KR100477943B1 - Method for polymerizing cyclic olefins containing polar functional groups - Google Patents

Abstract

The present invention is a catalyst comprising a monomer comprising a norbornene-based monomer containing a polar functional group, a transition metal compound of Group 10; Ii) an organic compound comprising a Group 15 element as a first promoter; And iii) addition polymerization at a polymerization temperature of 80 to 130 DEG C while contacting with a catalyst component of a catalyst system comprising a salt capable of providing an anion comprising a Group 13 element as a second cocatalyst It provides a method for producing a cyclic olefin-based addition polymer comprising a polar functional group.

Description

Cyclic olefin polymerization method containing a polar functional group {METHOD FOR POLYMERIZING CYCLIC OLEFINS CONTAINING POLAR FUNCTIONAL GROUPS}

The present invention relates to a process for the polymerization of cyclic olefins, and more particularly to a process for producing cyclic olefin polymers containing polar functional groups in high yield and high molecular weight.

Until now, the inorganic materials such as silicon oxide and silicon nitride have been mainly used in the information electronics industry. As the demand for small size and high efficiency devices increases, the need for high functional new materials increases. Due to these high functional properties, there is a growing interest in polymers having low dielectric constant and hygroscopicity, excellent metal adhesion, strength, thermal stability and transparency, and high glass transition temperature (Tg> 250 ° C.).

Such polymers include insulating films of semiconductors or TFT-LCDs, polarizer protective films, multichip modules, integrated circuits (ICs), printed circuit boards, encapsulants of electronic materials or flat panel displays. It can be used as a material for optics, such as. Cyclic olefin polymer is a polymer composed of cyclic monomers such as norbornene, and has excellent transparency, heat resistance, and chemical resistance, and has very low birefringence and water absorption rate compared to existing olefinic polymers. It can be applied to various medical materials such as optical materials, capacitor films, information electronic materials such as low dielectric materials, low absorbing syringes, blister packaging, and the like.

In this regard, the cyclic olefin polymerization technology may include Ring Opening Metathesis Polymerization (ROMP), ring opening metathesis polymerization followed by hydrogenation (HROMP), copolymerization with ethylene, and homogeneous polymerization, as shown in Scheme 1 below. Transition metal catalysts such as sen compounds, Ni and Pd compounds are used. These catalysts show different polymerization characteristics and polymer structures through changes in core metals, ligands, and catalyst compositions.

Scheme 1

Since the polymer produced by the ROMP includes one double bond per monomer repeating unit, the thermal stability and the oxidative stability are greatly decreased, and are mainly used as a thermosetting resin. The thermosetting resin thus prepared is disclosed in US Pat. No. 5,011,730 by Tenny et al. That it is used as a circuit board by reaction injection molding.

However, as described above, there are problems of thermal stability, oxidation stability, and low glass transition temperature. In order to overcome the properties of ROMP-resins, attempts have been made to hydrogenate ROMP-polymers with a catalyst such as Pd or Raney-Ni to make a stable main chain. However, hydrogenated polymers also exhibit problems of increased oxidative stability but reduced thermal stability. In addition, the increase in costs caused by the increase in manufacturing steps is an obstacle to commercial applications.

The copolymer of norbornene with ethylene was first manufactured by Leuna, using a titanium-based Ziegler-Natta catalyst, but the copolymer produced due to residual impurities was not transparent and the Tg was less than 140 ° C. Limited (Koinzer, P. et al., German Patent No. 109,224) Although a product called Apel has been obtained using a homogeneous vanadium catalyst, this method has a problem in that the activity of the catalyst is low and the amount of oligomer is large. The use of zirconium-based metallocene catalysts has been reported to yield high molecular weight polymers with a low molecular weight distribution (Plastic News, Feb. 27, 1995, p. 24). However, as the concentration of the cyclic olefin monomer increases, the activity decreases, and the copolymer exhibits a low glass transition temperature (Tg <200 ° C.). In addition, even if the thermal stability is increased, the mechanical strength is weak and there is a disadvantage that the chemical resistance to the solvent or halogenated hydrocarbon solvent is low.

Addition polymerization of the cyclic olefin monomers has been reported by Gyrod et al. To norbornene polymerization using [Pd (C ₆ H ₅ CN) Cl ₂ ] ₂ catalyst (Gaylord, NG; Deshpande, AB; Mandal, BM). Martan, MJ Macromol.Sci.-Chem. 1977, A11 (5), 1053-1070). Polynorbornene prepared by a zirconium-based metallocene catalyst has very high crystallinity, insoluble in general organic solvents, pyrolysis without showing glass transition temperature (Kaminsky, W .; Bark, A .; Drake, I. Stud. Surf. Catal. 1990, 56, 425). On the other hand, polynorbornene obtained using the above-mentioned Pd-metal catalyst is dissolved in organic solvents such as tetrachloroethylene, chlorobenzene, and dichlorobenzene, and its molecular weight is 100,000 or more, and Tg is It is 300 degreeC or more.

Generally, polymers require adhesion to metal surfaces such as silicon, silicon oxide, silicon nitride, alumina, copper, aluminum, gold, silver, platinum, titanium, nickel, tantalum, and chromium in order to be used for information electronic materials. do. In the case of polyimide and BCB, the following method was introduced to increase metal adhesion (US Pat. No. 4,831,172).

The substrate is treated with an organosilicon coupling agent such as amino-propyltriethoxysilane or triethoxyvinylsilane and then reacted with a polymer or polymer precursor. At this time, the amino group or vinyl group suspended on the substrate reacts with the substituent of the polymer or the polymer precursor to form a bridge group connecting the substrate and the polymer. However, this method is a multi-step process and requires a coupling agent.

The chemical and physical properties of norbornene polymers can be controlled by introducing functional groups into norbornene monomers to introduce metal adhesion and various electrical and optical properties. However, when polymerizing a norbornene monomer containing a polar functional group, since the polar functional group reacts with the active catalyst species to act as a poison of the catalyst, the polymerization reaction is difficult to proceed and the molecular weight of the polymer is low even if it proceeds (US Patent No. 3,330,815). number).

Recently, several methods have been introduced to overcome this problem. In the first method, the norbornene monomer to which the polar functional group is introduced is polymerized by silane, alkylaluminum, or borane to prevent the polar functional group from reacting with the catalytically active species (Fink, G. et al. Macromol. Chem Phys. 1999, 200, 881). However, this method is limited in introducing norbornene monomer into the polymer chain and has low polymerization activity. Moreover, post-treatment is required to remove the introduced silane, aluminum and borane again.

In a second method, a method of introducing a monomer containing a polar functional group into a terminal portion of a polymer as a chain termination agent has also been proposed (US Pat. No. 5,179,171). In this case, however, the polymer was thermally unstable and the physical and chemical properties and metal adhesion were not significantly improved.

In connection with the introduction of polar functional groups, many studies have been conducted on the polymerization of norbornene monomers including ester groups, acetyl groups, or silyl groups (Risse et al., Macromolecules, 1996, Vol. 29, 2755-2763; Risse et al., Makromol. Chem. 1992, Vol. 193, 2915-2927; Sen et al., Organometallics 2001, Vol. 20 , 2802-2812, Goodall et al., US Pat. No. 5,705,503; Lipian et al., WO 00/20472).

When the norbornene or ester norbornene monomers were polymerized by cationic [Pd (CH ₃ CN) ₄ ] [BF ₄ ] ₂ catalysts, the polymerization yield was low and tended to selectively polymerize only exo isomers (Sen, A .; Lai, T.-WJ Am. Chem. Soc. 1981, 103, 4627-4629). After that, Lisse et al. Activate the palladium compound, [(η ³ -ally) PdCl] ₂ with a promoter such as AgBF ₄ , or AgSbF ₆ , or use a catalyst such as [Pd (RCN) ₄ ] [BF ₄ ] ₂ . Used. Sen et al. [(1,5-Cyclooctadiene) (CH 3) Pd (Cl)] phosphine such as PPh ₃ and _{^{Na + [3,5- (CF 3)}} 2 C 6 H 3] 4 B - like Activated as a promoter. U. S. Patent No. 5,705, 503 also describes a polymerization process using a catalyst system (activating [(η ³ -ally) PdCl] ₂ with AgBF ₄ or AgSbF ₆ ) similar to that reported by Lisse et al.

When polymerizing norbornene containing such an ester group or an acetyl group, it is difficult to use the catalyst in an excess of about 1/100 to 1/400 of the monomer and to remove the catalyst residue after the polymerization. WO 00/20472, reported by Lipian et al., Polymerized norbornene-based monomers using a small amount of catalyst, but looking at the described examples, most of norbornene-based monomers are alkylnorbornene or alkylnorbone. Non-polar monomers such as nene and silylnorbornene are polymerized. In the case of the polymerization of ester norbornene is shown in Example 117, the initial dose of ester norbornene is only 5% of the amount of butyl norbornene, and thus it can be seen that it is not effective for the polymerization method of ester norbornene. Although the content of ester norbornene is not indicated in the prepared polymer, it can be expected that the amount is very small. In addition, Example 134 shows the polymerization of norbornene containing an acetyl group, in which case also shows a very inefficient polymerization method, the polymerization yield is only about 5%.

