Catalyst Composition for Ring Opening Metathesis Polymerization of Cyclic Olefin and Method for Preparing Cyclic Olefin Polymer Using the Same

Abstract

The present invention relates to a catalyst composition for ring-opening double decomposition polymerization of cyclic olefin monomers and a method for producing a cyclic olefin polymer using the same. More specifically, the invention relates to a catalyst composition for ring-opening double decomposition polymerization of cyclic olefin monomers capable of ring-opening double decomposition polymerization of cyclic olefin monomers within the same reaction system, and a method for producing a cyclic olefin polymer using the same.

Description

Technology Field

[0001] The present invention relates to a catalyst composition for ring-opening double decomposition polymerization of cyclic olefin monomers and a method for producing a cyclic olefin polymer using the same. More specifically, the invention relates to a catalyst composition for ring-opening double decomposition polymerization of cyclic olefin monomers capable of ring-opening double decomposition polymerization of cyclic olefin monomers within the same reaction system, and a method for producing a cyclic olefin polymer using the same. Background Technology

[0002] Until now, inorganic materials such as silicon oxide or silicon nitride have been primarily used in the information and electronics industry. However, as the need for small and highly efficient devices increases, the need for high-performance new materials is growing. As materials capable of satisfying these high-performance requirements, there is growing interest in oligomers or polymers that have low dielectric constant and water absorption, excellent metal adhesion, mechanical strength, heat resistance, and transparency, and a high glass transition temperature (Tg > 250 ℃).

[0003] These oligomers or polymers can be used as electronic materials such as insulating films for semiconductors or TFT-LCDs, protective films for polarizers, multichip modules, integrated circuits (ICs), printed circuit boards, encapsulators 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 conventional olefin polymers, they have excellent transparency, heat resistance, and chemical resistance, and have very low birefringence and water absorption rates, so they can be applied in various ways as optical materials such as CDs, DVDs, and POF (Plastic Optical Fiber), information electronic materials such as capacitor films and low dielectrics, and medical materials such as low-absorption syringes and blister packaging.

[0005] U.S. Patent No. 5705503 discloses a method for polymerizing norbornene monomers using [(Allyl)PdCl]2 / AgSbF6 as a catalyst complex, as a catalyst used to polymerize such cyclic olefin-based polymers. However, since the ratio of catalyst to monomer is 1:100 to 1:250 and the amount of catalyst used is excessive, a large amount of catalyst residue remains in the polymer obtained at the end, and there is a concern that the polymer will deteriorate due to thermal oxidation in the future and that the light transmittance will also be poor.

[0006] In addition, U.S. Patent No. 6455650 describes a catalyst complex [(R') z M(L') x (L'') y ] b [WCA] d A method for polymerizing norbornene-based monomers using [the method] has been disclosed, but there was a problem that it was unsuitable for the manufacture of polymers because the yield of the norbornene-based monomers was very low at 5%.

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

[0008] U.S. Patent No. 5,705,503 (Registration Date: Jan. 6, 1998) U.S. Patent No. 6,455,650 (Publication Date: May 2, 2002) U.S. Patent No. 6,031,058 (Registration Date: Feb. 29, 2000) U.S. Patent No. 6,455,650 (Publication Date: May 2, 2002) The problem to be solved

[0009] The main objective of the present invention is to solve the aforementioned problems by providing a catalyst composition for ring-opening double decomposition of cyclic olefin monomers, which allows for the simple and economical production of a catalyst for cyclic olefin polymerization by enabling the preparation of the catalyst within the same reaction system, and enables the production of a cyclic olefin polymer with high catalytic activity in the polymerization of cyclic olefin monomers.

[0010] In addition, another objective of the present invention is to provide a method for producing a cyclic olefin polymer that 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 double decomposition polymerization of the above-mentioned cyclic olefin monomer. means of solving the problem

[0011] To achieve the above objectives, one embodiment of the present invention provides a catalyst composition for ring-opening double decomposition polymerization of cyclic olefin monomers, characterized by comprising: a ruthenium-containing metal precursor compound; a compound represented by the following chemical formula 1 or chemical formula 2; and an organoaluminum compound.

[0012] [Chemical Formula 1]

[0013]

[0014] [Chemical Formula 2]

[0015] P(R)3

[0016] 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, 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.

[0017] In a preferred embodiment of the present invention, the compound represented by Formula 1 may be characterized as being a compound represented by any one of the following Formulas 1a, 1b, and 1c.

