KR100876528B1 - Catalyst composition for the production of cyclic olefin polymer having a polar functional group - Google Patents

Abstract

The present invention relates to a method for producing a cyclic olefin polymer having a polar functional group, an olefin polymer produced by the method, an optically anisotropic film comprising the same, and a catalyst composition for producing the cyclic olefin polymer. According to the olefin polymerization method and the catalyst composition for polymerization according to the present invention, since the deactivation of the catalyst by the polar functional group of the monomer can be suppressed, the polyolefin can be produced with high molecular weight and high polymerization yield of the polymer during polyolefin polymerization. In addition, the cyclic olefin containing a polar functional group is excellent in polymerization reactivity and the activity of the catalyst composition is maintained even under various polymerization conditions, so that it is very easy to apply to a mass production process.

Description

Catalyst composition for preparing a cyclic olefin polymer having a polar functional group {CATALYST COMPOSITION FOR POLYMERIZING A CYCLIC OLEFIN HAVING POLAR FUNCTIONAL GROUP}

The present invention relates to a method for producing a cyclic olefin polymer and a catalyst composition for manufacturing. More particularly, the present invention relates to a cyclic olefin system containing a polar functional group using a catalyst composition consisting of a Group 10 metal compound, an organophosphorus ligand, and a salt compound. A method for preparing a polymer, an olefin polymer prepared thereby, an optically anisotropic film comprising the polymer and a catalyst composition for producing a cyclic olefin polymer having a polar functional group.

This application claims the benefit of the filing date of Korean Patent Application No. 10-2006-0054367 filed with the Korea Patent Office on June 16, 2006, the entire contents of which are incorporated herein.

In the information and electronics industry, inorganic materials such as silicon oxide and silicon nitride have been mainly used. As the need for small size and high efficiency devices increases, the need for high functional new materials increases. It is becoming. Materials that can meet these high functional property requirements include low dielectric constant and low water absorption, metal adhesion, mechanical strength, heat resistance and transparency ( There is a growing interest in polymers that are excellent in transparency and have a 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 an electronic material.

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. Therefore, CD, DVD, POF (Plastic Optical) Optical materials, such as optical fibers, capacitor films, information electronic materials such as low dielectric materials, low absorbency syringes, and medical materials such as blister packaging.

Examples of the polymerization method of the cyclic olefin include Ring Opening Metathesis Polymerization (ROMP), copolymerization with ethylene, and addition polymerization methods, as shown in Scheme 1 below. Such polymerization reactions include metallocene compounds, Ni, Transition metal catalysts such as Pd-compounds are used. Depending on the core metal, ligand, and catalyst composition of these catalysts, the properties of the polymerization reaction and the properties of the obtained polymer may vary.

As catalysts used in ROMP, chloride or carbonyl organometallic compounds such as TiCl ₄ and WCl ₆ react with Lewis acid type promoters such as R ₃ Al and Et ₂ AlCl to react with metal carbenes or metals. It forms a catalytically active species in the form of cyclobutane (metallocyclobutane), which is reacted with a double bond of an olefin and is ring-opened through the ring intermediate of the metallacyclobutane to a final product having a double bond (Ivin, KJ; O'Donnel, JH; Rooney, JJ; Steward, CD Makromol. Chem. 1979, Vol. 180, 1975). Since the polymer produced by the ROMP includes one double bond per monomer repeating unit, thermal stability and oxidation stability are greatly reduced, and are mainly used as a thermosetting resin.

The copolymer of ethylene and norbornene was first manufactured using a titanium-based Ziegler-Natta catalyst by Leuna, 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).

As addition polymerization method of the cyclic olefin monomer, Gayrod et al. Reported a norbornene polymerization method using a [Pd (C ₆ H ₅ CN) Cl ₂ ] ₂ catalyst (Gaylord, NG; Deshpande, AB; Mandal, BM; Martan, MJ Macromol. Sci.-Chem. 1977, Vol. A11 (5), 1053-1070), polynorbornene prepared by a zirconium-based metallocene catalyst has very high crystallinity and general organic properties. It does not dissolve in solvents and exhibits no glass transition temperature and pyrolysis (Kaminsky, W .; Bark, A .; Drake, I. Stud. Surf. Catal. 1990, Vol. 56, 425). On the other hand, polynorbornene obtained using a Pd-metal catalyst is dissolved in an organic solvent such as tetrachloroethylene, chlorobenzene or dichlorobenzene, and has a molecular weight of 100,000 or more and Tg of 300 ° C or more.

However, in order to use polymers for information electronic materials, in general, polymers have adhesion to metal surfaces such as silicon, silicon oxide, silicon nitride, alumina, copper, aluminum, gold, silver, platinum, titanium, nickel, tantalum, and chromium. Is required. Thus, in the case of the norbornene-based polymers, attempts have been made to introduce polar functional groups into norbornene-based monomers in order to control metal adhesion and various electrical, optical and chemical physical properties.

U.S. Patent No. 3,330,815 discloses a method of polymerizing a norbornene-based monomer having a polar functional group by using (PhCN) ₂ PdCl ₂ dimer as a catalyst, but the catalytic species is inactivated by the polar functional group of the monomer to polymerize the reaction. As it becomes difficult to proceed, there is a problem that it is difficult to obtain a polymer having a molecular weight of 10,000 or more.

U.S. Patent 5,705,503 discloses a process for polymerizing norbornene-based monomers with polar functional groups using ((Allyl) PdCl) ₂ / AgSbF ₆ as catalyst complex, but the ratio of catalyst to monomer is from 1: 100 to 1 Since the amount of catalyst used is excessively 250, the catalyst residue remains in a large amount in the finally obtained polymer, and the polymer may be degraded by thermal oxidation in the future, and light transmittance may also be deteriorated.

When the ester norbornene monomer was polymerized by the cationic [Pd (CH ₃ CN) ₄ ] [BF ₄ ] ₂ catalyst, the polymerization yield was low and only the exo isomer was selectively polymerized (Sen, A. Lai, T.-WJ Am. Chem. Soc. 1981, Vol. 103, 4627-4629), when polymerizing norbornene containing ester groups or acetyl groups, the catalyst is about 1/100 to 1/400 of the monomers; Since it has to be used in excess, there was a problem that it is difficult to remove the catalyst residue after polymerization.

U.S. Patent No. 6,455,650 discloses a process for polymerizing norbornene-based monomers with functional groups using [(R ') _z M (L') _x (L '') _y ] _b [WCA] _d as catalyst complex. However, when polymerizing a norbornene-based monomer having a polar functional group, since the yield is very low as 5%, there is a problem that it is not suitable for the production of a polymer containing a polar functional group.

In Lipian et al. (Sen, et al., Organometallics 2001, Vol. 20, 2802-2812), [(1,5-Cyclooctadiene) (CH ₃ ) Pd (Cl)] is derived from an organophosphorus such as PPh ₃ and [ ^{Na] + [B (3,5- (} CF 3) 2 C 6 H 3) 4] - with an excess of the catalyst of from about 1/400 degree monomer prepared from the reaction of polymerizing norbornene-ester activated by a cocatalyst such It is reported that a polymer having a molecular weight of about 6,500 is obtained using a polymerization yield of 40% or less.

On the other hand, the catalyst systems used in the polymerization method are generally composed of a main catalyst, which is a metal complex, and a promoter, which is an ionic compound.

The homogeneous Ziegler-Natta catalyst system, which is a multi-site catalyst used in polymer polymerization in the past, uses methylaluminoxane (MAO) as a promoter for improving the reactivity of the catalyst. Because of economics and post-processing problem.

Since a single active site catalyst represented by a metallocene series has emerged, as a solution of this problem, a low charge and charge delocalization of -1 or -2, which can impart a single cationic active species to the catalyst precursor, are solved. Non-coordinating anions in the form of perfluoroarylborate, which have been shown to be readily available as promoters (Chem. Rev. 1988, Vol. 88, 1405-1421; Chem. Rev. 1993, Vol. 93, 927-942).

These anions are used in the form of salts with trityl or alkymide cations with alkydes or hydride removal reactions or with protonolysis. Representative borate promoter compounds include [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] and [PhNMe ₂ H] [B (C ₆ F ₅ ) ₄ ].

In the polymerization reaction, the cationic portion of the promoter reacts with the leaving group of the metal precursor to impart cationicity to the metal precursor and form an ion pair with the anionic portion of the promoter. At this time, the anion is weakly coordinated with the metal and easily exchanged with the olefin monomer, resulting in a polymerization reaction.

However, these ion pairs act as a catalytically active species, whereas they are thermally and chemically unstable, so they react sensitively to solvents, monomers, and the like to reduce the reactivity of the catalyst. In particular, in the case of the nitrogen-containing cocatalyst compound, a neutral amine compound is produced during the catalytic activity reaction, and this amine compound can strongly interact with the organometallic catalytic activity in the form of cation, which leads to a decrease in polymerization activity. In order to prevent this, it is known to use carbenium, oxonium and sulfonium cations instead of ammonium cations (European Patent No. EP 0426,637).

On the other hand, when cyclic olefins are polymerized using MAO or organoaluminum as cocatalysts, most of them show high polymerization activity in nonpolar norbornene polymerization such as norbornene, alkylnorbornene and silylnorbornene, whereas ester or acetyl norbornene It showed significantly lower polymerization activity for polar norbornene (US Pat. Nos. 5,468,819, 5,569,730, 5,912,313, 6,031,058, 6,455,650).

That is, in the case of the catalyst system for cyclic olefin polymerization having a polar functional group, a catalyst system was prepared using various promoters, but the catalyst reacts sensitively to the monomer, so that the catalyst is inactivated by the polar functional group or the thermal stability is low. The problem of being difficult to use for polymerization has been exposed, so that the polymerization yield, the molecular weight of the polymer obtained, and the amount of catalyst used to satisfy all practically required levels as in the case of general olefins having polar functional groups have not been obtained. In addition, when the excess catalyst was used, the obtained polymer was colored or there was a problem in transparency.

Therefore, to solve the problems with the prior art, it is possible to manufacture a high molecular weight cyclic olefin polymer containing a polar functional group in a high yield, addition polymerization method of a cyclic olefin having a polar functional group does not generate catalyst residues, etc. And a catalyst composition for producing a cyclic olefin polymer comprising a polar functional group.

The first technical problem to be achieved by the present invention is to prepare a cyclic olefin polymer having a high molecular weight and high yield without polarization of the catalyst by the polar functional group, moisture, oxygen in order to solve the problems of the prior art To provide a way.

A second technical object of the present invention is to provide a cyclic olefin polymer having a polar functional group having a high glass transition temperature and excellent thermal stability, oxidation stability, chemical resistance and metal adhesion.

The third technical problem to be achieved by the present invention is to provide an optically anisotropic film comprising the olefin polymer.

The fourth technical problem to be achieved by the present invention is to solve the problems of the prior art has a good thermal chemical stability, there is no deactivation of the catalyst by the polar functional group, the high molecular weight and high yield of the cyclic olefin polymer having a polar functional group It is to provide a catalyst composition that can be produced.

