KR101195186B1 - Norbornene polymer including photoreactive norbornene monomer and process of making the same - Google Patents

Abstract

The present invention relates to a photoreactive norbornene-based polymer comprising a norbornene-based monomer comprising a photoreactive functional group and a method for preparing the same, wherein the photoreactive norbornene-based polymer includes a specific photoreactive functional group, The electron density is changed according to the substituent to control the photoreactivity rate.

Photoreactive, norbornene-based monomer

Description

Norbornene-based polymer comprising a norbornene-based monomer including a photoreactor and a method for preparing the same {NORBORNENE POLYMER INCLUDING PHOTOREACTIVE NORBORNENE MONOMER AND PROCESS OF MAKING THE SAME}

The present invention relates to a photoreactive norbornene-based polymer, and more particularly, it is possible to control the photoreaction rate according to the electron density of the photoreactive substituent that is changed by changing the photoreactive substituent, to control the intermolecular photoreaction, and to the desired anisotropy It is to provide a norbornene-based polymer that can bring.

In recent years, as the size of liquid crystal displays has increased, the use of mobile phones, laptops, and the like has been gradually extended to home use such as wall-mounted TVs. Therefore, high definition, high quality, and wide viewing angles are required for liquid crystal displays. In particular, TFT-LCDs, which are driven by thin film transistors, independently drive individual pixels, and thus have excellent response speeds of liquid crystals and are capable of realizing high quality moving images.

In order to use a liquid crystal as an optical switch in such a TFT-LCD, the liquid crystal must be initially oriented in a predetermined direction on a layer in which a thin film transistor is formed on the innermost side of a display cell. A liquid crystal alignment layer is used for this purpose.

Background Art In the liquid crystal display, a method of orienting liquid crystals to date has applied a heat-resistant polymer such as polyimide onto a transparent glass to form a polymer alignment film, and then aligning the alignment film by rubbing the rotating roller wound around a rubbing cloth such as nylon and rayon at high speed. This is called the rubbing process.

However, the rubbing process destroys the thin film transistor because rubbing causes mechanical scratches on the liquid crystal aligning agent surface or generates high static electricity. In addition, defects are generated due to the fine fibers generated in the rubbing cloth, which is an obstacle in improving production yield.

In order to overcome the above problems of rubbing and to innovate in terms of productivity, a newly designed liquid crystal alignment method is UV, that is, liquid crystal alignment by light (hereinafter referred to as photo alignment).

Photo-alignment refers to a mechanism for forming a photopolymerizable liquid crystal alignment layer in which a photosensitive group bonded to a polymer by linearly polarized UV causes a photoreaction, and the main chain of the polymer is aligned in a predetermined direction, thereby aligning the liquid crystal.

Representative examples of such optical alignment are M. Schadt et al. (Jpn. J. Appl. Phys., Vol 31. \, 1992, 2155), Dae S. Kang et al. (US Pat. No. 5,464,669), Yuriy Reznikov (Jpn. J. Appl. Phys. Vol. 34, 1995, L1000).

As the photo-alignment polymer used in the above existing patents and papers, polycinnamate-based polymers such as poly (vinyl cinnamate) (PVCN) and poly (vinyl methoxycinnamate (PVMC) are mainly used. In the case of photo-alignment, a double bond of cinnamate reacts with a [2 + 2] cycloaddition reaction by irradiated UV to form a cyclobutane, thereby forming anisotropy. The alignment of the liquid crystal molecules is induced by arranging the liquid crystal molecules in one direction.

As an existing photo-alignment polymer, Japanese Patent Laid-Open Publication No. 11-181127 discloses a method for producing a polymeric alignment film having a side chain including photosensitive groups such as cinnamic acid groups in a main chain such as acrylate and methacrylate, and an alignment film produced thereby. However, the polymer has a disadvantage in that it is difficult to obtain sufficient alignment characteristics as desired even when exposed to light for a long time because mobility is poor. This is because the photoreceptor present in the polymer is not bound to the polarized light irradiated because it is bound to the main chain of the polymer. As a result, process efficiency decreases because it takes a long time to form a network polymer, and when the alignment process is finished for an appropriate time, the liquid crystal alignment of the fabricated liquid crystal display device is insufficient, resulting in a small dichroic ratio and a deterioration in contrast.

The present invention is a norbornene-based polymer that can control the photoreaction rate according to the electron density is changed by changing the photoreactive functional group, in order to solve the above problems, the yield and rate of the intermolecular [2 + 2] cyclo photoreaction It is an object of the present invention to provide a polymer that can control and give the desired anisotropy.

The present invention provides a norbornene polymer comprising a norbornene-based monomer having a photoreactive functional group.

The present invention also contains a procatalyst comprising a Group 10 transition metal, a first cocatalyst which provides a Lewis base capable of weakly coordinating with the metal of the procatalyst, and optionally a neutral Group 15 electron donor ligand. Provided is a polymerization method of the norbornene polymer, characterized in that the polymerization is carried out at a temperature of 10 ℃ to 200 ℃ in the presence of a catalyst mixture and a photoreactive norbornene-based monomer comprising a second cocatalyst to provide a compound.

The present invention also provides a photoalignment film and a hologram comprising the norbornene polymer.

Since the photoreactive norbornene-based polymer according to the present invention includes a specific photoreactive functional group, the electron density is changed according to the substituent of the photoreactive functional group to control the photoreactive rate.

Hereinafter, the present invention will be described in more detail.

The photoreactive norbornene-based polymer according to the present invention includes a norbornene-based monomer containing a specific photoreactive functional group, the electron density can be changed according to various substituents of the photoreactive functional group to control the photoreaction rate by UV .

Specifically, the photoreactive norbornene-based polymer includes a norbornene-based monomer including a photoreactive functional group prepared by covalently connecting cinnamate and norbornene having photoreactive properties, and various substituents that change the electron density. Substituting into changes the rate of photoreactivity.

The double bond of the cinnamate molecule reacts with light such as UV to form a π-π bond or a [2 + 2] bond with a nearby cinnamate double bond. Attaching the electron donor group or the electron acceptor group to the cinnamate group as a substituent affects the electron density of the double bond, which affects the photoreaction rate. For example, if a strong electron acceptor group such as F or NO ₂ is used as a substituent, the electron density of the cinnamate double bond is reduced and the pp orbital bond force of the π bond is weakened and is rapidly broken, thus making it possible to break more quickly. It is easy to combine [2 + 2].

The norbornene-based polymer according to the present invention is characterized by including a photoreactive norbornene-based monomer represented by the following formula (1).

