Catalyst composition for ring-opening metathesis polymerization of cycloolefin-based monomers and method for preparing cycloolefin-based polymer using same

Abstract

The present invention relates to a catalyst composition for ring-opening metathesis polymerization of cycloolefin-based monomers and a method for preparing a cycloolefin-based polymer using same and, more specifically, to a catalyst composition for ring-opening metathesis polymerization of cycloolefin-based monomers, capable of ring-opening metathesis polymerization of cycloolefin-based monomers within the same reaction system, and a method for preparing a cycloolefin-based polymer using same.

Description

Catalyst composition for ring-opening metathesis polymerization of cyclic olefin monomers and method for producing cyclic olefin polymers using the same

[0001] The present invention relates to a catalyst composition for ring-opening metathesis polymerization of a cyclic olefin monomer and a method for producing a cyclic olefin polymer using the same, and more particularly, to a catalyst composition for ring-opening metathesis polymerization of a cyclic olefin monomer capable of ring-opening metathesis polymerization of a cyclic olefin monomer in the same reaction system and a method for producing a cyclic olefin polymer using the same.

[0002] Until now, inorganic materials such as silicon oxide and silicon nitride have been primarily used in the information and electronics industry. However, the growing need for small, highly efficient devices is fueling the need for high-performance new materials. Interest is growing in oligomers and polymers that can satisfy these high-performance requirements, which feature low dielectric constants and water absorption, excellent metal adhesion, mechanical strength, heat resistance, and transparency, as well as high glass transition temperatures (Tg > 250°C).

[0003] These oligomers or polymers can be used as electronic materials such as insulating films for semiconductors or TFT-LCDs, polarizing plate protective films, multichip modules, integrated circuits (ICs), printed circuit boards, encapsulating materials for electronic materials, or flat panel displays.

[0004] In particular, cyclic olefin polymers are polymers composed of cyclic monomers such as norbornene, and compared to existing olefin polymers, they have superior transparency, heat resistance, and chemical resistance, and very low birefringence and water absorption, so they can be applied in various ways, such as optical materials such as CDs, DVDs, and POF (Plastic Optical Fiber), information and electronic materials such as capacitor films and low-k dielectrics, and medical materials such as low-absorbency syringes and blister packaging.

[0005] As a catalyst used for polymerizing such cyclic olefin polymers, U.S. Patent No. 5,705,503 discloses a method for polymerizing norbornene monomers using [(Allyl)PdCl]2 / AgSbF6 as a catalyst complex. However, since the catalyst to monomer ratio is 1:100 to 1:250, which is an excessive amount of catalyst, a large amount of catalyst residue remains in the final polymer obtained, and there is a concern that the polymer may deteriorate due to thermal oxidation in the future, and there is also a concern that light transmittance may deteriorate.

[0006] Also, U.S. Patent No. 6,455,650 discloses a catalyst complex [(R') z M(L') x (L'') y ] b [WCA] d A method for polymerizing a norbornene monomer is disclosed, but when polymerizing a norbornene monomer, the yield is very low at 5%, so there was a problem that it was not suitable for producing a polymer.

[0007] Therefore, a catalyst system capable of polymerizing cyclic olefin monomers in an economical manner without generating catalyst residues, etc. is required.

[0008] [Prior Art Literature]

[0009] [Patent Document]

[0010] (Patent Document 1) U.S. Patent No. 5705503 (Registration Date: January 6, 1998)

[0011] (Patent Document 2) U.S. Patent No. 6,455,650 (Published: May 2, 2002)

[0012] (Patent Document 3) U.S. Patent No. 6031058 (Registration Date: February 29, 2000)

[0013] (Patent Document 4) U.S. Patent No. 6,455,650 (Published: May 2, 2002)

[0014] The main purpose of the present invention is to solve the above-mentioned problems, and to provide a catalyst composition for ring-opening metathesis polymerization of a cyclic olefin monomer, which can produce a catalyst for cyclic olefin polymerization simply and economically by producing the catalyst in the same reaction system, and which can produce a cyclic olefin polymer with high catalytic activity in the polymerization of the cyclic olefin monomer.

[0015] In addition, another object of the present invention is to provide a method for producing a cyclic olefin polymer, which can economically produce a cyclic olefin polymer that cannot be provided by addition polymerization, by polymerizing a cyclic olefin monomer in the presence of a catalyst composition for ring-opening metathesis polymerization of the above cyclic olefin monomer.

[0016] In order to achieve the above object, one embodiment of the present invention provides a catalyst composition for ring-opening metathesis polymerization of a cyclic olefin monomer, characterized in that it comprises a ruthenium-containing metal precursor compound; a compound represented by the following chemical formula 1 or chemical formula 2; and an organoaluminum compound.

[0017] [Chemical Formula 1]

[0018]

[0019] [Chemical Formula 2]

[0020] P(R)3

[0021] In the above chemical formulas 1 and 2, Y is a carbon atom or a nitrogen atom, Z is selected from the group consisting of an oxygen atom; a sulfur atom; and -(CH2)-;, m is an integer of 0 to 3, and R is each independently selected from the group consisting of a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms; a substituted or unsubstituted allyl group having 3 to 20 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 12 carbon atoms; and a substituted or unsubstituted aryl group having 6 to 40 carbon atoms.

[0022] In a preferred embodiment of the present invention, the compound represented by the chemical formula 1 may be characterized as being a compound represented by any one of the following chemical formulas 1a, 1b, and 1c.