The present invention to achieve the first technical problem,

In the method for producing a cyclic olefin polymer containing a polar functional group,

A Group 10 metal-containing procatalyst represented by Formula 1 below;

An organophosphorus ligand represented by Formula 2 below; And,

A cocatalyst that is a salt compound that weakly coordinates with the Group 10 metal represented by Formula 3 and provides anions;

Contacting the catalyst mixture consisting of with a monomer solution comprising a cyclic olefinic monomer comprising a polar functional group;

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

In Chemical Formula 1,

Each X is independently a hetero atom selected from S, O and N;

R ₁ are each independently -CH = CHR ²⁰ , -OR ²⁰ , -SR ²⁰ , -N (R ²⁰ ) ₂ , -N = NR ²⁰ , -P (R ²⁰ ) ₂ , -C (O) R ²⁰ , -C (R ²⁰ ) = NR ²⁰ , -C (O) OR ²⁰ , -OC (O) OR ²⁰ , -OC (O) R ²⁰ , -C (R ²⁰ ) = CHC (O) R ²⁰ , -R ²¹ C (O) R ²⁰ , —R ²¹ C (O) OR ²⁰ , or —R ²¹ OC (O) R ²⁰ ; Wherein in R ²⁰ are each independently hydrogen, halogen, linear or branched C 1 -C 5 alkyl, linear or branched having 1-5 carbon atoms in the haloalkyl carbon atoms of 5 to 10 cycloalkyl, straight or branched having 2 to Alkenyl of 5, linear or branched haloalkenyl of 2 to 5 carbon atoms, substituted or unsubstituted aralkyl of 7 to 24 carbon atoms; R ²¹ is hydrocarbylene having 1 to 20 carbon atoms;

R ₂ is each independently linear or branched alkyl having 1 to 20 carbon atoms, linear or branched alkenyl having 2 to 20 carbon atoms, linear or branched vinyl having 2 to 20 carbon atoms, or having 5 to 5 carbon atoms unsubstituted or substituted with a hydrocarbon. Cycloalkyl of 12, aryl having 6 to 40 carbon atoms unsubstituted or substituted with hydrocarbon, aralkyl having 7 to 15 carbon atoms substituted or unsubstituted with hydrocarbon, or alkynyl having 3 to 20 carbon atoms;

M is a Group 10 metal;

p is 0 to 2;

In Chemical Formula 2,

a, b and c are integers from 1 to 3;

Z, Z 'and Z "are each independently oxygen, sulfur, silicon, or nitrogen,

Except that Z, Z 'and Z "are the same atom,

R ₃ , R ₄ And R ₅ are each independently hydrogen; Linear or branched alkyl of 1 to 20 carbon atoms; Linear or branched alkoxy of 1 to 20 carbon atoms; Linear or branched allyl having 3 to 20 carbon atoms; Linear or branched alkenyl having 2 to 20 carbon atoms; Linear or branched vinyl of 2 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted with hydrocarbon having 3 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with alkoxy or a hydrocarbon; Aralkyl having 7 to 15 carbon atoms unsubstituted or substituted with alkoxy or a hydrocarbon; Aralkyl substituted with a substituent including a hetero ring; Alkylaryl having 7 to 15 carbon atoms unsubstituted or substituted with alkoxy or a hydrocarbon; Alkylaryl substituted with a substituent including a hetero ring; Alkynyl having 3 to 20 carbon atoms; Silyl, each independently substituted with linear or branched alkyl of 1 to 10 carbon atoms; Silyl independently each substituted with linear or branched alkoxy having 1 to 10 carbon atoms; Silyl each independently substituted with a substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Silyl substituted each independently with substituted or unsubstituted aryl having 6 to 40 carbon atoms; Silyl substituted each independently with substituted or unsubstituted aryloxy having 6 to 40 carbon atoms; Siloxy independently substituted with linear or branched alkyl of 1 to 10 carbon atoms; Siloxy substituted each independently with substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Or siloxy each independently substituted or unsubstituted with aryl having 6 to 40 carbon atoms, wherein each of the substituents is halogen or haloalkyl having 1 to 20 carbon atoms, and R ₄ And R ₅ may be linked to each other to form a ring, in the substituent including the hetero ring, the hetero ring includes both an aromatic or aliphatic ring,

In Chemical Formula 3,

[Cat] is a cation and is a cation of hydrogen, a Group 1 metal, a Group 2 metal, or a transition metal; And it is any one selected from the group consisting of organic cations containing these cations,

[Ani] is an anion that can be weakly coordinated with the metal M of Chemical Formula 1, and includes borate, aluminate, [SbF ₆ ]-, [PF ₆ ]-, [AsF ₆ ]-, and 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-CH ₃ C ₆ H ₄ SO ₃ ]-), [SO ₃ CF ₃ ]-, borabenzene, and halogen It is any one selected from the group consisting of substituted or unsubstituted carborane.

According to an embodiment of the present invention, in the method for preparing the cyclic olefin polymer including the polar functional group, contacting the catalyst mixture with a monomer solution including the cyclic olefin monomer including the polar functional group is 80 ° C. It is preferable to carry out at -150 degreeC.

According to another embodiment of the present invention, in the method for preparing a cyclic olefin-based polymer including the polar functional group, it is preferable that the borate or aluminate of Chemical Formula 3 is composed of an anion represented by the following Chemical Formula 3a or Chemical Formula 3b:

In Chemical Formulas 3a and 3b,

M 'is boron or aluminum;

Each R ₆ is independently halogen; Linear or branched alkyl of 1 to 20 carbon atoms unsubstituted or substituted with halogen; Linear or branched alkenyl of 2 to 20 carbon atoms unsubstituted or substituted with halogen; Cycloalkyl substituted or unsubstituted with 3 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with a hydrocarbon; Aryl having 6 to 40 carbon atoms substituted with linear or branched trialkylsiloxy having 3 to 20 carbon atoms or linear or branched triarylsiloxy having 18 to 48 carbon atoms; Or aralkyl having 7 to 15 carbon atoms which is unsubstituted or substituted with halogen.

According to another embodiment of the present invention, in the method for preparing a cyclic olefin polymer including the polar functional group, the cyclic olefin monomer is preferably a compound represented by the following formula (4):

In Chemical Formula 4,

m is an integer from 0 to 4;

At least one of R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ”represents a polar functional group and the rest are nonpolar functional groups;

R ₇ , R ₇ ′, R ₇ ″ and R ₇ ″ are the same as or different from each other, and each independently hydrogen; halogen; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkyl having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenyl of 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynyl having 3 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkyl having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy Aryl having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or a polar group comprising at least one of oxygen, nitrogen, phosphorus, sulfur, silicon, and boron;

R ₇ and R ₇ ′, or R ₇ ″ and R ₇ ″ are connected to each other to form an alkylidene group having 1 to 10 carbon atoms, or R ₇ or R ₇ ′ is selected from R ₇ ″ and R ₇ ″ May be linked to any one of a saturated or unsaturated aliphatic ring having 4 to 12 carbon atoms, or an aromatic ring having 6 to 24 carbon atoms,

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The polar functional group is -R ₈ OR ₉ , -OR ₉ , -OC (O) OR ₉ , -R ₅ OC (O) OR ₉ , -C (O) OR ₉ , -R ₈ C (O) OR ₉ , -C (O) R ₉ , -R ₈ C (O) R ₉ , -OC (O) R ₉ , -R ₈ OC (O) R ₉ ,-(R ₈ O) _n -OR ₉ ,-(OR ₈ ) _n -OR ₉ , -C (O) -OC (O) R ₉ , -R ₈ C (O) -OC (O) R ₉ , -SR ₉ , -R ₈ SR ₉ , -SSR ₉ ,- R ₈ SSR ₉ , -S (= O) R ₉ , -R ₈ S (= O) R ₉ , -R ₈ C (= S) R _9- , -R ₈ C (= S) SR ₉ , -R ₈ SO ₃ R ₉ , -SO ₃ R ₉ , -R ₈ N = C = S, -N = C = S, -NCO, -R ₈ -NCO, -CN, -R ₈ CN, -NNC (= S ) R ₉ , -R ₈ NNC (= S) R ₉ , -NO ₂ , -R ₈ NO ₂ ,

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Is;

In the polar functional group,

R ₈ is the same as or different from each other, and each independently halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, Linear or branched alkylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from carbonyloxy, halocarbonyloxy, aryloxy, haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenylene having 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynylene having 3 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkylene having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Arylene having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Alkoxylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy , Carbonyloxyylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy,

R ₉ , R ₁₀ and R ₁₁ are the same as or different from each other, and each independently hydrogen; halogen; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkyl having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenyl of 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynyl having 3 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkyl having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Aryl having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Alkoxy having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy , Carbonyloxy of 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy,

n is each independently an integer of 1 to 10.

According to another embodiment of the present invention, the procatalyst represented by Chemical Formula 1 and the organophosphorus ligand represented by Chemical Formula 2 are represented by Chemical Formula 5 in the method for preparing the cyclic olefin polymer including the polar functional group, respectively. It is preferably a procatalyst, which is an organophosphorus ligand represented by the following formula (6):

In Chemical Formula 5,

X 'and Y' are each independently a hetero atom selected from S and O;

R ₁ ′, R ₂ ′, R ₂ ″, and R ₂ ″ are each independently linear or branched alkyl having 1 to 20 carbon atoms; Linear or branched alkenyl having 2 to 20 carbon atoms; Linear or branched vinyl of 2 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted with hydrocarbon having 5 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with a hydrocarbon; Aralkyl having 7 to 15 carbon atoms which is unsubstituted or substituted with hydrocarbons; Or alkynyl having 3 to 20 carbon atoms;

M is a Group 10 metal;

r and s are each independently 0 to 2 and r + s = 2;

In Chemical Formula 6,

R ₃ , R ₄ and R ₅ are the same as defined in the formula (2).

According to another embodiment of the present invention, the procatalyst represented by the formula (1) and the organophosphorus ligand represented by the formula (2) in the method for producing a cyclic olefin polymer containing the polar functional group are each represented by the formula It is preferred that the Pd metal-containing procatalyst is represented and the organophosphorus ligand represented by the following formula (8) or (9):

In Chemical Formula 7,

R ₁ ′, R ₂ ′, R ₂ ″, and R ₂ ″ are the same as defined in Formula 5 above;

r and s are each independently 0 to 2 and r + s = 2;

In Chemical Formula 8,

R ₂₃ and R ₂₄ are each independently hydrogen; Linear or branched alkyl of 1 to 20 carbon atoms; Linear or branched allyl having 3 to 20 carbon atoms; Linear or branched alkenyl having 2 to 20 carbon atoms; Linear or branched vinyl of 2 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted with hydrocarbon having 3 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with alkoxy or a hydrocarbon; Aralkyl having 7 to 15 carbon atoms which is unsubstituted or substituted with hydrocarbons; Alkylaryl unsubstituted or substituted with alkoxy or hydrocarbon; Alkylaryl substituted with a substituent including an aliphatic hetero ring; Or alkynyl having 3 to 20 carbon atoms, and the two R ₂₄ may be connected to each other to form a ring.

According to another embodiment of the present invention, the organophosphorus ligand represented by Formula 2 in the method for preparing a cyclic olefin polymer including the polar functional group is preferably represented by the following Formula 9:

In Chemical Formula 9,

CY ₁ is a substituted or unsubstituted ring containing two O atoms and one P atom, and each of R ₂₃ is independently hydrogen; Linear or branched alkyl of 1 to 20 carbon atoms; Linear or branched allyl having 3 to 20 carbon atoms; Linear or branched alkenyl having 2 to 20 carbon atoms; Linear or branched vinyl of 2 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted with hydrocarbon having 3 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with a hydrocarbon; Aralkyl having 7 to 15 carbon atoms which is unsubstituted or substituted with hydrocarbons; Or alkynyl having 3 to 20 carbon atoms.