In Formula 1,

p is an integer from 0 to 4,

At least one of R ₁ , R ₂ , R ₃ , and R ₄ is a radical selected from the group consisting of Formulas 1a, 1b, and 1c,

The remainder are each independently hydrogen, halogen, substituted or unsubstituted C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₂ -C ₂₀ alkenyl, substituted or unsubstituted C ₃ -C ₁₂ cycloalkyl , Substituted or unsubstituted C ₆ -C ₄₀ aryl; Substituted or unsubstituted C ₇ -C ₁₅ aralkyl; Substituted or unsubstituted C ₂ -C ₂₀ alkynyl; And a non-hydrocarbonaceous polar group comprising at least one oxygen, nitrogen, phosphorus, sulfur, silicon, or boron,

R ₁ , R ₂ , R ₃ , and R ₄ are hydrogen, halogen, or R ₁ unless they are polar functional groups. And R ₂ , or R ₃ With R ₄ May be linked to each other to form an alkylidene group of C ₁ -C ₁₀ , or R ₁ or R ₂ is R ₃ and R ₄ May be linked to any of the C ₄ -C ₁₂ saturated or unsaturated cyclic group rings, or C ₆ -C ₂₄ aromatic cyclic compounds:

In Chemical Formulas 1a, 1b and 1c,

A is a simple bond, substituted or unsubstituted C ₁ -C ₂₀ alkylene, carbonyl, carboxy, substituted or unsubstituted C ₆ -C ₄₀ arylene and substituted or unsubstituted C ₆ -C ₄₀ hetero Selected from arylene;

B is a simple bond, oxygen, sulfur, or -NH-;

X is oxygen or sulfur;

R ₉ is a simple bond, substituted or unsubstituted C ₁ -C ₂₀ alkylene, substituted or unsubstituted C ₂ -C ₂₀ alkenylene, substituted or unsubstituted C ₃ -C ₁₂ cycloalkylene, substituted Or unsubstituted C ₆ -C ₄₀ arylene, substituted or unsubstituted C ₇ -C ₁₅ aralkylene, and substituted or unsubstituted C ₂ -C ₂₀ alkynylene;

R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ Are each independently substituted or unsubstituted C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₁ -C ₂₀ alkoxy, substituted or unsubstituted C ₆ -C ₃₀ aryloxy, substituted or unsubstituted C C ₆ -C ₄₀ heteroaryl, substituted or unsubstituted C ₆ -C ₄₀ alkoxy containing _6- C ₄₀ aryl, group 14, 15 or 16 heteroelements (N, O, S, etc.) It is selected from the group consisting of aryl and a halogen element.

The non-hydrocarbonaceous polar group of Formula 1 is

-OR ₆ , -R ₅ OR ₆ , -OC (O) OR ₆ , -R ₅ OC (O) OR ₆ , -C (O) OR ₆ , -R ₅ C (O) OR _6, -C (O R ₆ , -R ₅ C (O) R ₆ , -OC (O) R ₆ , -R ₅ OC (O) R ₆ ,-(R ₅ O) _p -OR ₆ , (p is from 1 to 10 Integer),-(OR ₅ ) _p -OR ₆ (p is an integer from 1 to 10), -C (O) -OC (O) R ₆ , -R ₅ C (O) -OC (O) R ₆ , -SR ₆ , -R ₅ SR ₆ , -SSR ₆ , -R ₅ SSR ₆ , -S (= O) R ₆ , -R ₅ S (= O) R ₆ , -R ₅ C (= S) R ₆ , -R ₅ C (= S) SR ₆ , -R ₅ SO ₃ R ₆ , -SO ₃ R ₆ , -R ₅ N = C = S, -N = C = S, -NCO, R ₅ -NCO, -CN, -R ₅ CN, -NNC (= S) R ₆ , -R ₅ NNC (= S) R ₆ , -NO ₂ , -R ₅ NO ₂ ,

It may include one or more selected from the group consisting of,

Each R ₅ in the functional group is substituted or unsubstituted C ₁ -C ₂₀ alkylene, substituted or unsubstituted C ₂ -C ₂₀ alkenylene, substituted or unsubstituted C ₃ -C ₁₂ cycloalkylene , Substituted or unsubstituted C ₆ -C ₄₀ arylene, substituted or unsubstituted C ₇ -C ₁₅ aralkylene, substituted or unsubstituted C ₂ -C ₂₀ It can be selected from alkynylene,

R ₆ , R ₇ , and R ₈ Are each independently hydrogen, halogen, substituted or unsubstituted C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₂ -C ₂₀ alkenyl, substituted or unsubstituted C ₃ -C ₁₂ cycloalkyl, Substituted or unsubstituted C ₆ -C ₄₀ aryl, substituted or unsubstituted C ₇ -C ₁₅ aralkyl, substituted or unsubstituted C ₂ -C ₂₀ alkynyl, and the like.

In this case, preferably, when R ₁ of Formula 1 is a compound represented by Formula 1b, at least one of R ₂ , R ₃ , and R ₄ is a compound selected from the group consisting of Formulas 1a, 1b, and 1c. to be.

In addition, R ₁ of Formula ₁ is necessarily a compound represented by Formula 1b, at least one of R ₂ , R ₃ , and R ₄ is a radical selected from the group consisting of Formula 1a, 1b and 1c, Formula 1b R ₁₄ is most preferably necessarily selected from the group consisting of methyloxy, benzyloxy and methyl.

The factor affecting photoreactivity is in the spectrum of a light source that is generally used. When the polymer has an absorption wavelength of UV peak corresponding to the spectrum of the light source, the photoreaction may occur more easily. For example, when the polymer has an absorption wavelength of the UV peak as shown in FIG. 1, photoreactivity is excellent.

Therefore, the photoreactive norbornene-based polymer according to the present invention has a photoreactive functional group having a peak in a range similar to the absorption wavelength of the UV peak, for example, a functional group represented by the formula (1b) including methyloxy, benzyloxy, methyl and the like. Excellent photoreactivity.

In the substituent of the heteroaryl group of C ₆ -C ₄₀ aryl, and Group 14, Group 15 or Group 16 of C ₆ -C ₄₀ contains the hetero elements may comprise the formula:

At least one of R ′ ₁₀ to R ′ ₁₈ in the formula is necessarily substituted or unsubstituted C ₁ -C ₂₀ alkoxy, or substituted or unsubstituted C ₆ -C ₃₀ aryloxy,

The remainder is each independently substituted or unsubstituted C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₁ -C ₂₀ alkoxy, substituted or unsubstituted C ₆ -C ₃₀ aryloxy, and substituted or unsubstituted C ₆ -C ₄₀ aryl.

The photoreactive norbornene-based polymer according to the present invention includes a repeating unit represented by the following Chemical Formula 2:

In Formula 2,

n is 50 to 5,000, and p, R ₁ , R ₂ , R ₃ , and R ₄ are the same as defined in Chemical Formula 1.

Looking at the definition of the above-described substituents in detail as follows.

"Alkyl" means a straight or branched chain saturated monovalent hydrocarbon moiety of 1 to 20, preferably 1 to 10, more preferably 1 to 6 carbon atoms. Alkyl groups may be optionally substituted by one or more halogen substituents. Examples of alkyl groups include methyl, ethyl, propyl, 2-propyl, n-butyl, iso-butyl, tert-butyl, pentyl, hexyl, dodecyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, Dichloromethyl, trichloromethyl, iodomethyl, bromomethyl and the like.

"Alkenyl" means a straight or branched chain monovalent hydrocarbon moiety of 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms comprising at least one carbon-carbon double bond. . Alkenyl groups may be bonded through a carbon atom comprising a carbon-carbon double bond or through a saturated carbon atom. Alkenyl groups may be optionally substituted by one or more halogen substituents. Examples of the alkenyl group include ethenyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, pentenyl, 5-hexenyl, dodecenyl, and the like.

