JP2009511731A - Method for producing cyclic olefin polymer - Google Patents

Abstract

A method for producing a cyclic olefin polymer by addition polymerization of a cyclic olefin monomer, a metal catalyst complex represented by the following chemical formula 1, a cyclic olefin monomer represented by the following chemical formula 2, and A method for producing a cyclic olefin-based polymer comprising a step of contacting the olefin polymer.
[M (L ₁ ) _x (L ′ ₂ ) _y (L ₃ ) _z ] _a [Ani] _b (1)
[Wherein M is a Group 10 metal, [M (L ₁ ) _x (L ′ ₂ ) _y (L ₃ ) _z ] is a cationic complex, and L ₁ includes an anionic hydrocarbyl. L ′ ₂ is a neutral ligand, L ₃ is an N-heterocyclic carbene ligand, and [Ani] is an anion that can be weakly coordinated to the metal M. , X is 1 or 2, y is 0 to 4, z is 1 or 2, 2 ≦ x + y + z ≦ 6, a and b are numbers indicating anions that can be weakly coordinated with cations, respectively, It is a number between 1 and 10 showing the charge balance of the catalyst compound, and when a plurality of ligands are present in the complex molecule, they are the same or different from each other]

[In the above formula, m is an integer of 0 to 4, and R ₇ , R ₇ ′, R ₇ ″, and R ₇ ′ ″ each independently represent a polar functional group or a nonpolar functional group. Thereby, even when a cyclic olefin monomer containing a polar functional group is contained, a high-molecular-weight cyclic olefin addition polymer can be produced in a high yield, and the polymer produced by the above method has excellent heat resistance. . ]

Description

  The present invention relates to a method for producing a cyclic olefin polymer using a metal catalyst complex and a polymer produced by the method, and more specifically, a metal having an N-heterocyclic carbene (NHC) as a ligand. The present invention relates to a method for producing a cyclic olefin polymer using a catalyst complex and a polymer produced by the method.

  The cyclic olefin polymer is a polymer composed of a cyclic monomer such as norbornene, which is superior in transparency, heat resistance and chemical resistance compared to existing olefin polymers, and has a birefringence and moisture absorption rate. Such as CD, DVD, plastic optical fiber (POF), capacitor film, information electronic material such as low dielectric material, low water-absorbing syringe, Blister Packaging, etc. Various medical materials can be applied. In particular, polynorbornene has been widely used as an electronic material because it has a high glass transition temperature and a high refractive index as an amorphous polymer, and has a low dielectric constant. [(A) T. has been promoted. F. A. Haselwander, W. Heitz, S.H. A. Krugel, J.A. H. Wendorff, Macromolecules, 1997, 30, 534, (b) T.W. F. A. Haselwander, W. Heitz, S.H. A. Krugel, J.A. H. Wendorff, Macromol. Chem, Phys. 1996, 197, 3435. ].

  Monomeric norbornene is very easy to polymerize because it can be easily polymerized into polymers by various palladium or nickel complexes and co-catalysts [Ni: (a) WO 95 14048 A1 (1995), B.C. F. Goodrich Co. , Invs. : B. L. Goodall, G. M.M. Benedikt, L. H. McIntosh III, D.W. A. Barnes; Chem. Abstr. 1995, 123, 341322p, (b) EP 445755 A2 (1991), IdemitsuKosan Co. Ltd .. , Invs. : H. Maezawa, J.A. Aiura, S.A. Asahi. Chem. Abstr. 1991, 115, 256943 g. , Pd: (a) US 3330815 (1967), Union Carbide Corp. , Invs. : J. E. McKeon, P.A. S. Starcher; Chem. Abstr. 1967, 67, 64884 g, (b) F.R. Hojabri, M.H. M.M. Mohaddes, A.D. Talab, Polymer 1976, 17, 710. ].

  However, norbornene monomers consisting of saturated hydrocarbon rings have low solubility in organic solvents, and their ability to adsorb with metals essential for use as electronic materials is reduced, which limits their application. there were. Accordingly, various studies have been actively conducted to overcome such disadvantages. Among them, the method that can change the physical properties of the polymer most easily is to control the poor solubility of general polynorbornene and to change the chemical structure of the monomer in order to obtain new physical properties. And a method of introducing a new functional group. Among them, the problem relating to the low solubility in the organic solvent can be easily solved by introducing a polar functional group into the norbornene monomer. The different ones include norbornene / ethane copolymer [(a) H. Cherdron, M.C. J. et al. Brekner, F.A. Osan, Angew. Makromol. Chem. 1994, 223, 121, (b) M.M. Arndt, I.D. Beulich, Macromol. Chem. Phys. 1998, 199, 1221], or copolymer of norbornene substituted with norbornene / functional group [T. F. A. Haselwander, W. Heitz, M.C. Maskos, Macromol. Rapid. Commun. 1997, 198, 3963] has been actively researched, but it has also become possible to contribute to increasing the adsorption force between different objects through such copolymerization.

The catalyst used for polymerizing such a cyclic olefin polymer was a catalyst composite, and mainly used was a catalyst composite containing an organic phosphine compound as a σ electron donor ligand. For example, US Pat. No. 6,455,650 uses [(R ′) _z M (L ′) _x (L ″) _y ] _b [WCA] _d as the catalyst complex, As a ligand used in the method, a method of polymerizing a norbornene-based monomer having a functional group using a phosphine compound and a hydrocarbon containing a hydrocarbyl group such as an allyl group is disclosed. In the literature by Sen et al. (Sen et al., Organometallics 2001, Vol. 20, 2802-2812), [(1,5-cyclooctadiene) (CH ₃ ) Pd (Cl)] is expressed as PPh ₃ . A reaction of activating phosphine and co-catalyst such as [Na] ⁺ [B (3,5- (CF ₃ ) ₂ C ₆ H ₃ ) ₄ ] ⁻ to polymerize ester norbornene is disclosed.

  However, when a phosphine cocatalyst is added separately, in order for the catalyst precursor to change to an active catalyst, it must go through a separate step, and in the presence of a cyclic olefin monomer with a polar functional group, There was a problem that the catalytic activity was greatly reduced.

  On the other hand, recently, reactions in which norbornene containing a polar functional group is polymerized using a phosphonium compound as a cocatalyst are described in Korean Patent Application Nos. 2004-0052612 and 2004-0074307.

  Recently, in order to synthesize monomeric aromatic olefins (eg stilbene), EP 07211953 B1 describes a metal catalyst complex having an N-heterocyclic carbene (NHC) as a ligand instead of a phosphine ligand. The contents are presented. However, here, only alkyl groups or sulfonated alkyl groups are mainly used as substituents for the N-heterocycle in the Examples.

  By the way, among various methods for improving the performance of the metal catalyst, it is possible to consider the electronic effect of the ligand while changing a part of the ligand to various functional groups. Improvements in catalyst performance due to such changes in ligand electronic effects can be found in various literatures. For example, it has been published that Grubbs is modifying the substituent of a ruthenium carbene catalyst ligand while adjusting the electronic effect of the ligand to improve the catalytic activity [(a) Trnka, T. et al. M.M. Grubbs, R .; H. Acc. Chem. Res. 2001, 34, 18-29, (b) Love, J. et al. A. Sanford, M .; S. Day, M .; W. Grubbs, R .; H. J. et al. Am. Chem. Soc. 2003, 125, 10103-10109].

Speaking of the catalysts used in polymer synthesis, Weymouth plays an important role in the electronic effects of ligands in controlling the stereoselectivity of polymerized propylene using zirconocene catalysts. [Lin, S. Hauptman, E .; Lal, T .; K. Waymouth, R .; M.M. Quan, R .; W. Ernst, A .; B. J. et al. Mol. Catal. A: Chem. 1998, 136, 23-33]. In addition, when the coat is copolymerized with carbon dioxide (CO ₂ ) and epoxide (epoxide) using a β-diiminate zinc alkoxide catalyst, a part of the ligand is converted to cyano (cyano). ) Announced that the rate of polymer polymerization was dramatically increased by replacing the functional group [Moore, D. et al. R. Cheng, M .; Lobkovsky, E .; B. Coates, G .; W. Angew. Chem. , Int. Ed. 2002, 41, 2599-2602].

However, a part of the N-heterocyclic carbene (NHC) ligand has been changed to various functional groups that affect the electron density of the ligand, thus further improving the performance of the metal catalyst by the electronic effect of the ligand. No examples have been reported. Accordingly, there is a need for a new polymerization method for producing a cyclic olefin-based polymer by using a metal catalyst complex exhibiting improved performance by substituting various functional groups with an N-heterocyclic carbene ligand.
WO95 14048A1 (1995) US Pat. No. 6,455,650 Korean Patent Application No. 2004-0052612 Korean Patent Application No. 2004-0074307 US 3308815 (1967) EP 445755 A2 (1991) T.A. F. A. Haselwander, W. Heitz, S.H. A. Krugel, J.A. H. Wendorff, Macromolecules, 1997, 30, 534 T.A. F. A. Haselwander, W. Heitz, S.H. A. Krugel, J.A. H. Wendorff, Macromol. Chem, Phys. 1996, 197, 3435. B. F. Goodrich Co. , Invs. : B. L. Goodall, G. M.M. Benedikt, L. H. McIntosh III, D.W. A. Barnes Chem. Abstr. 1995, 123, 341322p H. Maezawa, J.A. Aiura, S.A. Asahi. Chem. Abstr. 1991, 115, 256943 g. , Pd: J. et al. E. McKeon, P.A. S. Starcher; Chem. Abstr. 1967, 67, 64884g F. Hojabri, M.H. M.M. Mohaddes, A.D. Talab, Polymer 1976, 17, 710. H. Cherdron, M.C. J. et al. Brekner, F.A. Osan, Angew. Makromol. Chem. 1994, 223, 121 M.M. Arndt, I.D. Beulich, Macromol. Chem. Phys. 1998, 199, 1221 T.A. F. A. Haselwander, W. Heitz, M.C. Maskos, Macromol. Rapid. Commun. 1997, 198, 3963 Trnka, T. M.M. Grubbs, R .; H. Acc. Chem. Res. 2001, 34, 18-29 Love, J. A. Sanford, M .; S. Day, M .; W. Grubbs, R .; H. J. et al. Am. Chem. Soc. 2003, 125, 10103-10109 Lin, S .; Hauptman, E .; Lal, T .; K. Waymouth, R .; M.M. Quan, R .; W. Ernst, A .; B. J. et al. Mol. Catal. A: Chem. 1998, 136, 23-33 Moore, D.C. R. Cheng, M .; Lobkovsky, E .; B. Coates, G .; W. Angew. Chem. , Int. Ed. 2002, 41, 2599-2602

  The first technical problem to be solved by the present invention is to provide a process for producing a cyclic olefin polymer using a new metal catalyst complex.

  The second technical problem to be solved by the present invention is to provide an olefin polymer produced by the method for producing a cyclic olefin polymer.

  In order to achieve the first technical problem, the present invention is a method for producing a cyclic olefin polymer by addition polymerization of a cyclic olefin monomer, the metal catalyst represented by the following chemical formula 1 Provided is a method for producing a cyclic olefin polymer comprising the step of bringing a complex into contact with a cyclic olefin monomer represented by the following chemical formula 2.

Where M is a Group 10 metal;
[M (L ₁ ) _x (L ′ ₂ ) _y (L ₃ ) _z ] is a cationic complex,
L ₁ is a ligand comprising an anionic hydrocarbyl;
L ′ ₂ is a neutral ligand,
L ₃ is an N-heterocyclic carbene ligand;
[Ani] is an anion that can be weakly coordinated to the metal M;
x is 1 or 2, y is 0 to 4, z is 1 or 2, 2 ≦ x + y + z ≦ 6,
a and b are each a number indicating a cation and an anion that can be weakly coordinated, and is a number between 1 and 10 that balances the charge of the entire catalyst compound, and the ligand is a complex molecule. And when there are a plurality of them, they are the same as or different from each other.