In Chemical Formula 9, substituents that may be substituted for CY ₁ include linear or branched alkyl having 1 to 20 carbon atoms; Linear or branched alkoxy of 1 to 20 carbon atoms; Linear or branched allyl having 3 to 20 carbon atoms; Linear or branched alkenyl having 2 to 20 carbon atoms; Linear or branched vinyl of 2 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted with hydrocarbon having 3 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with alkoxy or a hydrocarbon; Aralkyl having 7 to 15 carbon atoms unsubstituted or substituted with alkoxy or a hydrocarbon; Aralkyl substituted with a substituent including a hetero ring; Alkylaryl having 7 to 15 carbon atoms unsubstituted or substituted with alkoxy or a hydrocarbon; Alkylaryl substituted with a substituent including a hetero ring; And alkynyl having 3 to 20 carbon atoms.

According to another embodiment of the invention, the organophosphorus ligand represented by the formula (2) in the method for producing a cyclic olefin polymer containing the polar functional group is at least one selected from compounds represented by the following formulas (10) to (14) It is preferable.

According to another embodiment of the present invention, a hetero atom in which the metal is Pd, p = 2 and directly coordinated to the metal in the procatalyst represented by Chemical Formula 1 in the method for preparing the cyclic olefin polymer including the polar functional group And a ligand comprising acetylacetonate or acetate, wherein the organophosphorus ligand represented by Formula 2 is represented by the following Formula 10: (3,5-dioxa-4-phospha-cyclohepta [2,1-a; 3,4-a '] dinaphthalen-4-yl) dimethylamine ((3,5-dioxa-4-phospha-cyclohepta [2,1-a; 3,4-a'] dinaphthalen-4-yl) dimethylamine ), [Cat] is N, N-dimethylphenyl ammonium and [Ani] is tetrakispentafluorophenylborate in the cocatalyst represented by the formula (3).

[Formula 10]

According to another embodiment of the present invention, in the method for preparing a cyclic olefin polymer including the polar functional group, the ratio of the organophosphorus ligand to the procatalyst is preferably 0.5 to 10 moles with respect to 1 mole of the procatalyst. .

According to another embodiment of the present invention, in the method for preparing the cyclic olefin polymer including the polar functional group, the ratio of the cocatalyst to the procatalyst is preferably 0.5 to 10 moles with respect to 1 mole of the procatalyst.

According to another embodiment of the present invention, in the method for preparing the cyclic olefin polymer including the polar functional group, the catalyst mixture is preferably supported on the particulate support.

According to another embodiment of the present invention, in the method for preparing a cyclic olefin polymer including the polar functional group, the particulate support is silica, titania, silica / chromia, silica / chromia / titania, silica / alumina, aluminum Preference is given to at least one selected from the group consisting of phosphate gels, silanized silica, silica hydrogels, montmorillonite clays and zeolites.

According to another embodiment of the present invention, in the method for producing a cyclic olefin polymer including the polar functional group, the organic solvent used by dissolving the catalyst mixture is dichloromethane, dichloroethane, toluene, chlorobenzene and mixtures thereof. It is preferably one selected from the group consisting of.

According to another embodiment of the present invention, in the method for preparing the cyclic olefin polymer including the polar functional group, the total amount of the organic solvent in the reaction system is preferably 50 to 800% of the total monomer weight in the monomer solution.

According to another embodiment of the present invention, in the method for preparing a cyclic olefin polymer including the polar functional group, the catalyst mixture preferably includes a metal catalyst complex consisting of the procatalyst, an organophosphorus ligand and a promoter. .

According to another embodiment of the present invention, in the method for preparing the cyclic olefin polymer including the polar functional group, it is preferable that the catalyst mixture is added to the monomer solution in the solid phase.

According to another embodiment of the present invention, in the method for preparing a cyclic olefin polymer including the polar functional group, the catalyst mixture is 1/400 to 1 / 200,000 relative to the total number of moles of monomer in the monomer solution based on the procatalyst component. It is preferable to add to the reaction system in the ratio of.

According to another embodiment of the present invention, in the method for producing a cyclic olefin polymer including the polar functional group, it is preferable that the monomer solution further includes a cyclic olefin compound containing no polar functional group.

According to another embodiment of the present invention, in the method for producing a cyclic olefin polymer including the polar functional group, the cyclic olefin polymer including the polar functional group is a cyclic olefin homopolymer including the polar functional group, It is preferable to include the copolymer of the cyclic olefin monomers containing another polar functional group, or the copolymer of the cyclic olefin monomer containing a polar functional group and the cyclic olefin monomer which does not contain a polar functional group.

According to another embodiment of the present invention, the weight average molecular weight (M _w ) of the cyclic olefin-based polymer including the polar functional group in the method for producing the polar functional group is 10,000 to 1,000,000 desirable.

According to another embodiment of the present invention, it is preferable that the monomer solution further comprises a linear or branched olefin having 1 to 20 carbon atoms in the method for producing a cyclic olefin polymer including the polar functional group.

The present invention to achieve the second technical problem,

As a polymer produced by the method according to the above,

It is an addition polymer of the cyclic olefin monomer containing a polar functional group represented by the following formula (3),

It provides a cyclic olefin polymer comprising a polar functional group, characterized in that the weight average molecular weight (M _w ) is 10,000 to 1,000,000.

[Formula 4]

In Chemical Formula 4,

m, R ₇ , R ₇ ′, R ₇ ″, and R ₇ ″ are the same as above.

The present invention to achieve the third technical problem,

It provides an optically anisotropic film comprising a cyclic olefin polymer containing a polar functional group according to the above.

According to the exemplary embodiment of the present invention, the optically anisotropic film preferably has a thickness retardation value (R _th ) represented by Equation 1 below: 70 to 1,000 nm. For reference, the in-plane retardation value (R _e ) is defined by Equation 2 below:

In Equations 1 and 2,

n _x is the refractive index of the slow axis in plane measured at the wavelength of 550 nm;

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

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

d is the thickness of the film.

According to another embodiment of the present invention, the optically anisotropic film is n _x ≒ n _y > a refractive index between n _z (n _x is a refractive index of a slow axis (slow axis) in a plane; n _y is refractive index of fast axis (fast axis); n _z is the refractive index being in the thickness direction) a negative liquid crystal display to satisfy the It is preferable that it is a negative C-plate type optical compensation film.

The present invention to achieve the fourth technical problem,

A Group 10 metal-containing procatalyst having a ligand comprising a hetero atom that is directly coordinated with the metal represented by Formula 1;

An organophosphorus ligand represented by Formula 2 below; And

A cocatalyst that is a salt compound that weakly coordinates with the Group 10 metal represented by Formula 3 and provides anions;

It provides a catalyst composition for preparing a cyclic olefin-based polymer comprising a polar functional group comprising:

[Formula 1]

In Formula 1, X, R ₁ , R ₂ , M, and p are the same as above,

[Formula 2]

In Formula 2, a, b, c, Z, Z ', Z ", R ₃ , R ₄ And R ₅ is the same as above,

[Formula 3]

In Formula 3, [Cat] and [Ani] are the same as above.

According to one embodiment of the present invention, in the catalyst composition for preparing a cyclic olefin-based polymer including the polar functional group, the borate or aluminate of Formula 3 is preferably composed of an anion represented by the following Formula 3a or 3b:

[Formula 3a]

[Formula 3b]

In Formulas 3a and 3b, M 'and R ₆ are the same as above.

According to another embodiment of the present invention, the procatalyst represented by Formula 1 and the organophosphorus ligand represented by Formula 2 are each represented by Formula 5 in the catalyst composition for preparing a cyclic olefin polymer including the polar functional group. It is preferable that it is a procatalyst, the organophosphorus ligand represented by following formula (6):

[Formula 5]

In Formula 5, X ', Y', R ₁ ', R ₂ ', R ₂ ", R ₂ '", M, r, and s are the same as above;

[Formula 6]

In Formula 6, R ₃ , R ₄ and R ₅ are the same as above.

According to another embodiment of the present invention, the procatalyst represented by Formula 1 and the organophosphorus ligand represented by Formula 2 are each represented by Formula 7 in the catalyst composition for preparing a cyclic olefin polymer including the polar functional group. It is preferred that the Pd metal-containing procatalyst is represented and the organophosphorus ligand represented by the following formula (8) or (9):

[Formula 7]

In Formula 7, R ₁ ′, R ₂ ′, R ₂ ″, and R ₂ ″ are the same as above;

r and s are each independently 0 to 2 and r + s = 2;

[Formula 8]

In Formula 8, R ₂₃ and R ₂₄ are the same as above.

According to another embodiment of the present invention, the organophosphorus ligand represented by Formula 2 in the catalyst composition for preparing a cyclic olefin polymer including the polar functional group is preferably represented by the following Formula 9:

[Formula 9]

In Chemical Formula 9, CY ₁ is a substituted or unsubstituted ring including two O atoms and one P atom, and each of R ₂₃ is independently hydrogen; Linear or branched alkyl of 1 to 20 carbon atoms; Linear or branched allyl having 3 to 20 carbon atoms; Linear or branched alkenyl having 2 to 20 carbon atoms; Linear or branched vinyl of 2 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted with hydrocarbon having 3 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with a hydrocarbon; Aralkyl having 7 to 15 carbon atoms which is unsubstituted or substituted with hydrocarbons; Or alkynyl having 3 to 20 carbon atoms.

In Chemical Formula 9, substituents that may be substituted for CY ₁ include linear or branched alkyl having 1 to 20 carbon atoms; Linear or branched alkoxy of 1 to 20 carbon atoms; Linear or branched allyl having 3 to 20 carbon atoms; Linear or branched alkenyl having 2 to 20 carbon atoms; Linear or branched vinyl of 2 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted with hydrocarbon having 3 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with alkoxy or a hydrocarbon; Aralkyl having 7 to 15 carbon atoms unsubstituted or substituted with alkoxy or a hydrocarbon; Aralkyl substituted with a substituent including a hetero ring; Alkylaryl having 7 to 15 carbon atoms unsubstituted or substituted with alkoxy or a hydrocarbon; Alkylaryl substituted with a substituent including a hetero ring; And alkynyl having 3 to 20 carbon atoms.

According to another embodiment of the present invention, the organophosphorus ligand represented by Formula 2 in the catalyst composition for preparing a cyclic olefin-based polymer including the polar functional group is at least one selected from compounds represented by Formula 10 to Formula 14 It is preferable.

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

According to another embodiment of the present invention, in the catalyst composition for preparing a cyclic olefin polymer including the polar functional group, the metal is Pd, p = 2, and directly coordinated with the metal in the procatalyst represented by Chemical Formula 1 The ligand comprising a hetero atom is acetylacetonate or acetate, and the ligand represented by Formula 2 is represented by the following Formula 10 (3,5-dioxa-4-phospha-cyclohepta [2,1-a ; 3,4-a '] dinaphthalen-4-yl) dimethylamine ((3,5-dioxa-4-phospha-cyclohepta [2,1-a; 3,4-a'] dinaphthalen-4-yl) dimethylamine), [Cat] is N, N-dimethylphenyl ammonium and [Ani] is tetrakispentafluorophenylborate in the first cocatalyst represented by Chemical Formula 3.

