cyclic Olefin Polymer), and more particularly, to a norbornene polymer and a manufacturing method thereof.

Acrylic resins, polycarbonate resins, and the like have been widely known and used in the related art, but acrylic resins have excellent transparency, but have problems such as heat resistance, and polycarbonate resins have a large birefringence. There has been a problem with suitability.

In recent years, to overcome the disadvantages of the conventional transparent resin, COP has been developed as a transparent resin for optical materials with good transparency and heat resistance, and low birefringence, and its application fields are used in optical lens optical disks, optical fibers, etc. Applications are growing rapidly on the film side.

In the case of optical lenses, many lens products such as pickup lenses, prisms, OCD camera lenses, and projector lenses utilizing the advantages of COP's low birefringence, high heat resistance, and low absorption are commercialized. As optical disk applications, CDs and MDs, which utilize COP's low birefringence and formability, have been commercialized. Attempts have been made to apply them to high density MOs and DVDs. Commercialization of a plastic optical fiber (POF) into a heat-resistant COP-based POF utilizing high heat resistance of COP is under consideration.

In the case of COP, the optical film is a thermoplastic resin, and thus it is used as a retardation film of a TFT type LCD and a transparent conductive film for a touch panel. Transparency shows excellent characteristics similar to glass and its wavelength dispersion characteristics are smaller than those of other materials. Especially, its transparency is used because of its advantages of low birefringence, high heat resistance and low absorption. It can be applied to the base film of various functional films such as retardation film.

Accordingly, as the demand for optical material parts such as LCDs increases in recent years, high heat resistance, low birefringence, and low absorption COP, in particular, norbornene-based polymers are required.

The present invention provides a norbornene-based polymer having excellent thermal and optical properties, in particular, a norbornene-based polymer having a very high glass transition temperature of 200 ° C. or more and a method of manufacturing the same.

Norbornene-based polymer according to an embodiment of the present invention includes a structural unit represented by the formula (1).

Formula 1

R 1 and R 2 are each independently C 1 to C 20 aliphatic, alicyclic or aromatic hydrocarbons, aliphatic hydrocarbons composed of carbon and oxygen of 1 to 20 carbon atoms, halogen atom substituted aliphatic carbon atoms of 1 to 20 carbon atoms, alicyclic or aromatic hydrocarbons, carbon atoms 1 to 20 silicon compound substituted aliphatic or cycloaliphatic or aromatic hydrocarbon, or a structure in which they are connected to each other.

Here, the structural unit represented by the formula (1) is preferably a structural unit represented by the formula (2) or formula (3).

Formula 2

Formula 3

The norbornene-based polymer according to the second embodiment of the present invention includes a structural unit represented by the formula (4) as a hydrogenation reaction of the norbornene-based polymer of the formula (1).

Formula 4

R 1 and R 2 are each independently C 1 to C 20 aliphatic, alicyclic or aromatic hydrocarbons, aliphatic hydrocarbons composed of carbon and oxygen of 1 to 20 carbon atoms, halogen atom substituted aliphatic carbon atoms of 1 to 20 carbon atoms, alicyclic or aromatic hydrocarbons, carbon atoms 1 to 20 silicon compound substituted aliphatic or cycloaliphatic or aromatic hydrocarbon, or a structure in which they are connected to each other.

Here, the structural unit represented by the formula (4) is a hydrogenated reaction of the norbornene-based polymer containing the structural unit represented by the formula (2) or formula (3) is preferably a structural unit represented by the formula (5) or (6).

Formula 5

6

Norbornene-based polymers having Formulas 1 to 6 have a polystyrene reduced number average molecular weight (Mn) of 50,000 to 1,000,000 and a weight average molecular weight (Mw) as measured by gel permeation chromatography (GPC). It is more preferable that it is 50,000-3,000,000, molecular weight distribution (Mw / Mn) is 1.0-4.0, and it is more preferable that the decomposition temperature of 1 weight% is 300 degreeC or more as a result of Thermograminetric Analysis (TGA; Thermograminetric Analysis).

In addition, norbornene-based polymers including the formulas 4 to 6 has a high glass transition temperature characteristics of more than 200 ℃ glass transition temperature is very excellent thermal properties.