In addition, the literature published in 2001 (Sen et al., Organometallics 2001, Vol. 20 , 2802-2812) published by the same authors as the inventors of the above international publication (WO 00/20472) shows that The polymerization yield is 40% or less, has a low molecular weight of about 6500 and shows that about 1/400 of the catalyst amount is used. Lisse et al. (Risse et al., Macromolecules , 1996, Vol. 29, 2755-2763) use a catalyst of [(η ³ -ally) PdCl] ₂ and AgBF ₄ or AgSbF ₆ to provide methylester norbornene. Polymerization yield of about 60% was obtained at the time of polymerization, but a low molecular weight of about 12,000 and an excess of catalyst amount of about 1/50 of the monomer were used. The reason for the excessive use of the catalyst amount is that a polar functional group such as an ester group or an acetyl group of norbornene is coordinated to the active site of the catalyst so that a double bond of norbornene does not coordinate to the catalytically active site or exhibits steric hindrance or a cationic type active site. Is known to be neutralized electronically by polar functional groups, resulting in weak interactions with norbornene double bonds (Risse et al., Macromolecules, 1996, Vol. 29 , 2755-2763; Risse et al., Makromol. Chem. 1992, Vol. 193 , 2915-2927).

In particular, norbornene monomers containing ester groups have different polymerization activities depending on the ratio of exo and endo isomers. When the endo isomer reacts with the catalyst, the central metal, the double bond of norbornene, and the ester group of norbornene form a complex of six six-membered rings, allowing strong interaction with the central metal. In the case of the exo isomer, it is difficult for the ester group of norbornene to form a complex in three dimensions, and thus the exo isomer exhibits superior polymerization properties to the endo isomer. These results have been demonstrated experimentally by structural analysis of Pt metal-esternorbornene complexes (Sen et al., Organometallics 2001, Vol. 20 , 2802-2812). Endo isomers having polar functional groups are known to act as catalyst poisons that reduce the performance of the catalyst in the polymerization reaction.

Therefore, the prior art regarding cyclic olefin polymerization including polar functional groups has shown the use of excess catalyst, low polymerization yield, low molecular weight in view of polymerization performance and efficiency, in particular in terms of polymerization yield and molecular weight.

In view of the problems of the prior art, an object of the present invention is to provide a polymerization method capable of producing a cyclic olefin-based addition polymer containing a polar functional group in high molecular weight and high yield.

Another object of the present invention is to provide a method for preparing a homopolymer, copolymer, or terpolymer of a norbornene-based monomer containing a polar functional group.

Another object of the present invention is low dielectric constant, low hygroscopicity, high glass transition temperature, excellent thermal and oxidative stability, excellent chemical resistance and toughness, metal adhesion It is to provide a method for producing a cyclic olefin based addition polymer containing this excellent polar functional group.

It is a further object of the present invention to provide a process for the preparation of cyclic olefin based addition polymers comprising polar functional groups which adhere well to a substrate of a metal such as copper, silver or gold.

Another object of the present invention to provide a method for producing a cyclic olefin-based addition polymer comprising a polar functional group having excellent optical properties that can be used as an optical film and a protective film of a polarizing plate.

It is still another object of the present invention to provide a method for producing a cyclic olefin based addition polymer including a polar functional group that can be used in an electronic material such as an integrated circuit, a printed circuit board, or a multichip module.

It is another object of the present invention to provide a method for preparing a cyclic olefin based addition polymer comprising a polar functional group which can be attached to a substrate of an electronic material without a coupling agent.

Still another object of the present invention is to provide an optical film including a cyclic olefin based addition polymer including a polar functional group.

In order to achieve the above object, the present invention provides a method for producing a cyclic olefin polymer comprising a polar functional group having a molecular weight (Mw) of at least 100,000,

Monomers including norbornene-based monomers containing polar functional groups

Iii) a Group 10 transition metal compound of a compound represented by the following Chemical Formula 1 or a compound represented by the following Chemical Formula 2 as a catalyst;

Ii) an organic compound comprising a Group 15 element as a first promoter; And

Iii) a salt capable of providing an anion containing a Group 13 element as a second promoter

Addition polymerization at a polymerization temperature of 80 to 130 ° C. while being in contact with the catalyst component of the catalyst system comprising a

It provides a method for producing a cyclic olefin-based addition polymer comprising a polar functional group comprising:

(Formula 1)

(Formula 2)

In the formula 1, and formula 2,

M is a Group 10 metal;

n is 1 or 2;

R ¹ , and R ² are each independently hydrogen; Linear or branched alkyl, alkenyl, or vinyl of 1 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Aryl having 6 to 40 carbon atoms including a hetero atom; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Alkynyl having 3 to 20 carbon atoms; Or linear or branched alkyl having 1 to 10 halogen atoms, or aryl;

R ³ is hydrogen; halogen; Linear or branched alkyl, allyl, alkenyl, or vinyl having 1 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted by hydrocarbon having 5 to 12 carbon atoms; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Alkyl or aryl having 6 to 40 carbon atoms including hetero elements; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Or alkynyl having 3 to 20 carbon atoms.

In another aspect, the present invention provides an optical film comprising a cyclic olefin-based addition polymer containing a polar functional group prepared by the above production method.

Hereinafter, the present invention will be described in detail.

The present invention finds that addition-polymerization of norbornene-based monomers containing polar functional groups at specific polymerization temperatures under specific catalyst systems can produce cyclic olefin based addition polymers containing high molecular weight polar functional groups in high yield. The invention was completed.

Conventionally, the cyclic olefin addition polymer containing a polar functional group can be produced in extremely low yield with only a low molecular weight, but the production method of the present invention provides a cyclic olefin addition in which a high molecular weight polar functional group is introduced in a high yield. Polymers can be prepared.

In the case of general organometallic polymerization catalysts, increasing the polymerization temperature tends to increase the polymerization yield, decrease the molecular weight or thermally decompose the catalyst (Kaminsky et al. Angew. Chem. Int. Ed., 1985, vol 24 507; Brookhart et al. Chem. Rev. 2000, vol 100, 1169; Resconi et al. Chem. Rev. 2000, vol 100, 1253). In particular, the molecular weight decreases as the polymerization temperature increases because the polymer chain is separated from the catalyst by moving hydrogen located at the β-position of the polymer bonded to the catalyst to the catalyst.

On the other hand, as mentioned in the description of the prior art, the polar functional group of the norbornene monomer interacts with the cationic catalyst at room temperature to block the catalytically active site inserted by the double bond of norbornene, thereby lowering the polymerization yield and molecular weight. In addition, hydrogen placed in the β-position of the norbornene polymer bonded to the catalyst is difficult to form a three-dimensional structural environment that can interact with the catalyst due to the inherent characteristics of the norbornene monomer, and β-hydrogen is difficult to move to the catalyst, thereby increasing the polymerization temperature. This can increase the molecular weight (Kaminsky et al. Macromol. Symp. 1995, vol 97, 225). However, catalysts used to prepare norbornene polymers containing polar functional groups known in the art are mostly thermally decomposed when the polymerization temperature is raised to 80 ° C. or higher, so that high molecular weight polymers cannot be obtained.

However, the catalyst system of the present invention can produce a cyclic olefin polymer containing a high molecular weight polar functional group with a high yield even when the polymerization temperature is increased. In particular, when the polymerization temperature is set at 80 to 130 ° C., a cyclic olefin-based polymer including a high molecular weight polar functional group can be produced in a high yield by activating a catalytically active site deactivated by the polar functional group of norbornene.

The present invention provides a polymerization method for obtaining a cyclic olefin polymer having a polar functional group having a polymerization yield of 40% or more and a high molecular weight of 100,000 or more in a polymerization temperature range of 80 to 130 ° C. This is because the catalyst system of the present invention is thermally stable so as not to decompose at a temperature of 80 ° C. or higher, thereby preventing the interaction of the norbornene monomer with the cationic catalyst of the polar functional group to form a catalytically active site. As a result, a double bond of norbornene can be inserted into the formed catalyst site and a polymer can be formed. The catalyst system of the present invention was confirmed through spectroscopic analysis that the catalyst component of the compound of Formula 1 or Formula 2 was not decomposed at a temperature of 80 ° C. or higher. A cyclic olefin polymer containing a molecular weight polar functional group is obtained.

The temperature at which this polymerization reaction proceeds is 80 to 130 ° C. However, when the polymerization temperature is set above 130 ° C., the catalytic component is thermally decomposed to lower the activity, making it difficult to prepare a cyclic olefin polymer containing a high molecular weight polar functional group.

The catalyst system used in the addition polymerization of the monomer containing the polar functional group of the present invention is a) a catalyst, a compound represented by the formula (1), or a Group 10 transition metal compound of the compound represented by the formula (2), b) agent The cocatalyst of 1 includes an organic compound containing a group 15 element, and c) a second cocatalyst, a salt capable of providing an anion containing a group 13 element.

The transition metal compound of Group 10, which is a catalyst of a), is a compound in which a ligand of acetylacetonate form is coordinated with a Group 10 transition metal, and exhibits high activity without thermal decomposition at a polymerization temperature of 80 to 130 ° C.

The organic compound containing a group 15 element as the first cocatalyst of b) is an organic compound having a non-covalent electron pair that may serve as an electron donor, and the compound represented by the following formula (3) or the compound represented by the formula (4) desirable:

(Formula 3)

P (R ⁴ ) _3-c [X (R ⁴ ) _d ] _c

In the formula (3),

c is an integer from 0 to 3; X is oxygen, sulfur, silicon, or nitrogen;

Each R ⁴ is hydrogen; Linear or branched alkyl of 1 to 20 carbon atoms, alkoxy, allyl, alkenyl, or vinyl; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Or alkynyl having 3 to 20 carbon atoms; Tri (linear or branched alkyl) having 1 to 10 carbon atoms, tri (linear or branched alkoxy) having 1 to 10 carbon atoms; Tri (cycloalkyl) silyl substituted or unsubstituted with hydrocarbons of 5 to 12 carbon atoms; Tri (aryl having 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon) silyl; Tri (aryloxy of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon); Tri (linear or branched alkyl of 1 to 10 carbon atoms) siloxy; Tri (cycloalkyl having 5 to 12 carbon atoms, substituted or unsubstituted with hydrocarbon) siloxy; Or tri (aryl having 6 to 40 carbon atoms substituted or unsubstituted with hydrocarbon) siloxy; Wherein each substituent may be substituted with linear or branched haloalkyl, or halogen.