[0023] [Chemical Formula 1a]

[0024]

[0025] [Chemical Formula 1b]

[0026]

[0027] [Chemical Formula 1c]

[0028]

[0029] In a preferred embodiment of the present invention, the compound represented by the chemical formula 2 may be characterized by being selected from the group consisting of tricyclohexyl phosphine, triisopropyl phosphine, tryphenyl phosphine, tri-t-butyl phosphine, and dicyclohexyl-t-butyl phosphine.

[0030] In a preferred embodiment of the present invention, the compound represented by the chemical formula 1 may be characterized by the following chemical formula 1c.

[0031] [Chemical Formula 1c]

[0032]

[0033] In a preferred embodiment of the present invention, the compound represented by the chemical formula 2 may be characterized as being tricyclohexyl phosphine.

[0034] In a preferred embodiment of the present invention, the organoaluminum compound may be characterized by being at least one selected from the group consisting of trimethyl aluminum (TMA), triethyl aluminum (TEA), triisobutyl aluminum (TIBAL), dimethyl chloro aluminum (DMCA), and diethyl chloroaluminum (DECA).

[0035] In a preferred embodiment of the present invention, the compound represented by the chemical formula 1 or 2 may be included in an amount of 1 to 5 moles per mole of the ruthenium-containing metal precursor compound.

[0036] In a preferred embodiment of the present invention, the organic aluminum compound may be included in an amount of 1 to 40 moles per mole of the ruthenium-containing metal precursor compound.

[0037] Another embodiment of the present invention provides a method for producing a cyclic olefin polymer, characterized in that it comprises a step of ring-opening metathesis polymerizing a cyclic olefin monomer in the presence of a catalyst composition for ring-opening metathesis polymerization of the cyclic olefin monomer.

[0038] In another preferred embodiment of the present invention, in the catalyst composition for ring-opening metathesis polymerization of the cyclic olefin monomer, the ruthenium-containing metal precursor compound and the compound represented by the following chemical formula 1 or chemical formula 2 may be characterized in that they are formed as a complex compound in-situ during the ring-opening metathesis polymerization.

[0039] In another preferred embodiment of the present invention, the cyclic olefin monomer may be characterized by being at least one selected from the group consisting of norbornene, dicyclopentadiene, cyclopentadiene, cyclopentene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and derivatives thereof.

[0040] In another preferred embodiment of the present invention, the cyclic olefin monomer may be characterized as being a compound represented by the following chemical formula 4.

[0041] [Chemical Formula 4]

[0042]

[0043] In the above chemical formula 4, n is an integer from 0 to 4, and R 11 Inland R 14 are the same or different, and each independently selected from the group consisting of a hydrogen atom; a halogen atom; a hydroxyl group; a carboxyl group; a linear or branched alkyl group having 1 to 20 carbon atoms; a cycloalkyl group having 3 to 12 carbon atoms; an aryl group having 6 to 20 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; and an acyl group having 1 to 10 carbon atoms.

[0044] According to the present invention, since the formation of a catalytically active species in the same reaction system in situ during polymerization of a cyclic olefin monomer is possible, the catalyst synthesis process or the residual impurity removal process can be omitted, thereby enabling the economical and environmentally friendly production of a catalyst and a cyclic olefin polymer through the omission of catalyst synthesis and purification steps.

[0045] In addition, the cyclic olefin polymer manufactured using the catalyst according to the present invention not only has a stereoselectivity, a high molecular weight, and a glass transition temperature (Tg) that allows for molding processability, which are not achieved by free radical polymerization, but also can provide a ring-opening metathesis polymer in a form that cannot be provided by addition polymerization.

[0046] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

[0047] Throughout this specification, whenever a part is said to 'include' a component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise specifically stated.

[0048] The present invention relates to a catalyst composition for ring-opening metathesis polymerization of a cyclic olefin monomer, characterized in that it comprises, in one aspect, a ruthenium-containing metal precursor compound; a compound represented by the following chemical formula 1 or chemical formula 2; and an organoaluminum compound.

[0049] [Chemical Formula 1]

[0050]

[0051] [Chemical Formula 2]

[0052] P(R)3

[0053] In the above chemical formulas 1 and 2, Y is a carbon atom or a nitrogen atom, Z is selected from the group consisting of an oxygen atom; a sulfur atom; and -(CH2)-;, m is an integer of 0 to 3, and R is each independently selected from the group consisting of a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms; a substituted or unsubstituted allyl group having 3 to 20 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 12 carbon atoms; and a substituted or unsubstituted aryl group having 6 to 40 carbon atoms.

[0054] More specifically, a catalyst composition for ring-opening metathesis polymerization of a cyclic olefin monomer according to one embodiment of the present invention comprises a ruthenium-containing metal precursor compound; a compound represented by the following chemical formula 1 or 2; and an organoaluminum compound, thereby forming a ruthenium complex compound instantaneously during the ring-opening metathesis polymerization process of the cyclic olefin monomer, thereby producing the cyclic olefin monomer into a polymer.

[0055] In the present invention, the metal precursor compound is a compound containing ruthenium that exhibits excellent catalytic activity in the ring-opening metathesis polymerization reaction of a cyclic olefin monomer. Any precursor such as a salt compound or complex of ruthenium can be used without particular limitation. The salt compound may be a salt compound that can be dissolved in an organic solvent, and specific examples thereof include acetate, nitrate, sulfate, carbonate, hydroxide, halide, and hydrate thereof. The complex may be exemplified by an acetylacetonate complex, a phosphine complex, and the like.