The norbornene-based polymer manufacturing method of the third embodiment of the present invention is prepared by adding a monomer of formula (7) to a solvent to prepare a solution of 0.01 ~ 1M concentration, heating the temperature of the solution to 60 ~ 130 ℃, compared to the monomer The polymerization is carried out by adding a catalyst so that the molar ratio of the catalyst is 50 to 250: 1.

Formula 7

R 1 and R 2 are each independently C 1 to C 20 aliphatic, alicyclic or aromatic hydrocarbons, aliphatic hydrocarbons composed of carbon and oxygen of 1 to 20 carbon atoms, halogen atom substituted aliphatic carbon atoms of 1 to 20 carbon atoms, alicyclic or aromatic hydrocarbons, carbon atoms 1 to 20 silicon compound substituted aliphatic or cycloaliphatic or aromatic hydrocarbon, or a structure in which they are connected to each other.

Here, the monomer of Formula 7 is preferably a monomer of Formula 8 or Formula 9.

Formula 8

Formula 9

In addition, the catalyst used in the polymerization reaction of the present invention may be a Grubbs catalyst, and a first generation Grubbs catalyst or a second generation Grubbs catalyst may be used.

Thus, the present invention provides a norbornene-based polymer having excellent thermal properties, in particular, a norbornene-based polymer having a very high glass transition temperature of 200 ° C. or more and a method for preparing the same, which is a pickup lens, a prism, an OCD camera lens, a projector It can be usefully used for optical fibers such as lenses, optical fibers, and the like, and in particular, it can be very useful as a base film of various functional optical films such as LCD substrate film, lens film, diffusion film, retardation film.

EMBODIMENT OF THE INVENTION Hereinafter, the Example of this invention is described.

-Synthesis of Exo-NDA (Nadic anhydride)

Castner, et al., J. Mol. Catal. According to the examples of 1982 , 15 , 47, 0.5 mol (66 g) dicyclopentadiene (FW132) and 1 mol (98 g) maleic anhydride (FW98) were dissolved in 1 L dichlorobenzene and added to Autoclave and reacted for 4 hours at 185 ° C as shown in Scheme 1 below. The solution was cooled to room temperature, and the precipitate produced was filtered to obtain a mixture of about 70% exo-NDA (FW164) and about 30% endo-NDA (FW164). The mixture was recrystallized with ethyl acetate to obtain a mixture of about 90% exo-NDA and about 10% endo-NDA, and the results of GC-MS (m / z 164) for the result are shown in FIG. 1.

Scheme 1

Hydrogenated NDA of Exo-NDA (hereinafter NDA (H)). ₂ Synthesis of)

Dissolve 26g of the exo-NDA (FW164) so obtained in ethyl acetate 250mL Pt / C (10wt %) was added to the catalyst weighed 0.26g hydrogen balloon hydrogenation reaction for 12 hours, of the formula 10 NDA (H ₂ (FW166) was prepared and the catalyst was removed using a Celite column. In addition, the results of GC-MS (m / z 166) for NDA (H ₂ ) (FW166) of Chemical Formula 8 thus obtained are shown in FIG. 2.

Formula 10

-Synthesis of Phthalimide

The phthalic anhydride (FW148) was reacted by applying the method of Liu, et al, Applied Radiation and Isotopes 2006, 64 , 760 as follows.

23 g of phthalic anhydride and 28 g of urea were added to 100 mL of xylene in 500 mL RBF and refluxed at 160 ° C. for 2 hours. Xylene was discarded and ethanol 100mL was added and refluxed at 90 ° C. for 2 hours to synthesize Phthalimide through the reaction as in Scheme 2. After cooling the solution, the precipitated product was obtained, Phthalimide (FW147), and the results of GC-MS (m / z 147) are shown in FIG. 3.

Scheme 2

-Synthesis of NDI (H ₂ ) (Nadicimide)

Such as the synthesis of Phthalimide NDA (H ₂ ) (FW166) was reacted by the method. That is, 26 g of 500 mL NDA (H ₂ ) and 28 g of urea were contained in 100 mL of xylene and refluxed at 160 ° C. for 2 hours. Xylene was discarded and ethanol 250mL was added and refluxed again at 90 ° C. for 2 hours to synthesize NDI (H ₂ ) (Nadicimide) through the same reaction as in Scheme 3. After cooling the solution, the precipitated product was obtained as NDI (H ₂ ) (FW165), the result of GC-MS (m / z 165) is shown in FIG.