"Cycloalkyl" means a saturated or unsaturated non-aromatic monovalent monocyclic, bicyclic or tricyclic hydrocarbon moiety of 3 to 12 ring carbons and may be optionally substituted by one or more halogen substituents. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cyclooctyl, decahydronaphthalenyl, adamantyl, norbornyl (ie, bicyclo [2,2, 1] hept-5-enyl).

"Aryl" means a monovalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety having 6 to 20, preferably 6 to 12 ring atoms, which may be optionally substituted by one or more halogen substituents or the like. . Examples of the aryl group include phenyl, naphthalenyl, fluorenyl and the like.

"Alkoxyaryl" means that at least one hydrogen atom of the aryl group as defined above is substituted with an alkoxy group. Examples of the alkoxyaryl group are methoxyphenyl, ethoxyphenyl, propoxyphenyl, butoxyphenyl, pentoxyphenyl, hexoxyphenyl, heptoxy, octoxy, nanoxy, methoxybiphenyl, methoxynaphthalenyl, Methoxy fluorenyl, methoxy anthracenyl, and the like.

"Aralkyl" means that at least one hydrogen atom of the alkyl group as defined above is substituted with an aryl group, and may be optionally substituted with one or more halogen substituents. For example, benzyl, benzhydryl, trityl, etc. are mentioned.

"Alkynyl" means a monovalent hydrocarbon moiety of 2 to 20 carbon atoms, preferably 2 to 10, more preferably 2 to 6, straight or branched chains containing at least one carbon-carbon triple bond. do. Alkynyl groups may be bonded through a carbon atom comprising a carbon-carbon triple bond or through a saturated carbon atom. Alkynyl groups may be optionally substituted by one or more halogen substituents. For example, ethynyl, propynyl, etc. are mentioned.

"Alkylene" means a straight or branched chain saturated divalent hydrocarbon moiety of 1 to 20, preferably 1 to 10, more preferably 1 to 6 carbon atoms. Alkylene groups may be optionally substituted by one or more halogen substituents. Examples of the alkyl group include methylene, ethylene, propylene, butylene, hexylene and the like.

"Alkenylene" refers to a straight or branched chain divalent hydrocarbon moiety of 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms comprising at least one carbon-carbon double bond. it means. Alkenylene groups may be bonded through a carbon atom comprising a carbon-carbon double bond and / or through a saturated carbon atom. Alkenylene groups may be optionally substituted by one or more halogen substituents.

"Cycloalkylene" means a saturated or unsaturated non-aromatic divalent monocyclic, bicyclic or tricyclic hydrocarbon moiety of 3 to 12 ring carbons and may be optionally substituted by one or more halogen substituents. For example, cyclopropylene, cyclobutylene, etc. are mentioned.

"Arylene" means a divalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety having 6 to 20, preferably 6 to 12 ring atoms, which may be optionally substituted by one or more halogen substituents. have. The aromatic portion of the aryl group contains only carbon atoms. Phenylene etc. are mentioned as an example of an arylene group.

"Aralkylene" means a divalent moiety wherein at least one hydrogen atom of the alkyl group as defined above is substituted with an aryl group, and may be optionally substituted by one or more halogen substituents. For example, benzylene etc. can be mentioned.

"Alkynylene" refers to a straight or branched divalent hydrocarbon moiety of 2 to 20 carbon atoms, preferably 2 to 10, more preferably 2 to 6 carbon atoms, including one or more carbon-carbon triple bonds do. Alkynylene groups may be bonded through a carbon atom comprising a carbon-carbon triple bond or through a saturated carbon atom. Alkynylene groups may be optionally substituted by one or more halogen substituents. For example, ethynylene, propynylene, etc. are mentioned.

The norbornene polymer according to the present invention comprises a procatalyst comprising a transition metal of group 10, a first cocatalyst which provides a Lewis base capable of weakly coordinating with the metal of the procatalyst, and optionally a neutral group 15 electron donor. In the presence of a catalyst mixture consisting of a second cocatalyst and a photoreactive norbornene-based monomer which provides a compound containing a ligand, it may be polymerized at a temperature of 10 ° C to 200 ° C. If the reaction temperature is less than 10 ℃ causes a problem that the polymerization activity is very low, and if the reaction temperature is greater than 200 ℃ may cause a problem of decomposition of the catalyst is not preferred.

The catalyst mixture comprises 1 to 1000 moles of a first cocatalyst which provides a Lewis base capable of weakly coordinating with the metal of the precatalyst with respect to 1 mole of procatalyst comprising a Group 10 transition metal, and optionally neutral It is preferred to include 1 to 1000 moles of a second cocatalyst which provides a compound containing a Group 15 electron donor ligand. When the content of the first and second cocatalysts is less than 1 mole, there is a problem that the catalyst activation is not made, and when the content of the first and second cocatalysts is greater than 1000 moles, the catalyst activity is lowered.

The procatalyst comprising the Group 10 transition metal is easily separated by the first cocatalyst which provides the Lewis acid to easily participate in the Lewis acid-base reaction so that the central transition metal can be converted into a catalytically active species. Compounds with Lewis base groups leaving off can be used. Such as [(Allyl) Pd (Cl)] ₂ (Allylpalladium chloride dimer), (CH ₃ CO ₂ ) ₂ Pd [Palladium (II) acetate], [CH ₃ COCH = C (O−) CH ₃ ] ₂ Pd [Palladium (II) acetylacetonate], NiBr (NP (CH ₃ ) ₃ ) ₄ , [PdCl (NB) O (CH ₃ )] _2, and the like.

In addition, the first procatalyst, which provides a Lewis base capable of weakly coordinating with the metal of the procatalyst, easily reacts with the Lewis base to form a vacancy in the transition metal, and also to stabilize the transition metal thus formed. Compounds that provide weak coordination with metal compounds or compounds that provide them can be used. For example, boranes such as B (C ₆ F ₅ ) ₃ or borates such as dimethylanilinium tetrakis (pentafluorophenyl) borate, methylaluminoxane (MAO) or Al (C ₂ H ₅ ) there is a transition metal halide such as an alkyl aluminum, or AgSbF _6, such as _3.

In addition, a compound which activates the catalyst by making the first cocatalyst and the second cocatalyst into one salt may be used. For example, a compound made by ion bonding an alkyl phosphine and a borane compound may be used.

The present invention provides a photoalignment film and a hologram comprising the norbornene polymer.

The photoalignment film according to the present invention may be prepared by methods and materials known in the art, except for using the photoreactive polymer according to the present invention described above.

In one specific embodiment of the present invention, the photoalignment film according to the present invention is applied to a substrate, such as a polarizing plate, a solution containing the photoreactive norbornene-based polymer, the solvent is removed to form a film and then polarized in a predetermined direction It can be produced by irradiating the polarized ultraviolet rays thus provided to give anisotropy to the surface of the film and then curing.

In addition, the photoreactive norbornene-based polymer may be used as a holographic material that can store data by giving a refractive index difference by a laser. The single crystal materials used in the conventional hologram materials had stability problems such as loss of stored data. Sensitivity problems can be solved by using the above photoreactive polymer.

The present invention is explained in more detail using the following examples and comparative examples. The invention is not limited to the following examples.