[Formula 10]

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The method for producing a cyclic olefin polymer containing a polar functional group according to the present invention can suppress the deactivation of the catalyst by the polar functional group, moisture and oxygen of the monomer, and because of the excellent activity of the catalyst and high stability, A polymer having a molecular weight can be prepared and the amount of catalyst used relative to the monomer can be reduced, so that the step of removing the catalyst residue is not necessary separately.

The arrow in Formula 1 indicates that the ligand is coordinated to the metal.

The present invention provides a method for producing a cyclic olefin polymer containing a polar functional group, comprising: a Group 10 metal-containing procatalyst represented by the following general formula (1); An organophosphorus ligand represented by Formula 2; And a cocatalyst that is a salt compound that weakly coordinates the Group 10 metal represented by Formula 3 and provides anions; contacting the catalyst mixture with a monomer solution comprising a cyclic olefin-based monomer comprising a polar functional group; It provides a method for producing a cyclic olefin-based polymer comprising a polar functional group comprising:

[Formula 1]

In Chemical Formula 1,

Each X is independently a hetero atom selected from S, O and N;

R ₁ are each independently -CH = CHR ²⁰ , -OR ²⁰ , -SR ²⁰ , -N (R ²⁰ ) ₂ , -N = NR ²⁰ , -P (R ²⁰ ) ₂ , -C (O) R ²⁰ , -C (R ²⁰ ) = NR ²⁰ , -C (O) OR ²⁰ , -OC (O) OR ²⁰ , -OC (O) R ²⁰ , -C (R ²⁰ ) = CHC (O) R ²⁰ , -R ²¹ C (O) R ²⁰ , —R ²¹ C (O) OR ²⁰ , or —R ²¹ OC (O) R ²⁰ ; Wherein in R ²⁰ are each independently hydrogen, halogen, linear or branched C 1 -C 5 alkyl, linear or branched having 1-5 carbon atoms in the haloalkyl carbon atoms of 5 to 10 cycloalkyl, straight or branched having 2 to Alkenyl of 5, linear or branched haloalkenyl of 2 to 5 carbon atoms, substituted or unsubstituted aralkyl of 7 to 24 carbon atoms; R ²¹ is hydrocarbylene having 1 to 20 carbon atoms;

R ₂ is each independently linear or branched alkyl having 1 to 20 carbon atoms, linear or branched alkenyl having 2 to 20 carbon atoms, linear or branched vinyl having 2 to 20 carbon atoms, or having 5 to 5 carbon atoms unsubstituted or substituted with a hydrocarbon. Cycloalkyl of 12, aryl having 6 to 40 carbon atoms unsubstituted or substituted with hydrocarbon, aralkyl having 7 to 15 carbon atoms substituted or unsubstituted with hydrocarbon, or alkynyl having 3 to 20 carbon atoms;

M is a Group 10 metal;

p is 0 to 2;

[Formula 2]

In Chemical Formula 2,

a, b and c are integers from 1 to 3;

Z, Z 'and Z "are each independently oxygen, sulfur, silicon, or nitrogen,

Except that Z, Z 'and Z "are the same atom,

R ₃ , R ₄ And R ₅ are each independently hydrogen; Linear or branched alkyl of 1 to 20 carbon atoms; Linear or branched alkoxy of 1 to 20 carbon atoms; Linear or branched allyl having 3 to 20 carbon atoms; Linear or branched alkenyl having 2 to 20 carbon atoms; Linear or branched vinyl of 2 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted with hydrocarbon having 3 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with alkoxy or a hydrocarbon; Aralkyl having 7 to 15 carbon atoms unsubstituted or substituted with alkoxy or a hydrocarbon; Aralkyl substituted with a substituent including a hetero ring; Alkylaryl having 7 to 15 carbon atoms unsubstituted or substituted with alkoxy or a hydrocarbon; Alkylaryl substituted with a substituent including a hetero ring; Alkynyl having 3 to 20 carbon atoms; Silyl, each independently substituted with linear or branched alkyl of 1 to 10 carbon atoms; Silyl independently each substituted with linear or branched alkoxy having 1 to 10 carbon atoms; Silyl each independently substituted with a substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Silyl substituted each independently with substituted or unsubstituted aryl having 6 to 40 carbon atoms; Silyl substituted each independently with substituted or unsubstituted aryloxy having 6 to 40 carbon atoms; Siloxy independently substituted with linear or branched alkyl of 1 to 10 carbon atoms; Siloxy substituted each independently with substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Or siloxy each independently substituted or unsubstituted with aryl having 6 to 40 carbon atoms, wherein each of the substituents is halogen or haloalkyl having 1 to 20 carbon atoms, and R ₄ And R ₅ may be linked to each other to form a ring, in the substituent including the hetero ring, the hetero ring includes both an aromatic or aliphatic ring,

[Formula 3]

In Chemical Formula 3,

[Cat] is a cation and is hydrogen; Cations of Group 1 metals, Group 2 metals, or transition metals; And it is any one selected from the group consisting of organic cations containing these cations,

More specifically, lithium, sodium, potassium, rubidium, or cesium ions are preferred as cations of the Group 1 metal, and particularly preferred are lithium, sodium or potassium ions; As cations of Group 2 metals, beryllium, magnesium, calcium, strontium or barium ions are preferred, and magnesium, calcium, strontium or barium ions are particularly preferred; As the cation of the transition metal, zinc, silver or thallium ions are preferable; As an organic group containing a cation, ammonium, phosphonium, carbonium, or a silyllium cation is preferable.

As an organic group containing a cation, for example, [NHR ¹⁵ ₃ ] ⁺ , [NR ¹⁵ ₃ ] ⁺ , [PHR ¹⁵ ₃ ] ⁺ , [PR ¹⁵ ₃ ] ⁺ , [CR ¹⁵ ₃ ] ⁺ , [SiR ¹⁵ _3] ^{+ And} the like, wherein R ¹⁵ is each independently a hydrocarbyl, silylhydrocarbyl, or perfluorocarbyl group, each of which is 1 to 24 carbon atoms connected in a linear, branched or cyclic manner; And more preferably 1 to 12 carbon atoms connected in a linear, branched or cyclic fashion. Each R ¹⁵ in the organic group containing the cation may be the same as or different from each other.

A perfluorocarbyl group means a functional group in which all hydrogen atoms connected to carbon are substituted with fluorine atoms. Hydrocarbyl groups have the same meaning as hydrocarbons. The silylhydrocarbyl group means a functional group to which a silyl group is linked to a hydrocarbon group.

Representative hydrocarbyl groups or hydrocarbon groups are linear or branched alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Linear or branched alkenyl having 2 to 20 carbon atoms; Cycloalkenyl having 3 to 20 carbon atoms; Aryl having 6 to 24 carbon atoms; Or arylalkyl having 7 to 24 carbon atoms, but not limited thereto, and all substituents usable in the art are possible.

[Ani] is an anion that can be weakly coordinated with the metal M of Chemical Formula 1, and includes borate, aluminate, [SbF ₆ ]-, [PF ₆ ]-, [AsF ₆ ]-, and 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-CH ₃ C ₆ H ₄ SO ₃ ]-), [SO ₃ CF ₃ ]-, borabenzene, and halogen It is any one selected from the group consisting of substituted or unsubstituted carborane.

In the preparation method, the procatalyst is highly stable against a monomer having a polar reactor, moisture, oxygen, etc., and the organophosphorus ligand and the cocatalyst react with the Group 10 metal procatalyst to activate the procatalyst as a cationic catalyst, and The organophosphorus ligand stabilizes the cationic form of the catalyst to prevent inactivation of the catalyst by polar groups, moisture and oxygen of the polar monomer.

According to one embodiment of the present invention, in the method for preparing the cyclic olefin polymer including the polar functional group, the step of contacting the catalyst mixture with the monomer solution containing the cyclic olefin monomer including the polar functional group is 80 ° C. It is preferable to carry out at -150 degreeC.

In more detail with regard to the limitation of the reaction temperature, in the case of a general organometallic polymerization catalyst, the polymerization yield increases when the polymerization temperature is increased, while the molecular weight of the polymer decreases or the catalyst is pyrolyzed to show no polymerization activity. (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 ). As the polymerization temperature increases, the molecular weight decreases 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.

In contrast, the polar functional group of the norbornene monomer interacts with the cationic catalyst at room temperature, thereby blocking the catalytic active site inserted by the double bond of norbornene, resulting in lower polymerization yield and molecular weight. In the case of hydrogen placed at the β-position of the norbornene polymer, it 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 the molecular weight increases because β-hydrogen is difficult to move to the catalyst ( Kaminsky et al. Macromol. Symp. 1995, vol 97, 225). Therefore, although it is necessary to raise the polymerization temperature, catalysts used in the production of norbornene polymers containing polar functional groups known in the art are mostly thermally decomposed when the polymerization temperature is raised above 80 ° C. to obtain high molecular weight polymers. Could not. However, in the case of the catalyst used in the present invention, it is thermally stable so as not to decompose at a temperature of 80 ° C. or higher, thereby preventing the interaction between the polar functional group of the norbornene monomer and the cationic catalyst at a high temperature, thereby forming a catalytically active site. As a result, the cyclic olefin polymer containing a high molecular weight polar functional group can be produced in high yield. On the other hand, when the polymerization temperature exceeds 150 ° C, the catalyst component is thermally decomposed to lower the activity, making it difficult to produce a cyclic olefin polymer containing a high molecular weight polar functional group.

In addition, the organophosphorus ligand in the catalyst constituents used in the present invention has excellent stability even in the presence of polar functional groups, moisture, oxygen and other impurities as described above. Therefore, unlike conventional organophosphorus ligands (e.g., trialkyl phosphine compounds) that have excellent activity only when used in an in-situ air-blocking atmosphere, they can be stored in solution for a long time and the solvent is purified. Is not required and its activity remains intact even when exposed to air. Therefore, the production method of the present invention can be used flexibly in various production environments, which is particularly important for industrial mass production.

That is, the production method of the present invention, a Group 10 metal-containing procatalyst represented by the formula (1); The catalyst mixture consisting of the organophosphorus ligand represented by the formula (2) and the cocatalyst of the salt compound represented by the formula (3) is contacted with a monomer solution containing a cyclic olefin monomer containing a polar functional group at 80 ℃ to 150 ℃ It is characterized by high thermal activity without loss of stability even when exposed to polar functional groups, moisture and oxygen without pyrolysis.

In the preparation method of the present invention, the borate or aluminate of the formula (3) is preferably composed of an anion represented by the following formula (3a) or (3b):

[Formula 3a]

[Formula 3b]

In Chemical Formulas 3a and 3b,

M 'is boron or aluminum;

Each R ₆ is independently halogen; Linear or branched alkyl of 1 to 20 carbon atoms unsubstituted or substituted with halogen; Linear or branched alkenyl of 2 to 20 carbon atoms unsubstituted or substituted with halogen; Cycloalkyl substituted or unsubstituted with 3 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with a hydrocarbon; Aryl having 6 to 40 carbon atoms substituted with linear or branched trialkylsiloxy having 3 to 20 carbon atoms or linear or branched triarylsiloxy having 18 to 48 carbon atoms; Or aralkyl having 7 to 15 carbon atoms which is unsubstituted or substituted with halogen.