[0018] [Chemical Formula 1a]

[0019]

[0020] [Chemical Formula 1b]

[0021]

[0022] [Chemical Formula 1c]

[0023]

[0024] In a preferred embodiment of the present invention, the compound represented by Formula 2 may be characterized as being selected from the group consisting of tricyclohexylphosphine, triisopropylphosphine, tryphenylphosphine, tri-t-butylphosphine, and dicyclohexyl-t-butylphosphine.

[0025] In a preferred embodiment of the present invention, the compound represented by Chemical Formula 1 may be characterized as having the following Chemical Formula 1c.

[0026] [Chemical Formula 1c]

[0027]

[0028] In a preferred embodiment of the present invention, the compound represented by the chemical formula 2 may be characterized as tricyclohexyl phosphine.

[0029] In a preferred embodiment of the present invention, the organoaluminum compound may be characterized as being one or more selected from the group consisting of trimethyl aluminum (TMA), triethyl aluminum (TEA), triiso-butyl aluminum (TIBAL), dimethyl chloro aluminum (DMCA), and diethyl chloroaluminum (DECA).

[0030] In a preferred embodiment of the present invention, the compound represented by Formula 1 or 2 may be characterized by being included in an amount of 1 mole to 5 moles per mole of ruthenium-containing metal precursor compound.

[0031] In a preferred embodiment of the present invention, the organoaluminum compound may be characterized by being included in an amount of 1 mole to 40 moles per mole of ruthenium-containing metal precursor compound.

[0032] Another embodiment of the present invention provides a method for producing a cyclic olefin polymer, characterized by including the step of ring-opening double-decomposing a cyclic olefin monomer in the presence of a catalyst composition for ring-opening double-decomposing of the cyclic olefin monomer.

[0033] In another preferred embodiment of the present invention, the ruthenium-containing metal precursor compound and the compound represented by the following formula 1 or formula 2 in the catalyst composition for ring-opening double decomposition polymerization of the cyclic olefin monomer may be characterized by being formed as a complex compound in the same reaction system (in-situ) during ring-opening double decomposition polymerization.

[0034] In another preferred embodiment of the present invention, the cyclic olefin monomer may be characterized as being one or more selected from the group consisting of norbornene, dicyclopentadiene, cyclopentadiene, cyclopentene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and derivatives thereof.

[0035] 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.

[0036] [Chemical Formula 4]

[0037]

[0038] In the above chemical formula 4, n is an integer from 0 to 4, and R 11 to R 14 The groups are identical or different and are 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. Effects of the invention

[0039] According to the present invention, since it is possible to form a catalytic active species in situ within the same reaction system during the polymerization of cyclic olefin monomers, the catalyst synthesis process and the residual impurity removal process can be omitted, thereby enabling the production of a catalyst and a cyclic olefin polymer in an economical and environmentally friendly manner by eliminating the catalyst synthesis and purification steps.

[0040] In addition, the cyclic olefin-based polymer produced by the catalyst according to the present invention not only possesses stereoselectivity that does not result from free radical polymerization, high molecular weight, and a glass transition temperature (Tg) that allows for molding, but can also provide a ring-opening metadecomposition polymer in a form that cannot be provided by addition polymerization. Specific details for implementing the invention

[0041] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by a skilled expert in the art to which the present invention pertains. In general, the nomenclature used herein is well known and commonly used in the art.

[0042] Throughout this specification, when a part is described as 'comprising' a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components.

[0043] In one aspect, the present invention relates to a catalyst composition for ring-opening double decomposition polymerization of cyclic olefin monomers, characterized by comprising: a ruthenium-containing metal precursor compound; a compound represented by the following formula 1 or formula 2; and an organoaluminum compound.

[0044] [Chemical Formula 1]

[0045]

[0046] [Chemical Formula 2]

[0047] P(R)3

[0048] 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, 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.

[0049] More specifically, a catalyst composition for ring-opening double decomposition 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 chemical formula 2; and an organoaluminum compound; thereby instantaneously forming a ruthenium complex during the ring-opening double decomposition polymerization process of the cyclic olefin monomer, thereby enabling the cyclic olefin monomer to be produced as a polymer.