Scheme 3

-Synthesis of N-Amino-phthalimide

Dey, et al., J. Org, Chem. The method of 2007, 72 , 9395 was applied and reacted as in Scheme 4. In other words, add 23 g of Phthalimide (FW147), 12 mL of hydrazine, and 150 mL of ethanol to 250 mL RBF in an ice-bath, and stir for 2 hours.Then, add the solution to 300 mL of ice water and deposit N-Amino- as a precipitate. Only phthalimide (FW 162) was collected by filtration, and the results of GC-MS (m / z 162) are shown in FIG. 5.

Scheme 4

N-Amino-NDI (H ₂ ) Synthesis

Kas'yan, et al. Russian J. Org. Chem. The method of 2005, 41 , 1122 was applied and reacted as in Scheme 5. NDI (H ₂ ) (FW165) 28.7g, hydrazine 12.7mL, ethanol 150mL was added to 250mL RBF and refluxed for 12 hours. After cooling to room temperature, the resulting N-Amino-NDI (H ₂ ) (FW180) was extracted with chloroform, and the results of GC-MS (m / z 180) for the result are shown in FIG. 6.

Scheme 5

Synthesis of Monomer

Heitz, et al., Macromol. Chem. Phys. The method of 1999 , 200 , 338 was applied and reacted as follows. N-Amino-phthalimide (FW162) 14g, NDA (FW164) 15.5g, acetic acid 90mL was added to 250mL RBF and refluxed for 2 hours. Thereafter, after cooling to room temperature, the precipitate was obtained by filtering out the monomer of Formula 8 (FW308), GC-MS (m / z 308) results are shown in FIG.

Synthesis of Monomer of Formula 9

Add 16 g of N-Amino-NDI (H ₂ ) (FW180), 16.4 g of NDA (FW164), 90mL of acetic acid to 250mL RBF, reflux for 2 hours, cool down to room temperature, and deposit the precipitated monomer of Formula 9 (FW 326). It was obtained by filtration, and the results of GC-MS (m / z 326) are shown in FIG. 8.

-Synthesis of norbornene-based polymer (poly (phthalimide-NDI)) comprising a structural unit of formula (2) and norbornene-based polymer poly (NDI (H2) -NDI) comprising a structural unit of formula (3)

In two 250 mL RBF, 4.088 g of Formula 8 monomer and 4.358 g of Formula 9 monomer were dissolved in 130 mL of dimethylformamide (each concentration was about 0.1 M), and the temperature of the solution was heated to 100 ° C. At this time, the inside of the container is replaced with nitrogen gas or argon gas. Thereafter, 56 mg of Grubbs 2nd generation catalyst (200: 1 molar ratio of monomer to catalyst) was added to initiate polymerization for 3 hours, and then 1 mL of ethyl vinyl ether was added for 12 hours. Then, the solution was added dropwise to cold ether to precipitate the polymer, and the precipitate was filtered and dried to dissolve again in dimethylformamide at a concentration of 5 to 10 wt%, reprecipitated in ether to remove the catalyst, and thus, a norbornene system including the structural unit of Formula 2 Norbornene-based polymer poly (NDI (H2) -NDI) comprising a polymer (poly (phthalimide-NDI)) and a structural unit of Formula 3 was synthesized, respectively.

The graphs of the respective GPCs (2 PLgel 5 μm Mixed-D columns, DMF (50 mM LiBr) solvent, 70 ° C., 0.8 mL / min, RI detector) are shown in FIG. 9 and FIG. , Weight average molecular weight and molecular weight distribution (Mw / Mn: PDI) are shown in Table 1 below.

poly (phthalimide-NDI) poly (NDI (H2) -NDI) Mn 241,000 190,000 Mw 372,000 236,000 PDI 1.54 1.24

-Synthesis of norbornene-based polymer (poly (phthalimide-NDI)) comprising a structural unit of formula (5) and norbornene-based polymer poly (NDI (H2) -NDI) comprising a structural unit of formula (6)