In the production method of the present invention, the cyclic olefin monomer is preferably a compound represented by the following general formula (4):

[Formula 4]

In Chemical Formula 4,

m is an integer from 0 to 4;

At least one of R ₇ , R ₇ ′, R ₇ ″, and R ₇ ″ represents a polar functional group and the rest are nonpolar functional groups;

R ₇ , R ₇ ′, R ₇ ″, and R ₇ ″ are the same as or different from each other, and each independently hydrogen; halogen; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkyl having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenyl of 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynyl having 3 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkyl having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy Aryl having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or a polar group comprising at least one of oxygen, nitrogen, phosphorus, sulfur, silicon, and boron;

R ₇ and R ₇ ′, or R ₇ ″ and R ₇ ″ are connected to each other to form an alkylidene group having 1 to 10 carbon atoms, or R ₇ or R ₇ ′ is selected from R ₇ ″ and R ₇ ″ May be linked to any one of a saturated or unsaturated aliphatic ring having 4 to 12 carbon atoms, or an aromatic ring having 6 to 24 carbon atoms,

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The polar functional group is -R ₈ OR ₉ , -OR ₉ , -OC (O) OR ₉ , -R ₅ OC (O) OR ₉ , -C (O) OR ₉ , -R ₈ C (O) OR ₉ , -C (O) R ₉ , -R ₈ C (O) R ₉ , -OC (O) R ₉ , -R ₈ OC (O) R ₉ ,-(R ₈ O) _n -OR ₉ ,-(OR ₈ ) _n -OR ₉ , -C (O) -OC (O) R ₉ , -R ₈ C (O) -OC (O) R ₉ , -SR ₉ , -R ₈ SR ₉ , -SSR ₉ ,- R ₈ SSR ₉ , -S (= O) R ₉ , -R ₈ S (= O) R ₉ , -R ₈ C (= S) R _9- , -R ₈ C (= S) SR ₉ , -R ₈ SO ₃ R ₉ , -SO ₃ R ₉ , -R ₈ N = C = S, -N = C = S, -NCO, -R ₈ -NCO, -CN, -R ₈ CN, -NNC (= S ) R ₉ , -R ₈ NNC (= S) R ₉ , -NO ₂ , -R ₈ NO ₂ ,

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Is;

In the polar functional group,

R ₈ is the same as or different from each other, and each independently halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, Linear or branched alkylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from carbonyloxy, halocarbonyloxy, aryloxy, haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenylene having 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynylene having 3 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkylene having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Arylene having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Alkoxylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy , Carbonyloxyylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy,

R ₉ , R ₁₀ and R ₁₁ are the same as or different from each other, and each independently hydrogen; halogen; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkyl having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenyl of 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynyl having 3 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkyl having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy Aryl having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Alkoxy having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy , Carbonyloxy of 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy,

n is each independently an integer of 1 to 10.

In the preparation method of the present invention, it is preferable that the procatalyst represented by Chemical Formula 1, the organophosphorus ligand represented by Chemical Formula 2, are the procatalyst represented by Chemical Formula 5, and the organic phosphorus ligand represented by Chemical Formula 6, respectively:

[Formula 5]

In Chemical Formula 5,

X 'and Y' are each independently a hetero atom selected from S and O;

R ₁ ′, R ₂ ′, R ₂ ″, and R ₂ ″ are each independently linear or branched alkyl having 1 to 20 carbon atoms; Linear or branched alkenyl having 2 to 20 carbon atoms; Linear or branched vinyl of 2 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted with hydrocarbon having 5 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with a hydrocarbon; Aralkyl having 7 to 15 carbon atoms which is unsubstituted or substituted with hydrocarbons; Or alkynyl having 3 to 20 carbon atoms;

M is a Group 10 metal;

r and s are each independently 0 to 2 and r + s = 2;

[Formula 6]

In Chemical Formula 6,

R ₃ , R ₄ and R ₅ are the same as defined in the formula (2).

In the preparation method of the present invention, the procatalyst represented by Chemical Formula 1 and the organophosphorus ligand represented by Chemical Formula 2 may be represented by Chemical Formula 7, respectively. More preferably, it is a Pd metal-containing procatalyst represented and an organophosphorus ligand represented by the following formula (8):

[Formula 7]

In Formula 7, R ₁ ′, R ₂ ′, R ₂ ″, and R ₂ ″ are the same as above;

r and s are each independently 0 to 2 and r + s = 2;

[Formula 8]

In Chemical Formula 8,

R ₂₃ and R ₂₄ are each independently hydrogen; Linear or branched alkyl of 1 to 20 carbon atoms; Linear or branched allyl having 3 to 20 carbon atoms; Linear or branched alkenyl having 2 to 20 carbon atoms; Linear or branched vinyl of 2 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted with hydrocarbon having 3 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with alkoxy or a hydrocarbon; Aralkyl having 7 to 15 carbon atoms which is unsubstituted or substituted with hydrocarbons; Alkylaryl unsubstituted or substituted with alkoxy or hydrocarbon; Alkylaryl substituted with a substituent including an aliphatic hetero ring; Or alkynyl having 3 to 20 carbon atoms, and the two R ₂₄ may be connected to each other to form a ring.

When the two R ₂₄ are connected to each other to form a ring in the method of preparing a cyclic olefin polymer including the polar functional group, Chemical Formula 8 may be represented by the following Chemical Formula 9.

[Formula 9]

In Chemical Formula 9,

CY ₁ is a substituted or unsubstituted ring containing two O atoms and one P atom, and each of R ₂₃ is independently hydrogen; Linear or branched alkyl of 1 to 20 carbon atoms; Linear or branched allyl having 3 to 20 carbon atoms; Linear or branched alkenyl having 2 to 20 carbon atoms; Linear or branched vinyl of 2 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted with hydrocarbon having 3 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with a hydrocarbon; Aralkyl having 7 to 15 carbon atoms which is unsubstituted or substituted with hydrocarbons; Or alkynyl having 3 to 20 carbon atoms.

In Chemical Formula 9, substituents that may be substituted for CY ₁ include linear or branched alkyl having 1 to 20 carbon atoms; Linear or branched alkoxy of 1 to 20 carbon atoms; Linear or branched allyl having 3 to 20 carbon atoms; Linear or branched alkenyl having 2 to 20 carbon atoms; Linear or branched vinyl of 2 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted with hydrocarbon having 3 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with alkoxy or a hydrocarbon; Aralkyl having 7 to 15 carbon atoms unsubstituted or substituted with alkoxy or a hydrocarbon; Aralkyl substituted with a substituent including a hetero ring; Alkylaryl having 7 to 15 carbon atoms unsubstituted or substituted with alkoxy or a hydrocarbon; Alkylaryl substituted with a substituent including a hetero ring; And alkynyl having 3 to 20 carbon atoms.

More specifically, the organophosphorus ligand represented by Formula 2 in the method for preparing the cyclic olefin polymer including the polar functional group is preferably a compound represented by the following Formula 10 to Formula 14, but is not necessarily limited thereto. .

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

In the preparation method of the present invention, in the procatalyst represented by Chemical Formula 1, the metal is Pd, p = 2, and a ligand including a hetero atom that is directly coordinated with the metal is acetylacetonate or acetate. The ligand represented is (3,5-dioxa-4-phospha-cyclohepta [2,1-a; 3,4-a '] dinaphthalen-4-yl) dimethylamine (( 3,5-dioxa-4-phospha-cyclohepta [2,1-a; 3,4-a '] dinaphthalen-4-yl) dimethylamine) and [Cat] in the first promoter represented by Chemical Formula 3 N, N-dimethylphenyl ammonium, and [Ani] is preferably tetrakispentafluorophenylborate.

[Formula 10]

The organophosphorus ligand used in the production method of the present invention has an electronic stabilizing ability and serves to thermally and chemically activate the transition metal compound. The ratio of the organophosphorus ligand to the procatalyst containing the Group 10 transition metal used in the method for preparing a cyclic olefin polymer including the polar functional group of the present invention may be 0.5 to 10 moles with respect to 1 mole of the procatalyst, If the number of moles of the organophosphorus ligand is less than 0.5 mole, the activation effect of the procatalyst is weak, and when it exceeds 10 moles, the molecular weight decreases, which is not preferable.

Salt compounds used as cocatalysts in the production process of the present invention have the ability to activate the procatalyst with a cationic form of catalyst. The ratio of the cocatalyst to the procatalyst containing the transition metal of Group 10 used in the method for preparing a cyclic olefin-based polymer including the polar functional group of the present invention may be 0.5 to 10 moles with respect to 1 mole of the procatalyst. When the mole number of the cocatalyst is less than 0.5 mole, the activation effect of the procatalyst is weak, and when it exceeds 10 moles, the polymer is discolored.

The catalyst mixture consisting of the procatalyst, the organophosphorus ligand and the cocatalyst used in the present invention may be supported on a particulate support, and the particulate support may be silica, titania, silica / chromia, silica / chromia / titania, Silica / alumina, aluminum phosphate gel, silanized silica, silica hydrogel, montmorillonite clay or zeolite. Thus, when used by being supported on the particulate support, there is an advantage that the molecular weight distribution can be adjusted according to the use, and the apparent density of the obtained polymer can be improved.

The catalyst mixture used in the present invention may be added directly into a solid phase without using a solvent, but may be added after preparing an activated catalyst solution by mixing them on a solvent. The procatalyst, an organic phosphorus ligand and a crude The catalyst may be dissolved in a separate solution and added during polymerization. Solvents that can be used when dissolving the catalyst mixture in a solvent include dichloromethane, dichloroethane, toluene, chlorobenzene or mixtures thereof.

In the present invention, the total amount of the organic solvent in the reaction system may be 50% to 800% with respect to the total monomer weight in the monomer solution, preferably 50% to 400%, when less than 50%, the solution viscosity is too high during the polymerization reaction. It is difficult to stir and the unreacted monomers remain, which lowers the polymerization yield, and the viscosity is so high that an excessive amount of solvent is required to dilute the solution, which causes a problem of commercialization. Both yield and molecular weight tend to decrease.

The catalyst mixture used in the present invention may be a metal catalyst complex composed of the procatalyst, the organophosphorus ligand and the cocatalyst, and the amount of the catalyst mixture is 1 / to the total number of moles of the monomer in the monomer solution based on the procatalyst component. It may be in the range of 400 to 1 / 200,000. That is, it is possible to polymerize norbornene-based monomers containing polar functional groups in high yield while using a much smaller amount of catalyst than conventional catalyst systems. The amount used is more preferably 1/500 to 1 / 20,000, most preferably 1 / 5,000 to 1 / 15,000.

If the molar ratio of the procatalyst to the monomer exceeds 1/400, there is a problem in catalyst removal, and if it is less than 1 / 200,000, there is a problem of low polymerization activity.

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 containing a polar group is an endo, It consists of an exo isomer mixture and the composition ratio of the mixture is irrelevant. In the method of the present invention, the monomer solution may further include a cyclic olefin containing no polar functional group.