[0050] In the present invention, the metal precursor compound is a compound containing ruthenium that exhibits excellent catalytic activity in the ring-opening double decomposition polymerization reaction of a cyclic olefin monomer. Any precursor such as a ruthenium salt compound or complex can be used without special limitations. The salt compounds can be salt compounds that are soluble in organic solvents. Specifically, examples include acetates, nitrates, sulfates, carbonates, hydroxides, halides, and hydrates thereof. Examples of complexes include acetylacetonate complexes and phosphine complexes.

[0051] Meanwhile, in the present invention, the compound represented by Formula 1 or Formula 2 is a ligand compound that instantaneously coordinates to the aforementioned metal precursor compound introduced together during the polymerization reaction of a cyclic olefin monomer to form a complex compound in the same reaction system (in-situ).

[0052] At this time, X of the above 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 may be an integer from 0 to 3, preferably m may be an integer between 1 and 2.

[0053] In addition, R of the above formula 2 may each 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.

[0054] These compounds represented by the above chemical formula 1 or chemical formula 2 can easily provide non-covalent electron pairs to the ruthenium ligand due to their abundant electron density, so they can be applied to the polymerization reaction of cyclic olefin monomers in situ and exhibit high reaction activity.

[0055] Specifically, a compound represented by Formula 1 according to one embodiment of the present invention may be characterized as being a compound represented by any one of the following Formulas 1a, 1b, and 1c, and preferably, the compound represented by Formula 1 may be Formula 1c.

[0056] [Chemical Formula 1a]

[0057]

[0058] [Chemical Formula 1b]

[0059]

[0060] [Chemical Formula 1c]

[0061]

[0062] In addition, the compound represented by Chemical Formula 2 can specifically be selected from the group consisting of tricyclohexyl phosphine, triisopropyl phosphine, triphenyl phosphine, tri-t-butyl phosphine, and dicyclohexyl-t-butyl phosphine, and preferably, in terms of stereochemistry and electronics, it can be tricyclohexyl phosphine, etc.

[0063] The compound represented by the above chemical formula 1 or 2 may be included in an amount of 1 mole to 5 moles, preferably 1 mole to 3 moles, per 1 mole of the ruthenium-containing metal precursor compound. When the above content ratio is satisfied, the monodentate or bidentate ligands can be coordinated to the metal precursor compound to form a complex compound in the same reaction system with high yield.

[0064] In the present invention, the complex compound formed in the same reaction system between the ruthenium-containing metal precursor compound and the compound represented by the following Chemical Formula 1 or Chemical Formula 2 is formed by the coordination bonding of the compound represented by Chemical Formula 1 or 2 to the ruthenium of the metal precursor compound, and specifically may include at least one of the following Chemical Formulas 5 to 8.

[0065] [Chemical Formula 5]

[0066]

[0067] [Chemical Formula 6]

[0068]

[0069] [Chemical Formula 7]

[0070]

[0071] [Chemical Formula 8]

[0072]

[0073] 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 NO, a halogen group or an atom capable of acting as 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 hydroxyl group, an alkoxy group and a halogen group.

[0074] In X1 and X2 of the above chemical formulas 5 to 8, the halogen group may be one or more 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.

[0075] Meanwhile, in the present invention, the organoaluminum compound performs the role of activating the ruthenium component of the metal precursor compound and may be one or more 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 may be triiso-butyl aluminum (TIBAL).

[0076] The above organoaluminum compound may be included in an amount of 1 mole to 40 moles, preferably 2 moles to 27 moles, per 1 mole of ruthenium-containing metal precursor compound. When the above content ratio is satisfied, it can be activated to instantaneously form a ruthenium-alkylidene unit [Ru=CR2, where R is a hydrogen atom, alkyl, aryl, etc.].

[0077] The above catalyst composition for ring-opening double decomposition of cyclic olefins is introduced together with the cyclic olefin monomer during the polymerization of the desired cyclic olefin monomer to form a cyclic olefin polymer. It can be prepared by instantaneously coordinating a compound of Formula 1 or 2 to the ruthenium atom of a metal precursor compound during the ring-opening double decomposition polymerization reaction of the cyclic olefin monomer to form a complex compound.