Preparation Example 1 Synthesis of 4-methoxy cinnamic acid

4-methoxy benzaldehyde (10g, 73.4mmol), malonic acid (15.3g, 2eq.), Piperidine (0.625g, 0.1eq.) And pyridine ) (17.4g, 3eq.) And stirred at room temperature for about 1 hour. The temperature was raised to 80 ° C. and then stirred for 12 hours. After the reaction, the temperature was lowered to room temperature, 1M HCl was added slowly, and the solution was titrated to have a pH of about 4. The resulting powder was filtered and washed with water, and the powder was dried in a vacuum oven. Yield 91%.

¹ H-NMR (CDCl ₃ , ppm): 4.01 (s, 3H) 6.34 (d, 1H) 6.93 (d, 2H) 7.51 (d, 2H) 7,75 (d, 1H).

Preparation Example 2 Synthesis of 4-methyl cinnamic acid

4-methyl benzaldehyde (10 g, 73.4 mmol), malonic acid (15.3 g, 2 eq.), Piperidine (0.625 g, 0.1 eq.) And pyridin ( 17.4 g, 3eq.) And stirred at room temperature for about 1 hour After raising the temperature to 80 ° C., the mixture was stirred for 12 hours After the reaction, the temperature was lowered to room temperature and 1M HCl was slowly added to the pH of the solution. Titrate to about 4. The resulting powder was filtered, washed with water and dried in a vacuum oven, yield: 91%.

¹ H-NMR (CDCl ₃ , ppm): 2.82 (s, 3H) 6.34 (d, 1H) 7.20 (d, 2H) 7.50 (d, 2H) 7,75 (d, 1H).

Preparation Example 3 Synthesis of 4-ethyl cinnamic acid

4-ethyl benzaldehyde (50g, 0.373mol), malonic acid (77.6g, 2eq.), Piperidine (3.18g, 0.1eq.) And pyridine (88.5 g, 3eq.) And stirred at room temperature for about 1 hour. The temperature was raised to 80 ° C. and then stirred for 12 hours. After the reaction, the temperature was lowered to room temperature, 1M HCl was added slowly, and the solution was titrated to have a pH of about 4. The resulting powder was filtered and washed with water, and the powder was dried in a vacuum oven. Yield 83%.

¹ H-NMR (CDCl ₃ , ppm): 1.25 (t, 3H) 2.69 (q, 2H) 6.40 (d, 1H) 7.25 (d, 2H) 7.49 (d, 2H) 7,80 (d, 1H).

Preparation Example 4 Synthesis of 4-Cl cinnamic acid

4-Cl benzaldehyde (20g, 0.142mol), malonic acid (29.5g, 2eq.), Piperidine (1.21g, 0.1eq.) And pyridine (33.7g, 3eq.) And stirred at room temperature for about 1 hour. The temperature was raised to 80 ° C. and then stirred for 12 hours. After the reaction, the temperature was lowered to room temperature, 1M HCl was added slowly, and the solution was titrated to have a pH of about 4. The resulting powder was filtered and washed with water, and the powder was dried in a vacuum oven. Yield: 90%.

¹ H-NMR (CDCl ₃ , ppm): 6.42 (d, 1H) 7.44 (d, 2H) 7.75 (d, 2H) 7.80 (d, 1H).

Preparation Example 5 Synthesis of 4-F cinnamic acid

4-F benzaldehyde (4-F benzaldehyde) (10 g, 80.6 mol), malonic acid (29.5 g, 2 eq.), Piperidine (1.21 g, 0.1 eq.), Pyridine (33.7g, 3eq.) And stirred at room temperature for about 1 hour. The temperature was raised to 80 ° C and then stirred for 12 hours. After the reaction, the temperature was lowered to room temperature, 1M HCl was added slowly, and the solution was titrated to have a pH of about 4. The resulting powder was filtered and washed with water, and the powder was dried in a vacuum oven. Yield: 90%.

¹ H-NMR (CDCl ₃ , ppm): 6.42 (d, 1H) 7.44 (d, 2H) 7.75 (d, 2H) 7.80 (d, 1H).

Preparation Example 6 Synthesis of 4-benzyloxy cinnamic acid

4-benzyloxy benzaldehyde (10g, 47.1mmol), malonic acid (11.4g, 2eq.), Piperidine (0.47g, 0.1eq.) And pyridine ) (13.03g, 3eq.) And stirred at room temperature for about 1 hour. The temperature was raised to 80 ° C. and then stirred for 12 hours. After the reaction, the temperature was lowered to room temperature, 1M HCl was added slowly, and the solution was titrated to have a pH of about 4. The resulting powder was filtered and washed with water, and the powder was dried in a vacuum oven. Yield 88%.

¹ H-NMR (CDCl ₃ , ppm): 5.11 (s, 2H) 6.35 (m, 1H) 6.99 (d, 2H) 7.28-7.53 (m, 7H) 7.65 (m, 1H).

Preparation Example 7 Synthesis of 3-Cl cinnamic acid

3-Cl benzaldehyde (10g, 71.1mmol), malonic acid (14.8g, 2eq.), Piperidine (0.61g, 0.1eq.) And pyridine (16.9g, 3eq.) And stirred at room temperature for about 1 hour. The temperature was raised to 80 ° C and then stirred for 12 hours. After the reaction, the temperature was lowered to room temperature, 1M HCl was added slowly, and the solution was titrated to have a pH of about 4. The resulting powder was filtered and washed with water, and the powder was dried in a vacuum oven.

Yield: 97%.

¹ H-NMR (CDCl ₃ , ppm): 6.45 (d, 1 H) 7.34-7.62 (m, 4 H) 7.72 (d, 1 H).

Preparation Example 8 Synthesis of 3-F cinnamic acid

3-F benzaldehyde (5g, 40.1mmol), malonic acid (8.38g, 2eq.), Piperidine (0.34g, 0.1eq.), Pyridine (9.52 g, 3eq.) And stirred at room temperature for about 1 hour. The temperature was raised to 80 ° C. and then stirred for 12 hours. After the reaction, the temperature was lowered to room temperature, 1M HCl was added slowly, and the solution was titrated to have a pH of about 4. The resulting powder was filtered and washed with water, and the powder was dried in a vacuum oven.

Yield 84%.

¹ H-NMR (CDCl ₃ , ppm): 6.43 (d, 1 H) 7.12-7.41 (m, 4 H) 7.75 (d, 1 H).

Preparation Example 9 Synthesis of 3- (naphthalen-1-yl) acrylic acid (3- (naphthalene-1-yl) acrylic acid)

1-naphthaldehyde (1-naphthaldehyde) (30 g, 0.192 mol), malonic acid (40 g, 2 eq.), Piperidine (1.63 g, 0.1 eq.) To pyridine ( 45.6g, 3eq.) And stirred at room temperature for about 1 hour. The temperature was raised to 80 ° C. and then stirred for 12 hours. After the reaction, the temperature was lowered to room temperature, 1M HCl was added slowly, and the solution was titrated to have a pH of about 4. The resulting powder was filtered and washed with water, and the powder was dried in a vacuum oven. Yield 94%.