In this case, the cyclic olefin-based addition polymer including the polar functional group of the present invention may be polymerized by addition polymerization of norbornene-based monomers including at least one polar functional group in the presence of the catalyst system described above, or different polar functional groups may be used. Addition or polymerization of norbornene-based monomers comprising a bi- or terpolymer copolymer consisting of norbornene-based monomers containing a polar functional group, or addition of norbornene-based monomers containing a polar functional group and norbornene not containing a polar functional group The polymerization may be carried out to copolymerize to prepare a binary or terpolymer.

The addition polymerization of the present invention is carried out by dissolving or mixing a norbornene-based monomer and a catalyst in a solvent, as in a conventional method for polymerizing norbornene-based polymers. 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% or more, and the molecular weight (M _w ) of the prepared addition polymer is high molecular weight of at least 10,000 to 1,000,000. Can have In addition, the molecular weight is preferably adjusted to 100,000 to 1,000,000 if the production of an optical film using an addition polymer. In order to control the molecular weight, it may further include linear or branched, cyclic olefins having 1 to 20 carbon atoms. Specifically, examples of the olefin include 1-hexene, 1-octene, cyclopentene, ethylene and the like. These olefins are inserted at the growing polymer chain ends, and a polymer chain having a desired molecular weight is formed by a reaction in which the hydrogen at the β-position of the inserted olefin is easily removed.

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

The norbornene-based polymer comprising a polar functional group prepared according to the production method of the present invention is an addition homopolymer only of the cyclic olefin-based monomer including the polar functional group represented by Formula 4, or a ring including two or more polar functional groups. It may be an addition copolymer of type olefinic monomers, and may further include other olefinic monomers.

The present invention provides a cyclic olefinic polymer comprising a polar functional group. Preferably, the norbornene-based polymer comprising a polar functional group prepared according to the production method of the present invention is an addition polymer of the cyclic olefin-based monomer including the polar functional group represented by the formula (4), the weight average molecular weight (M _w Is a cyclic olefin polymer comprising polar functional groups having from 10,000 to 1,000,000.

When the weight average molecular weight is less than 10,000, there is a problem that the film is brittle when manufacturing the film, and when the molecular weight is more than 1,000,000, it is difficult to dissolve in an organic solvent and the workability is poor.

The polymer is a cyclic olefin polymer which 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, etc., and has excellent thermal stability and strength. In addition, the polymer may be attached to a substrate of an electronic material without a coupling agent, and may be attached to a metal substrate such as copper, silver, or gold, a protective film of a polarizing plate, or the like. The optical property is excellent enough to be used as, and can be used for electronic materials such as integrated circuits, printed circuit boards, or multichip modules.

The present invention can be produced using an optically anisotropic film that can control the birefringence (birefringence) that could not be conventionally manufactured using the polymer.

Conformational units of common cyclic olefins have one or two stable rotational states, which can lead to extended forms such as polyimide backed by a rigid phenyl ring. When a polar group is introduced into a norbornene-based polymer having such an extended form, the interaction between molecules is increased by introducing a polar group than a polymer having a compact form, and thus a directional order for packing between molecules. ) And may be optically and electrically anisotropic.

The birefringence may be adjusted according to the type and content of the polar functional group 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 manufactured, and thus an optical compensation film for liquid crystal display (LCD) in various modes. It can be prepared by.

The optically anisotropic film can be prepared in the form of a film or a sheet by dissolving the cyclic olefin-based addition polymer containing the polar functional group according to the present invention in a solvent, a solvent casting method, blend of one or more of these cyclic olefin-based polymer It is also possible to produce a film from the film.

The method for preparing a film by dissolving the cyclic olefin additive polymer in a solvent is performed 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 10,000 cps for solvent casting, more preferably 300 to 8,000 cps. In the manufacture of the film, a plasticizer, a deterioration-preventing agent, a UV stabilizer, or an antistatic agent is used to improve the mechanical strength, heat resistance, light resistance, and handling properties of the film. additives such as agents) may be added.

The film thus prepared has an optically anisotropic film characteristic of thickness direction retardation value (R _th ) represented by Equation 1 below 70 to 1,000 nm. For reference, the in-plane retardation value (R _e ) is defined by Equation 2 below:

[Equation 1]

[Equation 2]

In Equations 1 and 2, n _x is a refractive index of a slow axis in a plane measured at 550 nm; n _y is the refractive index of the fast axis in plane measured at wavelength 550 nm; n _z is a 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 relationship in which the refractive index of the film is n _x ≒ n _y > n _z (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 a 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 in various modes.

In addition, the present invention is a Group 10 metal-containing procatalyst having a ligand containing a hetero atom that is directly coordinated to the metal represented by the formula (1); An organophosphorus ligand represented by Formula 2; It provides a catalyst composition for producing a cyclic olefin-based polymer comprising a polar functional group comprising; and a cocatalyst that is weakly coordinated with the Group 10 metal represented by the formula (3) and provides an anion.

In the catalyst composition, the borate or aluminate of Chemical Formula 3 is preferably composed of an anion represented by Chemical Formula 3a or Chemical Formula 3b.

Meanwhile, in the catalyst composition for preparing a cyclic olefin polymer including the polar functional group, the procatalyst represented by Chemical Formula 1 and the organophosphorus ligand represented by Chemical Formula 2 may be represented by Chemical Formula 5, respectively. More preferably, the organophosphorus ligand represented is

In the catalyst composition for preparing the cyclic olefin polymer including the polar functional group, the procatalyst represented by Formula 1 and the organophosphorus ligand represented by Formula 2 are represented by Formula 7, respectively. Even more preferred are the Pd metal-containing procatalyst represented and the organophosphorus ligand represented by the formula (8). In addition, the organophosphorus ligand represented by Formula 2 is preferably an organophosphorus ligand represented by Formula 9.

In particular, the organophosphorus ligand represented by Formula 2 is preferably an organophosphorus compound represented by Formula 10 to Formula 14.

More specifically, in the catalyst composition for producing a cyclic olefin polymer containing the polar functional group, a hetero atom in which the metal is Pd, p = 2, and is directly coordinated with the metal in the procatalyst represented by the formula (1) The ligand is acetylacetonate or acetate, and the organophosphorus ligand represented by Formula 2 is represented by Formula 10 (3,5-dioxa-4-phospha-cyclohepta [2,1-a; 3). , 4-a '] dinaphthalen-4-yl) dimethylamine ((3,5-dioxa-4-phospha-cyclohepta [2,1-a; 3,4-a'] dinaphthalen-4-yl) dimethylamine) In the first cocatalyst represented by Chemical Formula 3, [Cat] is preferably N, N-dimethylphenyl ammonium, and [Ani] is tetrakispentafluorophenylborate.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments, but the present invention is not limited thereto.

In the following preparations and examples, all operations dealing with air or water sensitive compounds were carried out using standard Schlenk technique or dry box technology. 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), and 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 sodium / benzophenone and dichloromethane was used by distillation purification in CaH ₂ .

<Production of Monomer Having Polar Functional Group>

< Production Example  1> 5- Norborneen -2- methyl  Preparation of Acetate

DCPD (Aldrich, 248ml, 1.852mol), allyl acetate (Aldrich, 500ml, 4.63mol) and hydroquinone (0.7g, 0.006mol) were added to a 2L high pressure reactor and the temperature was raised to 190 ° C. The reaction was carried out for 5 hours while stirring at 300 rpm, and when finished, the reaction was cooled and transferred to a distillation apparatus. Vacuum distillation was carried out in 1 torr using a vacuum pump to obtain a product at 56 ° C. (yield: 30%, exo / endo = 57/43).

1 H-NMR (300 MHz, CDCl ₃ ): δ 6.17 to 5.91 (m, 2H), 4.15 to 3.63 (m, 2H), 2.91 to 2.88 (m, 2H), 2.38 (m, 1H), 2.05 (s, 3H ), 1.83 (m, 1H), 1.60-1.25 (m, 2H), 0.57 (m, 1H).

<Production of Additive Polymer>

< Example  1> 5- Norborneen -2- methyl  Polymerization of acetate ( Phosphoramidite  Compound A)

Dissolving 79.2mg (0.0988mmol 2eq.) In dichloromethane ^{_{2ml - Pd (OAc) 2 33.3mg}} (. 0.0494mmol, 1eq) and _{[C 6 H 5 NMe 2 H} ] + [B (C 6 F 5) 4] 90 ° C containing 4 ml of 2-norbornene-2-methyl acetate (NB-CH ₂ -O- C (O) -CH ₃ ) (24.7 mmol, AANB / Pd = 500/1) and 8 ml of toluene Into a 100 ml Schlenk flask. Then, (3,5-dioxa-4-phospha-cyclohepta [2,1-a; 3,4-a '] dinaphthalen-4-yl) dimethylamine (( 3,5-Dioxa-4-phospha-cyclohepta [2,1-a; 3,4-a '] dinaphthalen-4-yl) dimethylamine) 17.8 mg (0.0494 mmol, 1eq., Phosphoramidite compound A) 2 ml of this dissolved dichloromethane was added to a Schlenk flask. Then, the mixture was stirred for 16 hours while maintaining at 90 ° C. The polymerization solution was then added to excess ethanol to yield 2.86 g of polymer (yield 70%). The weight average molecular weight (M _w ) of this polymer was 129,500, and Mw / Mn was 1.39.

< Example  2> 5- Norborneen -2- methyl  Polymerization of acetate ( Phosphoramidite  Compound B)

In a 100 ml Schlenk flask, 4 ml of 5-norbornene-2-methyl acetate (NB-CH ₂ -OC (O) -CH ₃ ) (24.7 mmol, monomer / Pd = 500/1) and 12 ml of toluene were added. Then _{Pd (OAc) 2 33.3mg (.} 0.0494mmol, 1eq) and _{[C 6 H 5 NMe 2 H} ] + [B (C 6 F 5) 4] - dichloromethane is dissolved 79.2 mg (0.0988mmol 2eq.) 2 ml of methane solution was added. Stirring was carried out while raising the temperature of the Schlenk flask to 90 ° C. 0.16 ml of dibenzyl diisopropylphosphoramidite (phosphoamidite compound B) exposed to air was dissolved in 10 ml of dichloromethane, and only 1 ml was taken out (0.016 ml, 0.0494). mmol, 1eq.) into the flask. Then, the mixture was stirred for 16 hours while maintaining at 90 ° C. After cooling to room temperature, the polymerization solution was added to excess ethanol to give 2.13 g (52%) of product. The weight average molecular weight of the polymer (M _w) was 139,800, Mw / Mn was 1.91.

< Example  3> 5- Norborneen -2- methyl  Polymerization of acetate ( Phosphoramidite  Compound C)

5-norbornene-2-methyl acetate (NB-CH ₂ -OC (O) -CH ₃ ) (4 mL, 24.7 mmol, NB is norbornene) and toluene (12 mL) were added to a 100 mL Schlenk flask. It was. Palladium Acetate (Pd (OAc) ₂ ) (OAc = acetate, 33.3 mg, 49.4 μmol) and N, N-dimethylphenylammonium (tetrakispentafluorophenyl) borate ([C ₆ H ₅ N (CH ₃ ) ₂ H ] [B (C ₆ F ₅ ) ₄ ]) (79.2mg, 98.8μmol) was added 2mL of dichloromethane to dissolve and then added to the monomer solution. The reaction temperature was raised to 90 ° C. and stirred. 0.16 ml of di-tert-butyl-N, N-diisopropylamidite (phosphoamidite compound C) exposed to air Was dissolved in 10 ml of dichloromethane, and 1 ml of this was added (Di-tert-butyl N, N-diisopropylphosphoramidite 0.016 ml, 49.4 μmol) to a monomer solution. Subsequently, the reaction temperature was stirred at 90 ° C. for 16 hours. After the reaction was cooled down to room temperature, 100 mL toluene was added to dilute the polymer solution having a high viscosity, and this 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 3.28 g of 5-norbornene-2-methyl acetate polymer (80 wt% based on the charged monomer). The weight average molecular weight of the polymer (M _w) was 107,300, Mw / Mn was 1.72.