(Formula 4)

(R ⁵ ) ₂ P-(R ⁶ )-P (R ⁵ ) ₂

In the formula (4),

R ⁵ is as defined in formula (3);

R ⁶ is linear or branched alkyl, alkenyl, or vinyl of 1 to 5 carbon atoms; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl of 6 to 20 carbon atoms, substituted or unsubstituted with hydrocarbon; Or aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon.

In addition, the salt capable of providing an anion including the Group 13 element as the second cocatalyst of c) is preferably a salt represented by the following formula (5):

(Formula 5)

[Cat] _a [Anion] _b

In the formula (5),

Cat is hydrogen; Cations of Group 1 metals, Group 2 metals, or transition metals; And a cation selected from the group consisting of organic cations containing these cations, to which a group 15 organic compound having a weakly bound lone pair of electrons of b) may be bonded;

Anion is an anion that can be weakly coordinated with the metal M of the compound of Formula 1 or Formula 2, and includes borate, aluminate, [SbF ₆ ] ^- , [PF ₆ ] ^- , [AsF ₆ ] ^- , and perfluoroacetate. (perfluoroacetate; [CF ₃ CO ₂ ] ^- ), perfluoropropionate ([C ₂ F ₅ CO ₂ ] ^- ), perfluorobutyrate ([CF ₃ CF ₂ CF ₂ CO ₂ ] ^-), perchlorate ^{_{(perchlorate; [ClO 4] -}} ), para-toluenesulfonate (p-toluenesulfonate; [p- CH 3 C 6 H 4 SO 3] -), [SO 3 CF 3] -, see other benzene And an anhydride selected from the group consisting of carborane substituted or unsubstituted with halogen;

a and b represent the number of cations and anions, respectively, which are set to match the charge so that cat and anion are electrically neutral.

The organic group including the cation of Formula 5 is [NH (R ⁷ ) ₃ ] ⁺ , or [N (R ⁷ ) ₄ ] ⁺ ammonium; [PH (R ⁷ ) ₃ ] ⁺ , or [P (R ⁷ ) ₄ ] ⁺ phosphonium; [C (R ⁷ ) ₃ ] ⁺ phosphorus carbonium, [H (OEt ₂ ) ₂ ] ⁺ , [Ag] ⁺ , [Cp ₂ Fe] ⁺ is preferably selected from the group consisting of. Wherein each R ⁷ is linear or branched alkyl of 1 to 20 carbon atoms, alkyl or silyl alkyl substituted by halogen; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Cycloalkyl or silyl cycloalkyl substituted by halogen; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Aryl or silyl aryl substituted with halogen; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Or aralkyl or silyl aralkyl substituted with halogen.

In addition, the borate or aluminate of the formula (5) is preferably an anion represented by the formula (5a) or (5b).

(Formula 5a)

[M '(R ") ₄ ]

(Formula 5b)

[M '(OR ") ₄ ]

In the formula of Formula 5a and Formula 5b,

M 'is boron or aluminum;

Each R ″ is a halogen element; linear or branched alkyl of 1 to 20 carbon atoms, substituted or unsubstituted with halogen, or alkenyl; cycloalkyl substituted or unsubstituted with 5 to 12 carbon atoms; substituted with hydrocarbon Or unsubstituted aryl having 6 to 40 carbon atoms, linear or branched trialkylsiloxy having 3 to 20 carbon atoms or aryl having 6 to 40 carbon atoms substituted with linear or branched triarylsiloxy having 18 to 48 carbon atoms; Substituted or unsubstituted aralkyl having 7 to 15 carbon atoms.

The catalyst system comprises: i) 1 mole of the transition metal compound of Group 10; Ii) 1-3 moles of organic compound comprising group 15 element; And iii) used in addition polymerization of norbornene-based monomers with a composition ratio of 1 to 2 moles of salt capable of providing an anion comprising a Group 13 element.

The catalyst usage (based on catalyst components) of these catalyst systems ranges from 1/2500 to 1/20000 of the weight of norbornene-based monomers containing polar functional groups that are added to the addition polymerization, while using much less catalyst than conventional catalyst systems. The norbornene-based monomer can be polymerized. More preferred catalyst usage of the catalyst system is 1/5000 to 1/20000 relative to norbornene monomer.

Each catalyst component of the catalyst system is a mixture obtained by combining a transition metal compound of Group 10, an organic compound containing a Group 15 element, and a salt compound capable of providing an anion containing a Group 13 element, or a mixture thereof. It is added during addition polymerization in the form of a complex salt. The dosing method may be introduced into the polymerization by mixing them on a solvent to prepare an activated catalyst solution, or may be introduced when polymerizing solutions of respective catalyst components of the catalyst system, respectively.

The monomer used when preparing the cyclic olefin addition polymer containing a polar functional group of the present invention is a norbornene monomer containing a polar functional group. The cyclic norbornene-based monomer or norbornene derivative may include at least one norbornene (bicyclo [2,2,1] hept-2-ene) such as It means the monomer containing a unit.

(Formula 6)

The cyclic olefin-based addition polymer comprising a polar functional group of the present invention is subjected to addition polymerization of norbornene-based monomers comprising at least one polar functional group in the presence of the above-described catalyst system to prepare a homo polymer or include different polar functional groups. Addition or polymerization of norbornene-based monomers to prepare a binary or tertiary copolymer consisting of norbornene-based monomers containing a polar functional group, or by addition polymerization of norbornene-based monomers containing a polar functional group and norbornene not containing a polar functional group Copolymerization can produce binary or terpolymers.

The norbornene-based monomer containing such a polar functional group is preferably a compound represented by the following formula (7).

(Formula 7)

In the formula (7),

m is an integer from 0 to 4,

R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ At least one of-(CH ₂ ) _n C (O) OR ¹² ,-(CH ₂ ) _n OC (O) R ¹² ,-(CH ₂ ) _n OC (O) OR ¹² ,-(CH ₂ ) _n C (O) R ¹² ,-(CH ₂ ) _n OR ¹² ,-(CH ₂ O) _n -OR ¹² ,-(CH ₂ ) _n C (O) -OC (O) R ¹² ,-(CH ₂ ) _n C (O) NH ₂ ,-(CH ₂ ) _n C (O) NHR ¹² ,-(CH ₂ ) _n C (O) N (R ¹² ) ₂ ,-(CH ₂ ) _n NH ₂ ,-(CH ₂ ) _n NHR ¹² ,-(CH ₂ ) _n N (R ¹² ) ₂ ,-(CH ₂ ) _n OC (O) NH ₂ ,-(CH ₂ ) _n OC (O) NHR ¹² ,-(CH ₂ ) _n OC (O) N (R ¹² ) ₂ ,-(CH ₂ ) _n C (O) Cl,-(CH ₂ ) _n SR ¹² ,-(CH ₂ ) _n SSR ¹² ,-(CH ₂ ) _n SO ₂ R ¹² ,-(CH ₂ ) _n SO ₂ R ¹² ,-(CH ₂ ) _n OSO ₂ R ¹² ,-(CH ₂ ) _n SO ₃ R ¹² ,-(CH ₂ ) _n OSO ₃ R ¹² ,-(CH ₂ ) _n B (R ¹² ) ₂ ,-(CH ₂ ) _n B (OR ¹² ) ₂ ,-(CH ₂ ) _n B (R ¹² ) (OR ¹² ),-(CH ₂ ) _n N = C = S ,-(CH ₂ ) _n NCO,-(CH ₂ ) _n N (R ¹² ) C (= 0) R ¹² ,-(CH ₂ ) _n N (R ¹² ) C (= 0) (OR ¹² ),- (CH ₂ ) _n CN,-(CH ₂ ) _n NO ₂ , , ,-(CH ₂ ) _n P (R ¹² ) ₂ ,-(CH ₂ ) _n P (OR ¹² ) ₂ ,-(CH ₂ ) _n P (R ¹² ) (OR ¹² ),-(CH ₂ ) _n P (= O) (R ¹² ) ₂ ,-(CH ₂ ) _n P (= O) (OR ¹² ) ₂ , and-(CH ₂ ) _n P (= O) (R ¹² ) (OR ¹² ) A polar functional group selected from

      The rest are hydrogen; halogen; Linear or branched alkyl, alkenyl or vinyl of 1 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms, optionally substituted with hydrocarbons; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Or alkynyl having 3 to 20 carbon atoms,

N is an integer of 0 to 10, and R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are R ⁸ and R ⁹ or R ¹⁰ and R ¹¹ unless they are polar functional groups, hydrogen, or halogen. May be connected to each other to form an alkylidene group having 1 to 10 carbon atoms, or R ⁸ or R ⁹ may be connected to any one of R ¹⁰ and R ¹¹ to be a saturated or unsaturated cyclic group having 4 to 12 carbon atoms, or Can form an aromatic ring compound of 6 to 17,

R ¹² included in the polar functional group may be each hydrogen, linear or branched alkyl having 1 to 20 carbon atoms, alkenyl or vinyl; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms, optionally substituted with hydrocarbons; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Alkynyl having 3 to 20 carbon atoms.

The norbornene addition polymer comprising a polar functional group prepared according to the method of the present invention comprises at least 0.1 to 99.9 mol% of a norbornene-based monomer comprising a polar functional group, wherein the norbornene comprising a polar group is an endo, exo isomer mixture. The composition ratio is irrelevant.