[0056] Meanwhile, in the present invention, the compound represented by Chemical Formula 1 or Chemical Formula 2 is a ligand compound that is instantaneously coordinated to the aforementioned metal precursor compound introduced together during the polymerization reaction of a cyclic olefin monomer to form a complex compound in-situ.

[0057] At this time, X in the chemical formula 1 may be a carbon atom or a nitrogen atom, Z may be selected from the group consisting of an oxygen atom, a sulfur atom or -(CH2)-, preferably an oxygen atom or -(CH2)-, and m is an integer from 0 to 3, preferably m may be an integer of 1 and 2.

[0058] In addition, R in the above chemical formula 2 may be independently selected from the group consisting of a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms; a substituted or unsubstituted allyl group having 3 to 20 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 12 carbon atoms; and a substituted or unsubstituted aryl group having 6 to 40 carbon atoms.

[0059] The compound represented by the above chemical formula 1 or 2 can easily provide an unshared electron pair to the ligand of ruthenium due to its abundant electron density, and thus can be applied to the polymerization reaction of a cyclic olefin monomer in the same reaction system (in situ) to exhibit high reaction activity.

[0060] Specifically, the compound represented by Chemical Formula 1 according to one embodiment of the present invention may be characterized as a compound represented by any one of Chemical Formula 1a, Chemical Formula 1b, and Chemical Formula 1c below, and preferably, the compound represented by Chemical Formula 1 may be Chemical Formula 1c.

[0061] [Chemical Formula 1a]

[0062]

[0063] [Chemical Formula 1b]

[0064]

[0065] [Chemical Formula 1c]

[0066]

[0067] In addition, the compound represented by chemical formula 2 may be specifically selected from the group consisting of tricyclohexyl phosphine, triisopropyl phosphine, triphenyl phosphine, tri-t-butyl phosphine, and dicyclohexyl-t-butyl phosphine, and may preferably be tricyclohexyl phosphine in terms of steric and electronic aspects.

[0068] The compound represented by the above chemical formula 1 or 2 may be included in an amount of 1 to 5 moles, preferably 1 to 3 moles, per mole of the ruthenium-containing metal precursor compound. When the above content ratio is satisfied, a monodentate or bidentate ligand can be coordinated to the metal precursor compound to form a complex compound in the same reaction system with a high yield.

[0069] In the present invention, the complex formed in the same reaction system by the ruthenium-containing metal precursor compound and the compound represented by the following chemical formula 1 or 2 is formed by coordination bonding the compound represented by the above chemical formula 1 or 2 to the ruthenium of the metal precursor compound, and may specifically include at least one of the following chemical formulas 5 to 8.

[0070] [Chemical Formula 5]

[0071]

[0072] [Chemical Formula 6]

[0073]

[0074] [Chemical Formula 7]

[0075]

[0076] [Chemical Formula 8]

[0077]

[0078] In the above chemical formulas 5 to 8, Y is a carbon atom or a nitrogen atom, Z and m are substantially the same as Z and m described in chemical formulas 1 and 2, L is a group containing an atom capable of acting as NO, a halogen group, or a monodentate ligand, and X1 and X2 are the same or different and can each be independently selected from the group consisting of an acetoxy group, a hydroxy group, an alkoxy group, and a halogen group.

[0079] In X1 and X2 of the above chemical formulas 5 to 8, the halogen group may be at least one selected from the group consisting of a chlorine atom (Cl), a bromine atom (Br), and an iodine atom (I), and the alkoxy group may be an alkoxy group having 1 to 5 carbon atoms.

[0080] Meanwhile, in the present invention, the organic aluminum compound serves to activate the ruthenium component of the metal precursor compound, and may be at least one selected from the group consisting of trimethyl aluminum (TMA), triethyl aluminum (TEA), triiso-butyl aluminum (TIBAL), dimethyl chloro aluminum (DMCA), and diethyl chloroaluminum (DECA), and preferably triiso-butyl aluminum (TIBAL).

[0081] The above organic aluminum compound may be included in an amount of 1 to 40 moles, preferably 2 to 27 moles, per mole of the ruthenium-containing metal precursor compound. When the above content ratio is satisfied, it can be activated to instantly form a ruthenium-alkylidene unit [Ru=CR2, where R is a hydrogen atom, alkyl, aryl, etc.].

[0082] The above-mentioned catalyst composition for cyclic olefin ring-opening metathesis polymerization is introduced together with a cyclic olefin monomer during the polymerization of the desired cyclic olefin monomer to form a cyclic olefin polymer. It can be manufactured by instantaneously coordinating a compound of chemical formula 1 or 2 to a ruthenium atom of a metal precursor compound during the ring-opening metathesis polymerization reaction of the cyclic olefin monomer to form a complex compound.

[0083] At this time, the catalyst composition for cyclic olefin polymerization may be introduced when each component is dissolved in an inert solvent during cyclic olefin monomer polymerization. Non-limiting examples of the inert solvent include aromatic hydrocarbons such as benzene, toluene, xylene, benzonitrile, chlorobenzene, nitrobenzene, adiponitrile, anisole, and phenylnonane; aliphatic hydrocarbons having 5 to 20 carbon atoms such as pentane, hexane, heptane, and adiponitrile; halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride; Non-fluorinated, saturated substituted aliphatic hydrocarbons and / or aromatic hydrocarbons having 1 to 20 carbon atoms, including compounds selected from the group consisting of alcohols such as methanol, propanol, butanol, isopropanol, and 2,4-ditert-butyl phenol; ketones such as acetone; carboxylic acids such as propanoic acid and acetic acid; esters such as ethyl acetate, ethyl benzoate, dimethyl succinate, butyl acetate, tri n-butyl phosphate, and dimethyl phosphate; ethers such as tetraethylene glycol dimethyl ether (tetraglyme), and mixtures thereof, and aromatic hydrocarbons can be preferably used.