[0078] At this time, the cyclic olefin polymerization catalyst composition may be introduced during the polymerization of cyclic olefin monomers, with each component dissolved in an inert solvent. Non-limiting examples of the inert solvent include aromatic hydrocarbons such as benzene, toluene, xylene, benzonitrile, chlorobenzene, nitrobenzene, adiponitrile, anisole, and phenirnonane; aliphatic hydrocarbons having 5 to 20 carbon atoms such as pentane, hexane, heptane, and adiponitrile; and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride. Examples include unfluorinated, saturated substituted aliphatic hydrocarbons having 1 to 20 carbon atoms and / or aromatic hydrocarbons, including compounds selected from the group including alcohols such as methanol, propanol, butanol, isopropanol, and 2,4-ditertiarybutylphenol; 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 preferably aromatic hydrocarbons may be used.

[0079] In another aspect, the present invention relates to a method for producing a cyclic olefin polymer, characterized by comprising the step of carrying out a ring-opening double-decomposition polymerization reaction of a cyclic olefin monomer in the presence of the aforementioned catalyst composition for ring-opening double-decomposition polymerization of cyclic olefins.

[0080] Any cyclic olefin monomer capable of forming a polymer may be used as the above-mentioned cyclic olefin monomer. As an example of such a cyclic olefin monomer in the present invention, 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 may be used, and preferably, it may be a compound represented by the following chemical formula 4.

[0081] [Chemical Formula 4]

[0082]

[0083] In the above chemical formula 4, n is an integer from 0 to 4, and R 11 to R 14 The groups are identical or different and are 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.

[0084] In the above chemical formula 4, n is an integer from 0 to 2, and R 11 to R 14It is preferable for polymerization purposes that the groups are identical 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.

[0085] In the present invention, the above-mentioned cyclic olefin monomer may be reacted alone, or two or more cyclic olefin monomers may be reacted. At this time, the cyclic olefin monomer may be used without limitation as long as it is a cyclic olefin monomer capable of polymerizing with the cyclic olefin monomer.

[0086] When polymerizing cyclic olefin monomers using the cyclic olefin ring-opening double decomposition catalyst composition 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.

[0087] At this time, the cyclic olefin monomer can be mixed and reacted in an amount of 300 to 10,000 moles relative 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 relative to 1 mole of the ruthenium-containing metal precursor compound, it is economically disadvantageous due to the excessive use of the catalyst, and if more than 10,000 moles are used, a problem may arise in which the polymerization yield is lowered due to a decrease in the amount of catalyst composition used relative to the cyclic olefin monomer.

[0088] In addition, when polymerizing a cyclic olefin monomer using the cyclic olefin ring-opening double-decomposition catalyst composition of the present invention, a two-pot polymerization reaction may be performed by first mixing one or more components of the cyclic olefin ring-opening double-decomposition catalyst composition with the cyclic olefin monomer and then mixing the remaining components of the catalyst composition, or a one-pot polymerization reaction may be performed by mixing the catalyst composition with the cyclic olefin monomer all at once.

[0089] The above reaction can be carried out in a batch, semi-continuous, or continuous manner, and the reaction conditions can be performed at 0°C to 120°C, preferably at room temperature, for 1 hour to 26 hours. If the reaction is carried out at 0°C or for less than 1 hour, a problem may arise where the reaction does not proceed sufficiently, and if carried out at 120°C or for more than 26 hours, the polymer chains may decompose, resulting in a decrease in molecular weight or gelation.

[0090] The cyclic olefin polymer prepared in this way has double bonds within the polymer and forms a saturated polymer through a hydrogenation reaction, allowing it to proceed to the next hydrogenation step without removing residual catalyst after polymerization. Furthermore, it possesses stereoselectivity that does not result from free radical polymerization, high molecular weight, and a glass transition temperature (Tg) suitable for molding, as well as a form that cannot be provided by addition polymerization.

[0091] The present invention will be described in detail below based on examples, but the present invention is not limited by the following examples.

[0092] <Preparation Examples 1 to 3: Preparation of Ligand Compounds>

[0093] <Preparation Example 1: Preparation of 2-(piperidine-1-ylmethyl)quinoline(L1)>

[0094] 2-(piperidine-1-ylmethyl)quinoline (hereinafter, L1) was prepared by the following method with reference to 'Tetrahedron Letters 2018, 59, 1723.'

[0095] 4.28 g (20.0 mmol) of 2-(chloromethyl)quinoline hydrochloride 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 reacted at room temperature for 24 hours to obtain the 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 vacuum drying, and the resulting mixture was vacuum distilled to prepare 2.63 g (58.0%) of the yellow solid compound 2-(piperidine-1-ylmethyl)quinoline represented by Chemical Formula 1a.