The addition polymerization of the present invention polymerizes by dissolving and mixing a norbornene-based monomer and a catalyst in a solvent as in the conventional polymerization method of norbornene-based polymer. The solvent used for the addition polymerization is dichloromethane (CH ₂ Cl ₂ ), dichloroethane (CH ₂ ClCH ₂ Cl), toluene, chlorobenzene (C ₆ H ₅ Cl) capable of dissolving the catalyst system consisting of the three components. It is preferable to use a polar solvent such as, and the amount of the solvent is preferably 0.5 to 4 times the volume of the monomer to be polymerized.

When the cyclic olefin-based addition polymer including a polar functional group is prepared by the polymerization method of the present invention, it may be prepared in a high yield of at least 40% by weight, and the molecular weight (Mw) of the prepared addition polymer may have a high molecular weight of at least 100,000 or more. Can be. In addition, the molecular weight is preferably adjusted to 100,000 to 1,000,000 if the optical film is prepared using the addition polymer.

Therefore, in the past, the cyclic olefin-based addition polymer containing a polar functional group was produced in a very low yield and only at a low molecular weight. However, the production method of the present invention provides a cyclic olefin type in which a high molecular weight polar functional group is introduced at a high yield. Additional polymers can be prepared.

The production method of the present invention is a cyclic olefin polymerization method containing a polar functional group that can avoid the degradation of the catalytic activity by the endo isomer containing a polar functional group can be obtained excellent polymerization results using a very small amount of catalyst. In addition, the norbornene-based polymer comprising a polar functional group produced by the production method of the present invention is transparent, has excellent adhesion to a polymer having a metal or other polar functional groups, has a low dielectric constant that can be used as an insulating electronic material, heat It is a cyclic olefin polymer having excellent stability and strength. In addition, the polymer can be attached to a substrate of an electronic material without a coupling agent, can be attached to a metal substrate such as copper, silver, or gold, and can be used as a protective film of a polarizing plate. It has excellent characteristics and can be used in electronic materials such as integrated circuits, printed circuit boards or multichip modules.

The present invention can be produced as an optically anisotropic film which can control the birefringence which could not be conventionally prepared by using the cyclic olefin-based addition polymer containing a high molecular weight polar functional group obtained in the above high yield.

Since the conformational unit of a general cyclic olefin has one or two stable rotational states, it may be extended to form a polyimide having a rigid phenyl ring as a main chain. extended conformation). The introduction of polar groups into norbornene-based polymers with extended conformation increases the intermolecular interactions due to the introduction of polar groups than polymers with compact conformation. Thus, the inventors have found that they may have an directional order in the intermolecular packing and thus have optical and electrical anisotropy.

Therefore, the optically anisotropic film which can control birefringence can be manufactured using the cyclic olefin type addition polymer containing a high molecular weight polar group manufactured by the high yield by the manufacturing method of this invention. The birefringence can be adjusted according to the type and content of the polar functional groups introduced into the cyclic olefin-based addition polymer, and in particular, it is easy to control the refractive index in the thickness direction to be produced. ) Can be prepared as an optical compensation film.

In the method for producing an optically anisotropic film, a cyclic olefin-based addition polymer containing a polar functional group is dissolved in a solvent to prepare a film or a sheet by a solvent casting method. It is also possible to prepare films from blends of one or more of these cyclic olefin polymers.

The method for preparing a film by dissolving the cyclic olefin additive polymer in a solvent is carried out by adding the cyclic olefin additive polymer to the solvent at a polymer content of 5 to 95% by weight, more preferably 10 to 60% by weight, at room temperature. It is preferable to prepare by stirring. In this case, the viscosity of the prepared solution is preferably 100 to 10000 cps, more preferably 300 to 8000 cps for solvent casting, and in order to improve the mechanical strength, heat resistance, light resistance, and handleability of the film, a plasticizer, a deterioration inhibitor, and an ultraviolet stabilizer. Or an additive such as an antistatic agent may be added.

The film thus produced has an optically anisotropic film characteristic with a retardation value R _th represented by the following formula (1) of 70 to 1000 nm:

(Equation 1)

In Equation 1,

n _y is the refractive index of the in-plane fast axis measured at a wavelength of 550 nm,

n _z is the refractive index in the thickness direction measured at a wavelength of 550 nm,

d is the thickness of the film.

A film having such optical anisotropy has a refractive index of the film in a relationship of n _x = n _y &gt; n _z (n _x is a refractive index of a slow axis in plane, n _y is a refractive index of a fast axis, n _z satisfies the refractive index in the thickness direction, and thus it can be used as a negative C-plate type optical compensation film for liquid crystal displays (LCDs) in various modes.

The present invention will be described in more detail with reference to the following examples. However, an Example is for illustrating this invention and is not limited only to these.

EXAMPLE

All operations dealing with air or water sensitive compounds were carried out using standard Schlenk techniques or dry box techniques. Nuclear magnetic resonance spectra were obtained using a Bruker 300 spectrometer, ¹ H NMR at 300 MHz and ¹³ C NMR at 75 MHz. The molecular weight and molecular weight distribution of the polymer were measured using gel permeation chromatography (GPC), in which polystyrene samples were used as the standard. Thermal analyzes such as TGA and DSC were performed using a TA Instrument (TGA 2050; heating rate 10 K / min).

Toluene was purified by distillation in potassium / benzophenone and dichloromethane and chlorobenzene were purified by distillation in CaH ₂ .

Preparation Example 1

(Synthesis of 5-norbornene-2-carboxylic acid methyl ester)

DCPD (dicyclopentadiene, Aldrich, 256.5 mL, 1.9 mol), methyl acrylate (Aldrich, 405 mL, 4.5 mol) and hydroquinone (3.2 g, 0.03 mol) were added to a 2 L high-pressure reactor, and the temperature was raised to 180 ° C. After reacting for 6 hours while stirring at 300 rpm, when the reaction was completed, the reaction was cooled and transferred to a distillation apparatus. Distillation under reduced pressure to 1 torr using a vacuum pump to give the product at 50 ℃ (yield: 86%, exo / endo = 58/42).

1 H-NMR (300 MHz in CDCl ₃ ): 6.11 (m, 2H), 3.67 (s, exo, 3H), 3.60 (s, endo, 3H), 3.17 (s, 1H), 3.01 (m, 1H), 2.89 (m, 1H), 2.20 (m, 1H), 1.88 (m, 1H), 1.42 (m, 2H)

Preparation Example 2

(Synthesis of 5-norbornene-2-carboxylic acid butyl ester)

DCPD (dicyclopentadiene, Aldrich, 180 mL, 1.34 mol), butyl acrylate (JUNSEI, 500 mL, 3.49 mol) and hydroquinone (2.7 g, 0.025 mol) were added to a 2 L high-pressure reactor, and the temperature was raised to 190 ° C. After 5 hours of stirring at 300 rpm, the reaction was cooled and transferred to a distillation apparatus. Distillation under reduced pressure to 1 torr using a vacuum pump to give the product at 80 ℃ (yield: 78%, exo / endo = 55/45).

1 H-NMR (300 MHz in CDCl ₃ ): 6.12 (m, 2H), 4.09 (t, 2H), 3.17 (s, 1H), 3.04 (s, 1H), 2.92 (m, 1H), 2.20 (m, 1H ), 1.90 (m, 1H), 1.60 (m, 2H), 1.40 (m, 4H), 0.94 (t, 3H)

Example 1

(5-norbornene-2-carboxylic acid methyl ester polymerization in the presence of dichloromethane solvent-preparation using Pd (acac) ₂ (acac = acetylacetonate) as a catalyst)

Pd (acac) ₂ (3.5 mg, 11 μmol), dimethylanilinium tetrakispentafluorophenyl) borate (14.5 mg, 22 ?? mol), tricyclohexylphosphine in a dry box (3.0 mg, 11 μmol) was charged to a 250 mL Schlenk flask. 5 ml of dichloromethane was added to the flask to dissolve it, and 5-norbornene-2-carboxylic acid methyl ester (10 mL, 55.6 mmol) prepared in Preparation Example 1 was added at room temperature to raise the reaction temperature to 80 ° C. The dichloromethane solvent was removed under partial vacuum while raising to 80 ° C. The reaction was carried out at 80 ° C. for 18 hours. Over time, the viscosity of the reaction solution became high and after 10 hours it became hard to stir. After 18 hours of reaction, 50 mL of toluene was added to dissolve the cured polymer, which was added to an excess of ethanol to obtain a white copolymer precipitate. The precipitate was collected by filtration with a glass funnel and dried in a vacuum oven at 80 ° C. for 24 hours to obtain 4.97 g of a 5-norbornene-2-carboxylic acid methyl ester polymer (48.6 wt% based on the total amount of monomer introduced).

Examples 2-8

(Polymerization of 5-norbornene-2-carboxylic Acid Methyl Ester to Change in Polymerization Temperature in the Presence of Dichloromethane Solvent-Preparation Using Pd (acac) ₂ as Catalyst)

Using the same amount of dichloromethane solvent (5 mL) in the same manner as in Example 1 and changing the amount of Pd (acac) ₂ catalyst to 5,000: 1 molar ratio and 10,000: 1 molar ratio of the monomers, as shown in Table 1, 5-norbornene-2-carboxylic acid methyl ester polymer was prepared while changing the polymerization temperature to 80, 90, 100, 110 ℃. Table 1 below shows the polymerization results.

Polymerization of 5-norbornene-2-carboxylic acid methyl ester with Pd (acac) ₂ catalyst in the presence of dichloromethane solvent division Monomer (mL) Temperature (℃) Hours (h) yield Mw Mw / Mn [g] [%] Example 1 MENB (10) 80 18 5.08 48.6 197,600 2.09 Example 2 MENB (10) 90 18 7.06 67.5 185,100 2.16 Example 3 MENB (10) 100 10 7.98 76.3 166,300 2.15 Example 4 MENB (10) 110 10 8.30 79.4 149,400 2.45 Example 5 MENB (17) 80 18 3.91 22.0 167,200 2.31 Example 6 MENB (17) 90 18 8.13 45.7 200,800 2.04 Example 7 MENB (17) 100 10 8.45 47.5 145,500 2.05 Example 8 MENB (17) 120 10 13.57 76.3 155,800 2.13

In Table 1, MENB is 5-norbornene-2-carboxylic acid methyl ester.