[0084] From another perspective, the present invention relates to a method for producing a cyclic olefin polymer, characterized in that it comprises a step of subjecting a cyclic olefin monomer to a ring-opening metathesis polymerization reaction in the presence of a catalyst composition for cyclic olefin ring-opening metathesis polymerization as described above.

[0085] Any cyclic olefin monomer capable of forming a polymer may be used as the cyclic olefin monomer. In the present invention, examples of the cyclic olefin monomer include one or more selected from norbornene (Nb) and its derivatives, dicyclopentadiene (DCPD) and its derivatives, cyclopentadiene (CPD) and its derivatives, cyclopentene (Cp) and its derivatives, cyclobutene (Cb) and its derivatives, cyclohexene (Chx) and its derivatives, cycloheptene (Chp) and its derivatives, and cyclooctene (Cot) and its derivatives, and preferably, it may be a compound represented by the following chemical formula 4.

[0086] [Chemical Formula 4]

[0087]

[0088] In the above chemical formula 4, n is an integer from 0 to 4, and R 11 Inland R 14 are the same or different, and each independently selected from the group consisting of a hydrogen atom; a halogen atom; a hydroxyl group; a carboxyl group; a linear or branched alkyl group having 1 to 20 carbon atoms; a cycloalkyl group having 3 to 12 carbon atoms; an aryl group having 6 to 20 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; and an acyl group having 1 to 10 carbon atoms.

[0089] In the above chemical formula 4, n is an integer from 0 to 2, and R 11 Inland R 14are the same or different, and each independently selected from the group consisting of a hydrogen atom; a carboxyl group; a linear or branched alkyl group having 1 to 5 carbon atoms; a cycloalkyl group having 3 to 12 carbon atoms; an aryl group having 6 to 18 carbon atoms; an alkoxy group having 1 to 5 carbon atoms; and an acyl group having 1 to 6 carbon atoms, which is preferable in terms of polymerization.

[0090] In the present invention, the above-mentioned cyclic olefin monomer may be reacted alone, or two or more cyclic olefin monomers may be reacted. In this case, any cyclic olefin monomer that can be polymerized with a cyclic olefin monomer may be used without limitation.

[0091] When polymerizing a cyclic olefin monomer using the catalyst composition for cyclic olefin ring-opening metathesis polymerization of the present invention, the reaction may be carried out in a slurry phase, a liquid phase, or a gas phase. When the reaction is carried out in a liquid phase or a slurry phase, a solvent or the olefin itself may be used as a medium. The solvent used at this time may be one or more solvents selected from the group consisting of methylene chloride, 1,2-dichlorobenzene, toluene, n-pentane, n-hexane, n-heptane, chlorobenzene, dichloromethane, chloroform, 1,2-dichloroethane, and 1,1,2,2-tetrachloroethane.

[0092] At this time, the cyclic olefin monomer can be reacted by mixing 300 to 10,000 moles of the cyclic olefin monomer with respect to 1 mole of the ruthenium-containing metal precursor compound of the catalyst composition, and preferably 600 to 10,000 moles. If less than 300 moles of the cyclic olefin monomer are used with respect to 1 mole of the ruthenium-containing metal precursor compound, it is economically disadvantageous due to excessive use of the catalyst, and if it exceeds 10,000 moles, the polymerization yield may be lowered due to a decrease in the amount of the catalyst composition used compared to the cyclic olefin monomer.

[0093] In addition, when polymerizing a cyclic olefin monomer using the catalyst composition for cyclic olefin ring-opening metathesis polymerization of the present invention, one or more components of the catalyst composition for cyclic olefin ring-opening metathesis polymerization may be first mixed with the cyclic olefin monomer and then the components of the remaining catalyst composition may be mixed to perform a polymerization reaction (two-pot), or the catalyst composition may be mixed with the cyclic olefin monomer all at once to perform a polymerization reaction (one-pot).

[0094] The above reaction can be carried out in batch, semi-continuous or continuous manner, and the reaction conditions can be carried out at 0℃ to 120℃, preferably at room temperature (room temperature) for 1 hour to 26 hours. If the reaction is carried out at 0℃ or for less than 1 hour, the problem of the reaction not progressing sufficiently may occur, and if it is carried out at 120℃ or for more than 26 hours, the polymer chains may be decomposed, resulting in a decrease in molecular weight or gelation.

[0095] The cyclic olefin polymer manufactured in this way has a double bond within the polymer, and thus can proceed to the next hydrogenation step without removing the catalyst residue after polymerization, and has a glass transition temperature (Tg) that allows for stereoselectivity, high molecular weight, and molding processability that are not achieved by free radical polymerization, and can have a form that cannot be provided by addition polymerization.

[0096] Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to the following examples.

[0097] <Manufacturing Examples 1 to 3: Preparation of Ligand Compounds>

[0098] <Manufacturing Example 1: Preparation of 2-(piperidine-1-ylmethyl)quinoline (L1)>

[0099] 2-(piperidine-1-ylmethyl)quinoline (hereinafter, L1) was prepared by the following method with reference to 'Tetrahedron Letters 2018, 59, 1723.'