In the above formula, m is an integer from 0 to 4,
R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ each independently represents a polar functional group or a non-polar functional group;
R ₇ , R ₇ ′, R ₇ ″ and R _w ′ ″ may be connected to each other to form a C ₄ -C ₁₂ saturated or unsaturated ring group, or a C ₆ -C ₂₄ aromatic ring;
The non-polar functional groups, hydrogen; _halogen; C 1 linear or branched alkyl _{-C 20,} haloalkyl, alkenyl, _haloalkenyl; C for 3 _{-C 20} linear or branched alkynyl, haloalkynyl; alkyl, alkenyl , Alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl substituted or unsubstituted C ₃ -C ₁₂ cycloalkyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl substituted or unsubstituted C 3 _6- C ₄₀ aryl; or selected from, but not limited to, the group consisting of alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl substituted or unsubstituted C ₇ -C ₁₅ aralkyl Not something .

The polar working group is a non-hydrocarbon polar group comprising at least one or more oxygen, nitrogen, phosphorus, sulfur, silicon, or boron;
^{-R 8 OR 9, -OR 9,} -OC (O) OR 9, -R 8 OC (O) OR 9, -C (O) R 9, -R 8 C (O) R 9, -OC (O ^{) R 9, -R 8 C (} O) OR 9, -C (O) OR 9, -R 8 OC (O) R 9, - (R 8 O) k -OR 9, - (OR 8) k - ^{OR 9, -C (O) -O} -C (O) R 9, -R 8 C (O) -O-C (O) R 9, -SR 9, -R 8 SR 9, -SSR 8, - ^{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, -P (R}} 9) 2, -R 8 P (R 9) 2, -P (= O) (R 9) 2, -R 8 P (= O) (R 9) 2, and It is selected from the group consisting of the following formulas, but is not limited to them.

In the polar working group, each R ⁸ and R ¹¹ is C ₁ -C ₂₀ linear or branched alkylene, haloalkylene, alkenylene, haloalkenylene; C ₃ -C ₂₀ linear or branched alkynylene, haloalkynylene. Alkyl or alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl substituted or unsubstituted C ₃ -C ₁₂ cycloalkylene; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl substituted or unsubstituted _C 6 _{-C 40} arylene; or alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, a _C 7 _{-C 15} aralkylene substituted or non-substituted haloalkynyl,
Each R ⁹ , R ¹² , R ¹³ and R ¹⁴ is hydrogen; halogen; C ₁ -C ₂₀ linear or branched alkyl, haloalkyl, alkenyl, haloalkenyl; C ₃ -C ₂₀ linear or branched. alkynyl, haloalkynyl, alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl or haloalkynyl a substituted or unsubstituted _C 3 _{-C 12} cycloalkyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or halo, alkynyl substituted or unsubstituted _C 6 _{-C 40} aryl, alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or a substituted or unsubstituted _C 7 _{-C 15} aralkyl in haloalkynyl; or alkoxy, haloalkoxy, shea Le, siloxy, aryloxy, halo aryloxy, arylcarbonyloxy, halo carbonyloxy,
Each k is an integer of 1 to 10.

  According to one embodiment of the present invention, in the method for producing the cyclic olefin polymer, the N-heterocyclic carbene ligand is one or more selected from the group consisting of the following chemical formulas 4A to 4D. Is desirable

Wherein R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ and R ₃₀ are independently hydrogen, C ₁ -C ₂₀ linear or branched alkyl, C ₃ -C ₁₂ cycloalkyl, C ₃ linear or branched alkenyl of _{2 -C 20,} C 6 -C _{15 cycloalkenyl,} C of 3 _{-C 20} linear or branched _allyl, C 6 _{-C 30} aryl, _C 6 _{-C 30} aryl containing a hetero atom Or a C ₇ -C ₃₀ aralkyl, wherein each said functional group is substituted with one or more hydrocarbyl and / or heteroatom substituents, such substituents may be C ₁ -C ₅ linear or molecular branched _alkyl, linear or branched haloalkyl of C 1 -C _5, linear or branched alkenyl of C 2 -C _5, haloalkenyl, halogen, sulfur, oxygen, nitrogen, phosphorus or phenyl Can include a group, said phenyl group is a linear or branched alkyl of C ₁ -C _5, linear or branched haloalkyl of C ₁ -C _5, but is optionally substituted by halogen and hetero atom However, it is not limited to them.

  The alkenyl may include allyl and vinyl.

According to another embodiment of the present invention, in the method for producing the cyclic olefin polymer, the [Ani] is an anion that can be weakly coordinated with the Group 10 metal M, and includes borate, aluminate, [SbF ₆ ]-, [PF ₆ ]-, [AsF ₆ ]-, perfluoroacetate ([CF ₃ CO ₂ ]-), perfluoropropionate ([C ₂ F ₅ CO ₂ ]-), perfluorobutyrate ( _{[CF 3 CF 2 CF 2 CO} 2] -), perchlorate _([ClO 4] -), para - toluenesulfonate _{([p-CH 3 C 6} H 4 SO 3] -), [SO 3 CF 3] - Desirably, any one selected from the group consisting of boratabenzene, and carborane substituted or unsubstituted with halogen.

  According to still another embodiment of the present invention, in the method for producing the cyclic olefin polymer, the borate or aluminate is preferably made of an anion represented by the following chemical formula 5A or chemical formula 5B.

Where M ′ is boron or aluminum;
Each R ₃₀ is independently halogen; halogen substituted or unsubstituted C ₁ -C ₂₀ linear or branched alkyl, alkenyl; halogen substituted or unsubstituted C ₃ -C ₁₂ cycloalkyl; halogen or carbon _{C 6} to linear or branched triarylsiloxy of C 3 linear or branched trialkyl _{-C 20} siloxy or _C 18 _{-C 48} is replaced _{-; C} 6 _-C substituted or unsubstituted hydrogen ₄₀ aryl C ₄₀ aryl; C ₇ -C ₁₅ aralkyl substituted or unsubstituted with halogen or hydrocarbon.

  According to another embodiment of the present invention, in the method for producing the cyclic olefin polymer, the metal catalyst complex may be represented by the following chemical formula 6:

In the above formula, M, L ₁ , L ′ ₂ , L ₃ , [Ani], a and b are as defined above.

  According to still another embodiment of the present invention, it is preferable that the metal catalyst complex is represented by the following chemical formulas 7A to 7D in the method for producing the cyclic olefin polymer.

Wherein M, L ₁ , L ′ ₂ , [Ani], a and b are as defined above;
R ₁ to R ₆ are each independently hydrogen, halogen, C ₁ -C ₂₀ linear or branched alkyl, alkoxy, allyl, alkenyl or vinyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or substituted or unsubstituted _C 3 _{-C 12} cycloalkyl in haloalkynyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or a substituted or unsubstituted _C 6 _{-C 40} aryl in haloalkynyl; alkyl, alkenyl, alkynyl , Halogen, haloalkyl, haloalkenyl, or haloalkynyl substituted or unsubstituted C ₇ -C ₁₅ aralkyl; or C ₃ -C ₂₀ alkynyl, wherein the alkenyl may include allyl and vinyl.
At least one of R ₁ to R ₆ is halogen; or a halogen-containing alkyl group, aryl group, aralkyl group, or alkylaryl group.

  According to another embodiment of the present invention, in the method for producing the cyclic olefin polymer, the metal catalyst complex is preferably represented by the following chemical formula 8:

In the above formula, M, L ₁ , L ′ ₂ , [Ani], R ₁ , R ₂ , R ₅ , a and b are as defined above.

  According to another embodiment of the present invention, it is preferable that the metal catalyst complex is represented by the following chemical formula 9 in the method for producing the cyclic olefin polymer.

In the above formula, M, L ′ ₂ , [Ani], R ₁ , R ₂ , R ₅ , a and b are as defined above, and the following formula is C ₃ allyl.

At least one of R ₁ , R ₂ and R ₅ is halogen; or an alkyl group, aryl group, aralkyl group or alkylaryl group containing a halogen.

Meanwhile, according to an embodiment of the present invention, in the structure of the metal catalyst complex used in the production method of the present invention, at least one of the R ₁ , R ₂ and R ₅ is halogen; It can be an alkyl group, an aryl group, an aralkyl group or an alkylaryl group.

  According to still another embodiment of the present invention, it is preferable that the metal catalyst complex is supported on a fine particle support in the method for producing the cyclic olefin polymer.

  According to still another embodiment of the present invention, in the method for producing the cyclic olefin polymer, the fine particle support is silica, titania, silica / chromia, silica / chromia / titania, silica / alumina, aluminum phosphate. Desirable is a gel, silanized silica, silica hydrogel, montmorillonite clay or zeolite.

  According to another embodiment of the present invention, in the method for producing the cyclic olefin polymer, the metal catalyst complex is dissolved in an organic solvent selected from the group consisting of dichloromethane, dichloroethane, toluene, chlorobenzene and a mixture thereof. It is desirable to use it.

  According to still another embodiment of the present invention, it is preferable that the metal catalyst complex is charged into a monomer solution in a solid phase in the method for producing the cyclic olefin polymer.

  According to still another embodiment of the present invention, in the method for producing the cyclic olefin polymer, the cyclic olefin polymer has a cyclic olefin homopolymer having a polar functional group, and the cyclic olefin polymer has a polar functional group different from each other. It is desirable to include a copolymer of an olefin monomer and a copolymer of a cyclic olefin monomer having a polar functional group and a cyclic olefin monomer having no polar functional group.

According to still another embodiment of the present invention, in the method for producing the cyclic olefin polymer, the cyclic olefin polymer may have a weight average molecular weight (M _w ) of 20,000 to 500,000. .

In order to achieve the second technical problem, the present invention provides:
A cyclic olefin polymer produced by the above method,
Provided is a cyclic olefin polymer containing a polar functional group having a weight average molecular weight of 20,000 to 500,000.

  According to an embodiment of the present invention, the cyclic olefin polymer is preferably represented by the following Formula 11.

Wherein m, R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ are the same as defined in Formula 2;
One or more of R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ are polar functional groups,
n represents a polymerization degree and is a real number of 100 to 5,000.

  According to another embodiment of the present invention, the cyclic olefin polymer may be represented by the following chemical formula 12.

Wherein m, R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ are the same as defined in Formula 2;
One or more of R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ are polar functional groups,
R ₁₇ , R ₁₇ ′, R ₁₇ ″ and R ₁₇ ′ ″ are each independently a nonpolar working group, the nonpolar working group being hydrogen; halogen; C ₁ -C ₂₀ linear or molecular branched alkyl, haloalkyl, alkenyl, haloalkenyl; C for ₃ -C ₂₀ linear or branched alkynyl, haloalkynyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl or substituted or non-substituted haloalkynyl, C _3- C ₁₂ cycloalkyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl substituted or unsubstituted C ₆ -C ₄₀ aryl; or alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or substituted haloalkynyl or unsubstituted C Is selected from the group consisting of -C ₁₅ aralkyl,
m may be different from each other,
n ′ represents a degree of polymerization and is a real number of 100 to 2,500,
c and d are molar ratios, c + d = 1,
0.1 ≦ c ≦ 0.95 and 0.05 ≦ d ≦ 0.9.

  According to another embodiment of the present invention, it is preferable that the cyclic olefin polymer is represented by the following chemical formula 13.

Wherein m, R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ are the same as defined in Formula 2;
One or more of R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ are polar functional groups,
m may be different from each other,
n ″ represents a degree of polymerization and is a real number of 100 to 2,500,
e and f are molar ratios, e + f = 1,
0.1 ≦ e ≦ 0.9 and 0.1 ≦ f ≦ 0.9,
The structures of the repeating unit having the molar ratio e and the repeating unit having the molar ratio f are different from each other.

  In the case of the method for producing a cyclic olefin polymer according to the present invention, even when a cyclic olefin monomer containing a polar functional group is contained, a high-molecular-weight cyclic olefin addition polymer can be produced in a high yield. The polymer has excellent heat resistance.

  Hereinafter, the present invention will be described in detail.

  When a cyclic olefin polymer is produced by the method according to the present invention, a cyclic olefin addition polymer can be produced in a high yield even when a cyclic olefin monomer containing a polar functional group is contained. The coalescence is excellent in heat resistance.