¹ H-NMR (CDCl ₃ , ppm): 6.61 (d, 1H) 7.25-7.32 (t, 1H) 7.52-7.66 (m, 2H) 7.80-7.99 (m, 3H) 8.22-8.28 (d, 1H) 8.70 (d, 1H).

Preparation Example 10 Synthesis of 4-nitro cinnamic acid

4-nitro benzaldehyde (20g, 0.132mol), malonic acid (27.5g, 2eq.), Piperidine (1.12g, 0.1eq.), Pyridine (31.3 g, 3eq.) And stirred at room temperature for about 1 hour. The temperature was raised to 80 ° C. and then stirred for 12 hours. After the reaction, the temperature was lowered to room temperature, 1M HCl was added slowly, and the solution was titrated to have a pH of about 4. The resulting powder was filtered and washed with water, and the powder was dried in a vacuum oven. Yield 58%.

¹ H-NMR (CDCl ₃ , ppm): 6.22 (d, 1H) 7.25 (d, 1H) 7.43 (d, 2H) 7.88 (d, 2H).

Example 1 Synthesis of 2- (4-methoxy cinnamic ester-5-norbornene)

4-methoxy cinnamic acid (20 g, 0.112 mol), 5-norbornene-2-methanol (13.9 g, 0.112 mol), zirconium acetate hydroxide Seed (zirconium (IV) acetate hydroxide) (0.54 g, 0.02 eq.) Was added to toluene (100 ml) and stirred. The temperature was raised to 145 ° C. under N ₂ atmosphere and subjected to azeotropic reflux for 24 hours. After the reaction, the temperature was lowered to room temperature, and ethyl acetate was added by 100v%. Extract with 1M HCl and wash once more with water. The organic layer was dried over Na ₂ SO ₄ , blown off with a solvent, and a highly viscous liquid substance was obtained. Yield 83%. Purity (GC): 94%.

Example 2 Synthesis of 2- (4-methyl cinnamic ester) -5-norbornene (2- (4-methyl cinnamic ester) -5-norbornene)

4-methyl cinnamic acid (10 g, 61.7 mmol), 5-norbornene-2-methanol (7.66 g, 61.7 mmol), zirconium acetate hydroxide (zirconium (IV) acetate hydroxide) (0.3 g, 0.02 eq.) was added to toluene (50 ml) and stirred. The temperature was raised to 145 ° C. under N ₂ atmosphere and subjected to azeotropic reflu for 24 hours. After the reaction, the temperature was lowered to room temperature, and ethyl acetate was added by 100v%. Extract with 1M HCl and wash once more with water. The organic layer was dried over Na ₂ SO ₄ , blown off with a solvent, and a highly viscous liquid substance was obtained. Yield 93%. Purity (GC): 91%.

Example 3 Synthesis of 2- (4-ethyl cinnamic ester) -5-norbornene

4-ethyl cinnamic acid (10 g, 56.8 mmol), 5-norbornene-2-methanol (7.05 g, 56.8 mol), zirconium acetate hydroxide ( zirconium (IV) acetate hydroxide) (0.28 g, 0.02eq.) was added to toluene (50 ml) and stirred. The temperature was raised to 145 ° C. under N ₂ atmosphere and subjected to azeotropic reflux for 24 hours. After the reaction, the temperature was lowered to room temperature, and ethyl acetate was added by 100v%. Extract with 1M HCl and wash once more with water. The organic layer was dried over Na ₂ SO ₄ , blown off with a solvent, and a highly viscous liquid substance was obtained. Yield 91%. Purity (GC): 84%.

Example 4 Synthesis of 2- (4-Cl cinnamic ester) -5-norbornene (2- (4-Cl cinnamic ester) -5-norbornene)

4-Cl cinnamic acid (10 g, 54.7 mmol), 5-norbornene-2-methanol (6.79 g, 54.7 mol), zirconium acetate hydroxide ( zirconium (IV) acetate hydroxide) (0.21 g, 0.02 eq.) was added to toluene (50 ml) and stirred. The temperature was raised to 145 ° C. under N ₂ atmosphere and subjected to azeotropic reflux for 24 hours. After the reaction, the temperature was lowered to room temperature, and ethyl acetate was added by 100v%. Extract with 1M HCl and wash once more with water. The organic layer was dried over Na ₂ SO ₄ , blown off with a solvent, and a highly viscous liquid substance was obtained. Yield: 73%. Purity (GC): 91%.

Example 5 Synthesis of 2- (4-F cinnamic ester) -5-norbornene (2- (4-F cinnamic ester) -5-norbornene)

4-F cinnamic acid (10 g, 60 mmol), 5-norbornene-2-methanol (7.45 g, 60 mol), zirconium acetate hydroxide (zirconium ( IV) acetate hydroxide) (0.3 g, 0.02 eq.) Was added to toluene (50 ml) and stirred. The temperature was raised to 145 ° C. under N ₂ atmosphere and subjected to azeotropic reflux for 24 hours. After the reaction, the temperature was lowered to room temperature, and ethyl acetate was added by 100v%. Extract with 1M HCl and wash once more with water. The organic layer was dried over Na ₂ SO ₄ , blown off with a solvent, and a highly viscous liquid substance was obtained. Yield 68%. Purity (GC): 92%.

Example 6 Synthesis of 2- (4-benzyloxy cinnamic ester) -5-norbornene

4-benzyloxy cinnamic acid (10 g, 39.3 mmol), 5-norbornene-2-methanol (4.88 g, 39.3 mol), zirconium acetate hydroxide (zirconium (IV) acetate hydroxide) (0.20 g, 0.02eq.) was added to toluene (50 ml) and stirred. The temperature was raised to 145 ° C. under N ₂ atmosphere and subjected to azeotropic reflux for 48 hours. After the reaction, the temperature was lowered to room temperature, and ethyl acetate was added by 100v%. Extract with 1M HCl and wash once more with water. The organic layer was dried over Na ₂ SO ₄ , blown off with a solvent, and a highly viscous liquid substance was obtained. Yield 80%. Purity (GC): 90%.

Example 7 Synthesis of 2- (3-Cl cinnamic ester) -5-norbornene (2- (3-Cl cinnamic ester) -5-norbornene)

3-Cl cinnamic acid (10 g, 54.7 mmol), 5-norbornene-2-methanol (6.8 g, 54.7 mol), zirconium acetate hydroxide ( zirconium (IV) acetate hydroxide (0.26 g, 0.02 eq.) was added to toluene (50 ml) and stirred. The temperature was raised to 145 ° C. under N ₂ atmosphere and subjected to azeotropic reflux for 24 hours. After the reaction, the temperature was lowered to room temperature, and ethyl acetate was added by 100v%. Extract with 1M HCl and wash once more with water. The organic layer was dried over Na ₂ SO ₄ , blown off with a solvent, and a highly viscous liquid substance was obtained. Yield 92%. Purity (GC): 92%.