[0100] 2-(chloromethyl)quinoline hydrochloride (4.28 g, 20.0 mmol) was dissolved in 50 ml of distilled water, and then 1.70 g (20.0 mmol) of piperidine was added and mixed. 2.24 g (40.0 mmol) of KOH was slowly added to the mixture, and the mixture was reacted at room temperature for 24 hours to obtain a reaction product. The obtained reaction product was extracted with 50 ml of methylene chloride, and the remaining water was removed with anhydrous MgSO4 and filtered. The filtered solvent was removed by drying under reduced pressure, and the obtained mixture was distilled under reduced pressure to obtain 2.63 g (58.0%) of a yellow solid compound represented by chemical formula 1a, 2-(piperidine-1-ylmethyl)quinoline.

[0101] <Manufacturing Example 2: Preparation of 4-(quinolin-2-ylmethyl)morpholine (L2)>

[0102] 4-(quinolin-2-ylmethyl)morpholine (hereinafter, L2) was prepared by the following method with reference to 'Tetrahedron Letters 2018, 59, 1723.'

[0103] 2-(chloromethyl)quinoline hydrochloride (4.67 g, 21.8 mmol) was dissolved in 50 ml of distilled water, and morpholine (1.90 g, 21.8 mmol) was added thereto and mixed. KOH (2.45 g, 43.6 mmol) was slowly added to the mixture, and the mixture was reacted at room temperature for 24 hours to obtain a reaction product. The obtained reaction product was extracted through 50 ml of methylene chloride, and the remaining water was removed with anhydrous MgSO4 and filtered. The filtered solvent was removed by drying under reduced pressure, and the obtained mixture was distilled under reduced pressure to obtain 2.84 g (57.0%) of a yellow, highly viscous liquid compound represented by chemical formula 1b, 4-(quinolin-2-ylmethyl)morpholine.

[0104] <Manufacturing Example 3: Preparation of 1-(naphthalen-2-ylmethyl)piperidine (L3)>

[0105] 2-(chloromethyl)naphthalene (3.53 g, 20.0 mmol) was dissolved in 25 ml of methylene chloride, and then piperidine (1.70 g, 20.0 mmol) was added and mixed. KOH (1.68 g, 30.0 mmol) and distilled water (10 ml) were slowly added to the mixture, and the mixture was reacted at room temperature for 4 days to obtain a reaction product. The obtained reaction product was extracted with methylene chloride, and the remaining water was removed with anhydrous MgSO4 and filtered. The filtered solvent was removed by drying under reduced pressure, and the obtained mixture was distilled under reduced pressure to obtain 3.01 g (66.5%) of a yellow solid compound represented by chemical formula 1c, 1-(naphthalen-2-ylmethyl)piperidine.

[0106] 1H NMR (500 MHz; CDCl3): δ7.84-7.80 (3H, m, Naphthalene-H), 7.75 (1H, s, Naphthalene-H), 7.52 (1H, dd,J= 8.45 Hz, Naphthalene-H), 7.46 (2H, m, Naphthalene-H), 3.65 (2H, s, NPiperidine-CH2-Naphthalene), 2.45 (4H, s, Piperidine-H), 1.61 (4H, quin,J= 11.23 Hz, Piperidine-H), 1.46 (2H, m, Piperidine-H)

[0107] <Examples 1 to 3 and Comparative Examples 1 to 3: Preparation of norbornene polymer in the same reaction system (in-situ)>

[0108] Example 1: Ring-opening metathesis polymerization using a catalyst composition consisting of RuCl3, L3, and TiBA

[0109] 1-1: One-pot method

[0110] Ring-opening metathesis polymerization of norbornene was performed in a flame-dried flask under argon using the Schlenk technique. As described in Table 1, RuCl3(anhyedrous) (0.1085 g; 25 μmol), the ligand compound L3 of Preparation Example 3 (0.0112 g; 50 μmol), and 10 ml of chlorobenzene were added to a 100 ml Schlenk flask, mixed, and stirred in an oil bath preheated to 60 °C for 1 hour. To this, a norbornene solution in which norbornene (1.500 g, 15.93 mmol) was dissolved in 10 ml of chlorobenzene was added, mixed, and triisobutylaluminium (TiBA, 0.1 ml, 0.397 mmol) was added, and the flask was sealed and the reaction was performed with stirring at 60 °C for 6 hours. To measure the conversion of monomers after the reaction, NMR analysis was performed using tetralin as a reference substance, and the results are shown in Table 2.

[0111] 1-2: Two-pot method

[0112] The ring-opening metathesis polymerization of norbornene (NB) using a two-pot method was performed by first activating RuCl3 with triisobutylaluminium, and the ring-opening metathesis polymerization of norbornene was performed by applying the Schlenk technique under argon in a flame-dried flask. As described in Table 1, RuCl3 (anhydrous) (0.1085 g; 25 μmol), the ligand compound L3 of Preparation Example 3 (0.0112 g; 50 μmol), and 10 ml of chlorobenzene were added to a 100 ml Schlenk flask, mixed, and stirred in an oil bath preheated to 60 °C for 30 minutes. Triisobutylaluminium (TiBA, 0.1 ml, 0.397 mmol) was then mixed at 60 °C for 30 minutes. A solution of activated norbornene (1,500 g, 15.93 mmol) was mixed with 10 ml of chlorobenzene and added to the flask. The flask was then sealed and the reaction was carried out with stirring at 60°C for 6 hours. After the reaction, NMR analysis was performed using tetralin as a reference substance to measure the monomer conversion rate, and the results are shown in Table 2.