Example 9

(Polymerization of 5-norbornene-2-carboxylic acid methyl ester in the presence of dichloromethane solvent-Preparation using Pd (acac) ₂ as catalyst; 1 equivalent of borate cocatalyst for Pd catalyst)

Pd (acac) ₂ (3.5 mg, 11 μmol), dimethyl anilniumtetrakiss (pentafluorophenyl) borate (7.3 mg, 11 μmol), tricyclohexylphosphine (3.0 in a dry box mg, 11 μmol) was added to a 250 mL Schlenk flask.

5 ml of dichloromethane was dissolved in the flask, and 5-norbornene-2-carboxylic acid methyl ester (10 mL, 55.6 mmol) prepared in Preparation Example 1 was added at room temperature to raise the reaction temperature to 80 ° C. The dichloromethane solvent was removed under partial vacuum while raising to 80 ° C. The reaction was carried out at 80 ° C. for 18 hours. Over time, the viscosity of the reaction solution became high and after 10 hours it became hard to stir. After 18 hours of reaction, 50 mL of toluene was added to dissolve the polymer, which was added to an excess of ethanol to obtain a white copolymer precipitate. The precipitate was collected by filtration with a glass funnel and dried in a vacuum oven at 80 ° C. for 24 hours to obtain 7.43 g of a 5-norbornene-2-carboxylic acid methyl ester polymer (71.0 wt% based on the total amount of monomer introduced). The molecular weight (Mw) was 184,500 and Mw / Mn was 2.08.

Example 10

(Preparation of 5-norbornene-2-carboxylic acid methyl ester polymerization under dichloromethane solvent and polymerization temperature of 90 ° C. using Pd (acac) ₂ as a catalyst; 1 equivalent of borate cocatalyst for Pd catalyst)

In the same manner as in Example 9, the same amount of dichloromethane solvent (5 mL) and Pd (acac) _{2 as} catalyst (5,000: 1 molar ratio than monomer) were used, and 5 was prepared in Preparation Example 1 at a polymerization temperature of 90 ° C. Norbornene-2-carboxylic acid methyl ester polymerization was carried out.

As a result, 7.95 g (76.0 wt% of the total monomers introduced) of 5-norbornene-2-carboxylic acid methyl ester polymer was obtained. The molecular weight (Mw) was 181,800 and Mw / Mn was 2.13.

Example 11

(5-norbornene-2-carboxylic acid butyl ester polymerization in the presence of dichloromethane solvent-preparation using Pd (acac) ₂ as catalyst)

Pd (acac) ₂ (6.0 mg, 20 μmol), dimethyl aniliniumtetrakiss (pentafluorophenyl) borate (32.0 mg, 40 μmol), tricyclohexylphosphine (5.6) in a dry box mg, 20 μmol) was added to a 250 mL Schlenk flask. 5 ml of dichloromethane was dissolved in the flask, and 5-norbornene-2-carboxylic butyl ester (20 mL, 100 mmol) prepared in Preparation Example 2 was added at room temperature, and the reaction temperature was raised to 80 ° C. The CH ₂ Cl ₂ solvent was removed under partial vacuum while raising to 80 ° C. The reaction was carried out at 80 ° C. for 18 hours. Over time, the viscosity of the reaction solution became high and after 10 hours it became hard to stir. After 18 hours, 50 mL of toluene was added to dissolve the polymer, which was added to an excess of ethanol to obtain a white copolymer precipitate. The precipitate was collected by filtration with a glass funnel and dried in a vacuum oven at 80 ° C. for 24 hours to obtain 7.28 g of a 5-norbornene-2-carboxylic acid butyl ester polymer (37.4 wt% based on the total amount of monomer introduced).

Examples 12-14

(Polymerization of 5-norbornene-2-carboxylic acid methyl ester and 5-norbornene-2-carboxylic acid butyl ester in the presence of dichloromethane solvent in the presence of dichloromethane solvent-Preparation using Pd (acac) ₂ as catalyst)

In the same manner as in Example 11, the same amount of dichloromethane solvent (5 mL) and Pd (acac) ₂ catalyst amount (5,000: 1 molar ratio than monomer) were used, and the polymerization temperature was changed to 90, 100, and 110 ° C., respectively. 5-norbornene-2-carboxylic acid butyl ester polymerization prepared in Example 2 was carried out. Table 2 below shows the polymerization results.

Polymerization of 5-norbornene-2-carboxylic acid butyl ester with Pd (acac) ₂ catalyst in the presence of dichloromethane solvent division Monomer (mL) Temperature (℃) Hours (h) yield Mw Mw / Mn [g] [%] Example 11 BENB (20) 80 18 7.28 37.4 213,700 1.72 Example 12 BENB (20) 90 18 14.02 72.1 186,200 2.07 Example 13 BENB (20) 100 10 18.43 95.0 157,100 1.88 Example 14 BENB (20) 120 4 16.30 84.0 130,000 1.85

BENB in Table 2 is 5-norbornene-2-carboxylic acid butyl ester.

Example 15

(5-norbornene-2-carboxylic acid butyl ester polymerization in the presence of chlorobenzene solvent-preparation using Pd (acac) ₂ as a catalyst)

Pd (acac) ₂ (6.0 mg, 20 μmol), dimethyl aniliniumtetrakiss (pentafluorophenyl) borate (32.0 mg, 40 μmol), tricyclohexylphosphine (5.6) in a dry box mg, 20 μmol) was added to a 250 mL Schlenk flask. 10 mL of chlorobenzene was added to the flask to dissolve it, and 5-norbornene-2-carboxylic acid butyl ester (20 mL, 100 mmol) prepared in Preparation Example 2 was added at room temperature to raise the reaction temperature to 80 ° C. The viscosity of the reaction solution became high while the reaction was in progress at 80 ° C. After 18 hours, the reaction was stopped and 50 mL of toluene was added to dilute the solution, and then added to an excess of ethanol to obtain a white copolymer precipitate. The precipitate was collected by filtration with a glass funnel and dried in a vacuum oven at 80 ° C. for 24 hours to obtain 6.93 g of 5-norbornene-2-carboxylic acid butyl ester polymer (35.7 wt% based on the total amount of monomer introduced).

Examples 16-18

(Polymerization of 5-norbornene-2-carboxylic Butyl Ester with Change in Polymerization Temperature in the Presence of Chlorobenzene Solvent-Preparation using Pd (acac) ₂ as Catalyst)

In the same manner as in Example 15, 5-norbornene-2 using the same amount of catalyst (5000: 1 mole ratio as monomer) and the same amount of chlorobenzene solvent (10 mL) while changing the polymerization temperature to 90, 100, and 110 ° C. Carboxylic acid butyl ester polymerization was performed. Table 3 below shows the polymerization results.

Polymerization of 5-norbornene-2-carboxylic acid butyl ester with Pd (acac) ₂ catalyst in the presence of chlorobenzene solvent division Monomer (mL) Temperature (℃) Hours (h) yield Mw Mw / Mn [g] [%] Example 15 BENB (20) 80 18 6.93 35.7 165,800 1.98 Example 16 BENB (20) 90 18 12.86 66.1 149,400 2.02 Example 17 BENB (20) 100 18 14.37 73.9 138,700 2.00 Example 18 BENB (20) 110 18 17.28 88.9 113,800 1.96

Example 19

(Polymerization of 5-norbornene-2-carboxylic acid butyl ester in the presence of toluene solvent-preparation using Pd (acac) ₂ as catalyst)

Pd (acac) ₂ (6.0 mg, 20 μmol), dimethyl aniliniumtetrakiss (pentafluorophenyl) borate (32.0 mg, 40 μmol), tricyclohexylphosphine (5.6) in a dry box mg, 20 μmol) was added to a 250 mL Schlenk flask. 10 ml of toluene was added to this flask to dissolve it, and 5-norbornene-2-carboxylic acid butyl ester (20 mL, 100 mmol) prepared in Example 2 was added at room temperature to raise the reaction temperature to 80 ° C. The viscosity of the reaction solution became high while the reaction was in progress at 80 ° C. After 18 hours, the reaction was stopped and 50 mL of toluene was added to dilute the solution, and then added to an excess of ethanol to obtain a white copolymer precipitate. The precipitate was collected by filtration with a glass funnel and dried in a vacuum oven at 80 ° C. for 24 hours to obtain 7.14 g of 5-norbornene-2-carboxylic acid butyl ester polymer (36.7 wt% based on the total amount of monomer introduced).

Examples 20-22

(5-norbornene-2-carboxylic acid butyl ester polymerization on the change of polymerization temperature in the presence of toluene solvent-preparation using Pd (acac) ₂ as catalyst)

In the same manner as in Example 19, 5-norbornene was used with the same catalyst amount (5000: 1 molar ratio to monomer) and toluene volume ratio to monomer to 2: 1, and the polymerization temperature was changed to 80, 90, 100 and 110 ° C, respectively. 2-carboxylic acid butyl ester polymerization was performed. Table 4 below shows the polymerization results.