Example 8 Synthesis of 2- (3-F cinnamic ester) -5-norbornene (2- (3-F cinnamic ester) -5-norbornene)

3-F cinnamic acid (5 g, 43 mmol), 5-norbornene-2-methanol (5.35 g, 43 mol), zirconium acetate hydroxide (zirconium ( IV) acetate hydroxide) (0.21 g, 0.02 eq.) Was added to toluene (50 ml) and stirred. The temperature was raised to 145 ° C. under N ₂ atmosphere and subjected to azeotropic reflux for 24 hours. After the reaction, the temperature was lowered to room temperature, and ethyl acetate was added by 100v%. Extract with 1M HCl and wash once more with water. The organic layer was dried over Na ₂ SO ₄ , blown off with a solvent, and a highly viscous liquid substance was obtained. Yield 54%. Purity (GC): 73%

Example 9 Synthesis of 2- (3- (naphthalen-1-yl) acrylic ester) -5-norbornene (2- (3- (naphthalene-1-yl) acrylic ester) -5-norbornene)

3- (naphthalene-1-yl) acrylic acid (20 g, 0.1 mol), 5-norbornene-2-methanol (12.4 g) , 0.1 mol), zirconium (IV) acetate hydroxide (0.486 g, 0.02 eq.) Was added to toluene (100 ml) and stirred. The temperature was raised to 145 ° C. under N ₂ atmosphere and subjected to azeotropic reflux for 24 hours. After the reaction, the temperature was lowered to room temperature, and ethyl acetate was added by 100v%. Extract with 1M HCl and wash once more with water. The organic layer was dried over Na ₂ SO ₄ , blown off with a solvent, and a highly viscous liquid material was obtained. Yield 72%. Purity (GC): 93%

Example 10 Synthesis of 2- (4-nitro cinnamic ester) -5-norbornene

4-nitro cinnamic acid (10 g, 51.8 mmol), 5-norbornene-2-methanol (6.43 g, 51.8 mmol), zirconium acetate hydroxide ( zirconium (IV) acetate hydroxide) (0.25g, 0.02eq.) was added to toluene (50ml) and stirred. The temperature was raised to 145 ° C. under N ₂ atmosphere and subjected to azeotropic reflux for 24 hours. After the reaction, the temperature was lowered to room temperature, and ethyl acetate was added by 100 v%. Extract with 1M HCl and wash once more with water. The organic layer was dried over Na ₂ SO ₄ , blown off with a solvent, and a highly viscous liquid substance was obtained. Yield 51%. Purity (GC): 22%

Example 11 Polymerization of 2- (4-methoxy cinnamic ester) -5-norbornene (2- (4-methoxy cinnamic ester) -5-norbornene)

2- (4-methoxy cinnamic ester) -5-norbornene (2- (4-methoxy cinnamic ester) -5-norbornene) (5 g, 17.6 mmol) was dissolved in toluene (15 ml), followed by N ₂ was stirred for 30 minutes. Raise the temperature to 90 ° C., Pd (acetate) ₂ (1.32 mg, 5.86 μmol), tris (cyclohexyl) hydrogen phosphino tetrakis (pentafluorobenz) dissolved in methylene chloride (1 ml) Borate (tris (cyclohexyl) hydrogen phosphino tetrakis (pentafluorobenz) borate) (11.8 mg, 12.3 μmol) was added. Stir at 90 ° C. for 15 hours. After the reaction, the temperature was lowered to room temperature, and then precipitated using ethanol. After the filter, it was dried in a vacuum oven.

Yield 88%. Mw: 184k (PDI = 4.17).

Example 12 Polymerization of 2- (4-methyl cinnamic ester) -5-norbornene (2- (4-methyl cinnamic ester) -5-norbornene)

2- (4-methyl cinnamic ester) -5-norbornene (2- (4-methyl cinnamic ester) -5-norbornene) (5 g, 18.6 mmol) was dissolved in toluene (15 ml), followed by N ₂ Blowing was stirred for 30 minutes. Raise the temperature to 90 ° C, Pd (acetate) ₂ (4.18mg, 18.6μmol), tris (cyclohexyl) hydrogen phosphino tetrakis (pentafluorobenz) borate dissolved in methylene chloride (1ml) (tris (cyclohexyl) hydrogen phosphino tetrakis (pentafluorobenz) borate) (37.6 mg, 39.1 μmol) was added. Stir at 90 ° C. for 15 hours. After the reaction, the temperature was lowered to room temperature, and then precipitated using ethanol. After the filter, it was dried in a vacuum oven.

Yield 81%. Mw: 58k (PDI = 2.78).

Example 13 Polymerization of 2- (4-ethyl cinnamic ester) -5-norbornene (2- (4-ethyl cinnamic ester) -5-norbornene)

2- (4-ethyl cinnamic ester) -5-norbornene (2- (4-ethyl cinnamic ester) -5-norbornene) (5 g, 17.7 mmol) was dissolved in toluene (15 ml), followed by N ₂ Blowing was stirred for 30 minutes. Raise the temperature to 90 ° C, Pd (acetate) ₂ (3.96mg, 17.7μmol), tris (cyclohexyl) hydrogen phosphino tetrakis (pentafluorobenz) borate dissolved in methylene chloride (1ml) (tris (cyclohexyl) hydrogen phosphino tetrakis (pentafluorobenz) borate) (35.7 mg, 37.2 μmol) was added. Stir at 90 ° C. for 15 hours. After the reaction, the temperature was lowered to room temperature, and then precipitated using ethanol. After the filter, it was dried in a vacuum oven.

Yield 81%. Mw: 45k (PDI = 2.07).

Example 14 Polymerization of 2- (4-Cl cinnamic ester) -5-norbornene (2- (4-Cl cinnamic ester) -5-norbornene)

2- (4-Cl cinnamic ester) -5-norbornene (2- (4-Cl cinnamic ester) -5-norbornene) (5 g, 17.3 mmol) was dissolved in toluene (15 ml), followed by N ₂ Blowing was stirred for 30 minutes. Raise the temperature to 90 ° C, Pd (acetate) ₂ (3.8mg, 17.3μmol), tris (cyclohexyl) hydrogen phosphino tetrakis (pentafluorobenz) borate dissolved in methylene chloride (1ml) (tris (cyclohexyl) hydrogen phosphino tetrakis (pentafluorobenz) borate) (34.9 mg, 36.3 μmol) was added. Stir at 90 ° C. for 15 hours. After the reaction, the temperature was lowered to room temperature, and then precipitated using ethanol, and the filter was dried in a vacuum oven.

Yield: 80%. Mw: 64k (PDI = 2.89).

Example 15 Polymerization of 2- (4-F cinnamic ester) -5-norbornene (2- (4-F cinnamic ester) -5-norbornene)

2- (4-F cinnamic ester) -5-norbornene (2-g (4-F cinnamic ester) -5-norbornene) (5 g, 18.4 mmol) was dissolved in toluene (15 ml), followed by N ₂ Blowing was stirred for 30 minutes. Raise the temperature to 90 ° C, Pd (acetate) ₂ (4.13mg, 18.4μmol), tris (cyclohexyl) hydrogen phosphino tetrakis (pentafluorobenz) borate dissolved in methylene chloride (1ml) (tris (cyclohexyl) hydrogen phosphino tetrakis (pentafluorobenz) borate) (37.2mg, 38.6μmol) was added. Stir at 90 ° C. for 15 hours. After the reaction, the temperature was lowered to room temperature, a precipitate was obtained using ethanol, and the filter was dried in a vacuum oven.

Yield 85%. Mw: 158k (PDI = 2.88).