[0113] Example 2: Ring-opening metathesis polymerization using a catalyst composition composed of RuCl3, PCy3, and TiBA

[0114] 2-1: One-pot method

[0115] A polymer was prepared in the same manner as in Example 1-1, but tricyclohexylphosphine (PCy3; 0.0140 g; 50 μmol) was added instead of the ligand compound L3 as described in Table 1, and then a polymerization reaction was performed at 60°C for 2 hours to prepare a polymer, and the results are shown in Table 2 in the same manner as in Example 1-1.

[0116] 2-2: Two-pot method

[0117] A polymer was prepared in the same manner as in Example 1-2, but tricyclohexylphosphine (PCy3, 0.0140 g; 50 μmol) was added instead of the ligand compound L3 as described in Table 1, and then a polymerization reaction was performed at 60°C for 2 hours to prepare a polymer, and the results are shown in Table 2 in the same manner as in Example 1-2.

[0118] Example 3: Ring-opening metathesis polymerization using a catalyst composition composed of Ru(NO)Cl3·xH2O, L3, and TiBA

[0119] 3-1: One-pot method

[0120] A polymer was prepared in the same manner as in Example 1-1, but instead of the ruthenium-containing metal precursor compound RuCl3 (0.1085 g; 25 μmol) as described in Table 1, Ru(NO)Cl3ㆍxH2O (0.0035 g; 15 μmol), the ligand compound L3 (0.0034 g; 15 μmol), and triisobutylaluminium (TiBA; 0.1 ml; 0.397 mmol) were added to prepare the polymer, and the results are shown in Table 2 in the same manner as in Example 1-1.

[0121] 3-2: Two-pot method

[0122] A polymer was prepared in the same manner as in Example 1-2, but instead of the ruthenium-containing metal precursor compound RuCl3 (0.1085 g; 25 μmol) as described in Table 1, Ru(NO)Cl3ㆍxH2O (0.0035 g; 15 μmol), the ligand compound L3 (0.0037 g; 15 μmol), and triisobutylaluminium (TiBA; 0.1 ml; 0.397 mmol) were added to prepare the polymer, and the results are shown in Table 2 in the same manner as in Example 1-2.

[0123] Example 4: Ring-opening metathesis polymerization using a catalyst composition composed of Ru(NO)Cl3·xH2O, PCy3, and TiBA

[0124] 4-1: One-pot method

[0125] A polymer was prepared in the same manner as in Example 3-1, but tricyclohexylphosphine (PCy3; 0.0042 g; 15 μmol) was added instead of the ligand compound L3 as described in Table 1, and the results are shown in Table 2 in the same manner as in Example 1-1.

[0126] 4-2: Two-pot method

[0127] A polymer was prepared in the same manner as in Example 3-2, but tricyclohexylphosphine (PCy3; 0.0042 g; 15 μmol) was added instead of the ligand compound L3 as described in Table 1, and the results are shown in Table 2 in the same manner as in Example 1-2.

[0128] Comparative Example 1: Ring-opening metathesis polymerization using TiBA

[0129] 1-1: One-pot method

[0130] A polymer was prepared in the same manner as in Example 1-1, but only triisobutylaluminium (TiBA; 0.20 ml; 0.79 mmol) was added as described in Table 1, and the results are shown in Table 2 in the same manner as in Example 1-1.

[0131] Comparative Example 2: RuCl3 and Ring-opening metathesis polymerization using TiBA

[0132] 2-1: One-pot method

[0133] A polymer was prepared in the same manner as in Example 1-1, but only RuCl3 (0.1085 g; 25 μmol) and triisobutylaluminium (TiBA; 0.252 ml; 1.00 mmol) were added as described in Table 1, and the polymer was polymerized at room temperature for 2 hours, and the results are shown in Table 2 in the same manner as in Example 1-1.

[0134] 2-2: Two-pot method

[0135] A polymer was prepared in the same manner as in Example 1-2, but only RuCl3 (0.1085 g; 25 μmol) and triisobutylaluminium (TiBA; 0.252 ml; 1.00 mmol) were added to toluene as described in Table 1, and polymerization was performed at room temperature for 2 hours to prepare a polymer, and the results are shown in Table 2 in the same manner as in Example 1-2.

[0136] Comparative Example 3: Ru(NO)Cl3·xH2O and Ring-opening metathesis polymerization using TiBA

[0137] 3-1: One-pot method

[0138] A polymer was prepared in the same manner as in Example 3-1, but Ru(NO)Cl was used as described in Table 1. 3ㆍ A polymer was prepared by polymerizing at room temperature for 2 hours by adding only xH2O (0.0035 g; 15 μmol) and triisobutylaluminium (TiBA; 0.1 ml, 0.397 mmol), and the results are shown in Table 2 in the same manner as in Example 1-1.

[0139] 3-2: Two-pot method

[0140] A polymer was prepared in the same manner as in Example 3-2, but Ru(NO)Cl was used as described in Table 1. 3·A polymer was prepared by polymerizing at room temperature for 2 hours by adding only xH2O (0.0035 g; 15 μmol) and triisobutylaluminium (TiBA; 0.1 ml, 0.397 mmol), and the results are shown in Table 2 in the same manner as in Example 1-2.