Polymerization of 5-norbornene-2-carboxylic acid butyl ester with Pd (acac) ₂ catalyst in the presence of toluene solvent division Monomer (mL) [Monomer] / [toluene] (volume ratio) Temperature (℃) Hours (h) yield Mw Mw / Mn [g] [%] Example 19 BENB (20) 2/1 80 18 7.14 36.7 128,100 1.93 Example 20 BENB (20) 2/1 90 18 11.66 60.0 128,100 1.94 Example 21 BENB (20) 2/1 100 18 15.69 80.7 120,300 1.93 Example 22 BENB (20) 2/1 110 18 17.59 90.4 96,500 2.06

Example 23

(Copolymerization of 5-norbornene-2-carboxylic acid methyl ester and 5-norbornene-2-carboxylic acid butyl ester in the presence of dichloromethane solvent-preparation using Pd (acac) ₂ as a catalyst)

Pd (acac) ₂ (6.0 mg, 20 μmol), dimethyl aniliniumtetrakiss (pentafluorophenyl) borate (32.0 mg, 40 μmol), tricyclohexylphosphine (5.6) in a dry box mg, 20 μmol) was added to a 250 mL Schlenk flask. 5 ml of dichloromethane was dissolved in the flask, and 5-norbornene-2-carboxylic acid methyl ester (9 mL, 50 mmol) prepared in Preparation Example 1 and 5-norbornene-2 prepared in Preparation Example 2 were dissolved. -Carboxylic acid butyl ester (10 mL, 50 mmol) was put at room temperature, and reaction temperature was raised to 80 degreeC. The dichloromethane solvent was removed under partial vacuum while raising to 80 ° C. The viscosity of the reaction solution became high while the reaction was in progress at 80 ° C. After 18 hours, the reaction was stopped and 50 mL of toluene was added to dilute the solution, and then added to an excess of ethanol to obtain a white copolymer precipitate. The precipitate was collected by filtration with a glass funnel, and the copolymer was dried at 80 ° C. for 24 hours in a vacuum oven to obtain a copolymer of 5-norbornene-2-carboxylic acid methyl ester and 5-norbornene-2-carboxylic acid butyl ester. 7.39 g (38.6 wt% based on the total amount of added monomers) was obtained.

Examples 24-26

(Copolymerization of 5-norbornene-2-carboxylic acid methyl ester and 5-norbornene-2-carboxylic acid butyl ester on the change of polymerization temperature in the presence of dichloromethane solvent-Preparation using Pd (acac) ₂ as catalyst)

In the same manner as in Example 23, using the same dichloromethane solvent (5 mL) and the amount of catalyst (5000: 1 mole ratio to monomer) and changing the polymerization temperature to 90, 100, 110 ℃, respectively 5-norbornene-2- Copolymerization of the carboxylic acid methyl ester and the 5-norbornene-2-carboxylic acid butyl ester was performed. Table 5 shows the copolymerization results for this.

Copolymerization of 5-norbornene-2-carboxylic acid methyl ester and 5-norbornene-2-carboxylic acid butyl ester on the change of polymerization temperature in the presence of dichloromethane solvent division Monomer (mL) Temperature (℃) Hours (h) yield Mw Mw / Mn [g] [%] Example 23 MENB (9) BENB (10) 80 18 7.39 38.6 213,200 2.17 Example 24 MENB (9) BENB (10) 90 18 7.99 41.8 171,500 2.10 Example 25 MENB (9) BENB (10) 100 18 16.02 83.7 182,300 2.13 Example 26 MENB (9) BENB (10) 110 18 17.80 93.1 164,600 2.43

Example 27

(Norbornene and 5-norbornene-2-carboxylic acid methyl ester copolymerization in the presence of toluene solvent-Preparation using Pd (acac) ₂ as a catalyst)

In dry box, Pd (acac) ₂ (5.0 mg, 17 μmol), dimethylanilinium tetrakispentafluorophenyl) borate (26 mg, 33 μmol), tricyclohexylphosphine (4.6 mg, 17 μmol) was added to a 250 mL Schlenk flask. 40 ml of toluene was added to the flask to dissolve it, followed by norbornene (9 mL, 82.5 mmol) and 5-norbornene-2-carboxylic acid methyl ester (12 mL, 82.5 mmol) prepared in Preparation Example 1 at room temperature. The reaction temperature was raised to 90 ° C. While the reaction proceeded at 90 ° C., the viscosity of the reaction solution increased. After 18 hours, the reaction was stopped and 50 mL of toluene was added to dilute the solution, and then added to an excess of ethanol to obtain a white copolymer precipitate. The precipitate was collected by filtration with a glass funnel and dried in a vacuum oven at 80 ° C. for 24 hours to obtain 15.28 g of a copolymer of norbornene and 5-norbornene-2-carboxylic acid methyl ester (75.6% by weight based on the total amount of monomers injected). The molecular weight (Mw) was 224,800 and Mw / Mn was 2.23.

Example 28

(Norbornene and 5-norbornene-2-carboxylic acid methyl ester copolymerization in the presence of toluene solvent-Preparation using Pd (acac) ₂ as a catalyst)

In dry box, Pd (acac) ₂ (4.8 mg, 16 μmol), dimethylanilinium tetrakispentafluorophenyl) borate (25.2 mg, 32 μmol), tricyclohexylphosphine (4.4 mg, 16 μmol) was added to a 250 mL Schlenk flask. 40 ml of toluene was added to the flask and dissolved, followed by norbornene (5.15 mL, 47 mmol) and 5-norbornene-2-carboxylic acid methyl ester (16 mL, 110 mmol) prepared in Preparation Example 1 at room temperature. The reaction temperature was raised to 90 ° C. While the reaction proceeded at 90 ° C., the viscosity of the reaction solution increased. After 18 hours, the reaction was stopped and 50 mL of toluene was added to dilute the solution, and then added to an excess of ethanol to obtain a white copolymer precipitate. The precipitate was collected by filtration through a glass funnel and dried in a vacuum oven at 80 ° C. for 24 hours to obtain 13.0 g of a copolymer of norbornene and 5-norbornene-2-carboxylic acid methyl ester (61.2 wt% based on the total amount of monomers injected). The molecular weight (Mw) was 164,800 and Mw / Mn was 2.03.

Example 29

(5-butyl norbornene and 5-norbornene-2-carboxylic acid methyl ester copolymerization in the presence of toluene solvent-preparation using Pd (acac) ₂ as a catalyst)

In dry box, Pd (acac) ₂ (4.2 mg, 14 μmol), dimethylanilinium tetrakispentafluorophenyl) borate (22.1 mg, 28 μmol), tricyclohexylphosphine (3.9 mg, 14 μmol) was added to a 250 mL Schlenk flask. 40 ml of toluene was added to the flask to dissolve it, and 5-butylnorbornene (11.8 mL, 63.7 mmol) and 5-norbornene-2-carboxylic acid methyl ester (10 mL, 68.7 mmol) prepared in Preparation Example 1 were used. Was added at room temperature and the reaction temperature was raised to 90 ° C. While the reaction proceeded at 90 ° C., the viscosity of the reaction solution increased. After 18 hours, the reaction was stopped and 50 mL of toluene was added to dilute the solution, and then added to an excess of ethanol to obtain a white copolymer precipitate. The precipitate was collected by filtration through a glass funnel and dried in a vacuum oven at 80 ° C. for 24 hours to obtain 15.15 g of a copolymer of norbornene and 5-norbornene-2-carboxylic acid methyl ester (73.2 wt% based on the total amount of monomers injected). The molecular weight (Mw) was 139,700 and Mw / Mn was 2.24.

Example 30

(5-butyl norbornene and 5-norbornene-2-carboxylic acid methyl ester copolymerization in the presence of toluene solvent-preparation using Pd (acac) ₂ as a catalyst)

In dry box, Pd (acac) ₂ (4.2 mg, 14 μmol), dimethylanilinium tetrakispentafluorophenyl) borate (22.1 mg, 28 μmol), tricyclohexylphosphine (3.9 mg, 14 μmol) was added to a 250 mL Schlenk flask. 40 ml of toluene was added to the flask to dissolve it, and 5-butylnorbornene (7.1 mL, 41.2 mmol) and 5-norbornene-2-carboxylic acid methyl ester (14 mL, 96.2 mmol) prepared in Preparation Example 1 were used. Was added at room temperature and the reaction temperature was raised to 90 ° C. While the reaction proceeded at 90 ° C., the viscosity of the reaction solution increased. After 18 hours, the reaction was stopped and 50 mL of toluene was added to dilute the solution, and then added to an excess of ethanol to obtain a white copolymer precipitate. The precipitate was collected by filtration through a glass funnel and dried in a vacuum oven at 80 ° C. for 24 hours to obtain 12.1 g of a copolymer of norbornene and 5-norbornene-2-carboxylic acid methyl ester (58.1 wt% based on the total amount of monomers injected). The molecular weight (Mw) was 115,760 and Mw / Mn was 1.96.

Example 31

(5-norbornene-2-yl acetate polymerization-preparation using (Pd (acac) ₂ ))

In a 250 ml Schlenk flask, 5-norbornene-2-yl acetate (5 g, 32.85 mmol) as a monomer and 9 ml of toluene purified with a solvent were added thereto. Pd (acac) ₂ (20.6 mg, 0.067 mmol), tricyclohexylphosphine (18.9 mg, 0.067 mmol) dissolved in 1 ml of toluene as a catalyst in this flask, and dimethylanilinium tetrakis in 2 ml of dichloromethane as a promoter. Pentafluorophenyl) borate (Dimethylanilinium tetrakis (pentafluorophenyl) borate) (107.4 mg, 0.134 mmol) was added thereto and reacted with stirring at 80 ° C. for 17 hours.

After 17 hours, the reaction product was added to an excess of ethanol to obtain a white copolymer precipitate. The precipitate was filtered with a glass funnel, and the recovered polymer was dried in a vacuum oven at 65 ° C. for 24 hours to obtain 4.69 g of norbornene carboxylic acid butyl ester polymer (yield: 93.8 wt% based on the total amount of monomers introduced).