Example 16 Polymerization of 2- (4-benzyloxy cinnamic ester) -5-norbornene

2- (4-benzyloxy cinnamic ester) -5-norbornene (5 g, 15.1 mmol) was dissolved in toluene (15 ml), followed by N ₂ was stirred for 30 minutes. Raise the temperature to 90 ° C, Pd (acetate) ₂ (3.39mg, 15.1μmol), tris (cyclohexyl) hydrogen phosphino tetrakis (pentafluorobenz) borate dissolved in methylene chloride (1ml) (tris (cyclohexyl) hydrogen phosphino tetrakis (pentafluorobenz) borate) (30.5mg, 31.7μmol) was added. Stir at 90 ° C. for 15 hours. After the reaction, the temperature was lowered to room temperature, a precipitate was obtained using ethanol, and the filter was dried in a vacuum oven.

Yield 63%. Mw: 46k (PDI = 2.55).

Example 17 Polymerization of 2- (3-Cl cinnamic ester) -5-norbornene (2- (3-Cl cinnamic ester) -5-norbornene)

2- (3-Cl cinnamic ester) -5-norbornene (2- (3-Cl cinnamic ester) -5-norbornene) (2.9 g, 10 mmol) was dissolved in toluene (10 ml), followed by N ₂ Blowing was stirred for 30 minutes. Raise the temperature to 90 ° C, Pd (acetate) ₂ (2.27mg, 10μmol), tris (cyclohexyl) hydrogen phosphino tetrakis (pentafluorobenz) borate dissolved in methylene chloride (1ml) tris (cyclohexyl) hydrogen phosphino tetrakis (pentafluorobenz) borate) (20.4mg, 21μmol) was added. Stir at 90 ° C. for 15 hours. After the reaction, the temperature was lowered to room temperature, a precipitate was obtained using ethanol, and the filter was dried in a vacuum oven.

Yield 60%. Mw: 32k (PDI = 2.11).

Example 18 Polymerization of 2- (3-F cinnamic ester) -5-norbornene (2- (3-F cinnamic ester) -5-norbornene)

2- (3-F cinnamic ester) -5-norbornene (2- (3-F cinnamic ester) -5-norbornene) (5 g, 18.4 mmol) was dissolved in toluene (15 ml), followed by N ₂ Blowing was stirred for 30 minutes. Raise the temperature to 90 ° C, Pd (acetate) ₂ (4.1 mg, 18.4 μmol), tris (cyclohexyl) hydrogen phosphino tetrakis (pentafluorobenz) borate dissolved in methylene chloride (1 ml) (tris (cyclohexyl) hydrogen phosphino tetrakis (pentafluorobenz) borate) (37.1mg, 38.6μmol) is added. Stir at 90 ° C. for 15 hours. After the reaction, the temperature was lowered to room temperature, a precipitate was obtained using ethanol, and the filter was dried in a vacuum oven.

Yield 42%. Mw: 23k (PDI = 2.05).

Example 19 Polymerization of 2- (3- (naphthalen-1-yl) acrylic ester) -5-norbornene (2- (3- (naphthalene-1-yl) acrylic ester) -5-norbornene)

2- (3- (naphthalen-1-yl) acrylic ester) -5-norbornene (2- (3- (naphthalene-1-yl) acrylic ester) -5-norbornene) (10 g, 32.8 mmol) to toluene ( toluene) (30 ml) and then stirred for 30 minutes with blowing N ₂ . Raise the temperature to 90 ° C, Pd (acetate) ₂ (7.4mg, 32.8μmol), tris (cyclohexyl) hydrogen phosphino tetrakis (pentafluorobenz) borate dissolved in methylene chloride (1ml) (tris (cyclohexyl) hydrogen phosphino tetrakis (pentafluorobenz) borate) (66mg, 68.9μmol) was added. Stir at 90 ° C. for 15 hours. After the reaction, the temperature was lowered to room temperature, a precipitate was obtained using ethanol, and the filter was dried in a vacuum oven. Yield 75%. Mw: 114k (PDI = 3.14).

Example 20 Polymerization of 2- (4-nitro cinnamic ester) -5-norbornene

2- (4-nitro cinnamic ester) -5-norbornene (4.74 g, 16.6 mmol) was dissolved in toluene (20 ml), followed by N ₂ was stirred for 30 minutes. Raise the temperature to 90 ° C, Pd (acetate) ₂ (1.24mg, 5.54μmol), tris (cyclohexyl) hydrogen phosphino tetrakis (pentafluorobenz) borate dissolved in methylene chloride (1ml) (tris (cyclohexyl) hydrogen phosphino tetrakis (pentafluorobenz) borate) (11.2 mg, 11.6 μmol) was added. Stir at 90 ° C. for 15 hours. After the reaction, the temperature was lowered to room temperature, a precipitate was obtained using ethanol, and the filter was dried in a vacuum oven.

Yield 18%.

      Example 21 Polymerization of (cinnamic ester) -5-norbornene ((cinnamic ester) -5-norbornene)

(Cinamic ester) -5-norbornene ((cinnamic ester) -5-norbornene) (4.22 g, 16.6 mmol) was dissolved in toluene (20 ml), and stirred for 30 minutes while blowing N ₂ . Raise the temperature to 90 ° C, Pd (acetate) ₂ (1.24mg, 5.54μmol), tris (cyclohexyl) hydrogen phosphino tetrakis (pentafluorobenz) borate dissolved in methylene chloride (1ml) (tris (cyclohexyl) hydrogen phosphino tetrakis (pentafluorobenz) borate) (11.2 mg, 11.6 μmol) was added. Stir at 90 ° C. for 15 hours. After the reaction, the temperature was lowered to room temperature, a precipitate was obtained using ethanol, and the filter was dried in a vacuum oven.

Yield 75%. Mw: 50k (PDI = 2.55).

<Experimental Example 1>

In order to confirm the photoreactivity rate of the photoreactive norbornene-based polymers obtained in Examples 11, 12, 13 and 16, the reactivity was observed by the change of birefringence by PEM (Photoelastic modulator). Each polymer was dissolved in cyclopentanone at 5 wt%, spin-coated on ITO glass at 4000 rpm, and then baked at a hot plate at 150 ° C. for about 2 minutes. . Then, the thickness was measured with a profiler, and the PEM was measured. However, since the reactivity may vary depending on the thickness of the thin film, by measuring the thickness with a profiler, the thickness of each thin film was coated so that the variation of the thickness was about 10%. At this time, the change in thickness was carried out by changing the concentration of the solution.

FIG. 1 is a spectrum of a UV light source used in the present invention, and FIG. 2 is a spectrum transmitted through a polarizing plate, and the data before and after using the polarizing plate in the spectrum of the UV light source were compared.

When using a polarizing plate, when looking at the UV spectrum, most of the light below 300nm is blocked, and the peak near 365nm is the largest.

3 is a UV absorption spectrum of norbornene-based polymers corresponding to Examples 11, 12, 14, 15, 16, and 18.

Figure 4 is a graph measuring the reaction rate of the norbornene-based polymer of Examples 11, 12, 13, 16 by PEM (Photoelastic modulator). In PEM, reactivity can be measured through changes in birefringence. This data confirms that the reactivity is different depending on the substituents. As a result, it is confirmed that the reactivity according to the light source can be controlled by controlling the photoreactivity by changing the electron density by the substituent and also affecting the UV absorption spectrum.