[0141] [Table 1]

[0142]

[0143] [Table 2]

[0144]

[0145] As shown in Table 2, in the case of Comparative Examples 1-1 to 3-2, it was confirmed that no norbornene polymer was produced, whereas in the case of Examples 1-1 to 4-2, a norbornene polymer was produced in the same reaction system.

[0146] <Examples 5 and 6: Preparation of butylnorbornene polymer in the same reaction system (in-situ)>

[0147] Example 5: Ring-opening metathesis polymerization using a catalyst composition composed of RuCl3, L3, and TiBA

[0148] A polymer was prepared in the same manner as in Example 1-1, but butylnorbornene (BuNB; 2.5 ml; 15 mmol) was added as described in Table 3, and then a polymerization reaction was performed at 60°C for 12 hours to prepare a polymer, and the results are shown in Table 4 in the same manner as in Example 1-1.

[0149] Example 6: Ring-opening metathesis polymerization using a catalyst composition composed of Ru(NO)Cl3·xH2O, PCy3, and TiBA

[0150] A polymer was prepared in the same manner as in Example 3-1, but butylnorbornene (BuNB; 2.5 ml; 15 mmol) was added as described in Table 3, and then a polymerization reaction was performed at 60°C for 12 hours to prepare a polymer, and the results are shown in Table 4 in the same manner as in Example 3-1.

[0151] [Table 3]

[0152]

[0153] [Table 4]

[0154]

[0155] As shown in Table 4, it was confirmed that butylnorbornene could be polymerized in the same reaction system using the catalyst compositions of Examples 5 and 6.

[0156] <Examples 7 and 8: Preparation of methyl bicyclo[2.2.1]hept-5-ene-2-carboxylate polymer in situ>

[0157] Example 7: Ring-opening metathesis polymerization using a catalyst composition consisting of RuCl3, L3, and TiBA

[0158] A polymer was prepared in the same manner as in Example 1-1, but methyl bicyclo[2.2.1]hept-5-ene-2-carboxylate (MeNB; 2.2 ml; 15 mmol) represented by the following chemical formula 10 was added as described in Table 5, and then a polymerization reaction was performed at 60°C for 12 hours to prepare a polymer, and the results are shown in Table 6 in the same manner as in Example 1-1.

[0159] [Chemical Formula 10]

[0160]

[0161] Example 8: Ring-opening metathesis polymerization using a catalyst composition composed of Ru(NO)Cl3·xH2O, PCy3, and TiBA

[0162] A polymer was prepared in the same manner as in Example 3-1, but methyl bicyclo[2.2.1]hept-5-ene-2-carboxylate (MeNB; 2.2 ml; 15 mmol) represented by the chemical formula 10 as described in Table 5 was added, and then a polymerization reaction was performed at 60°C for 12 hours to prepare a polymer, and the results are shown in Table 6 in the same manner as in Example 3-1.

[0163] [Table 5]

[0164]

[0165] [Table 6]

[0166]

[0167] As shown in Table 6, it was confirmed that methyl bicyclo[2.2.1]hept-5-ene-2-carboxylate could be polymerized in the same reaction system using the catalyst compositions of Examples 7 and 8.

[0168] <Examples 9 and 10: Preparation of methyl 2-methylbicyclo[2.2.1]hept-5-ene-2-carboxylate polymer in situ>

[0169] Example 9: Ring-opening metathesis polymerization using a catalyst composition consisting of RuCl3, L3, and TiBA

[0170] A polymer was prepared in the same manner as in Example 1-1, but methyl 2-methylbicyclo[2.2.1]hept-5-ene-2-carboxylate (MMENB; 1.53 g; 9.02 mmol) represented by the following chemical formula 11 was added as described in Table 7, and then a polymerization reaction was performed at 60°C for 16 hours to prepare a polymer, and the results are shown in Table 8 in the same manner as in Example 1-1.

[0171] [Chemical Formula 11]

[0172]

[0173] Example 10: Ring-opening metathesis polymerization using a catalyst composition composed of RuCl3, PCy3, and TiBA

[0174] A polymer was prepared in the same manner as in Example 2-1, but methyl 2-methylbicyclo[2.2.1]hept-5-ene-2-carboxylate (MMENB; 1.53 g; 9.02 mmol) represented by the chemical formula 11 as described in Table 7 was added, and then a polymerization reaction was performed at 60°C for 16 hours to prepare a polymer, and the results are shown in Table 8 in the same manner as in Example 1-1.

[0175] [Table 7]

[0176]

[0177] [Table 8]

[0178]

[0179] As shown in Table 8, it was confirmed that methyl 2-methylbicyclo[2.2.1]hept-5-ene-2-carboxylate could be polymerized in the same reaction system using the catalyst compositions of Examples 9 and 10.

[0180] <Examples 11 and 12: Preparation of copolymer of norbornene (NB) and methyl 2-methylbicyclo[2.2.1]hept-5-ene-2-carboxylate in the same reaction system>

[0181] Example 11: Ring-opening metathesis polymerization using a catalyst composition composed of RuCl3, L3, and TiBA

[0182] A polymer was prepared in the same manner as in Example 1-1, but methyl 2-methylbicyclo[2.2.1]hept-5-ene-2-carboxylate (MMENB; 1.24 g; 7.46 mmol) and norbornene (NB; 0.706 g; 7.5 mmol) represented by the chemical formula 11 as described in Table 9 were added, and then a polymerization reaction was performed at 60°C for 6 hours to prepare a polymer, and the results are shown in Table 10 in the same manner as in Example 1-1.