[0096] <Preparation Example 2: Preparation of 4-(quinolin-2-ylmethyl)morpholine(L2)>

[0097] 4-(quinolin-2-ylmethyl)morpholine (hereinafter, L2) was prepared by the following method with reference to 'Tetrahedron Letters 2018, 59, 1723.'

[0098] 4.67 g (21.8 mmol) of 2-(chloromethyl)quinoline hydrochloride was dissolved in 50 ml of distilled water, and then 1.90 g (21.8 mmol) of morpholine was added and mixed. 2.45 g (43.6 mmol) of KOH was slowly added to the mixture and reacted at room temperature for 24 hours to obtain the 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 vacuum drying, and the resulting mixture was vacuum distilled to prepare 2.84 g (57.0%) of 4-(quinolin-2-ylmethyl)morpholine, a yellow, highly viscous liquid compound represented by chemical formula 1b.

[0099] <Preparation Example 3: Preparation of 1-(naphthalen-2-ylmethyl)piperidine (L3)>

[0100] 3.53 g (20.0 mmol) of 2-(chloromethyl)naphthalene was dissolved in 25 ml of methylene chloride, and then 1.70 g (20.0 mmol) of piperidine was added and mixed. 1.68 g (30.0 mmol) of KOH and 10 ml of distilled water were slowly added to the mixture and reacted at room temperature for 4 days to obtain the 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 vacuum drying, and the resulting mixture was vacuum distilled to prepare 3.01 g (66.5%) of the yellow solid compound 1-(naphthalen-2-ylmethyl)piperidine represented by the chemical formula 1c.

[0101] 1 H 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)

[0103] <Examples 1 to 3 and Comparative Examples 1 to 3: Preparation of norbornene polymer in-situ>

[0104] Example 1: RuCl 3 Ring-opening double decomposition polymerization reaction using a catalyst composition consisting of L3 and TiBA

[0105] 1-1 : One-pot method

[0106] Ring-opening double decomposition polymerization of norbornene was carried out using the Schlenk technique under argon in a flame-dried flask. As described in Table 1, RuCl3(anhyedrous) (0.1085 g; 25 µmol), ligand compound L3 (0.0112 g; 50 µmol) of Preparation Example 3, and 10 ml of chlorobenzene were added to a 100 ml Schlenk flask and mixed, then stirred for 1 hour in an oil bath preheated to 60 °C. To this, a norbornene solution in which norbornene (1.500 g, 15.93 mmol) was dissolved in 10 ml of chlorobenzene was added and mixed, then triisobutylaluminium (TiBA, 0.1 ml, 0.397 mmol) was added, the flask was sealed, and the reaction was carried out at 60 °C for 6 hours while stirring. NMR analysis was performed using tetralin as a reference material to measure the conversion rate of the monomer after the reaction, and the results are shown in Table 2.

[0107] 1-2 : Two-pot method

[0108] The ring-opening double decomposition polymerization reaction of norbornene (NB) using the two-port method was first performed by activating RuCl3 using triisobutylaluminium, and the ring-opening double decomposition polymerization of norbornene was carried out using 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 and mixed, then stirred for 30 minutes in an oil bath preheated to 60 °C. To this, triisobutylaluminium (TiBA, 0.1 ml, 0.397 mmol) was added and mixed for 30 minutes at 60 °C. 1.500 g of activated norbornene solution and 10 ml of chlorobenzene were mixed and added to a flask. Then, the flask was sealed and the reaction was carried out at 60 °C for 6 hours while stirring. 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.

[0109] Example 2: RuCl 3 , PCy 3 ring-opening double decomposition polymerization reaction using a catalyst composition composed of and TiBA

[0110] 2-1 : One-pot method

[0111] A polymer was prepared in the same manner as in Example 1-1, but with tricyclohexylphosphine (PCy3; 0.0140 g; 50 µmol) added instead of ligand compound L3 as described in Table 1, and then the polymerization reaction was carried out at 60 °C for 2 hours to prepare the polymer, and the results are shown in Table 2 in the same manner as in Example 1-1.

[0112] 2-2 : Two-pot method

[0113] A polymer was prepared in the same manner as in Examples 1-2, but with tricyclohexylphosphine (PCy3, 0.0140 g; 50 µmol) added instead of ligand compound L3 as described in Table 1, and then the polymerization reaction was carried out at 60°C for 2 hours to prepare the polymer, and the results are shown in Table 2 in the same manner as in Examples 1-2.