Comparative Example 1

(5-norbornene-2-carboxylic acid butyl ester polymerization in the presence of dichloromethane solvent-preparation using Pd (acac) ₂ as catalyst)

Pd (acac) ₂ (6.0 mg, 20 μmol), dimethyl aniliniumtetrakiss (pentafluorophenyl) borate (32.0 mg, 40 μmol), tricyclohexylphosphine (5.6) in a dry box mg, 20 μmol) was added to a 250 mL Schlenk flask. 5 ml of dichloromethane was dissolved in the flask, and 5-norbornene-2-carboxylic butyl ester (20 mL, 100 mmol) prepared in Preparation Example 2 was added at room temperature, and the reaction temperature was raised to 60 ° C. The CH ₂ Cl ₂ solvent was removed under partial vacuum while raising to 60 ° C. The reaction was carried out at 60 ° C. for 18 hours. Over time, the viscosity of the reaction solution became high and after 10 hours it became hard to stir. After 18 hours, 50 mL of toluene was added to dissolve the polymer, which was added to an excess of ethanol to obtain a white copolymer precipitate. The precipitate was collected by filtration with a glass funnel and dried in a vacuum oven at 80 ° C. for 24 hours to obtain 1.23 g of 5-norbornene-2-carboxylic acid butyl ester polymer (6.4 wt% based on the total amount of monomer introduced).

Comparative Examples 2 to 6

(Polymerization of 5-norbornene-2-carboxylic acid methyl ester and 5-norbornene-2-carboxylic acid butyl ester in the presence of dichloromethane solvent in the presence of dichloromethane solvent-Preparation using Pd (acac) ₂ as catalyst)

In the same manner as in Example 11, using the same amount of dichloromethane solvent (5 mL) and Pd (acac) ₂ catalyst amount (5000: 1 molar ratio than monomer) and polymerization temperature to 65, 70, 75, 140, 150 ℃ The 5-norbornene-2-carboxylic acid butyl ester polymerization prepared in Example 2 was carried out while changing each. Table 6 below shows the polymerization results.

Polymerization of 5-norbornene-2-carboxylic acid butyl ester with Pd (acac) ₂ catalyst in the presence of dichloromethane solvent division Monomer (mL) Temperature (℃) Hours (h) yield Mw Mw / Mn [g] [%] Comparative Example 1 BENB (20) 60 18 1.23 6.4 124,600 1.54 Comparative Example 2 BENB (20) 65 18 1.30 6.7 134,200 1.67 Comparative Example 3 BENB (20) 70 18 1.52 7.8 137,100 1.68 Comparative Example 4 BENB (20) 75 18 2.15 11.1 146,100 1.88 Comparative Example 5 BENB (20) 140 4 16.76 86.0 87,100 1.74 Comparative Example 6 BENB (20) 150 4 12.50 64.3 54,000 1.88

1 is a graph showing the polymerization yield and molecular weight (Mw) according to polymerization temperature of Examples 11 to 14 and Comparative Examples 1 to 6 for 5-norbornene-2-carboxylic acid butyl ester polymerization in the presence of dichloromethane solvent. As can be seen in Figure 1, the molecular weight is less than 100,000, but the polymerization yield is less than 10% at less than 80 ℃, the polymerization yield is more than 60%, but molecular weight is 100,000 or less when it exceeds 130 ℃. These results show that norbornene polymerization performance with polar functional groups can be controlled by the polymerization temperature of 80 to 130 ℃.

Examples 31-32

(Film production)

The coating solution was prepared by mixing the polymers obtained in Examples 1 and 2 as shown in Table 1 below, and the coating solution was cast on a glass substrate using a knife coater or a bar coater, and then, at room temperature, 1 Drying was carried out for an hour and dried at 100 ° C. for 18 hours under a nitrogen atmosphere. After drying for 10 seconds at −10 ° C., the film on the glass substrate was peeled off with a knife to obtain a transparent film having a uniform thickness of less than 2%. The thickness and light transmittance at 400 to 700 nm for these films are shown together in Table 7 below.

division Film solution composition Film properties Polymer (parts by weight) Solvent (part by weight) Thickness (㎛) Light transmittance (%) Example 31 Polymer of Example 1 THF 560 114 92 Example 32 Polymer of Example 2 MC 360, and TOLUENE 200 120 92

In Table 1 above,

THF is tetrahydrofuran and MC is methylenechloride.

(Optical anisotropy measurement)

In each of the transparent films of Examples 31 to 32, the refractive index n was measured using an Abbe refractometer, and an in-plane retardation value was measured using an automatic birefringence meter (manufactured by prince measuring instrument; KOBRA-21 ADH). (R _e ) was measured, and the phase difference value (R _θ ) when the angle between the incident light and the film plane was 50 °, and the film thickness direction (with the in-plane x-axis) was measured according to the following equation (3). (R _th ) was obtained.

(Equation 3)

Furthermore, the refractive index difference (n _x -n _y ) and the refractive index difference (n _y -n _z ) were obtained by dividing the thickness of the film by the values of R _e and R _th . Table 8 (n _x -n _y ), R _θ , of each transparent film R _th , (n _y -n _z ) In summary.

division Polymer n (refractive index) (n _x -n _y ) x10 ³ R _th (nm / μm) (n _y -n _z ) x10 ³ Film of Example 31 Polymer of Example 1 1.52 0.008 - - Film of Example 32 Polymer of Example 2 1.50 0.009 2.13 2.13

In addition, when R _θ was measured by overlapping a triacetate cellulose film having n _y > n _z , the R _θ value of all the cyclic olefin films was increased, and R _th of the cyclic olefin film was negative in birefringence ( negative birefringence; n _y > n _z ).

The production method of the present invention is a cyclic olefin polymerization method containing a polar functional group that can avoid the degradation of the catalytic activity by the endo isomer containing a polar functional group, and can obtain excellent polymerization results while using a very small amount of catalyst. The norbornene-based polymer comprising a polar functional group prepared by the manufacturing method of the present invention is transparent, has excellent adhesion to metals or polymers having other polar functional groups, has a low dielectric constant, and can be used as an insulating electronic material. And cyclic olefin polymers having good strength. In addition, the optically anisotropic film of the cyclic olefin-based addition polymer comprising a polar functional group produced by the production method of the present invention can be adjusted in the thickness direction of the refractive index according to the type and content of the functional group introduced into the cyclic olefin-based addition polymer It can be used as an optical compensation film for liquid crystal display (LCD) in various modes.

1 is a graph showing polymerization yield and molecular weight (Mw) of Examples 11 to 14 and Comparative Examples 1 to 6 according to polymerization temperature.

Claims (16)