The present invention relates to a method for producing a cyclic olefin polymer by addition polymerization of a cyclic olefin monomer, which is a metal catalyst complex represented by the following chemical formula 1 and a cyclic olefin system represented by the following chemical formula 2. A method for producing a cyclic olefin polymer comprising the step of contacting with a monomer is provided:
[M (L ₁ ) _x (L ′ ₂ ) _y (L ₃ ) _z ] _a [Ani] _b (1)
M is a Group 10 metal, [M (L ₁ ) _x (L ′ ₂ ) _y (L ₃ ) _z ] is a cationic complex, and L ₁ is a ligand containing an anionic hydrocarbyl. , L ′ ₂ is a neutral ligand, L ₃ is an N-heterocyclic carbene ligand, [Ani] is an anion that can be weakly coordinated to the metal M, and x is 1 or 2, y is 0 to 4, z is 1 or 2, 2 ≦ x + y + z ≦ 6, a and b are numbers indicating a cation and an anion that can be weakly coordinated, respectively, and the charge of the entire catalyst compound In the case where a plurality of the ligands are present in the complex molecule, they may be the same as or different from each other.

  More specifically, in the above, M can be any group 10 metal, but is preferably nickel or palladium.

L ₁ is a ligand containing an anionic hydrocarbyl, and the anionic hydrocarbyl ligand has an anion in a closed shell electron configuration when the central metal is away from M. is any hydrocarbyl ligand, specifically, _hydrogen, C 1 linear or branched alkyl _{-C 20,} C 5 _{-C 10 cycloalkyl,} linear or branched alkenyl of C 2 _{-C 20,} C ₆ -C ₁₅ cycloalkenyl, include allyl ligand or their normal _morphology, C 6 _{-C 30} aryl, _C 6 _{-C 30} aryl and _C 7 _{-C 30} aralkyl ligand containing a hetero atom, wherein each functional group is an optionally substituted hydrocarbyl and / or heteroatom substituents, the such a substituent, a linear or branched alkyl of C ₁ -C ₅ Can include linear or branched haloalkyl of C ₁ -C _5, linear or branched alkenyl and haloalkenyl of C ₂ -C _5, a halogen, sulfur, oxygen, nitrogen, phosphorus and phenyl, said phenyl The groups are optionally substituted with, but are not limited to, C ₁ -C ₅ linear or branched alkyl, C ₁ -C ₅ linear or branched haloalkyl, halogen and heteroatoms. Absent.

  The alkenyl can include vinyl.

Moreover, as a ligand containing the anionic hydrocarbyl, R′C (O) O, R′C (O) CHC (O) R ′, R′C (O) S, R′C (S) O , R′C (S) S, R′O, (R ′) ₂ N, wherein R ′ is the same as defined above for L1,
The cycloalkyl and cycloalkenyl ligands can be single ring or multiple, and the aryl ligand can be a single ring (eg, phenyl) or a fused ring (eg, naphthyl). Any cycloalkyl, cycloalkenyl and aryl groups can be joined together to form a fused ring.
L′ 2 is a neutral ligand, and is a reaction diluent, a reaction monomer, DMF, DMSO, a C ₄ -C ₁₀ aliphatic diene, a C ₄ -C ₁₀ cycloaliphatic diene, specifically Includes butadiene, 1,6-hexadiene, cyclooctadiene and the like, and water, alkane chloride, alcohol, ether, ketone, nitrite, allene, phosphine oxide, organic carbonate or ester are also desirable.

In the above formula, m is an integer from 0 to 4,
R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ each independently represents a polar functional group or a non-polar functional group;
R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ can be linked together to form a C ₄ -C ₁₂ saturated or unsaturated ring group, or a C ₆ -C ₂₄ aromatic ring;
The non-polar functional groups, hydrogen; _halogen; C 1 linear or branched alkyl _{-C 20,} haloalkyl, alkenyl, _haloalkenyl; C for 3 _{-C 20} linear or branched alkynyl, haloalkynyl; alkyl, alkenyl , Alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl substituted or unsubstituted C ₃ -C ₁₂ cycloalkyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl substituted or unsubstituted C 3 _6- C ₄₀ aryl; or selected from, but not limited to, the group consisting of alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl substituted or unsubstituted C ₇ -C ₁₅ aralkyl Not a thing .

The polar working group is a non-hydrocarbon polar group comprising at least one or more oxygen, nitrogen, phosphorus, sulfur, silicon, or boron;
^{-R 8 OR 9, -OR 9,} -OC (O) OR 9, -R 8 OC (O) OR 9, -C (O) R 9, -R 8 C (O) R 9, -OC (O ^{) R 9, -R 8 C (} O) OR 9, -C (O) OR 9, -R 8 OC (O) R 9, - (R 8 O) k -OR 9, - (OR 8) k - ^{OR 9, -C (O) -O} -C (O) R 9, -R 8 C (O) -O-C (O) R 9, -SR 9, -R 8 SR 9, -SSR 8, - ^{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, -P (R}} 9) 2, -R 8 P (R 9) 2, -P (= O) (R 9) 2, -R 8 P (= O) (R 9) 2, and It is selected from the group consisting of the following formulas, but is not limited to them.

Wherein each R ⁸ and R ¹¹ is C ₁ -C ₂₀ linear or branched alkylene, haloalkylene, alkenylene, haloalkenylene; C ₃ -C ₂₀ linear or branched alkynylene, haloalkynylene; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, C ₃ -C substituted or unsubstituted in haloalkynyl ₁₂ cycloalkylene; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, substituted or non-substituted haloalkynyl C ₆ -C ₄₀ arylene; or alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl substituted or unsubstituted C ₇ -C ₁₅ aralkylene;
Wherein each R ⁹ , R ¹² , R ¹³ and R ¹⁴ is hydrogen; halogen; C ₁ -C ₂₀ linear or branched alkyl, haloalkyl, alkenyl, haloalkenyl; C ₃ -C ₂₀ linear or branched alkynyl, haloalkynyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl or haloalkynyl a substituted or unsubstituted C ₃ -C ₁₂ cycloalkyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl, halo C ₆ -C ₄₀ aryl substituted or unsubstituted on alkenyl, or haloalkynyl; C ₇ -C ₁₅ aralkyl substituted or unsubstituted on alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl; or alkoxy, Haloa Kokishi, silyl, siloxy, aryloxy, halo aryloxy, arylcarbonyloxy, halo carbonyloxy, each k is 1 to 10 integer.

In the metal catalyst complex used in the production method, L ₃ is an N-heterocyclic carbene ligand, and any one of structures given by the following chemical formulas 4A to 4D is preferable, but is not necessarily limited thereto. Any carbene compound known in the art that is N-heterocyclic can be used.

Wherein R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ and R ₃₀ are each independently hydrogen, C ₁ -C ₂₀ linear or branched alkyl, C ₃ -C ₁₂ cycloalkyl, C linear or branched alkenyl of _{2 -C 20,} C 6 -C _{15 cycloalkenyl,} linear or branched allyl _{C 3 -C 20, C 6 -C} 30 aryl, _C 6 _{-C 30} containing a hetero atom Aryl or C ₇ -C ₃₀ aralkyl, wherein each said functional group is substituted with one or more hydrocarbyl and / or heteroatom substituents, such substituents may be C ₁ -C ₅ linear or branched _alkyl, linear or branched haloalkyl of C 1 -C _5, linear or branched alkenyl of C 2 -C _5, haloalkenyl, halogen, sulfur, oxygen, nitrogen, phosphorus or Can include a phenyl group, said phenyl groups is optionally substituted linear or branched alkyl of C ₁ -C _5, linear or branched haloalkyl of C ₁ -C _5, halogen and hetero atom, However, the alkenyl may include allyl and vinyl.
In the metal catalyst complex used in the production method, [Ani] is an anion that can be weakly coordinated with the group 10 metal M, and includes borate, aluminate, [SbF ₆ ] −, [PF ₆ ] −, and [AsF ₆ ]. ] -, perfluoroacetate _{([CF 3 CO 2] -} ), perfluoro propionate _{([C 2 F 5 CO 2} ] -), perfluoro butyrate _{([CF 3 CF 2 CF 2} CO 2] -) , perchlorate _([ClO 4] -), para - toluenesulfonate _{([p-CH 3 C 6} H 4 SO 3] -), [SO 3 CF 3] -, boratabenzene, and carborane substituted or unsubstituted with a halogen Desirably, it is any one selected from the group consisting of:

More specifically, the metal catalyst complex preferably includes an anion in which the borate or aluminate is represented by the following chemical formula 5A or chemical formula 5B:
[M ′ (R ₃₀ ) ₄ ] (5A)
[M ′ (OR ₃₀ ) ₄ ] (5B)
Where M ′ is boron or aluminum;
Each R ₃₀ is independently halogen; halogen substituted or unsubstituted C ₁ -C ₂₀ linear or branched alkyl, alkenyl; halogen substituted or unsubstituted C ₃ -C ₁₂ cycloalkyl; halogen or carbon _{C 6} to linear or branched triarylsiloxy of C 3 linear or branched trialkyl _{-C 20} siloxy or _C 18 _{-C 48} is replaced _{-; C} 6 _-C substituted or unsubstituted hydrogen ₄₀ aryl C ₄₀ aryl; C ₇ -C ₁₅ aralkyl substituted or unsubstituted with halogen or hydrocarbon.

In the present invention, the metal catalyst complex used in the production of the cyclic olefin polymer is preferably represented by the following chemical formula 6.

In the above formula, M, L ₁ , L ′ ₂ , L ₃ , [Ani], a and b are as defined above.

  More preferably, the metal catalyst complex is represented by the following chemical formulas 7A to 7D.

Wherein M, L1, L′ 2, [Ani], a and b are as defined above;
R ₁ to R ₆ are each independently substituted with hydrogen, halogen, C ₁ -C ₂₀ linear or branched alkyl, alkoxy, alkenyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl. or unsubstituted _C 3 _{-C 12} cycloalkyl, alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or a substituted or unsubstituted _C 6 _{-C 40} aryl in haloalkynyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl , Haloalkenyl, or haloalkynyl substituted or unsubstituted C ₇ -C ₁₅ aralkyl; or C ₃ -C ₂₀ alkynyl, but is not limited thereto, provided that R ₁ to R ₆ At least one is halo Or an alkyl group, an aryl group, an aralkyl group or an alkylaryl group containing halogen. The alkenyl may include allyl and vinyl.

In the compounds represented by the chemical formulas 7A to 7D, R ₁ to R ₆ include at least one oxygen, nitrogen, phosphorus, sulfur, silicon, or boron instead of halogen as the polar functional group. It is also desirable to include a group. Such a functional group is not particularly limited as long as it can provide an electronic effect by pulling or extruding electrons, but is preferably a silyl group, a sulfone group, or a nitro group. Amino group, cyano group, acetyl group, ester group, carbonyl group, ether group and the like.

More preferably, the metal catalyst complex is represented by the following chemical formula 8.

In the above formula, M, L ₁ , L ′ ₂ , [Ani], R ₁ , R ₂ , R ₅ , a and b are as defined above.

  Most preferably, in the present invention, the metal catalyst complex is represented by the following chemical formula 9.

In the above formula, M, L ′ ₂ , R ₁ , R ₂ , R ₅ and [Ani] are as defined above.

  In particular, the metal catalyst complex may be represented by the following chemical formula 9A:

Where a and b are as defined above;
R ₂₁ and R ₂₂ are each independently C ₁ -C ₂₀ linear or branched alkyl, the following formula is C ₃ allyl, and X is halogen.

  In the present invention, in the method for producing a cyclic olefin polymer, the metal catalyst complex is preferably supported on a fine particle support, and the fine particle support is composed of silica, titania, silica / chromia, silica / chromia / Desirable is titania, silica / alumina, aluminum phosphate gel, silanized silica, silica hydrogel, montmorillonite clay or zeolite. Thus, when it is used by being supported on a fine particle support, there is an advantage that the molecular weight distribution can be adjusted depending on the application, and the apparent density of the resulting polymer can be improved.