10 wt% concentration of norbornene-based polymer (poly (phthalimide-NDI)) comprising the structural unit of Formula 2 and norbornene-based polymer poly (NDI (H2) -NDI) comprising the structural unit of Formula 3 in dimethylformamide After melting with Yoshida, et al., Polym. J. 1998, 30 , 819, RuHCl (CO) (PPh ₃ ) ₃ catalyst was added by 0.3% by weight of the polymer. The solution was placed in a 110 mL autoclave and filled with hydrogen to 80 atm, reacted at 165 ° C. for 4 hours, and then precipitated in ether to remove the catalyst, thereby removing the norbornene-based polymer comprising a structural unit of formula 5 (poly ( phthalimide-NDI)) and norbornene-based polymer poly (NDI (H2) -NDI) including the structural unit of Formula 6 were synthesized, respectively.

The respective NMR (300 MHz, JEOL) and GPC (2 PLgel 5 ㎛ Mixed-D column, DMF (50 mM LiBr) solvent, 70 ℃, 0.8 mL / min, RI detector) The result graph is shown in Figures 11-14 The number average molecular weight, weight average molecular weight, and molecular weight distribution (Mw / Mn: PDI) are shown in Table 2 below.

poly (phthalimide-NDI) poly (NDI (H2) -NDI) Mn 261,000 192,000 Mw 431,000 238,000 PDI 1.65 1.24

The temperature rise rate of the norbornene-based polymer (poly (phthalimide-NDI)) comprising the structural unit of formula (5) synthesized as described above and the norbornene-based polymer poly (NDI (H2) -NDI) comprising the structural unit of Formula 6, respectively Results of thermogravimetric analysis (TGA Q50, TA instruments) at 10 ° C./min are shown in FIGS. 15 and 16. That is, the decomposition onset point of poly (N-phthalimide-NDI) is 376 ℃, the 1% decomposition temperature is 340 ℃, and the decomposition onset point of poly (N-NDI (H ₂ ) -NDI) is 417 ℃, 1% decomposition temperature. Was 353 ° C.

In addition, the norbornene-based polymer (poly (phthalimide-NDI)) comprising the structural unit of formula (5) and norbornene-based polymer poly (NDI (H2) -NDI) comprising the structural unit of formula (6), respectively, the temperature increase rate of 10 ℃ The results of the differential scanning calorimeter (DSC 2910, TA instruments) at / min are shown in FIGS. 17 and 18. That is, the glass transition temperature of poly (N-phthalimide-NDI) was 291 ° C., and the glass transition temperature of poly (N-NDI (H ₂ ) -NDI) was not shown.

Preparation of a film using a norbornene-based polymer (poly (phthalimide-NDI)) comprising a structural unit of formula (5) and a norbornene-based polymer poly (NDI (H2) -NDI) comprising a structural unit of formula (6)

Norbornene-based polymer (poly (phthalimide-NDI)) comprising a structural unit of formula (5) synthesized as described above and each norbornene-based polymer poly (NDI (H2) -NDI) comprising a structural unit of formula 6 is 5 After dissolving in dimethylformamide at a concentration of ˜10 wt%, pouring it onto a clean glass plate and drying, the film was dried in a vacuum oven for one day to include a norbornene-based polymer (poly (phthalimide-NDI)) containing a structural unit of formula (5). The film was prepared with a thickness of 76 μm, and the film containing norbornene-based polymer poly (NDI (H 2) —NDI) including the structural unit of Chemical Formula 6 was prepared with a thickness of 63 μm.

In addition, the thermo-mechanical analysis (DMA 2980, 76 ° C poly (N-phthalimide-NDI) film and 63 μm thick poly (N-NDI (H ₂ ) -NDI) film at a temperature increase rate of 5 ℃ / min TA instruments), and the results are shown in FIGS. 19 and 20. That is, the glass transition temperature of poly (N-phthalimide-NDI) having a thickness of 76 µm was 276 ° C, and the glass transition temperature of poly (N-NDI (H ₂ ) -NDI) having a thickness of 63 µm was 339 ° C. The coefficient of thermal expansion (CTE) was 42ppm / ℃ for poly (N-phthalimide-NDI) and 63ppm / for poly (N-NDI (H ₂ ) -NDI) when calculated from 60 ℃ to 200 ℃. ° C.