[0114] Example 3: Ru(NO)Cl 3 ·xH 2 Ring-opening double decomposition polymerization reaction using a catalyst composition consisting of O, L3, and TiBA

[0115] 3-1 : One-pot method

[0116] 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)Cl3·xH2O (0.0035 g; 15 µmol), 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 were shown in Table 2 in the same manner as in Example 1-1.

[0117] 3-2 : Two-pot method

[0118] A polymer was prepared in the same manner as in Examples 1-2, but instead of the ruthenium-containing metal precursor compound RuCl3 (0.1085 g; 25 µmol) as described in Table 1, Ru(NO)Cl3·xH2O (0.0035 g; 15 µmol), 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 were shown in Table 2 in the same manner as in Examples 1-2.

[0119] Example 4: Ru(NO)Cl3 ·xH 2 O, PCy 3 ring-opening double decomposition polymerization reaction using a catalyst composition composed of and TiBA

[0120] 4-1 : One-pot method

[0121] A polymer was prepared in the same manner as in Example 3-1, but with tricyclohexylphosphine (PCy3; 0.0042 g; 15 µmol) added instead of ligand compound L3 as described in Table 1, and the results were shown in Table 2 in the same manner as in Example 1-1.

[0122] 4-2 : Two-pot method

[0123] A polymer was prepared in the same manner as in Example 3-2, but with tricyclohexylphosphine (PCy3; 0.0042 g; 15 µmol) added instead of ligand compound L3 as described in Table 1, and the results were shown in Table 2 in the same manner as in Example 1-2.

[0124] Comparative Example 1: Ring-opening double decomposition polymerization reaction using TiBA

[0125] 1-1 : One-pot method

[0126] A polymer was prepared in the same manner as in Example 1-1, but with only triisobutylaluminium (TiBA; 0.20 ml; 0.79 mmol) added as described in Table 1, and the results were shown in Table 2 in the same manner as in Example 1-1.

[0127] Comparative Example 2: RuCl 3 and Ring-opening double decomposition polymerization using TiBA

[0128] 2-1 : One-pot method

[0129] A polymer was prepared in the same manner as in Example 1-1, but with only RuCl3 (0.1085 g; 25 µmol) and triisobutylaluminium (TiBA; 0.252 ml; 1.00 mmol) added as described in Table 1, and polymerized at room temperature for 2 hours. The results were shown in Table 2 in the same manner as in Example 1-1.

[0130] 2-2 : Two-pot method

[0131] A polymer was prepared in the same manner as in Examples 1-2, except that only RuCl3 (0.1085 g; 25 µmol) and triisobutylaluminium (TiBA; 0.252 ml; 1.00 mmol) were used as described in Table 1. toluene A polymer was prepared by adding to and polymerizing at room temperature for 2 hours, and the results are shown in Table 2 in the same manner as in Examples 1-2.

[0132] Comparative Example 3: Ru(NO)Cl 3 ·xH 2 O and Ring-opening double decomposition polymerization using TiBA

[0133] 2-1 : One-pot method

[0134] The polymer was prepared in the same manner as in Example 3-1, except that Ru(NO)Cl as described in Table 1 3ㆍ A polymer was prepared by adding only xH2O (0.0035 g; 15 µmol) and triisobutylaluminium (TiBA; 0.1 ml, 0.397 mmol) and polymerizing at room temperature for 2 hours, and the results are shown in Table 2 in the same manner as in Example 1-1.

[0135] 2-2 : Two-pot method

[0136] The polymer was prepared in the same manner as in Example 3-2, except that Ru(NO)Cl as described in Table 1 3·A polymer was prepared by adding only xH2O (0.0035 g; 15 µmol) and triisobutylaluminium (TiBA; 0.1 ml, 0.397 mmol) and polymerizing at room temperature for 2 hours, and the results are shown in Table 2 in the same manner as in Examples 1-2.

[0137] [Table 1]

[0138]

[0139] [Table 2]

[0140]

[0141] As shown in Table 2, in the case of Comparative Examples 1-1 to 3-2, no norbornene polymer was produced, whereas in the case of Examples 1-1 to 4-2, it was confirmed that no norbornene polymer was produced in the same reaction system.