In the method for producing a cyclic olefin polymer containing a polar functional group having a molecular weight (Mw) of at least 100,000, Monomers including norbornene-based monomers containing polar functional groups Iii) a Group 10 transition metal compound of a compound represented by the following Chemical Formula 1 or a compound represented by the following Chemical Formula 2 as a catalyst; Ii) an organic compound comprising a Group 15 element as a first promoter; And Iii) a salt capable of providing an anion containing a Group 13 element as a second promoter Addition polymerization at a polymerization temperature of 80 to 130 ° C. while being in contact with the catalyst component of the catalyst system comprising a Method for producing a cyclic olefin based addition polymer comprising a polar functional group comprising: (Formula 1) (Formula 2) In the formula 1, and formula 2, M is a Group 10 metal; n is 1 or 2; R ¹ , and R ² are each independently hydrogen; Linear or branched alkyl, alkenyl, or vinyl of 1 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Aryl having 6 to 40 carbon atoms including a hetero atom; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Alkynyl having 3 to 20 carbon atoms; Or linear or branched alkyl having 1 to 10 halogen atoms, or aryl; R ³ is hydrogen; halogen; Linear or branched alkyl, allyl, alkenyl, or vinyl having 1 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted by hydrocarbon having 5 to 12 carbon atoms; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Alkyl or aryl having 6 to 40 carbon atoms including hetero elements; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Or alkynyl having 3 to 20 carbon atoms. The method of claim 1, The organic compound containing a group 15 element of b) is an organic compound having a non-covalent electron pair that can serve as an electron donor, a ring containing a polar functional group which is a compound represented by the following formula (3), or a compound represented by the formula (4) Process for preparing type olefinic addition polymer: (Formula 3) P (R ⁴ ) _3-c [X (R ⁴ ) _d ] _c In the formula (3), c is an integer from 0 to 3; X is oxygen, sulfur, silicon, or nitrogen; Each R ⁴ is hydrogen; Linear or branched alkyl of 1 to 20 carbon atoms, alkoxy, allyl, alkenyl, or vinyl; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Or alkynyl having 3 to 20 carbon atoms; Tri (linear or branched alkyl) having 1 to 10 carbon atoms, tri (linear or branched alkoxy) having 1 to 10 carbon atoms; Tri (cycloalkyl) silyl substituted or unsubstituted with hydrocarbons of 5 to 12 carbon atoms; Tri (aryl having 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon) silyl; Tri (aryloxy of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon); Tri (linear or branched alkyl of 1 to 10 carbon atoms) siloxy; Tri (cycloalkyl having 5 to 12 carbon atoms, substituted or unsubstituted with hydrocarbon) siloxy; Or tri (aryl having 6 to 40 carbon atoms substituted or unsubstituted with hydrocarbon) siloxy; Wherein each substituent may be substituted with linear or branched haloalkyl, or halogen, (Formula 4) (R ⁵ ) ₂ P-(R ⁶ )-P (R ⁵ ) ₂ In the formula (4), R ⁵ is as defined in formula (3); R ⁶ is linear or branched alkyl, alkenyl, or vinyl of 1 to 5 carbon atoms; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl of 6 to 20 carbon atoms, substituted or unsubstituted with hydrocarbon; Or aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon. The method of claim 1, Method for producing a cyclic olefin-based addition polymer containing a polar functional group is a salt represented by the formula (5) is a salt capable of providing an anion containing a group 13 element of c): (Formula 5) [Cat] _a [Anion] _b In the formula (5), Cat is hydrogen; Cations of Group 1 metals, Group 2 metals, or transition metals; And a cation selected from the group consisting of organic cations containing these cations, to which a group 15 organic compound having a weakly bound lone pair of electrons of b) may be bonded; Anion is an anion that can be weakly coordinated with the metal M of the compound of Formula 1 or Formula 2, and includes borate, aluminate, [SbF ₆ ] ^- , [PF ₆ ] ^- , [AsF ₆ ] ^- , and perfluoroacetate. (perfluoroacetate; [CF ₃ CO ₂ ] ^- ), perfluoropropionate ([C ₂ F ₅ CO ₂ ] ^- ), perfluorobutyrate ([CF ₃ CF ₂ CF ₂ CO ₂ ] ^-), perchlorate ^{_{(perchlorate; [ClO 4] -}} ), para-toluenesulfonate (p-toluenesulfonate; [p- CH 3 C 6 H 4 SO 3] -), [SO 3 CF 3] -, see other benzene And an anhydride selected from the group consisting of carborane substituted or unsubstituted with halogen; a and b represent the number of cations and anions, respectively, which are set to match the charge so that cat and anion are electrically neutral. The method of claim 3, wherein The organic group including the cation of Formula 5 is [NH (R ⁷ ) ₃ ] ⁺ , or [N (R ⁷ ) ₄ ] ⁺ ammonium; [PH (R ⁷ ) ₃ ] ⁺ , or [P (R ⁷ ) ₄ ] ⁺ phosphonium; [C (R ⁷ ) ₃ ] ⁺ phosphorus carbonium, [H (OEt ₂ ) ₂ ] ⁺ , [Ag] ⁺ , [Cp ₂ Fe] ⁺ , wherein each R ⁷ is linear or branched alkyl of 1 to 20 carbon atoms, alkyl or silyl alkyl substituted by halogen; carbon atoms substituted or unsubstituted by hydrocarbon Cycloalkyl of 12; cycloalkyl or silyl cycloalkyl substituted by halogen; aryl of 6 to 40 carbon atoms, substituted or unsubstituted; aryl or silyl aryl, substituted by halogen; carbon atoms substituted or unsubstituted by hydrocarbon To aralkyl from 15 to 15; or aralkyl or silyl aralkyl substituted with halogen). The method of claim 3, wherein Borate or aluminate of Formula 5 is a method for producing a cyclic olefin-based addition polymer comprising a polar functional group is an anion represented by the formula (5a) or (5b): (Formula 5a) [M '(R ") ₄ ] (Formula 5b) [M '(OR ") ₄ ] In the formula of Formula 5a and Formula 5b, M 'is boron or aluminum; Each R ″ is a halogen element; linear or branched alkyl of 1 to 20 carbon atoms, substituted or unsubstituted with halogen, or alkenyl; cycloalkyl substituted or unsubstituted with 5 to 12 carbon atoms; substituted with hydrocarbon Or unsubstituted aryl having 6 to 40 carbon atoms, linear or branched trialkylsiloxy having 3 to 20 carbon atoms or aryl having 6 to 40 carbon atoms substituted with linear or branched triarylsiloxy having 18 to 48 carbon atoms; Substituted or unsubstituted aralkyl having 7 to 15 carbon atoms. The method of claim 1, The catalyst system Viii) 1 mole of a transition metal compound of Group 10; Ii) 1-3 moles of organic compound comprising group 15 element; And Iii) 1 to 2 moles of salt capable of providing an anion comprising a Group 13 element The manufacturing method of the cyclic olefin type addition polymer containing the polar functional group by which addition polymerization is performed by the composition ratio of the. The method of claim 1, The catalyst system is a method of producing a cyclic olefin-based addition polymer containing a polar functional group of the catalyst amount of 1/2500 to 1/100000 based on the catalyst component of the transition metal compound of Group 10. The method of claim 1, The addition polymerization is a method for producing a cyclic olefin-based addition polymer comprising a polar functional group is carried out under a polar solvent. The method of claim 8, Method of producing a cyclic olefin-based addition polymer containing a polar functional group is 0.5 to 4 times the volume of the solvent to the monomer volume. The method of claim 1, Method for producing a cyclic olefin-based addition polymer comprising a polar functional group of the norbornene-based monomer containing a polar functional group is a compound represented by the following formula (7): (Formula 7) In the formula (7), m is an integer from 0 to 4, R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ At least one of-(CH ₂ ) _n C (O) OR ¹² ,-(CH ₂ ) _n OC (O) R ¹² ,-(CH ₂ ) _n OC (O) OR ¹² ,-(CH ₂ ) _n C (O) R ¹² ,-(CH ₂ ) _n OR ¹² ,-(CH ₂ O) _n -OR ¹² ,-(CH ₂ ) _n C (O) -OC (O) R ¹² ,-(CH ₂ ) _n C (O) NH ₂ ,-(CH ₂ ) _n C (O) NHR ¹² ,-(CH ₂ ) _n C (O) N (R ¹² ) ₂ ,-(CH ₂ ) _n NH ₂ ,-(CH ₂ ) _n NHR ¹² ,-(CH ₂ ) _n N (R ¹² ) ₂ ,-(CH ₂ ) _n OC (O) NH ₂ ,-(CH ₂ ) _n OC (O) NHR ¹² ,-(CH ₂ ) _n OC (O) N (R ¹² ) ₂ ,-(CH ₂ ) _n C (O) Cl,-(CH ₂ ) _n SR ¹² ,-(CH ₂ ) _n SSR ¹² ,-(CH ₂ ) _n SO ₂ R ¹² ,-(CH ₂ ) _n SO ₂ R ¹² ,-(CH ₂ ) _n OSO ₂ R ¹² ,-(CH ₂ ) _n SO ₃ R ¹² ,-(CH ₂ ) _n OSO ₃ R ¹² ,-(CH ₂ ) _n B (R ¹² ) ₂ ,-(CH ₂ ) _n B (OR ¹² ) ₂ ,-(CH ₂ ) _n B (R ¹² ) (OR ¹² ),-(CH ₂ ) _n N = C = S ,-(CH ₂ ) _n NCO,-(CH ₂ ) _n N (R ¹² ) C (= 0) R ¹² ,-(CH ₂ ) _n N (R ¹² ) C (= 0) (OR ¹² ),- (CH ₂ ) _n CN,-(CH ₂ ) _n NO ₂ , , ,-(CH ₂ ) _n P (R ¹² ) ₂ ,-(CH ₂ ) _n P (OR ¹² ) ₂ ,-(CH ₂ ) _n P (R ¹² ) (OR ¹² ),-(CH ₂ ) _n P (= O) (R ¹² ) ₂ ,-(CH ₂ ) _n P (= O) (OR ¹² ) ₂ , and-(CH ₂ ) _n P (= O) (R ¹² ) (OR ¹² ) A polar functional group selected from The rest are hydrogen; halogen; Linear or branched alkyl, alkenyl or vinyl of 1 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms, optionally substituted with hydrocarbons; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Or alkynyl having 3 to 20 carbon atoms, R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are not a polar functional group, hydrogen, or halogen, and R ⁸ and R ⁹ or R ¹⁰ and R ¹¹ May be connected to each other to form an alkylidene group having 1 to 10 carbon atoms, or R ⁸ or R ⁹ may be connected to any one of R ¹⁰ and R ¹¹ to be a saturated or unsaturated cyclic group having 4 to 12 carbon atoms, or Can form an aromatic ring compound of 6 to 17, R ¹² included in the polar functional group may be each hydrogen, linear or branched alkyl having 1 to 20 carbon atoms, alkenyl or vinyl; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms, optionally substituted with hydrocarbons; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Alkynyl having 3 to 20 carbon atoms. The method of claim 1, The cyclic olefin-based addition polymer including the polar functional group may be a cyclic olefin homopolymer including a polar functional group, a di- or terpolymer of cyclic olefin monomers including different polar functional groups, or a polar functional group. A method for producing a cyclic olefin-based addition polymer comprising a polar functional group which is a dipolymer or a terpolymer of a cyclic olefin monomer comprising and a cyclic olefin monomer not containing a polar functional group. The method of claim 1, The cyclic olefin-based addition polymer comprising a polar functional group is a method for producing a cyclic olefin-based addition polymer comprising a polar functional group having a molecular weight (Mw) of 100,000 to 1,000,000. A cyclic olefin based addition polymer comprising a polar functional group having a molecular weight (Mw) of at least 100,000, which is prepared by the process according to claim 1. An optically anisotropic film comprising a cyclic olefin-based addition polymer comprising a polar functional group having a molecular weight (Mw) of at least 100,000 produced by the production method of claim 1. The method of claim 14, An optically anisotropic film having a retardation value (R _th ) of the optically anisotropic film represented by the following formula 1 is 70 to 1000 nm: (Equation 1) In Equation 1, n _y is the refractive index of the in-plane fast axis measured at a wavelength of 550 nm, n _z is the refractive index in the thickness direction measured at a wavelength of 550 nm, d is the thickness of the film. The method of claim 14, In the optically anisotropic film, the refractive index of the film is n _x = n _y > n _z relationship (n _x is the refractive index of the in-plane slow axis, n _y is the refractive index of the fast axis, n _z is An optically anisotropic film which is a negative C-plate type optical compensation film for LCD (Liquid Crystal Display) which satisfies the refractive index of thickness direction).