In addition, UV-VIS spectrum (V-530, JASCO) of a poly (N-phthalimide-NDI) film having a thickness of 76 μm and a poly (N-NDI (H ₂ ) -NDI) film having a thickness of 63 μm was measured. The results are the same as in FIGS. 21 and 22. That is, the transmittance at 550 nm of poly (N-phthalimide-NDI) having a thickness of 76 μm was 81%, and the transmittance at 550 nm of poly (N-NDI (H ₂ ) -NDI) having a thickness of 63 μm was 85%.

In addition, the Abbe counter (Atago 4T, Atago) and birefringence meter (RETS-100RF,) of a poly (N-phthalimide-NDI) film having a thickness of 76 μm and a poly (N-NDI (H ₂ ) -NDI) film having a thickness of 63 μm Otsuka Electronics) was measured, and the results are shown in Table 3 below.

Poly (phthalimide-NDI) Poly (NDI (H2) -NDI) Nx at 550 nm 1.58555 1.51547 Ny at 550 nm 1.58551 1.51546 Nz at 550 nm 1.58394 1.51408 delta nxy 0.00004 0.00001 delta nxz 0.00161 0.00139

In addition, the results of WAXS (GADDS, Bruker) taken at 2theta 4-40 ° of a poly (N-phthalimide-NDI) film having a thickness of 76 μm and a poly (N-NDI (H ₂ ) -NDI) film having a thickness of 63 μm are shown in FIG. Same as 23, and as a result of this, a norbornene-based polymer comprising a structural unit of formula 5 (poly (phthalimide-NDI)) and a norbornene-based polymer comprising a structural unit of formula 6 poly (NDI (H2)- NDI) can be seen to be amorphous.

1 is a graph of the results of GC-MS measurement of the intermediate result for Exo-NDA synthesis of the Examples.

Figure 2 is a graph of the GC-MS measurement results for NDA (H ₂ ) (FW166) of formula 8 of the Example.

Figure 3 is a graph of GC-MS measurement results for Phthalimide (FW147) of the Example.

4 is a graph of GC-MS measurement results for NDI (H ₂ ) (FW165) of the example.

5 is a graph of a GC-MS measurement result for N-Amino-phthalimide (FW 162) of the Example.

FIG. 6 is a graph of GC-MS measurement results for N-Amino-NDI (H ₂ ) (FW180) of the Example. FIG.

7 is a graph of a GC-MS measurement result for the monomer of Formula 8 (FW308) of the Example.

8 is a graph of a GC-MS measurement result for the monomer of Formula 9 (FW 326) of the Example.

FIG. 9 is a graph of GC-MS measurement results for a norbornene-based polymer (poly (phthalimide-NDI)) including a structural unit of Chemical Formula 2 of an example. FIG.

10 is a graph of a GC-MS measurement result for a norbornene-based polymer (poly (NDI (H 2) -NDI)) including a structural unit of Chemical Formula 3 of an example.

FIG. 11 is a graph of NMR measurement results for a norbornene-based polymer (poly (phthalimide-NDI)) including a structural unit of Chemical Formula 5 of an example. FIG.

12 is a graph of a GC-MS measurement result of a norbornene-based polymer (poly (phthalimide-NDI)) including a structural unit of Chemical Formula 5 of an example.

FIG. 13 is a graph of NMR measurement results for a norbornene-based polymer (poly (NDI (H 2) —NDI)) including a structural unit represented by Chemical Formula 6 of an example. FIG.

14 is a graph of a GC-MS measurement result for a norbornene-based polymer (poly (NDI (H 2) -NDI)) including a structural unit of Chemical Formula 6 of an example.

FIG. 15 is a graph of TGA measurement results of a norbornene-based polymer (poly (phthalimide-NDI)) including a structural unit of Chemical Formula 5 of an example. FIG.

FIG. 16 is a graph of TGA measurement results of a norbornene-based polymer (poly (NDI (H 2) —NDI)) including a structural unit of Chemical Formula 6 of an example. FIG.

FIG. 17 is a graph of DSC measurement results of norbornene-based polymer (poly (phthalimide-NDI)) including a structural unit of Chemical Formula 5 of an example. FIG.

FIG. 18 is a graph of DSC measurement results of a norbornene-based polymer (poly (NDI (H 2) -NDI)) including a structural unit of Chemical Formula 6 of an example. FIG.