  In the method for producing the cyclic olefin polymer, the metal catalyst complex is desirably used by dissolving in an organic solvent selected from the group consisting of dichloromethane, dichloroethane, toluene, chlorobenzene, and a mixture thereof. The total amount of the solvent is 10% to 800%, more preferably 50% to 400%, based on the total monomer weight in the monomer solution. If it is less than 10%, the solution viscosity is too high during the polymerization reaction and stirring is difficult, and unreacted monomers remain, resulting in a decrease in the polymerization yield, and the viscosity is too high. There is a problem that the solution must be diluted by adding a solvent, and when it exceeds 800%, there is a problem that the polymerization reaction rate is slowed and the polymerization yield and the molecular weight are both reduced. In the present invention, in the method for producing the cyclic olefin polymer, the metal catalyst complex can be charged into a monomer solution in a solid phase.

  In the present invention, the method for producing the cyclic olefin-based polymer may be such that the metal catalyst complex is in the range of 1/50 to 1 / 100,000 in terms of the total monomer molar amount in the monomer solution. More preferably, the reaction system is charged in an amount of / 100 to 1/20000. When the ratio is less than 1/100, there is a problem in removing catalyst residues remaining in the polymer, and when it exceeds 1/20000, there is a problem that the polymerization yield decreases.

  In the production method of the present invention, the cyclic olefin polymer is composed of a cyclic olefin homopolymer having a polar functional group and a cyclic olefin monomer having different polar functional groups. And a copolymer of a cyclic olefin monomer having a polar functional group and a cyclic olefin monomer having no polar functional group.

  The norbornene addition polymer containing a polar functional group produced by the method of the present invention contains at least 0.1 to 99.9 mol% of a norbornene-based monomer containing a polar functional group. Consists of a mixture of endo isomers and exo isomers, but the composition ratio of the mixture is not limited. This is further supported by the examples.

The addition polymerization of the present invention is preferably performed by dissolving and mixing a norbornene monomer and a catalyst in a solvent as in a general method for producing a norbornene polymer. If a cyclic olefin polymer containing a polar functional group is produced by the production method of the present invention, it can be produced in a high yield of at least 40%, and the molecular weight (M _w ) of the produced addition polymer is at least 20, It can have a high molecular weight of 000 or more. Therefore, the production method of the present invention can produce a cyclic olefin polymer into which a high molecular weight polar functional group is introduced in a high yield. When the molecular weight is less than 20,000, there is a disadvantage that the mechanical properties are lowered, and when the molecular weight exceeds 500,000, there is a problem in the processability of the polymer.

The present invention also provides a cyclic olefin polymer produced by the method described above, which contains a polar functional group having a weight average molecular weight (M _w ) of 20,000 to 500,000. .

  More specifically, the cyclic olefin addition polymer is preferably represented by the following chemical formula 11.

Wherein m, R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ are the same as defined in Formula 2;
One or more of R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ are polar working groups, and n is a real number of 100 to 5,000 representing the degree of polymerization.

  The cyclic olefin addition polymer is preferably represented by the following chemical formula 12.

Wherein m, R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ are the same as defined in Formula 2;
One or more of R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ are polar functional groups, and R ₁₇ , R ₁₇ ′, R ₁₇ ″ and R ₁₇ ′ ″ are independent of each other. A non-polar working group: hydrogen; halogen; C ₁ -C ₂₀ linear or branched alkyl, haloalkyl, alkenyl, haloalkenyl; C ₃ -C ₂₀ linear or branched type alkynyl, haloalkynyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl or haloalkynyl a substituted or unsubstituted _C 3 _{-C 12} cycloalkyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or, Substituted or unsubstituted C ₆ -C ₄₀ aryl on haloalkynyl; or alkyl, alkenyl, alkynyl, halogen, haloalkyl Selected from the group consisting of alkyl, haloalkenyl, or haloalkynyl substituted or unsubstituted C ₇ -C ₁₅ aralkyl;
m may be different from each other,
n ′ represents a degree of polymerization and is a real number of 100 to 2,500,
c and d are molar ratios, c + d = 1,
0.1 ≦ c ≦ 0.95 and 0.05 ≦ d ≦ 0.9.

  The cyclic olefin addition polymer is preferably represented by the following chemical formula 13.

Wherein m, R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ are the same as defined in Formula 2;
One or more of R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ are polar functional groups, and m may be different from each other;
n ″ represents a degree of polymerization and is a real number of 100 to 2,500,
e and f are molar ratios, e + f = 1,
0.1 ≦ e ≦ 0.9 and 0.1 ≦ f ≦ 0.9,
The structures of the repeating unit having the molar ratio e and the repeating unit having the molar ratio f are different from each other.

  The norbornene-based polymer having a polar functional group produced according to the present invention is transparent while being excellent in thermal stability, and has excellent adhesion to metals and other polymers having a polar functional group. It is a cyclic olefin polymer with low dielectric constant and excellent strength that can be used for electronic materials. In addition, this polymer is attached to a substrate of an electronic material without a coupling agent, is well attached to a metal substrate such as copper, silver, or gold, and is optically enough to be used as a protective film for a polarizing plate. It has excellent characteristics and can be used for electronic materials such as integrated circuits, circuit printed circuit boards or multichip modules.

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

In the following preparation examples and examples, all operations dealing with air and water sensitive compounds were performed using standard Schlenk technique or glove box technique. Nuclear magnetic resonance spectra were obtained using a Bruker 300 spectrometer, ¹ H NMR was measured at 300 MHz, and ¹³ C NMR was measured at 75 MHz. The molecular weight and molecular weight distribution of the polymer were measured using GPC (gel permeation chromatography), and at this time, a polystyrene sample was used as a standard. Thermal analysis such as TGA (Thermogravimetric Analysis) was performed using TA Instrument (TGA 2050; heating rate 10 K / min). Toluene was purified by distillation from potassium / benzophenone, and dichloromethane and chlorobenzene were distilled from CaH ₂ and used.

Monomer Synthesis Production Example 1
Synthesis of 5-norbornene-2-carboxylic acid methyl ester (monomer b) (endo: exo = 100: 0) 5-norbornene-2-carboxylic acid (endo, exo mixture) (3.8 g, 27.5 mmol) Was dissolved in distilled water. I ₂ (9.4 g, 37, 1 mmol) and KI (19 g, 114 mmol) dissolved in 112 ml of distilled water were added to the reaction product, and reacted at room temperature for 3 hours. After the reaction, extraction with ethyl ether was performed to remove the solvent in the organic layer to obtain oily iodolactone. This compound was dissolved in a small amount of ethyl acetate and then recrystallized with hexane to obtain 50% pure iodolactone having crystallinity.
The obtained iodolactone (4.4 g, 16.6 mmol) was dissolved in 70 ml of glacial acetic acid and then cooled to 0 ° C. to slowly add zinc dust (21.5 g, 328 mmol). added. This reaction product was reacted at 15 ° C. for 3 hours, and further reacted at room temperature for 2 hours. Insoluble inorganic substances among the reactants were filtered, and the filtrate was diluted with water and extracted with ethyl ether. The organic layer was collected and dried over anhydrous MgSO ₄ . Fractional distillation was performed with a distillation apparatus to obtain pure 5-norbornene-2-carboxylic acid (endo isomer). After such an endo compound and Na ₂ CO ₃ were dissolved in acetone, CH ₃ I was slowly added. The solvent of the reaction product was removed, and pure endo compound b was obtained by silica column chromatography.

Production Example 2
Synthesis of 5-norbornene-2-carboxylic acid methyl ester (monomer b) (endo: exo = 5: 95) 5-norbornene-2-carboxylic acid (endo, exo mixture) (3.8 g, 27.5 mmol) Was dissolved in distilled water. I2 (9.4 g, 37, 1 mmol) and KI (19 g, 114 mmol) dissolved in 112 ml of distilled water were added to the reaction product and reacted at room temperature for 3 hours. After the reaction, the mixture was extracted with ethyl ether, and the aqueous layer was oxidized with 5% H ₂ SO ₄ . The oxidized aqueous layer was extracted with ethyl ether, the solvent of the organic layer was removed, and fractional distillation was performed to obtain 5-norbornene-2-carboxylic acid (endo: exo = 5: 95 mixture). Such a compound and Na ₂ CO ₃ were dissolved in acetone and then CH ₃ I was slowly added. The solvent of the reaction product was removed, and exo compound b was obtained by silica column chromatography.

Production of pre-catalyst Example 1
Preparation of Compound 1 (ArN═CH—CH═NAr, Ar≡2, 6-Me ₂ -4-BrC ₆ H ₂ ) 5.6 g (28 mmole) of 4-bromo-2,6-dimethylaniline and a 40% solution of glyoxal After 1.58 mL (14 mmole) was dissolved in 30 mL of methanol, 1 mL of formic acid was added and stirred for 48 hours. The reaction was filtered and dried in vacuo, yielding 4.1 g (70% yield) of yellow crystalline compound 1.
₁ H NMR (CDCl ₃ ): 8.06 (s, 2H), 7.24 (s, 4H), 2.15 (s, 12H),
¹³ C NMR (CDCl ₃ ): δ 163.98, 149.08, 131.37, 129.07, 118.16, 18.52
HRMS m / z calcd: 419.9386, obsd: 419.9387

Example 2
Preparation of Compound 2 (ArN═CH—CH═NAr, Ar≡2,6-iPr ₂ -4-IC ₆ H ₂ ) 4-iodo-2,6-diisopropylaniline 8.5 g (28 mmole) and glyoxal 40% solution After 1.58 mL (14 mmole) was dissolved in 30 mL of methanol, 1 mL of formic acid was added and stirred for 48 hours. The reaction was filtered and dried in vacuo, yielding 6.4 g (73% yield) of yellow crystalline compound 2.
¹ H NMR (CDCl ₃ ): 8.04 (s, 2H), 7.28 (s, 4H), 2.85 (m, 4H), 1.16 (d, 12H, 6.9 Hz),
¹³ C NMR (CDCl ₃ ): δ 163.53, 149.06, 139.66, 132.91, 90.57, 28.44, 23.58
HRMS m / z calcd: 628.0811, obsd: 628.0812

Example 3
Preparation of Compound 3 (ArN═CH—CH═NAr, Ar≡2,6-iPr ₂ -4-BrC ₆ H ₂ ) 7.2 g (28 mmole) of 4-bromo-2,6-diisopropylaniline and a 40% solution of glyoxal After 1.58 mL (14 mmole) was dissolved in 30 mL of methanol, 1 mL of formic acid was added and stirred for 48 hours. The reaction was filtered and dried in vacuo, yielding 5.2 g (70% yield) of yellow crystalline compound 3.
¹ H NMR (CDCl ₃ ): 8.07 (s, 2H), 7.32 (s, 4H), 2.87 (m, 4H), 1.18 (d, 12H, 6.9 Hz),
¹³ C NMR (CDCl ₃ ): δ 163.68, 147.26, 139.50, 126.90, 119.24, 90.57, 28.59, 23.63
HRMS m / z calcd: 532.1088, obsd: 532.10.89

Example 4
Preparation of Compound 4 [N, N′-bis (4-bromo-2,6-dimethylphenyl) imidazolium chloride] Compound 1 (3 g, 7.1 mmole) and paraformaldehyde (0.22 g, 7.1 mmole) in toluene (30 mL) Then, the mixture was refluxed at 100 ° C. until the paraformaldehyde was completely dissolved. After the reaction was cooled to 40 ° C., 1.7 mL (7.1 mmole) of hydrochloric acid (4 M HCl in dioxane) dissolved in 4 M concentration of dioxane was slowly added. After cooling to 70 ° C., the mixture was further refluxed for about 1 hour. After stirring at room temperature for 3 hours, the reaction was filtered and dried in vacuo, yielding 1.8 g (54% yield) of compound 4 as a gray powder.
1H NMR (CDCl ₃ ): 11.65 (s, 1H), 7.56 (s, 2H), 7.40 (s, 4H), 2.22 (s, 12H)
¹³ C NMR (CDCl ₃ ): δ 137.70, 137.34, 132.57, 131.96, 125.23, 124.71
HRMS m / z calcd: 432.9914, obsd: 432.9911