< Example  4> 5- Norborneen -2- methyl  Polymerization of acetate ( Phosphoramidite  Compound D)

Instead of 17.8 mg of (3,5-Dioxa-4-phospha-cyclohepta [2,1-a; 3,4-a '] dinaphthalen-4-yl) dimethylamine (phosphoamidite compound A) of Example 1 (3,5-Dioxa-4-phospha-cyclohepta [2,1-a; 3,4-a '] dinaphthalen-4-yl) [1-phenylethyl] amine ((3,5-Dioxa 4-phospha-cyclohepta [2,1-a; 3,4-a '] dinaphthalen-4-yl) [1-phenylethyl] amine) (phosphoamidite compound D) 21.5 mg (0.0494 mmol, 1eq. Was carried out in the same manner as in Example 1 except that was used. As a result, 2.92 g of 5-norbornene-2-methyl acetate polymer (71 wt% based on the charged monomers) was obtained. The weight average molecular weight (M _w ) of this polymer was 170,700 and Mw / Mn was 1.61.

< Example  5> 5- Norborneen -2- methyl  Polymerization of acetate ( Phosphoramidite  Compound E)

N, N-dimethyl-4,6-diphenyl-1,3,2-dioxaphosphorin-2-amine (N, N) of formula 13 in place of 17.8 mg of phosphoramidite compound A of Example 1 Same method as Example 1 except using 14.9 mg (0.0494 mmol, 1eq.) of -dimethyl-4,6-diphenyl-1,3,2-dioxaphophorinan-2-amine (phosphoamidite compound E) As a result, 2.84 g of 5-norbornene-2-methyl acetate polymer (69 wt% based on the charged monomers) was obtained, and the weight average molecular weight (M _w ) of the polymer was 143,000 and Mw / Mn was 1.89. .

< Example  6> 2-butyl-5- Norbornene  polymerization( Phosphoramidite  Compound F)

In a 100 ml Schlenk flask, 4 ml of 2-butyl-5-norbornene (23.2 mmol, monomer / Pd = 1,000 / 1) and 12 ml of toluene were added, and the temperature of the Schlenk flask was maintained at 70 ° C. Then _{Pd (OAc) 2 15.6mg (.} 0.0232mmol, 1eq) and _{[C 6 H 5 NMe 2 H} ] + [B (C 6 F 5) 4] - methylene dissolved the (2eq 0.0464mmol.) 37.2 mg 2 ml of chloride solution was added. Then (3,5-dioxa-4-phospha-cyclohepta [2,1-a; 3,4-a '] dinaphthalen-4-yl) bis [1-phenylethyl in the state of being exposed to air ] Amine ((3,5-dioxa-4-phospha-cyclohepta [2,1-a; 3,4-a '] dinaphthalen-4-yl) bis [1-phenylethyl] amine) (phosphoamidite compound F) 12.5 mg (0.0232 mmol, 1 eq.) Was dissolved in 1 ml of methylene chloride and placed in a flask. Stirring was carried out for 16 hours while maintaining the temperature of the Schlenk flask at 70 ° C. After the temperature was lowered to room temperature, the solution in the flask was slowly added to the excess ethanol to obtain 0.46 g (13%) of the polymer. The weight average molecular weight (M _w ) of this polymer was 36,000, and Mw / Mn was 1.29.

< Example  7> 2-butyl-5- Norbornene  polymerization( Phosphoramidite  Compound G)

2,2-dimethyl-4,4,8,8-tetraphenyl-tetrahydro- [1,3] dioxolo [4,5-e] [instead of 12.5 mg of the phosphoramidite compound F of Example 6 1,3,2] dioxaphosphine-6-yl) dimethylamine ((2,2-dimethyl-4,4,8,8-tetraphenyl-tetrahydro- [1,3] dioxolo [4,5-e] [1,3,2] dioxaphosphepin-6-yl) dimethylamine) (phosphoamidite compound G) was carried out in the same manner as in Example 6 except that 12.5 mg (0.0232 mmol, 1eq.) Of 1 was used. As a result, 2-butyl-5-norbornene 1.37 g of polymer (39% by weight of injected monomer) were obtained. The weight average molecular weight (M _w ) of this polymer was 37,000, and Mw / Mn was 1.37.

< Example  8> 2-butyl-5- Norbornene  polymerization( Phosphoramidite  Compound H)

2,6-dimethyl-3,5-dioxa-4-phospha-cyclohepta [2,1-a; 3,4-a '] di in place of 12.5 mg of the phosphoramidite compound F of Example 6 Naphthalen-4-yl) dimethylamine ((2,6-dimethyl-3,5-dioxa-4-phospha-cyclohepta [2,1-a; 3,4-a '] dinaphthalen-4-yl) dimethylamine) ( Phosphoramidate compound H) was carried out in the same manner as in Example 6, except that 9.0 mg (0.0232 mmol, 1eq.) Was used. As a result, 2.88 g (83% by weight of the injected monomer) of 2-butyl-5-norbornene polymer was obtained. The weight average molecular weight (M _w ) of this polymer was 78,000, and Mw / Mn was 2.06.

< Example  9> 2-butyl-5- Norbornene  polymerization( Phosphoramidite  Compound I)

(8.9.10,11,12,13,14,15-octahydro-3,5-dioxa-4-phospha-cyclohepta [2, instead of 12.5 mg of the phosphoramidite compound F of Example 6 1-a; 3,4-a '] dinaphthalen-4-yl) dimethylamine ((8.9.10,11,12,13,14,15-octhydro-3,5-dioxa-4-phospha-cyclohepta [ 2,1-a; 3,4-a '] dinaphthalen-4-yl) dimethylamine) (phosphoamidite compound I) Same as Example 6 except that 8.5 mg (0.0232 mmol, 1eq.) Was used. It was carried out by the method. As a result, 1.7 g of the 2-butyl-5-norbornene polymer was obtained (49% by weight of the injected monomer). The weight average molecular weight (M _w ) of this polymer was 226,000, and Mw / Mn was 2.10.

< Example  10> 5- Norborneen -2- Carboxylic acid methyl  Polymerization of esters ( Phosphoramidite  Compound A)

Dissolving 79.2mg (0.0988mmol 2eq.) In dichloromethane ^{_{2ml - Pd (OAc) 2 33.3mg}} (. 0.0494mmol, 1eq) and _{[C 6 H 5 NMe 2 H} ] + [B (C 6 F 5) 4] 3.76 g (24.7 mmol, monomer / Pd = 500/1) of 5-norbornene-2-carboxylic acid methyl ester (NB-CH ₂ -C (O) -O-CH ₃ ) and 8 ml of toluene Into a 100 ml Schlenk flask at 90 ° C. Then, (3,5-dioxa-4-phospha-cyclohepta [2,1-a; 3,4-a '] dinaphthalen-4-yl) dimethylamine (( 3,5-Dioxa-4-phospha-cyclohepta [2,1-a; 3,4-a '] dinaphthalen-4-yl) dimethylamine) 17.8 mg (0.0494 mmol, 1eq., Phosphoramidite compound A) 2 ml of this dissolved dichloromethane was added to a Schlenk flask. Then, the mixture was stirred for 16 hours while maintaining at 90 ° C. The polymerization solution was then added to excess ethanol to afford 2.74 g of polymer (yield 73%). The weight average molecular weight (M _w ) of this polymer was 89,700 and Mw / Mn was 1.92.

< Comparative example  1> 5- Norborneen -2- methyl  Polymerization of acetate ( Tricyclohexylphosphine )

The same procedure as in Example 1 was carried out except that 13.9 mg of a tricyclohexylphosphine compound exposed to air was used instead of 17.8 mg of phosphoramidite compound A. As a result, 0.73 g of 5-norbornene-2-methyl acetate polymer (18 wt% based on the charged monomers) was obtained. The weight average molecular weight (M _w ) of this polymer was 20,300 and Mw / Mn was 1.68.

< Comparative example  2> 5- Norborneen -2- methyl  Polymerization of acetate ( Triphenylphosphite )

Instead of 17.8 mg of phosphoramidite compound A, triphenylphosphite (P (OC ₆ H ₅ ) ₃ , triphenylphosphite, Z, Z ', and Z "in the above Formula 2 are all oxygen atoms. In the same manner, it was carried out in the same manner as in Example 1, except that 15.3.mg (0.0494 mmol) of the compound was used, as a result, 0.52 g of 5-norbornene-2-methyl acetate polymer (13 wt% based on the monomer injected). ) was thus obtained. this was the 18,900 weight average molecular weight (M _w of the polymer), Mw / Mn was 1.59.

<Optical Anisotropy  Manufacturing of Film>

< Experimental Example  1 to 2

The polymer obtained in Example 1 and Example 2 was mixed as shown in Table 1 below to prepare a coating solution, and the coating solution was cast on a glass substrate using a knife coater or a bar coater, and then 1 hour at room temperature. Dried and dried at 100 ° C. for 18 hours under a nitrogen atmosphere. After drying for 10 seconds after drying, 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 1 below.

In Table 1 above, THF is tetrahydrofuran and MC is methylene chloride.

<Optical Anisotropy  Measurement>

< Experimental Example  3 to 4>

The transparent films according to Experimental Examples 1 and 2 were each measured for the refractive index (n) using an Abbe refractometer and manufactured using an automatic birefringence analyzer (Oji scientific instrument; KOBRA-21 ADH). In-plane retardation value (R _e ) to measure the phase difference value (R _θ ) when the angle between the incident light and the film surface is 50 °, the film thickness direction (direction through the film) thickness) and the phase difference value (R _th ) between the in-plane x-axis.

In Equation 3,

θ is the angle of incidence,

θ _f is the refractive angle of the film.

In addition, 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 R _e and R _th values. Table 2 shows (n _x -n _y ), R _θ , R _th , and (n _y -n _z ) of each transparent film.

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, which indicates that R _th of the cyclic olefin film was negative in the thickness direction. (negative birefringence; n _y > n _z ).

According to the olefin polymerization method and the catalyst composition for polymerization according to the present invention, since the deactivation of the catalyst by the polar functional group of the monomer can be suppressed, the polyolefin can be produced with high molecular weight and high polymerization yield of the polymer during polyolefin polymerization. In addition, the cyclic olefin containing a polar functional group is excellent in polymerization reactivity and the activity of the catalyst composition is maintained even under various polymerization conditions, so that it is very easy to apply to a mass production process.