19 is a graph of DMA measurement results of a poly (N-phthalimide-NDI) film having a thickness of 76 μm of the Examples.

20 is a graph of the DMA measurement results of a poly (N-NDI (H ₂ ) -NDI) film having a thickness of 63 μm of the examples.

21 is a graph of UV-VIS spectrum measurement results of a poly (N-phthalimide-NDI) film having a thickness of 76 μm in Example.

FIG. 22 is a graph of UV-VIS spectrum measurement results of a poly (N-NDI (H ₂ ) -NDI) film having a thickness of 63 μm of Examples.

FIG. 23 shows WAXS (GADDS, Bruker) taken at 2theta 4-40 ° of a poly (N-phthalimide-NDI) film having a thickness of 76 μm and a poly (N-NDI (H ₂ ) -NDI) film having a thickness of 63 μm of the embodiment. Graph of measurement results.

Claims (10)

Norbornene-based polymer comprising a structural unit represented by the formula (1). Formula 1

R 1 and R 2 are each independently C 1 to C 20 aliphatic, alicyclic or aromatic hydrocarbons, aliphatic hydrocarbons composed of carbon and oxygen of 1 to 20 carbon atoms, halogen atom substituted aliphatic carbon atoms of 1 to 20 carbon atoms, alicyclic or aromatic hydrocarbons, carbon atoms 1 to 20 silicon compound substituted aliphatic or cycloaliphatic or aromatic hydrocarbon, or a structure in which they are connected to each other. The norbornene-based polymer according to claim 1, wherein the structural unit represented by Chemical Formula 1 is a structural unit represented by Chemical Formula 2 or Chemical Formula 3. Formula 2

Formula 3

Norbornene-based polymer comprising a structural unit represented by the formula (4). Formula 4

R 1 and R 2 are each independently C 1 to C 20 aliphatic, alicyclic or aromatic hydrocarbons, aliphatic hydrocarbons composed of carbon and oxygen of 1 to 20 carbon atoms, halogen atom substituted aliphatic carbon atoms of 1 to 20 carbon atoms, alicyclic or aromatic hydrocarbons, carbon atoms 1 to 20 silicon compound substituted aliphatic or cycloaliphatic or aromatic hydrocarbon, or a structure in which they are connected to each other. The norbornene-based polymer according to claim 1, wherein the structural unit represented by Chemical Formula 4 is a structural unit represented by Chemical Formula 5 or Chemical Formula 6. Formula 5

6

According to any one of claims 1 to 4, wherein the norbornene-based polymer has a polystyrene reduced number average molecular weight (Mn) of 50,000 ~ 1,000,000 measured by gel permeation chromatography (GPC), the weight A norbornene-based polymer characterized by an average molecular weight (Mw) of 50,000 to 3,000,000 and a molecular weight distribution (Mw / Mn) of 1.0 to 4.0. The norbornene-based polymer according to claim 3 or 4, wherein the norbornene-based polymer has a decomposition temperature of 1% by weight based on a thermograminetric analysis (TGA) of at least 300 ° C.  The norbornene-based polymer according to claim 3 or 4, wherein the norbornene-based polymer has a glass transition temperature of 200 ° C or higher. Injecting the monomer of the formula (7) into a solvent to prepare a solution of 0.01 ~ 1M concentration, Heating the temperature of the solution to 60 ~ 130 ℃, Method for producing a norbornene-based polymer to perform a polymerization reaction by adding a catalyst so that the ratio of the number of moles of the catalyst to the monomer is 50 ~ 250: 1. Formula 7

R 1 and R 2 are each independently C 1 to C 20 aliphatic, alicyclic or aromatic hydrocarbons, aliphatic hydrocarbons composed of carbon and oxygen of 1 to 20 carbon atoms, halogen atom substituted aliphatic carbon atoms of 1 to 20 carbon atoms, alicyclic or aromatic hydrocarbons, carbon atoms 1 to 20 silicon compound substituted aliphatic or cycloaliphatic or aromatic hydrocarbon, or a structure in which they are connected to each other. 8. The method of claim 7, wherein the monomer of Formula 7 is a monomer of Formula 8 or Formula 9. 9. Formula 8

Formula 9

8. The process for producing norbornene-based polymers according to claim 7, wherein the catalyst is a Grubbs catalyst.

Images