Example 5
Preparation of Compound 5 [N, N′-bis (4-iodo-2,6-diisopropylphenyl) imidazolium chloride] Compound 2 4.5 g (7.1 mmole) and paraformaldehyde 0.22 g (7.1 mmole) After dissolving in 30 mL of toluene, the mixture was refluxed at 100 ° C. until the paraformaldehyde was completely dissolved. After the reaction was cooled to 40 ° C., 1.7 mL (7.1 mmole) of hydrochloric acid (4 M HCl in dioxane) dissolved in 4 M concentration of dioxane was slowly added. After cooling to 70 ° C., the mixture was further refluxed for about 1 hour. After stirring at room temperature for 3 hours, the reaction was filtered and dried in vacuo to give 2.7 g (yield 60%) of compound 5 as a gray powder.
¹ H NMR (C ₂ D ₆ SO): 10.24 (s, 1H), 8.55 (s, 2H), 7.81 (s, 4H), 4.25 (m, 4H), 1.24 (D, 12H, 6.9Hz), 1.14 (d, 12H, 6.9Hz)
HRMS m / z calcd: 628.0811, obsd: 628.0812

Example 6
Preparation of Compound 6 [N, N′-bis (4-bromo-2,6-diisopropylphenyl) imidazolium chloride] Compound 3 (3.8 g, 7.1 mmole) and paraformaldehyde (0.22 g, 7.1 mmole) After dissolving in 30 mL of toluene, reflux at 100 ° C. until the paraformaldehyde is completely dissolved. After the reaction is cooled to 40 ° C., 1.7 mL (7.1 mmole) of hydrochloric acid (4 M HCl in dioxane) dissolved in 4 M concentration of dioxane is slowly added. After cooling to 70 ° C., the mixture is further refluxed for about 1 hour. After stirring at room temperature for 3 hours, the reaction is filtered and dried in vacuo to give 2.32 g (yield 60%) of compound 6 as a gray powder.
¹ H NMR (CDCl ₃ ): 11.24 (s, 1H), 7.76 (s, 2H), 7.45 (s, 4H), 2.36 (m, 4H), 1.24 (dd, 12H, 5.7Hz)
HRMS m / z calcd: 545.1166, obsd: 545.1167

Example 7
Preparation of Compound 7 [Chloro (η ³ -allyl)-(N, N′-bis (4-bromo-2,6-dimethylphenyl) imidazol-2-ylidene) -palladium] Compound 4 1.5 g (3.2 mmole) ) And 0.39 g (3.2 mmole) of potassium t-butoxide were dissolved in tetrahydrofuran, stirred for 4 hours, and the solvent was removed in vacuo. After being dissolved in toluene in a glove box, it was filtered through a tube on which Celite was laminated. The solvent toluene was removed under reduced pressure to obtain 0.9 g (65%) of a carbene compound as a gray solid. 0.9 g (2.1 mmole) of such a carbene compound and 0.38 g (1.05 mmole) of allyl palladium chloride dimer [(ally) PdCl] ₂ were dissolved in tetrahydrofuran and stirred for 1 hour. Then, after removing the solvent under reduced pressure and washing with pentane, the solid compound was filtered to obtain 1.2 g (92%) of Compound 7 as a gray powder.
¹ H NMR (300 Mz, CDCl ₃ ): δ 7.33 (s, 4H), 7.11 (s, 2H), 4.91 (m, 1H), 3.95 (d, 1H), 3.21 (D, 1H), 2.87 (d, 1H), 2.23 (s, 6H), 2.21 (s, 6H), 1.82 (d, 1H),
¹ H NMR (CDCl ₃ ): 7.33 (s, 4H), 7.11 (s, 2H), 4.91 (sep, 1H, 9Hz), 3.95 (dd, 1H, 1.5Hz), 3.21 (d, 1H, 6Hz), 2.87 (d, 1H, 13.5Hz), 2.22 (d, 12H, 10.2Hz), 1.82 (d, 1H, 11.7Hz)
¹³ C NMR (CDCl ₃ ): δ 138.32, 137.60, 132.42, 131.70, 123.45, 123.37, 115.07, 77.62, 73.52, 49.97, 18 .67
HRMS m / z calcd: 578.9262, obsd: 578.9263

Example 8
Preparation of Compound 8 [Chloro (η ³ -allyl)-(N, N′-bis (4-iodo-2,6-diisopropylphenyl) imidazol-2-ylidene) -palladium] Compound 5 2.0 g (3.2 mmole) ) And 0.39 g (3.2 mmole) of potassium t-butoxide were dissolved in tetrahydrofuran, stirred for 4 hours, and the solvent was removed in vacuo. After being dissolved in toluene in a glove box, it was filtered through a tube laminated with celite. The solvent toluene was removed under reduced pressure to obtain 1.24 g (65%) of a carbene compound as a gray solid. 1.24 g (2.1 mmole) of such a carbene compound and 0.38 g (1.05 mmole) of allyl palladium chloride dimer [(ally) PdCl] ₂ were dissolved in tetrahydrofuran and stirred for 1 hour. Then, after removing the solvent under reduced pressure and washing with pentane, the solid compound was filtered to obtain 1.49 g (yield 90%) of Compound 8 as a gray powder.
¹ H NMR (CDCl 3): 7.50 (s, 4H), 7.01 (s, 2H), 4.78 (m, 1H, 7.2 Hz), 3.89 (dd, 1H, 1.5 Hz) 2.97 (dd, 1 H, 6 Hz), 2.95 (dd, 2 H, 6.9 Hz), 2.68 (dd, 2 H, 6.6 Hz), 1.57 (d, 1 H, 12.3 Hz) 1.28 (d, 6H, 6.6 Hz), 1.22 (d, 6H, 6.6 Hz), 1.08 (d, 6H, 6.6 Hz), 0.98 (d, 6H, 6.Hz). 6Hz)
¹³ C NMR (CDCl ₃ ): δ 145.53, 132.54, 130.30, 127.61, 127.43, 126.29, 125.13, 68.29, 29.48, 25.96, 24 .99, 24.27, 13.54, 12.74
HRMS m / z calcd: 787.0237, obsd: 787.0238

Example 9
Preparation of Compound 9 [Chloro (η ³ -allyl)-(N, N′-bis (4-bromo-2,6-diisopropylphenyl) imidazol-2-ylidene) -palladium] Compound 6 1.74 g (3.2 mmole) ) And 0.39 g (3.2 mmole) of potassium t-butoxide were dissolved in tetrahydrofuran, stirred for 4 hours, and the solvent was removed in vacuo. After being dissolved in toluene in a glove box, it was filtered through a tube on which Celite was laminated. When toluene as a solvent was removed under reduced pressure, 1.02 g (63%) of a carbene compound was obtained as a gray solid. Such carbene compound (1.02 g, 2.0 mmole) and allylpalladium chloride dimer [(ally) PdCl] ₂ (0.36 g, 1.0 mmole) were dissolved in tetrahydrofuran and stirred for 1 hour. Then, after removing the solvent under reduced pressure and washing with pentane, the solid compound was filtered to obtain 1.24 g (yield 90%) of Compound 9 as a gray powder.
¹ H NMR (CDCl ₃ ): 7.37 (s, 4H), 7.13 (s, 2H), 4.84 (m, 1H, 5.7 Hz), 3.95 (dd, 1H, 1.5 Hz) ), 3.08 (m, 3H), 2.84 (d, 1H, 13.5 Hz), 2.78 (dd, 2H, 6.9 Hz), 1.62 (s, 1H), 1.36 ( d, 6H, 6.6 Hz), 1.30 (d, 6H, 6.6 Hz), 1.16 (d, 6H, 6.6 Hz), 1.06 (d, 6H, 6.6 Hz)
¹³ C NMR (CDCl 3): δ 145.5, 132.5, 130.3, 127.6, 127.4, 126.2, 125.1, 68.2, 29.4, 25.9, 24. 9, 24.2, 13.5, 12.7
HRMS m / z calcd: 691.0514, obsd: 691.0516
The structures of Compounds 1 to 9 prepared in Examples 1 to 9 are illustrated in Reaction Scheme 1 below.

Example 10 Production of Metal Catalyst Complex (Catalyst)
Preparation of Compound 10 0.2 g (0.351 mmol) of Compound 9 and 68 mg (0.351 mmol) of AgBF ₄ are dissolved in 5 ml of CH ₂ Cl ₂ and stirred for 1 hour. The reaction was filtered through celite to remove the solvent, yielding 0.2 g (92%) of gray powdered compound 10.
¹ H NMR (CDCl ₃ ): 7.43 (s, 4H), 7.24 (s, 2H), 4.84 (m, 1H), 4.45 (br, 1H), 3.34 (br, 1H), 2.64 (br, 4H), 2.32 (m, 1H), 2.21 (m, 1H), 1.30 (m, 12H), 1.19 (m, 12H)
The X-ray structure of the metal catalyst complex compound 10 is illustrated in FIG.

Production of Homopolymer and Copolymer The monomers and precatalysts used in the following polymerizations are as follows.

Example 11 (Homopolymerization of norbornene (monomer a))
Norbornene (5 g, 53.1 mmol) was charged into a 100 mL Schlenk flask containing toluene (15 mL). Pre-catalyst B and silver tetrafluoroborate (AgBF ₄ ) were dissolved in 5 ml of a 1: 1 mixed solution of methylene chloride: toluene in a glove box and stirred for 1 hour. Thereafter, 0.53 mmol of palladium catalyst filtered through a tube laminated with celite was added to the Schlenk flask, and stirred at a reaction temperature of 25 ° C. for 20 hours. After the reaction for 20 hours, the reaction mixture was added to an excessive amount of methanol to obtain a white copolymer precipitate. The copolymer obtained by filtering the precipitate through a glass funnel was dried in a vacuum oven at 80 ° C. for 24 hours to obtain a norbornene polymer (yield 99%).

Example 12
A norbornene polymer is produced by the same method as in Example 11 except that the catalyst amount, polymerization solvent, and polymerization time used are the same as shown in Table 1 below. A coalescence was produced.

Example 13
A norbornene polymer is produced by the same method as in Example 11, but the catalyst amount, polymerization solvent, and polymerization time used are the same as shown in Table 1 below. A coalescence was produced.

Comparative Example 1
A norbornene polymer is produced by the same method as in Example 11, but the amount of catalyst, polymerization solvent and polymerization time used are the same as shown in Table 1 below. A coalescence was produced.

Comparative Example 2
A norbornene polymer is produced in the same manner as in Example 11 except that the catalyst amount, polymerization solvent and polymerization time used are the same as shown in Table 1 below. A coalescence was produced.

Example 14
(Polymerization of 5-norbornene-2-carboxylic acid methyl ester (exo: endo = 95: 5, monomer b))
5-Norbornene-2-carboxylic acid methyl ester (5 ml, 33.0 mmol) having a relative ratio of exo and endo isomers of 95: 5 was charged into a 100 mL Schlenk flask containing toluene (15 mL). Pre-catalyst B and silver tetrafluoroborate (AgBF ₄ ) were dissolved in 5 ml of a 1: 1 mixed solution of methylene chloride: toluene in a glove box and stirred for 1 hour. Thereafter, 0.33 mmol of palladium catalyst filtered through a tube laminated with celite was added to the Schlenk flask, and stirred at a reaction temperature of 25 ° C. for 20 hours. After the reaction for 20 hours, this was put into an excessive amount of methanol to obtain a white copolymer precipitate. The copolymer obtained by filtering this precipitate through a glass funnel was dried in a vacuum oven at 80 ° C. for 24 hours to obtain a polymer (yield 71%).

Example 15
A 5-norbornene-2-carboxylic acid methyl ester polymer is produced in the same manner as in Example 14, but the catalyst amount, polymerization solvent, and polymerization time used are the same as shown in Table 2 below. A polymer was prepared using Precatalyst C.

Comparative Example 3
A 5-norbornene-2-carboxylic acid methyl ester polymer is produced in the same manner as in Example 14, but the catalyst amount, polymerization solvent, and polymerization time used are the same as shown in Table 2 below. A polymer was prepared using Precatalyst A.