5 is a graph showing the light anisotropy of each polymer according to the amount of light irradiation through the PEM. Although there are differences depending on the amount of light irradiation, it can be seen that the polymers of Examples 11 and 12 generally have high anisotropy compared to other materials such as Examples 15, 19, and 21.

1 is a spectrum of a UV light source used in the present invention.

2 is a spectrum transmitted through the polarizing plate of the present invention.

3 is a UV absorption spectrum of norbornene-based polymers corresponding to Examples 11, 12, 14, 15, 16, and 18.

Figure 4 is a graph measuring the reaction rate of the norbornene-based polymer of Examples 11, 12, 13, 16 by PEM (Photoelastic modulator).

5 is a graph showing the light anisotropy of each polymer according to the amount of light irradiation through the PEM.

Claims (10)

Norbornene polymer comprising a norbornene-based monomer which is a compound represented by the following formula (1) comprising a photoreactive functional group: [Formula 1]

In Formula 1, p is an integer from 0 to 4, At least one of R ₁ , R ₂ , R ₃ , and R ₄ is a radical of Formula 1b, and the others are each independently hydrogen, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted C ₁ -C ₂₀ . C ₂ -C ₂₀ alkenyl, substituted or unsubstituted C ₃ -C ₁₂ cycloalkyl, substituted or unsubstituted C ₆ -C ₄₀ aryl; Substituted or unsubstituted C ₇ -C ₁₅ aralkyl; Substituted or unsubstituted C ₂ -C ₂₀ alkynyl; And a non-hydrocarbonaceous polar group comprising at least one oxygen, nitrogen, phosphorus, sulfur, silicon, or boron, R ₁ , R ₂ , R ₃ , and R ₄ , unless hydrogen, halogen, or a polar functional group, R ₁ and R ₂ , or R ₃ and R ₄ are connected to each other to form an alkylidene group of C ₁ -C ₁₀ . Or R ₁ or R ₂ may be linked to any one of R ₃ and R ₄ to form a saturated or unsaturated cyclic group ring of C ₄ -C ₁₂ , or an aromatic cyclic compound having 6 to 24 carbon atoms, , [Chemical Formula 1b]

In Chemical Formula 1b, B is a simple bond, carbonyl, or carboxy; A is a simple bond or oxygen; R ₉ is a simple bond; R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ are each independently hydrogen, substituted or unsubstituted C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₁ -C ₂₀ alkoxy, substituted or unsubstituted C Aryloxy of _6- C ₃₀ , substituted or unsubstituted C ₆ -C ₄₀ aryl, C ₆ -C ₄₀ heteroaryl containing group 14, 15, 16 heteroelements, and substituted or unsubstituted C ₆ -C ₄₀ is selected from the group consisting of alkoxyaryl, R ₁₀ , At least one of R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ is not hydrogen. delete The norbornene polymer of claim 1, wherein R ₁ in Formula 1 is a compound represented by Formula 1b, and R ₁₄ in Formula 1b is selected from the group consisting of methyloxy, benzyloxy, and methyl. The norbornene polymer of claim 1, wherein the non-hydrocarbonaceous polar group comprises a compound: -OR ₆ , -R ₅ OR ₆ , -OC (O) OR ₆ , -R ₅ OC (O) OR ₆ , -C (O) OR ₆ , -R ₅ C (O) OR _6, -C (O R ₆ , -R ₅ C (O) R ₆ , -OC (O) R ₆ , -R ₅ OC (O) R ₆ ,-(R ₅ O) _p -OR ₆ , (p is from 1 to 10 Integer),-(OR ₅ ) _p -OR ₆ (p is an integer from 1 to 10), -C (O) -OC (O) R ₆ , -R ₅ C (O) -OC (O) R ₆ , -SR ₆ , -R ₅ SR ₆ , -SSR ₆ , -R ₅ SSR ₆ , -S (= O) R ₆ , -R ₅ S (= O) R ₆ , -R ₅ C (= S) R ₆ , -R ₅ C (= S) SR ₆ , -R ₅ SO ₃ R ₆ , -SO ₃ R ₆ , -R ₅ N = C = S, -N = C = S, -NCO, R ₅ -NCO, -CN, -R ₅ CN, -NNC (= S) R ₆ , -R ₅ NNC (= S) R ₆ , -NO ₂ , -R ₅ NO ₂ ,

It may include one or more selected from the group consisting of, Each R ₅ in the functional group is substituted or unsubstituted C ₁ -C ₂₀ alkylene, substituted or unsubstituted C ₂ -C ₂₀ alkenylene, substituted or unsubstituted C ₃ -C ₁₂ cycloalkylene , Substituted or unsubstituted C ₆ -C ₄₀ arylene, substituted or unsubstituted C ₇ -C ₁₅ aralkylene and substituted or unsubstituted C ₂ -C ₂₀ alkynylene, R ₆ , R ₇ , and R ₈ Are each independently hydrogen, halogen, substituted or unsubstituted C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₂ -C ₂₀ alkenyl, substituted or unsubstituted C ₃ -C ₁₂ cycloalkyl, Substituted or unsubstituted C ₆ -C ₄₀ aryl, substituted or unsubstituted C ₇ -C ₁₅ aralkyl, and substituted or unsubstituted C ₂ -C ₂₀ alkynyl. The method according to claim 1, the norbornene polymer in the heteroaryl substituents of C ₆ -C ₄₀ aryl, and Group 14, Group 15 or Group 16 of C ₆ -C ₄₀ contains the hetero elements is to comprise the formula:

At least one of R ′ ₁₀ to R ′ ₁₈ in the formula is necessarily substituted or unsubstituted C ₁ -C ₂₀ alkoxy, or substituted or unsubstituted C ₆ -C ₃₀ aryloxy, The remainder is each independently substituted or unsubstituted C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₁ -C ₂₀ alkoxy, substituted or unsubstituted C ₆ -C ₃₀ aryloxy, and substituted or unsubstituted C ₆ -C ₄₀ aryl. The norbornene polymer of claim 1, wherein the norbornene polymer comprises a repeating unit represented by Formula 2 below: [Formula 2]

In Formula 2, n is 50 to 5,000, and p, R ₁ , R ₂ , R ₃ , and R ₄ are the same as defined in Chemical Formula 1. A procatalyst comprising a Group 10 transition metal, a first cocatalyst which provides a Lewis base capable of weakly coordinating with the metal of the procatalyst, and optionally a compound containing a neutral Group 15 electron donor ligand A polymerization method of the norbornene polymer of claim 1, wherein the polymerization is carried out at a temperature of 10 ° C. to 200 ° C. in the presence of a catalyst mixture comprising a second cocatalyst and a photoreactive norbornene monomer. 8. The norbornene polymer of claim 7 wherein the catalyst mixture comprises 1 to 1000 moles of the first cocatalyst and optionally 1 to 1000 moles of the second cocatalyst with respect to 1 mole of the procatalyst. Manufacturing method. An optical alignment film comprising the norbornene polymer of claim 1. Hologram comprising the norbornene polymer of claim 1.

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