Claims (7)

A Group 10 metal-containing procatalyst having a ligand comprising a hetero atom that is directly coordinated with the metal represented by Formula 1; An organophosphorus ligand represented by Formula 2 below; And A promoter represented by the following formula (3); Catalyst composition for preparing a cyclic olefin polymer comprising a polar functional group comprising: [Formula 1]

In Chemical Formula 1, Each X is independently a hetero atom selected from S, O and N; R ₁ are each independently -CH = CHR ²⁰ , -OR ²⁰ , -SR ²⁰ , -N (R ²⁰ ) ₂ , -N = NR ²⁰ , -P (R ²⁰ ) ₂ , -C (O) R ²⁰ , -C (R ²⁰ ) = NR ²⁰ , -C (O) OR ²⁰ , -OC (O) OR ²⁰ , -OC (O) R ²⁰ , -C (R ²⁰ ) = CHC (O) R ²⁰ , -R ²¹ C (O) R ²⁰ , —R ²¹ C (O) OR ²⁰ , or —R ²¹ OC (O) R ²⁰ ; Wherein in R ²⁰ are each independently hydrogen, halogen, linear or branched C 1 -C 5 alkyl, linear or branched having 1-5 carbon atoms in the haloalkyl carbon atoms of 5 to 10 cycloalkyl, straight or branched having 2 to Alkenyl of 5, linear or branched haloalkenyl of 2 to 5 carbon atoms, substituted or unsubstituted aralkyl of 7 to 24 carbon atoms; R ²¹ is hydrocarbylene having 1 to 20 carbon atoms; R ₂ is each independently linear or branched alkyl having 1 to 20 carbon atoms, linear or branched alkenyl having 2 to 20 carbon atoms, linear or branched vinyl having 2 to 20 carbon atoms, or having 5 to 5 carbon atoms unsubstituted or substituted with a hydrocarbon. Cycloalkyl of 12, aryl having 6 to 40 carbon atoms unsubstituted or substituted with hydrocarbon, aralkyl having 7 to 15 carbon atoms substituted or unsubstituted with hydrocarbon, or alkynyl having 3 to 20 carbon atoms; M is a Group 10 metal; p is 0 to 2; [Formula 2]

In Chemical Formula 2, a, b and c are integers from 1 to 3; Z, Z 'and Z "are each independently oxygen, sulfur, silicon, or nitrogen, Except that Z, Z 'and Z "are the same atom, R ₃ , R ₄ And R ₅ are each independently hydrogen; Linear or branched alkyl of 1 to 20 carbon atoms; Linear or branched alkoxy of 1 to 20 carbon atoms; Linear or branched allyl having 3 to 20 carbon atoms; Linear or branched alkenyl having 2 to 20 carbon atoms; Linear or branched vinyl of 2 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted with hydrocarbon having 3 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with alkoxy or a hydrocarbon; Aralkyl having 7 to 15 carbon atoms unsubstituted or substituted with alkoxy or a hydrocarbon; Aralkyl substituted with a substituent including a hetero ring; Alkylaryl having 7 to 15 carbon atoms unsubstituted or substituted with alkoxy or a hydrocarbon; Alkylaryl substituted with a substituent including a hetero ring; Alkynyl having 3 to 20 carbon atoms; Silyl, each independently substituted with linear or branched alkyl of 1 to 10 carbon atoms; Silyl independently each substituted with linear or branched alkoxy having 1 to 10 carbon atoms; Silyl each independently substituted with a substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Silyl substituted each independently with substituted or unsubstituted aryl having 6 to 40 carbon atoms; Silyl substituted each independently with substituted or unsubstituted aryloxy having 6 to 40 carbon atoms; Siloxy independently substituted with linear or branched alkyl of 1 to 10 carbon atoms; Siloxy substituted each independently with substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Or siloxy each independently substituted or unsubstituted with aryl having 6 to 40 carbon atoms, wherein each of the substituents is halogen or haloalkyl having 1 to 20 carbon atoms, and R ₄ And R ₅ may be linked to each other to form a ring, in the substituent including the hetero ring, the hetero ring includes both an aromatic or aliphatic ring, [Formula 3]

In Chemical Formula 3, [Cat] is a cation and is hydrogen; Cations of Group 1 metals, Group 2 metals, or transition metals; And it is any one selected from the group consisting of organic cations containing these cations, [Ani] is an anion that can be weakly coordinated with the metal M of Chemical Formula 1, and includes borate, aluminate, [SbF ₆ ]-, [PF ₆ ]-, [AsF ₆ ]-, and 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-CH ₃ C ₆ H ₄ SO ₃ ]-), [SO ₃ CF ₃ ]-, borabenzene, and halogen It is any one selected from the group consisting of substituted or unsubstituted carborane. The catalyst composition for preparing a cyclic olefin-based polymer comprising a polar functional group according to claim 1, wherein the borate or aluminate of Formula 3 consists of an anion represented by the following Formula 3a or 3b: [Formula 3a]

[Formula 3b]

In Chemical Formulas 3a and 3b, M 'is boron or aluminum; Each R ₆ is independently halogen; Linear or branched alkyl of 1 to 20 carbon atoms unsubstituted or substituted with halogen; Linear or branched alkenyl of 2 to 20 carbon atoms unsubstituted or substituted with halogen; Cycloalkyl substituted or unsubstituted with 3 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with a hydrocarbon; Aryl having 6 to 40 carbon atoms substituted with linear or branched trialkylsiloxy having 3 to 20 carbon atoms or linear or branched triarylsiloxy having 18 to 48 carbon atoms; Or aralkyl having 7 to 15 carbon atoms which is unsubstituted or substituted with halogen. The polar functional group according to claim 1, wherein the procatalyst represented by Chemical Formula 1, the organophosphorus ligand represented by Chemical Formula 2 is a procatalyst represented by Chemical Formula 5, and an organophosphorus ligand represented by Chemical Formula 6, respectively. Catalyst composition for preparing a cyclic olefin polymer comprising: [Formula 5]

In Chemical Formula 5, X 'and Y' are each independently a hetero atom selected from S and O; R ₁ ′, R ₂ ′, R ₂ ″, and R ₂ ″ are each independently linear or branched alkyl having 1 to 20 carbon atoms; Linear or branched alkenyl having 2 to 20 carbon atoms; Linear or branched vinyl of 2 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted with hydrocarbon having 5 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with a hydrocarbon; Aralkyl having 7 to 15 carbon atoms which is unsubstituted or substituted with hydrocarbons; Or alkynyl having 3 to 20 carbon atoms; M is a Group 10 metal; r and s are each independently 0 to 2 and r + s = 2; [Formula 6]

In Chemical Formula 6, R ₃ , R ₄ And R ₅ are each independently hydrogen; Linear or branched alkyl of 1 to 20 carbon atoms; Linear or branched alkoxy of 1 to 20 carbon atoms; Linear or branched allyl having 3 to 20 carbon atoms; Linear or branched alkenyl having 2 to 20 carbon atoms; Linear or branched vinyl of 2 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted with hydrocarbon having 3 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with alkoxy or a hydrocarbon; Aralkyl having 7 to 15 carbon atoms unsubstituted or substituted with alkoxy or a hydrocarbon; Aralkyl substituted with a substituent including a hetero ring; Alkylaryl having 7 to 15 carbon atoms unsubstituted or substituted with alkoxy or a hydrocarbon; Alkylaryl substituted with a substituent including a hetero ring; Alkynyl having 3 to 20 carbon atoms; Silyl, each independently substituted with linear or branched alkyl of 1 to 10 carbon atoms; Silyl independently each substituted with linear or branched alkoxy having 1 to 10 carbon atoms; Silyl each independently substituted with a substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Silyl substituted each independently with substituted or unsubstituted aryl having 6 to 40 carbon atoms; Silyl substituted each independently with substituted or unsubstituted aryloxy having 6 to 40 carbon atoms; Siloxy independently substituted with linear or branched alkyl of 1 to 10 carbon atoms; Siloxy substituted each independently with substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms; Or siloxy each independently substituted or unsubstituted with aryl having 6 to 40 carbon atoms, wherein each of the substituents is halogen or haloalkyl having 1 to 20 carbon atoms, and R ₄ And R ₅ may be linked to each other to form a ring, and in the substituent including the hetero ring, the hetero ring includes both an aromatic or aliphatic ring. The method according to claim 1, wherein the procatalyst represented by the formula (1) and the organophosphorus ligand represented by the formula (2) are each represented by the formula Catalyst composition for preparing a cyclic olefin-based polymer comprising a polar functional group, characterized in that the Pd metal-containing procatalyst and an organophosphorus ligand represented by the following formula (8): [Formula 7]

In Chemical Formula 7, R ₁ ′, R ₂ ′, R ₂ ″, and R ₂ ″ are each independently linear or branched alkyl having 1 to 20 carbon atoms; Linear or branched alkenyl having 2 to 20 carbon atoms; Linear or branched vinyl of 2 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted with hydrocarbon having 5 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with a hydrocarbon; Aralkyl having 7 to 15 carbon atoms which is unsubstituted or substituted with hydrocarbons; Or alkynyl having 3 to 20 carbon atoms; r and s are each independently 0 to 2 and r + s = 2; [Formula 8]

In Chemical Formula 8, R ₂₃ and R ₂₄ are each independently hydrogen; Linear or branched alkyl of 1 to 20 carbon atoms; Linear or branched allyl having 3 to 20 carbon atoms; Linear or branched alkenyl having 2 to 20 carbon atoms; Linear or branched vinyl of 2 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted with hydrocarbon having 3 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with alkoxy or a hydrocarbon; Aralkyl having 7 to 15 carbon atoms which is unsubstituted or substituted with hydrocarbons; Alkylaryl unsubstituted or substituted with alkoxy or hydrocarbon; Alkylaryl substituted with a substituent including an aliphatic hetero ring; Or alkynyl having 3 to 20 carbon atoms, and the two R ₂₄ may be connected to each other to form a ring. The catalyst composition for preparing a cyclic olefin polymer comprising a polar functional group according to claim 1, wherein the organophosphorus ligand represented by Formula 2 is represented by the following Formula 9. [Formula 9]

In Chemical Formula 9, CY ₁ is a substituted or unsubstituted ring containing two O atoms and one P atom, and each of R ₂₃ is independently hydrogen; Linear or branched alkyl of 1 to 20 carbon atoms; Linear or branched allyl having 3 to 20 carbon atoms; Linear or branched alkenyl having 2 to 20 carbon atoms; Linear or branched vinyl of 2 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted with hydrocarbon having 3 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms unsubstituted or substituted with a hydrocarbon; Aralkyl having 7 to 15 carbon atoms which is unsubstituted or substituted with hydrocarbons; Or alkynyl having 3 to 20 carbon atoms. The catalyst composition for preparing a cyclic olefin polymer comprising a polar functional group according to claim 1, wherein the organophosphorus ligand represented by Formula 2 is represented by any one of the following Formulas 10 to 14. [Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

The organic catalyst of claim 1, wherein in the procatalyst represented by Chemical Formula 1, the metal is Pd, p = 2, and a ligand including a hetero atom that is directly coordinated with the metal is acetylacetonate or acetate, Phosphorus ligand is (3,5-dioxa-4-phospha-cyclohepta [2,1-a; 3,4-a '] dinaphthalen-4-yl) dimethylamine ((3 , 5-dioxa-4-phospha-cyclohepta [2,1-a; 3,4-a '] dinaphthalen-4-yl) dimethylamine), where [Cat] is N in the first promoter represented by Chemical Formula 3 Catalyst composition for preparing a cyclic olefin-based polymer comprising a polar functional group, wherein N-dimethylphenyl ammonium and [Ani] is tetrakispentafluorophenylborate: [Formula 10]