Example 16
(Polymerization of 5-norbornene-2-carboxylic acid methyl ester (exo: endo = 50: 50, monomer b))
5-norbornene-2-carboxylic acid methyl ester (5 ml, 33.0 mmol) having a relative ratio of exo and endo isomers of 50:50 was charged into a 100 mL Schlenk flask containing toluene (15 mL). Precatalyst C and silver tetrafluoroborate (AgBF ₄ ) were dissolved in 5 ml of a methylene chloride: toluene = 1: 1 mixed solution in a glove box and stirred for 1 hour. Thereafter, 0.33 mmol of palladium catalyst filtered through a tube laminated with celite was added to the Schlenk flask, and stirred at a reaction temperature of 25 ° C. for 20 hours. After the reaction for 20 hours, this was put into an excessive amount of methanol to obtain a white copolymer precipitate. The copolymer obtained by filtering the precipitate through a glass funnel was dried in a vacuum oven at 80 ° C. for 24 hours to obtain a polymer (yield 55%).

Example 17
(Polymerization of 5-norbornene-2-carboxylic acid methyl ester (exo: endo = 50: 50, monomer b))
5-Norbornene-2-carboxylic acid methyl ester (5 ml, 33.0 mmol) having a relative ratio of exo and endo isomers of 50:50 was charged into a 100 mL Schlenk flask containing chlorobenzene (15 mL). Pre-catalyst B and silver hexafluoroantimonate (AgSbF ₆ ) were dissolved in 5 ml of chlorobenzene in a glove box and stirred for 1 hour. Thereafter, 0.33 mmol of palladium catalyst filtered through a tube on which celite was laminated was put into the Schlenk flask and stirred at a reaction temperature of 25 ° C. for 6 hours. After the reaction for 6 hours, this was put into an excessive amount of methanol to obtain a white copolymer precipitate. The copolymer recovered by filtering this precipitate through a glass funnel was dried in a vacuum oven at 80 ° C. for 24 hours to obtain a polymer (yield 92%).

Example 18
A 5-norbornene-2-carboxylic acid methyl ester polymer is produced in the same manner as in Example 17, but the catalyst amount, polymerization solvent, and polymerization time used are the same as shown in Table 3 below. A polymer was prepared using Precatalyst C.

Comparative Example 4
A 5-norbornene-2-carboxylic acid methyl ester polymer is produced in the same manner as in Example 17, but the catalyst amount, polymerization solvent, and polymerization time used are the same as shown in Table 3 below. A polymer was prepared using Precatalyst A.

Example 19
(Polymerization of 5-norbornene-2-carboxylic acid methyl ester (exo: endo = 20: 80, monomer b))
5-norbornene-2-carboxylic acid methyl ester (5 ml, 33.0 mmol) having a relative ratio of exo and endo isomers of 20:80 was charged into a 100 mL Schlenk flask containing chlorobenzene (15 mL). Pre-catalyst B and silver hexafluoroantimonate (AgSbF ₆ ) were dissolved in 5 ml of chlorobenzene in a glove box and stirred for 1 hour. Thereafter, 0.33 mmol of palladium catalyst filtered through a tube on which celite was laminated was put into the Schlenk flask, and stirred at a reaction temperature of 25 ° C. for 12 hours. After the reaction for 12 hours, this was added to an excessive amount of methanol to obtain a white copolymer precipitate. The copolymer recovered by filtering this precipitate through a glass funnel was dried in a vacuum oven at 80 ° C. for 24 hours to obtain a polymer (yield 48%).

Example 20
A 5-norbornene-2-carboxylic acid methyl ester polymer is produced in the same manner as in Example 19, but the catalyst amount, polymerization solvent, and polymerization time used are the same as shown in Table 4 below. A polymer was prepared using Precatalyst C.

Comparative Example 5
A 5-norbornene-2-carboxylic acid methyl ester polymer is produced in the same manner as in Example 19, but the catalyst amount, polymerization solvent, and polymerization time used are the same as shown in Table 4 below. A polymer was prepared using Precatalyst A.

Example 21
(Polymerization of 5-norbornene-2-carboxylic acid butyl ester (exo: endo = 95: 5, monomer c))
5-Norbornene-2-carboxylic acid butyl ester (5 ml, 34.4 mmol) having a relative ratio of exo and endo isomers of 95: 5 is mixed with toluene: methylene chloride (CH ₂ Cl) = 21: 1 mixed solution (15 mL) Into a 100 mL Schlenk flask. The pre-catalyst B and silver tetrafluoroborate (AgBF ₄ ) were dissolved in 5 ml of a methylene chloride: toluene = 1: 1 mixed solution in a glove box and stirred for 1 hour. Thereafter, 0.17 mmol of palladium catalyst filtered through a tube on which celite was laminated was put into the Schlenk flask and stirred at a reaction temperature of 25 ° C. for 12 hours. After the reaction for 20 hours, this was put into an excessive amount of methanol to obtain a white copolymer precipitate. The copolymer obtained by filtering the precipitate through a glass funnel was dried in a vacuum oven at 80 ° C. for 24 hours to obtain a polymer (yield 74%).

Example 22
A 5-norbornene-2-carboxylic acid butyl ester polymer is produced in the same manner as in Example 21, but the catalyst amount, polymerization solvent, and polymerization time used are the same as shown in Table 5 below. A polymer was prepared using Precatalyst C.

Comparative Example 6
A 5-norbornene-2-carboxylic acid butyl ester polymer is produced in the same manner as in Example 21, but the catalyst amount, polymerization solvent, and polymerization time used are the same as shown in Table 5 below. A polymer was prepared using Precatalyst A.

Comparative Example 7
(Polymerization of 5-norbornene-2-carboxylic acid butyl ester (exo: endo = 95: 5, monomer c))
5-Norbornene-2-carboxylic acid butyl ester (5 ml, 34.4 mmol) with a relative ratio of exo and endo isomers of 95: 5 was charged into a 100 mL Schlenk flask containing chlorobenzene (15 mL). Precatalyst A and silver tetrafluoroborate (AgBF ₄ ) were dissolved in 5 ml of chlorobenzene in a glove box and stirred for 1 hour. Thereafter, 0.34 mmol of palladium catalyst filtered through a tube laminated with celite was added to the Schlenk flask, and stirred at a reaction temperature of 25 ° C. for 20 hours. After the reaction for 20 hours, this was put into an excessive amount of methanol to obtain a white copolymer precipitate. The copolymer recovered by filtering this precipitate through a glass funnel was dried in a vacuum oven at 80 ° C. for 24 hours to obtain a polymer (yield 76%).

Example 23
(Polymerization of 5-norbornene-2-carboxylic acid butyl ester (exo: endo = 95: 5, monomer c))
Contains 5-norbornene-2-carboxylic acid butyl ester (5 ml, 34.4 mmol) having a relative ratio of exo and endo isomers of 95: 5 in a toluene: methylene chloride (1: 1 mixture) solution (15 mL). A 100 mL Schlenk flask was charged. Precatalyst C and silver hexafluoroantimonate (AgSbF ₆ ) were dissolved in 5 ml of a methylene chloride: toluene = 1: 1 mixed solution in a glove box and stirred for 1 hour. Thereafter, 0.17 mmol of the palladium catalyst filtered through a tube laminated with celite was added to the above Schlenk, and the mixture was stirred at a reaction temperature of 25 ° C. for 12 hours. After the reaction for 12 hours, this was put into an excessive amount of methanol to obtain a white copolymer precipitate. The copolymer obtained by filtering the precipitate through a glass funnel was dried in a vacuum oven at 80 ° C. for 24 hours to obtain a polymer. Yield 95%).

Example 24
A 5-norbornene-2-carboxylic acid butyl ester polymer is produced in the same manner as in Example 23, but the anion, polymerization solvent, and polymerization time used are the same as shown in Table 6 below. Polymers were prepared by varying the catalyst ratio to monomer to 1,000 / 1.

Example 25
A 5-norbornene-2-carboxylic acid butyl ester polymer is produced in the same manner as in Example 23, but the anion, polymerization solvent, and polymerization time used are the same as shown in Table 6 below. Polymers were prepared with different catalyst to monomer ratios of 5,000 / 1.

Comparative Example 8
A 5-norbornene-2-carboxylic acid butyl ester polymer is produced in the same manner as in Example 23, but the anion, polymerization solvent, and polymerization time used are the same as shown in Table 6 below. Although the pre-catalyst A was used, the polymer was produced by changing the catalyst ratio with respect to the monomer to 1,000 / 1.

Comparative Example 9
A 5-norbornene-2-carboxylic acid butyl ester polymer is produced in the same manner as in Example 23, but the anion, polymerization solvent, and polymerization time used are the same as shown in Table 6 below. Although the pre-catalyst A was used, the polymer was produced by changing the catalyst ratio with respect to the monomer to 5,000 / 1.

Example 26
(Polymerization of 5-norbornene-2-methyl acetate (exo: endo = 40: 60, monomer d))
Methyl 5-norbornene-2-acetate (5 ml, 30.9 mmol) with a relative ratio of exo and endo isomers of 40:60 was charged into a 100 mL Schlenk flask containing 15 mL of toluene solvent. The pre-catalyst B and silver tetrafluoroborate (AgBF ₄ ) were dissolved in 5 ml of a methylene chloride: toluene = 1: 1 mixed solution in a glove box and stirred for 1 hour. Thereafter, 0.031 mmol of palladium catalyst filtered through a tube laminated with celite was added to the Schlenk flask, and the reaction temperature was 25 ° C., and the mixture was stirred for 20 hours. After the reaction for 20 hours, this was put into an excessive amount of methanol to obtain a white copolymer precipitate. The copolymer obtained by filtering the precipitate through a glass funnel was dried in a vacuum oven at 80 ° C. for 24 hours to obtain a polymer (yield 62%).

Example 27
A 5-norbornene-2-acetic acid methyl polymer is produced in the same manner as in Example 26, but the catalyst amount, anion, polymerization solvent and polymerization time used are the same as shown in Table 7 below. A polymer was prepared using Precatalyst C.

Comparative Example 10
A 5-norbornene-2-acetic acid methyl polymer is produced in the same manner as in Example 26, but the catalyst amount, anion, polymerization solvent and polymerization time used are the same as shown in Table 7 below. A polymer was prepared using Precatalyst A.

Example 28
(Copolymerization of norbornene and 5-norbornene-2-carboxylic acid methyl ester (3: 1))
Norbornene (3 g, 31.9 mmol), 5-norbornene-2-carboxylic acid methyl ester (1.6 mL, 10.6 mmol) and toluene (14 mL) were charged into a 100 mL Schlenk flask. The pre-catalyst B and silver tetrafluoroborate (AgBF ₄ ) were dissolved in 5 ml of a methylene chloride: toluene = 1: 1 mixed solution in a glove box and stirred for 1 hour. Thereafter, 0.42 mmol of palladium catalyst filtered through a tube on which celite was laminated was put into the Schlenk flask and stirred at a reaction temperature of 25 ° C. for 20 hours. After the reaction for 20 hours, this was put into an excessive amount of methanol to obtain a white copolymer precipitate. The copolymer obtained by filtering the precipitate through a glass funnel was dried in a vacuum oven at 80 ° C. for 24 hours to obtain a polymer (yield 70%).

Example 29
A copolymer of norbornene and 5-norbornene-2-carboxylic acid methyl ester was produced in the same manner as in Example 28. The amount of catalyst used, polymerization time, anion, as shown in Table 8 below, Although the solvent was the same, polymer was prepared using Precatalyst B.

Comparative Example 11
A copolymer of norbornene and 5-norbornene-2-carboxylic acid methyl ester was produced in the same manner as in Example 28. The amount of catalyst used, polymerization time, anion, as shown in Table 8 below, Although the solvent was the same, polymer was prepared using Precatalyst C.

Example 30
(Copolymerization of norbornene and 5-norbornene-2-carboxylic acid methyl ester (3: 1))
Norbornene (3 g, 31.9 mmol), 5-norbornene-2-carboxylic acid methyl ester (1.6 mL, 10.6 mmol) and toluene (14 mL) were charged into a 100 mL Schlenk flask. Precatalyst C and silver hexafluoroantimonate (AgSbF ₆ ) were dissolved in chlorobenzene in a glove box and stirred for 1 hour. Thereafter, 0.42 mmol of palladium catalyst filtered through a tube on which celite was laminated was put into the Schlenk flask, and stirred at a reaction temperature of 25 ° C. for 12 hours. After the reaction for 12 hours, this was put into an excessive amount of methanol to obtain a white copolymer precipitate. The copolymer obtained by filtering the precipitate through a glass funnel was dried in a vacuum oven at 80 ° C. for 24 hours to obtain a polymer (yield 98%).