[0143] <Examples 5 and 6: Preparation of Butylnorbornene Polymer in-situ>

[0144] Example 5: RuCl 3 Ring-opening double decomposition polymerization reaction using a catalyst composition consisting of L3 and TiBA

[0145] A polymer was prepared in the same manner as in Example 1-1, butylnorbornene (BuNB; 2.5 ml; 15 mmol) was added as described in Table 3, and then the polymerization reaction was carried out at 60 °C for 12 hours to prepare the polymer, and the results are shown in Table 4 in the same manner as in Example 1-1.

[0146] Example 6: Ru(NO)Cl 3 ·xH 2 O, PCy 3 ring-opening double decomposition polymerization reaction using a catalyst composition composed of and TiBA

[0147] A polymer was prepared in the same manner as in Example 3-1, butylnorbornene (BuNB; 2.5 ml; 15 mmol) was added as described in Table 3, and the polymerization reaction was carried out at 60°C for 12 hours to prepare the polymer, and the results are shown in Table 4 in the same manner as in Example 3-1.

[0148] [Table 3]

[0149]

[0150] [Table 4]

[0151]

[0152] As shown in Table 4, it was confirmed that butylnorbornene could be polymerized in the same reaction system using the catalyst composition in the case of Examples 5 and 6.

[0154] <Examples 7 and 8: Preparation of methyl bicyclo[2.2.1]hept-5-ene-2-carboxylate polymer in-situ>

[0155] Example 7: RuCl 3 Ring-opening double decomposition polymerization reaction using a catalyst composition consisting of L3 and TiBA

[0156] A polymer was prepared in the same manner as in Example 1-1, but with the addition of methyl bicyclo[2.2.1]hept-5-ene-2-carboxylate (MeNB; 2.2 ml; 15 mmol) represented by the following chemical formula 10 as described in Table 5, and then the polymerization reaction was carried out at 60 °C for 12 hours to prepare the polymer, and the results are shown in Table 6 in the same manner as in Example 1-1.

[0157] [Chemical Formula 10]

[0158]

[0159] Example 8: Ru(NO)Cl 3 ·xH 2 O, PCy 3 ring-opening double decomposition polymerization reaction using a catalyst composition composed of and TiBA

[0160] A polymer was prepared in the same manner as in Example 3-1, but with the addition of methyl bicyclo[2.2.1]hept-5-ene-2-carboxylate (MeNB; 2.2 ml; 15 mmol) represented by Chemical Formula 10 as described in Table 5, and then the polymerization reaction was carried out at 60 °C for 12 hours to prepare the polymer, and the results are shown in Table 6 in the same manner as in Example 3-1.

[0161] [Table 5]

[0162]

[0163] [Table 6]

[0164]

[0165] As shown in Table 6, it was confirmed that in the case of Examples 7 and 8, methyl bicyclo[2.2.1]hept-5-ene-2-carboxylate could be polymerized in the same reaction system using the catalyst composition.

[0167] <Examples 9 and 10: Preparation of methyl 2-methylbicyclo[2.2.1]hept-5-ene-2-carboxylate polymer in-situ>

[0168] Example 9: RuCl 3 Ring-opening double decomposition polymerization reaction using a catalyst composition consisting of L3 and TiBA

[0169] A polymer was prepared in the same manner as in Example 1-1, but with the addition of 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 as described in Table 7, and then the polymerization reaction was carried out at 60 °C for 16 hours to prepare the polymer, and the results are shown in Table 8 in the same manner as in Example 1-1.

[0170] [Chemical Formula 11]

[0171]

[0172] Example 10: RuCl 3 , PCy 3 ring-opening double decomposition polymerization reaction using a catalyst composition composed of and TiBA

[0173] A polymer was prepared in the same manner as in Example 2-1, but with the addition of methyl 2-methylbicyclo[2.2.1]hept-5-ene-2-carboxylate (MMENB; 1.53 g; 9.02 mmol) represented by Chemical Formula 11 as described in Table 7, and then the polymerization reaction was carried out at 60 °C for 16 hours to prepare the polymer, and the results are shown in Table 8 in the same manner as in Example 1-1.

[0174] [Table 7]

[0175]

[0176] [Table 8]

[0177]

[0178] As shown in Table 8, it was confirmed that in the case of Examples 9 and 10, methyl 2-methylbicyclo[2.2.1]hept-5-ene-2-carboxylate could be polymerized in the same reaction system using the catalyst composition.