[0183] Example 12: Ring-opening metathesis polymerization using a catalyst composition composed of RuCl3, PCy3, and TiBA

[0184] A polymer was prepared in the same manner as in Example 3-1, but methyl 2-methylbicyclo[2.2.1]hept-5-ene-2-carboxylate (MMENB; 1.24 g; 7.46 mmol) and norbornene (NB; 0.706 g; 7.5 mmol) represented by the chemical formula 11 as described in Table 9 were added, and then a polymerization reaction was performed at 60°C for 6 hours to prepare a polymer, and the results are shown in Table 10 in the same manner as in Example 3-1.

[0185] [Table 9]

[0186]

[0187] [Table 10]

[0188]

[0189] As shown in Table 10, it was confirmed that in the case of Examples 12 and 13, norbornene and methyl 2-methylbicyclo[2.2.1]hept-5-ene-2-carboxylate could be copolymerized in the same reaction system using the catalyst composition.

[0190] The present invention is not limited to the above-described embodiments and the attached drawings, and it will be apparent to a person skilled in the art to which the present invention pertains that various substitutions, modifications, and changes are possible within a scope that does not depart from the technical spirit of the present invention.

Claims

1. A catalyst composition for ring-opening metathesis polymerization of a cyclic olefin monomer, characterized by comprising: a ruthenium-containing metal precursor compound; a compound represented by the following chemical formula 1 or 2; and an organoaluminum compound: [Chemical Formula 1] [Chemical Formula 2] P(R)3 In the above chemical formulas 1 and 2, Y is a carbon atom or a nitrogen atom, Z is selected from the group consisting of an oxygen atom; a sulfur atom; and -(CH2)-; m is an integer from 0 to 3, R is each independently selected from the group consisting of a hydrogen atom; a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms; a substituted or unsubstituted allyl group having 3 to 20 carbon atoms; a substituted or unsubstituted cycloalkyl group having 3 to 12 carbon atoms; and a substituted or unsubstituted aryl group having 6 to 40 carbon atoms.

2. In paragraph 1, A catalyst composition for ring-opening metathesis polymerization of a cyclic olefin monomer, characterized in that the compound represented by the above chemical formula 1 is a compound represented by any one of the following chemical formulas 1a, 1b, and 1c. [Chemical Formula 1a] [Chemical Formula 1b] [Chemical Formula 1c] 3. In paragraph 1, A catalyst composition for ring-opening metathesis polymerization of a cyclic olefin monomer, characterized in that the compound represented by the above chemical formula 2 is selected from the group consisting of tricyclohexyl phosphine, triisopropyl phosphine, tryphenyl phosphine, tri-t-butyl phosphine, and dicyclohexyl-t-butyl phosphine.

4. In paragraph 1, A catalyst composition for ring-opening metathesis polymerization of a cyclic olefin monomer, characterized in that the compound represented by the above chemical formula 1 is of the following chemical formula 1c. [Chemical Formula 1c] 5. In paragraph 1, A catalyst composition for ring-opening metathesis polymerization of a cyclic olefin monomer, characterized in that the compound represented by the above chemical formula 2 is tricyclohexyl phosphine.

6. In paragraph 1, A catalyst composition for ring-opening metathesis polymerization of a cyclic olefin monomer, characterized in that the organic aluminum compound is at least one selected from the group consisting of trimethyl aluminum (TMA), triethyl aluminum (TEA), triiso-butyl aluminum (TIBAL), dimethyl chloro aluminum (DMCA), and diethyl chloroaluminum (DECA).

7. In paragraph 1, A catalyst composition for ring-opening metathesis polymerization of a cyclic olefin monomer, characterized in that the compound represented by the above chemical formula 1 or 2 is contained in an amount of 1 to 5 mol per 1 mol of a ruthenium-containing metal precursor compound.

8. In paragraph 1, A catalyst composition for ring-opening metathesis polymerization of a cyclic olefin monomer, characterized in that the organic aluminum compound is contained in an amount of 1 to 40 moles per mole of a ruthenium-containing metal precursor compound.

9. A method for producing a cyclic olefin polymer, characterized by comprising a step of ring-opening metathesis polymerizing a cyclic olefin monomer in the presence of a catalyst composition for ring-opening metathesis polymerization of the cyclic olefin monomer of any one of claims 1 to 8.

10. In paragraph 9, A method for producing a cyclic olefin polymer, characterized in that the ruthenium-containing metal precursor compound and the compound represented by the following chemical formula 1 or 2 in the catalyst composition for ring-opening metathesis polymerization of the cyclic olefin monomer are formed as a complex compound in-situ during ring-opening metathesis polymerization of the cyclic olefin monomer.

11. In paragraph 9, A method for producing a cyclic olefin polymer, characterized in that the cyclic olefin monomer is at least one selected from the group consisting of norbornene, dicyclopentadiene, cyclopentadiene, cyclopentene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene and derivatives thereof.

12. In paragraph 9, A method for producing a cyclic olefin polymer, characterized in that the cyclic olefin monomer is a compound represented by the following chemical formula 4: [Chemical Formula 4] In the above chemical formula 4, n is an integer from 0 to 4, and R 11 Inland R 14 are the same or different, and each independently selected from the group consisting of a hydrogen atom; a halogen atom; a hydroxyl group; a carboxyl group; a linear or branched alkyl group having 1 to 20 carbon atoms; a cycloalkyl group having 3 to 12 carbon atoms; an aryl group having 6 to 20 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; and an acyl group having 1 to 10 carbon atoms.

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