Example 31
(Copolymerization of norbornene and 5-norbornene-2-carboxylic acid butyl ester (3: 1))
Norbornene (3 g, 31.9 mmol), 5-norbornene-2-carboxylic acid butyl ester (1.54 mL, 10.6 mmol) and toluene (14 mL) were charged into a 100 mL Schlenk flask. The pre-catalyst B and silver tetrafluoroborate (AgBF ₄ ) were dissolved in 5 ml of a methylene chloride: toluene = 1: 1 mixed solution in a glove box and stirred for 1 hour. Thereafter, 0.42 mmol of palladium catalyst filtered through a tube on which celite was laminated was put into the Schlenk flask and stirred at a reaction temperature of 25 ° C. for 20 hours. After the reaction for 20 hours, this was put into an excessive amount of methanol to obtain a white copolymer precipitate. The copolymer recovered by filtering this precipitate through a glass funnel was dried in a vacuum oven at 80 ° C. for 24 hours to obtain a polymer (yield 72%).

Example 32
A copolymer of norbornene and 5-norbornene-2-carboxylic acid butyl ester is produced in the same manner as in Example 31, but the amount of catalyst used, polymerization time, anion, as shown in Table 9 below, Although the solvent was the same, polymer was prepared using Precatalyst C.

Comparative Example 12
A copolymer of norbornene and 5-norbornene-2-carboxylic acid butyl ester is produced in the same manner as in Example 31, but the amount of catalyst used, polymerization time, anion, as shown in Table 9 below, Although the solvent was the same, polymer was prepared using Precatalyst A.

Example 33
(Copolymerization of norbornene and 5-norbornene-2-carboxylic acid butyl ester (3: 1))
Norbornene (3 g, 31.9 mmol), 5-norbornene-2-carboxylic acid butyl ester (1.54 mL, 10.6 mmol) and toluene (14 mL) were charged into a 100 mL Schlenk flask. Precatalyst C and silver hexafluoroantimonate (AgSbF ₆ ) were dissolved in 5 ml of chlorobenzene in a glove box and stirred for 1 hour. Thereafter, 0.42 mmol of palladium catalyst filtered through a tube on which celite was laminated was put into the Schlenk flask, and stirred at a reaction temperature of 25 ° C. for 12 hours. After the reaction for 12 hours, this was put into an excessive amount of methanol to obtain a white copolymer precipitate. The copolymer recovered by filtering this precipitate through a glass funnel was dried in a vacuum oven at 80 ° C. for 24 hours to obtain a polymer (yield 87%).

Example 34
(Copolymerization of norbornene and 5-norbornene-2-carboxylic acid methyl ester (5: 1))
Norbornene (4 g, 42.5 mmol), 5-norbornene-2-carboxylic acid methyl ester (1.3 mL, 8.5 mmol) and toluene (14 mL) were charged into a 100 mL Schlenk flask. The pre-catalyst B and silver tetrafluoroborate (AgBF ₄ ) were dissolved in 5 ml of a methylene chloride: toluene = 1: 1 mixed solution in a glove box and stirred for 1 hour. Thereafter, 0.42 mmol of palladium catalyst filtered through a tube on which celite was laminated was put into the Schlenk flask and stirred at a reaction temperature of 25 ° C. for 20 hours. After the reaction for 20 hours, this was put into an excessive amount of methanol to obtain a white copolymer precipitate. The copolymer obtained by filtering the precipitate through a glass funnel was dried in a vacuum oven at 80 ° C. for 24 hours to obtain a polymer (yield 82%).

Example 35
A copolymer of norbornene and 5-norbornene-2-carboxylic acid methyl ester (5: 1) is produced in the same manner as in Example 34, but the catalyst amount and polymerization used are as shown in Table 10 below. Although the time, anion, and solvent were the same, a polymer was prepared using Precatalyst C.

Comparative Example 13
A copolymer of norbornene and 5-norbornene-2-carboxylic acid methyl ester (5: 1) is produced in the same manner as in Example 34, but the catalyst amount and polymerization used are as shown in Table 10 below. Although the time, anion, and solvent were the same, a polymer was prepared using Precatalyst A.

Example 36
(Copolymerization of norbornene and 5-norbornene-2-carboxylic acid methyl ester (5: 1))
Norbornene (4 g, 42.5 mmol), 5-norbornene-2-carboxylic acid methyl ester (1.3 mL, 8.5 mmol) and toluene (14 mL) were charged into a 100 mL Schlenk flask. Precatalyst C and silver hexafluoroantimonate (AgSbF ₆ ) were dissolved in chlorobenzene in a glove box and stirred for 1 hour. Thereafter, 0.42 mmol of palladium catalyst filtered through a tube on which celite was laminated was put into the Schlenk flask, and stirred at a reaction temperature of 25 ° C. for 12 hours. After the reaction for 12 hours, this was put into an excessive amount of methanol to obtain a white copolymer precipitate. The copolymer obtained by filtering the precipitate through a glass funnel was dried in a vacuum oven at 80 ° C. for 24 hours to obtain a polymer (yield 98%).

Example 37
(Copolymerization of norbornene and 5-norbornene-2-carboxylic acid butyl ester (5: 1))
Norbornene (4 g, 42.5 mmol), 5-norbornene-2-carboxylic acid butyl ester (1.2 mL, 8.5 mmol) and toluene (14 mL) were charged into a 100 mL Schlenk flask. The pre-catalyst B and silver tetrafluoroborate (AgBF ₄ ) were dissolved in 5 ml of a methylene chloride: toluene = 1: 1 mixed solution in a glove box and stirred for 1 hour. Thereafter, 0.42 mmol of palladium catalyst filtered through a tube on which celite was laminated was put into the Schlenk flask and stirred at a reaction temperature of 25 ° C. for 20 hours. After the reaction for 20 hours, this was put into an excessive amount of methanol to obtain a white copolymer precipitate. The copolymer obtained by filtering the precipitate through a glass funnel was dried in a vacuum oven at 80 ° C. for 24 hours to obtain a polymer (yield 74%).

Example 38
(Copolymerization of norbornene and 5-norbornene-2-carboxylic acid butyl ester (5: 1))
Norbornene (4 g, 42.5 mmol), 5-norbornene-2-carboxylic acid butyl ester (1.2 mL, 8.5 mmol) and toluene (14 mL) were charged into a 100 mL Schlenk flask. Precatalyst C and silver hexafluoroantimonate (AgSbF ₆ ) were dissolved in 5 ml of chlorobenzene in a glove box and stirred for 1 hour. Thereafter, 0.42 mmol of palladium catalyst filtered through a tube on which celite was laminated was put into the Schlenk flask, and stirred at a reaction temperature of 25 ° C. for 12 hours. After the reaction for 12 hours, this was put into an excessive amount of methanol to obtain a white copolymer precipitate. The copolymer obtained by filtering the precipitate through a glass funnel was dried in a vacuum oven at 80 ° C. for 24 hours to obtain a polymer (yield 89%).

Example 39
A copolymer of norbornene and 5-norbornene-2-carboxylic acid butyl ester (5: 1) is produced in the same manner as in Example 37, but the catalyst amount and polymerization used are as shown in Table 11 below. Although the time, anion, and solvent were the same, a polymer was prepared using Precatalyst C.

Comparative Example 14
A copolymer of norbornene and 5-norbornene-2-carboxylic acid butyl ester (5: 1) is produced in the same manner as in Example 37, but the catalyst amount and polymerization used are as shown in Table 11 below. Although the time, anion, and solvent were the same, a polymer was prepared using Precatalyst A.

Comparative Example 15
The experiment was performed in the same manner as in Example 11 except that [allyl PdCl] ₂ was used instead of the pre-catalyst A. However, the reaction did not proceed at all. The experimental results are shown in Table 12 below.

Comparative Example 16
The experiment was performed in the same manner as in Example 11 except that the salt compound AgBF ₄ was not used. However, the reaction did not proceed at all. The experimental results are shown in Table 12 below.

As shown in Examples 1 to 39, the metal catalyst complex according to the present invention is not only a norbornene having no substituent but also a homopolymerization and copolymerization of a norbornene monomer containing a polar substituent. In most cases, addition polymers were obtained in high yields without any reduction in catalyst activity by groups. And, in the case of using the pre-catalyst B (-I substituent) and the pre-catalyst C (-Br substituent) having a halogen substituent rather than the example using the pre-catalyst A having no halogen substituent, the weight average Increase in molecular weight (M _w ) by at least 5,000 or more (in the case of Examples 17 and 18 and Comparative Example 4: increase by 20,000 or more, in the case of Examples 19 and 20 and Comparative Example 5: 5,000 or more) Increase, Example 22 and Comparative Example 6: Increase by 10,000 or more, Example 25 and Comparative Example 8: Increase by 40,000 or more, Examples 26, 27 and Comparative Example 10: 10 , More than 1,000)) and showed relatively excellent catalytic ability. Such an improvement in performance is judged to be due to an improvement in catalytic ability due to a change in the electronic effect of the ligand.

More specifically, the production method of the present invention eliminates the electronic effect of the ligand by using a catalyst in which a carbene ligand having a functional group capable of providing the electronic effect of the ligand is used. The weight average molecular weight (M _w ) or yield was higher than when a catalyst was used.

In particular, in the case of norbornene containing a polar substituent, since the reactivity is generally low, an increase in yield as in the present invention or an increase in weight average molecular weight (M _w ) of 5,000 or more is commercially Judged to be important.

For example, in Sen et al. (Sen, et al., Organometallics 2001, Vol. 20, 2802-2812), [(1,5-cyclooctadiene) (CH ₃ ) Pd (Cl)] is changed to PPh ₃ . The ester norbornene was polymerized by activation with a cocatalyst such as phosphine and [Na] ⁺ [B (3,5- (CF ₃ ) ₂ C ₆ H ₃ ) ₄ ] ⁻ . However, under experimental conditions using about 1/400 of the catalyst as compared with the monomer, the polymerization yield was 40% or less, and the molecular weight of the polymer obtained was about 6,500.

In US Pat. No. 6,455,650, [(R ′) _z M (L ′) _x (L ″) _y ] _b [WCA] _d or the like is used as the catalyst complex, As a ligand used in the method, a hydrocarbon containing a hydrocarbyl group such as a phosphine and an allyl group is used, and a method for polymerizing a norbornene monomer having a functional group is disclosed. However, also in this case, when a norbornene monomer having a polar functional group such as a carbonyl group was polymerized, the yield was 5%, which was very low.

Thermal stability measurement (TGA)
The TGA measurement for about 4.4 to 4.6 mg of polynorbornene 2-carboxylic acid methyl ester (exo: endo = 50: 50) was performed under heating conditions of 10 ° C./min using Perkin-Elmer TGA-7. Nitrogen (N ₂ ) was blown in at a rate of 5 mL / min. The TGA experimental results of the homopolymer prepared according to Examples 16 to 18 and Comparative Example 4 are shown in FIG. As shown in FIG. 2, all polymers exhibited excellent thermal stability without change in weight up to temperatures of 300 ° C. or higher.

2 is an X-ray structure of a total metal catalyst ignition according to Example 10. 6 is a TGA (ThermoGravimetric Analysis) graph of norbornene homopolymer produced by Examples 16 to 18 and Comparative Example 4. FIG.