[0180] <Examples 11 and 12: Preparation of copolymers of norbornene (NB) and methyl 2-methylbicyclo[2.2.1]hept-5-ene-2-carboxylate in-situ>

[0181] Example 11: RuCl 3 Ring-opening double decomposition polymerization reaction using a catalyst composition consisting of L3 and TiBA

[0182] A polymer was prepared in the same manner as in Example 1-1, but with the addition of 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 Chemical Formula 11 as described in Table 9, and then the polymerization reaction was carried out at 60 °C for 6 hours to prepare the polymer, and the results are shown in Table 10 in the same manner as in Example 1-1.

[0183] Example 12: RuCl 3 , PCy3 ring-opening double decomposition polymerization reaction using a catalyst composition composed of and TiBA

[0184] A polymer was prepared in the same manner as in Example 3-1, but with the addition of 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 Chemical Formula 11 as described in Table 9, and then the polymerization reaction was carried out at 60 °C for 6 hours to prepare the 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 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 in the case of Examples 12 and 13.

[0190] It will be obvious to those skilled in the art that the present invention is not limited by the aforementioned embodiments and attached drawings, and that various substitutions, modifications, and changes are possible within the scope of the technical concept of the present invention.

Claims

Claim 1 A catalyst composition for ring-opening double decomposition polymerization of a cyclic olefin monomer, comprising: a ruthenium-containing metal precursor compound; a compound represented by the following Chemical Formula 1 or Chemical Formula 2; and an organoaluminum compound; wherein the ruthenium-containing metal precursor compound and the compound represented by the following Chemical Formula 1 or Chemical Formula 2 are formed as a complex compound in the same reaction system (in-situ) during the ring-opening double decomposition polymerization of the cyclic olefin monomer: [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, 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. Claim 2 A catalyst composition for ring-opening double decomposition polymerization of cyclic olefin monomers according to claim 1, characterized in that the compound represented by 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] Claim 3 A catalyst composition for ring-opening double decomposition polymerization of cyclic olefin monomers according to claim 1, characterized in that the compound represented by 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. Claim 4 A catalyst composition for ring-opening double decomposition polymerization of cyclic olefin monomers according to claim 1, characterized in that the compound represented by Chemical Formula 1 is Chemical Formula 1c. Claim 5 A catalyst composition for ring-opening double decomposition polymerization of cyclic olefin monomers, characterized in that, in claim 1, the compound represented by Chemical Formula 2 is tricyclohexyl phosphine. Claim 6 A catalyst composition for ring-opening double decomposition polymerization of cyclic olefin monomers according to claim 1, characterized in that the organoaluminum compound is one or more selected from the group consisting of trimethyl aluminum (TMA), triethyl aluminum (TEA), triiso-butyl aluminum (TIBAL), dimethyl chloro aluminum (DMCA), and diethyl chloroaluminum (DECA). Claim 7 A catalyst composition for ring-opening double decomposition polymerization of a cyclic olefin monomer, characterized in that, in claim 1, the compound represented by Chemical Formula 1 or 2 is included in an amount of 1 mole to 5 moles per 1 mole of a ruthenium-containing metal precursor compound. Claim 8 A catalyst composition for ring-opening double decomposition polymerization of a cyclic olefin monomer, characterized in that, in claim 1, the organoaluminum compound is included in an amount of 1 mole to 40 moles per 1 mole of a ruthenium-containing metal precursor compound. Claim 9 A method for producing a cyclic olefin polymer, comprising the step of ring-opening double-decomposing a cyclic olefin monomer in the presence of a catalyst composition for ring-opening double-decomposing a cyclic olefin monomer according to any one of claims 1 to 8, wherein in the catalyst composition for ring-opening double-decomposing a cyclic olefin monomer, a ruthenium-containing metal precursor compound and a compound represented by the following chemical formula 1 or chemical formula 2 are formed as complex compounds in the same reaction system (in-situ) during ring-opening double-decomposing a cyclic olefin monomer. Claim 10 delete Claim 11 A method for producing a cyclic olefin polymer according to claim 9, characterized in that the cyclic olefin monomer is one or more selected from the group consisting of norbornene, dicyclopentadiene, cyclopentadiene, cyclopentene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and derivatives thereof. Claim 12 A method for preparing a cyclic olefin polymer according to claim 9, 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 to R 14 The groups are identical or different and are 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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