Claims (18)

A method for producing a cyclic olefin polymer by addition polymerization of a cyclic olefin monomer,
A method for producing a cyclic olefin polymer comprising the step of contacting a metal catalyst complex represented by the following chemical formula 1 with a cyclic olefin monomer represented by the following chemical formula 2:
Where
M is a Group 10 metal,
[M (L ₁ ) _x (L ′ ₂ ) _y (L ₃ ) _z ] is a cationic complex,
L1 is a ligand comprising an anionic hydrocarbyl;
L ′ ₂ is a neutral ligand,
L ₃ is an N-heterocyclic carbene ligand;
[Ani] is an anion that can be weakly coordinated to the metal M;
x is 1 or 2, y is 0 to 4, z is 1 or 2, 2 ≦ x + y + z ≦ 6,
a and b are each a number indicating a cation and an anion that can be weakly coordinated, and is a number between 1 and 10 that balances the charge of the entire catalyst compound;
When a plurality of the ligands are present in the complex molecule, they are the same as or different from each other;
Where
m is an integer from 0 to 4,
R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ each independently represents a polar functional group or a non-polar functional group;
R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ can be linked together to form a C ₄ -C ₁₂ saturated or unsaturated ring group, or a C ₆ -C ₂₄ aromatic ring,
The non-polar functional groups, hydrogen; _halogen; C 1 linear or branched alkyl _{-C 20,} haloalkyl, alkenyl, _haloalkenyl; C for 3 _{-C 20} linear or branched alkynyl, haloalkynyl; alkyl, alkenyl , alkynyl, halogen, haloalkyl, haloalkenyl, or a substituted or unsubstituted C ₃ -C ₁₂ cycloalkyl in haloalkynyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl or substituted or non-substituted haloalkynyl, C ₆ -C ₄₀ aryl; or alkyl, alkenyl, alkynyl, selected from halogen, haloalkyl, haloalkenyl, or from the group consisting of substituted or unsubstituted _C 7 _{-C 15} aralkyl in haloalkynyl,
The polar working group is a non-hydrocarbon polar group comprising at least one or more oxygen, nitrogen, phosphorus, sulfur, silicon, or boron;
^{-R 8 OR 9, -OR 9,} -OC (O) OR 9, -R 8 OC (O) OR 9, -C (O) R 9, -R 8 C (O) R 9, -OC (O ^{) R 9, -R 8 C (} O) OR 9, -C (O) OR 9, -R 8 OC (O) R 9, - (R 8 O) k-OR 9, - (OR 8) k - ^{OR 9, -C (O) -O} -C (O) R 9, -R 8 C (O) -O-C (O) R 9, -SR 9, -R 8 SR 9, -SSR 8, - ^{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, - ^{_{8 NO 2, -P (R 9}} ) 2, -R 8 P (R 9) 2, -P (= O) (R 9) 2, -R 8 P (= O) (R 9) 2,
Selected from the group consisting of
The polar working group,
Each R ⁸ and R ¹¹ is C ₁ -C ₂₀ linear or branched alkylene, haloalkylene, alkenylene, haloalkenylene; C ₃ -C ₂₀ linear or branched alkynylene, haloalkynylene; alkyl, alkenyl, alkynyl. , Halogen, haloalkyl, haloalkenyl, haloalkynyl substituted or unsubstituted C ₃ -C ₁₂ cycloalkylene; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl substituted or unsubstituted C ₆ -C ₄₀ Arylene; or alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl substituted or unsubstituted C ₇ -C ₁₅ aralkylene;
Each R ⁹ , R ¹² , R ¹³ and R ¹⁴ is hydrogen; halogen; C ₁ -C ₂₀ linear or branched alkyl, haloalkyl, alkenyl, haloalkenyl; C ₃ -C ₂₀ linear or branched. alkynyl, haloalkynyl, alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl or haloalkynyl a substituted or unsubstituted _C 3 _{-C 12} cycloalkyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or halo, alkynyl substituted or unsubstituted _C 6 _{-C 40} aryl, alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or a substituted or unsubstituted _C 7 _{-C 15} aralkyl in haloalkynyl; or alkoxy, haloalkoxy, shea Le, siloxy, aryloxy, halo aryloxy, arylcarbonyloxy, halo carbonyloxy,
Each k is an integer of 1 to 10. The method for producing a cyclic olefin polymer according to claim 1, wherein the N-heterocyclic carbene ligand is one or more selected from the group consisting of the following chemical formulas 4A to 4D:
Where
R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ and R ₃₀ are each independently hydrogen, C ₁ -C ₂₀ linear or branched alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C. linear or branched alkenyl of _20, C 6 _{-C 15 cycloalkenyl,} C 3 _-C linear or branched allyl _20, C 6 _{-C 30} aryl, _C 6 _{-C 30} aryl or _{C 7} containing heteroatoms -C was ₃₀ aralkyl, wherein each of the functional group is substituted with one or more hydrocarbyl and / or heteroatom substituents, the such a substituent, a linear or branched alkyl of C ₁ -C ₅ C ₁ -C ₅ linear or branched haloalkyl, C ₂ -C ₅ linear or branched alkenyl, haloalkenyl, halogen, sulfur, oxygen, nitrogen, phosphorus or phenyl group It can include the phenyl group, C ₁ -C ₅ linear or branched alkyl, linear or branched haloalkyl of C ₁ -C _5, can be substituted by halogen and hetero atom. The [Ani] is an anion that can be weakly coordinated to the group 10 metal M, and includes borate, aluminate, [SbF ₆ ] −, [PF ₆ ] −, [AsF ₆ ] −, perfluoroacetate ([CF ₃ CO _2] -), perfluoro propionate _{([C 2 F 5 CO 2} ] -), perfluoro butyrate _{([CF 3 CF 2 CF 2} CO 2] -), perchlorate _([ClO 4] -) , para - toluenesulfonate _{([p-CH 3 C 6} H 4 SO 3] -), [SO 3 CF 3] -, boratabenzene, and any one selected from the group consisting of carborane substituted or unsubstituted with a halogen one The method for producing a cyclic olefin polymer according to claim 1, wherein The method for producing a cyclic olefin polymer according to claim 3, wherein the borate or aluminate comprises an anion represented by the following chemical formula 5A or 5B:
Where
M ′ is boron or aluminum,
Each R ₃₀ is independently halogen; halogen substituted or unsubstituted C ₁ -C ₂₀ linear or branched alkyl, alkenyl; halogen substituted or unsubstituted C ₃ -C ₁₂ cycloalkyl; halogen or carbon _{C 6} to linear or branched triarylsiloxy of C 3 linear or branched trialkyl _{-C 20} siloxy or _C 18 _{-C 48} is replaced _{-; C} 6 _-C substituted or unsubstituted hydrogen ₄₀ aryl C ₄₀ aryl; C ₇ -C ₁₅ aralkyl substituted or unsubstituted with halogen or hydrocarbon. The method for producing a cyclic olefin polymer according to claim 1, wherein the metal catalyst complex is represented by the following chemical formula 6.
Where
M, L ₁ , L ′ ₂ , L ₃ , [Ani], a and b are as defined in claim 1 above. The method for producing a cyclic olefin polymer according to claim 1, wherein the metal catalyst complex is represented by the following chemical formulas 7A to 7D:
Where
M, L1, L′ 2, [Ani], a and b are as defined in claim 1;
R ₁ to R ₆ are each independently hydrogen, halogen, C ₁ -C ₂₀ linear or branched alkyl, alkoxy, allyl, alkenyl or vinyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or substituted or unsubstituted _C 3 _{-C 12} cycloalkyl in haloalkynyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or a substituted or unsubstituted _C 6 _{-C 40} aryl in haloalkynyl; alkyl, alkenyl, alkynyl , Halogen, haloalkyl, haloalkenyl, or haloalkynyl substituted or unsubstituted C ₇ -C ₁₅ aralkyl; or C ₃ -C ₂₀ alkynyl. The method for producing a cyclic olefin polymer according to claim 1, wherein the metal catalyst complex is represented by the following chemical formula 8:
Where
M, L1, L′ 2, [Ani], a and b are as defined in claim 1;
R ₁ , R ₂ and R ₅ are each independently hydrogen, halogen, C ₁ -C ₂₀ linear or branched alkyl, alkoxy, allyl, alkenyl or vinyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl or a substituted or unsubstituted _C 3 _{-C 12} cycloalkyl in haloalkynyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or a substituted or unsubstituted _C 6 _{-C 40} aryl in haloalkynyl; alkyl , Alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl substituted or unsubstituted C ₇ -C ₁₅ aralkyl; or C ₃ -C ₂₀ alkynyl. The method for producing a cyclic olefin polymer according to claim 1, wherein the metal catalyst complex is represented by the following chemical formula 9:
Where
M, L′ 2, [Ani], a and b are as defined in claim 1;
R ₁ , R ₂ and R ₅ are each independently hydrogen, halogen, C ₁ -C ₂₀ linear or branched alkyl, alkoxy, allyl, alkenyl or vinyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl or a substituted or unsubstituted _C 3 _{-C 12} cycloalkyl in haloalkynyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or a substituted or unsubstituted _C 6 _{-C 40} aryl in haloalkynyl; alkyl , Alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or haloalkynyl substituted or unsubstituted C ₇ -C ₁₅ aralkyl; or C ₃ -C ₂₀ alkynyl;
Is a _{C 3} allyl.   The method for producing a cyclic olefin polymer according to claim 1, wherein the metal catalyst complex is supported on a fine particle support.   The fine particle support is silica, titania, silica / chromia, silica / chromia / titania, silica / alumina, aluminum phosphate gel, silanized silica, silica hydrogel, montmorillonite clay or zeolite. The method for producing a cyclic olefin polymer according to claim 9.   The method for producing a cyclic olefin polymer according to claim 1, wherein the metal catalyst complex is used by being dissolved in an organic solvent selected from the group consisting of dichloromethane, dichloroethane, toluene, chlorobenzene and a mixture thereof. .   2. The method for producing a cyclic olefin polymer according to claim 1, wherein the metal catalyst complex is charged into the monomer solution in a solid phase.   A cyclic olefin homopolymer in which the cyclic olefin polymer has a polar functional group, a copolymer of cyclic olefin monomers having different polar functional groups, and a cyclic olefin monomer having a polar functional group; The method for producing a cyclic olefin polymer according to claim 1, comprising a copolymer with a cyclic olefin monomer having no polar working group. The method for producing a cyclic olefin polymer according to claim 1, wherein the cyclic olefin polymer has a weight average molecular weight ( _Mw ) of 20,000 to 500,000. A cyclic olefin polymer produced by the method according to any one of claims 1 to 14,
A cyclic olefin polymer comprising a polar functional group having a weight average molecular weight of 20,000 to 500,000. The cyclic olefin polymer according to claim 15, wherein the polymer is represented by the following chemical formula 11:
Where
m, R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ are the same as defined in claim 1 above;
One or more of R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ are polar working groups, and n is a real number of 100 to 5,000 representing the degree of polymerization. The cyclic olefin polymer according to claim 15, wherein the polymer is represented by the following chemical formula 12.
Where
m, R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ are the same as defined in claim 1 above;
One or more of R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ are polar functional groups, and R ₁₇ , R ₁₇ ′, R ₁₇ ″ and R ₁₇ ′ ″ are independent of each other. A non-polar working group: hydrogen; halogen; C ₁ -C ₂₀ linear or branched alkyl, haloalkyl, alkenyl, haloalkenyl; C ₃ -C ₂₀ linear or branched type alkynyl, haloalkynyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl or haloalkynyl a substituted or unsubstituted _C 3 _{-C 12} cycloalkyl; alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, or, Substituted or unsubstituted C ₆ -C ₄₀ aryl on haloalkynyl; or alkyl, alkenyl, alkynyl, halogen, haloalkyl Selected from the group consisting of alkyl, haloalkenyl, or haloalkynyl substituted or unsubstituted C ₇ -C ₁₅ aralkyl;
m may be different from each other,
n ′ represents a degree of polymerization and is a real number of 100 to 2,500,
c and d are molar ratios, c + d = 1,
0.1 ≦ c ≦ 0.95 and 0.05 ≦ d ≦ 0.9. The cyclic olefin polymer according to claim 15, wherein the polymer is represented by the following chemical formula (13):
Where
m, R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ are the same as defined in claim 1 above;
One or more of R ₇ , R ₇ ′, R ₇ ″ and R ₇ ′ ″ are polar functional groups,
m may be different from each other,
n ″ represents a degree of polymerization and is a real number of 100 to 2,500,
e and f are molar ratios, e + f = 1,
0.1 ≦ e ≦ 0.9 and 0.1 ≦ f ≦ 0.9,
The structures of the repeating unit having the molar ratio e and the repeating unit having the molar ratio f are different from each other.