KR20240038430A - Composition for producing cyclic olefin polymer and preparation method of cyclic olefin polymer - Google Patents

Abstract

The present invention relates to a composition for producing a cyclic olefin polymer and a method for producing a cyclic olefin polymer, and more specifically, to a composition for producing an ultrahigh-molecular-weight cyclic olefin polymer (UHMWCOP) with a number average molecular weight (M _n ) of 1000 kDa or more. It relates to compositions and methods for producing cyclic olefin polymers.

Description

Composition for producing cyclic olefin polymer and preparation method of cyclic olefin polymer {Composition for producing cyclic olefin polymer and preparation method of cyclic olefin polymer}

The present invention relates to a composition for producing a cyclic olefin polymer and a method for producing a cyclic olefin polymer.

Since the production of polyethylene and polypropylene using Ziegler-Natta catalysts, the development of catalyst technology and the use of new types of monomers have led to the creation of cyclic olefin polymers.

Cyclic olefin polymers are amorphous hydrocarbon polymers consisting of a heavy cyclic skeleton in the chain, and have physical properties such as high optical transparency, high mechanical strength, high thermal/chemical stability, low water vapor permeability, and low dielectric constant. Currently, cyclic olefin polymers are used in a variety of fields as lightweight, highly durable plastic windows that can replace glass. Examples include packaging, medical plastics, diagnostic materials, optical lens electronic device substrates, and antenna materials. do.

The most common form of cyclic olefin polymer is the ethylene/norbornene copolymer, which is an inexpensive raw material, obtained by vinyl addition copolymerization of two monomers using a transition metal catalyst. Lose. Although these ethylene/norbornene copolymers have excellent strength, their application fields are limited due to their brittle nature. To overcome this limitation, Non-Patent Document 1 (Macromolecules 2021, 54, 14, 6762-6771) introduces a monomer containing a flexible substituent instead of ethylene, thereby creating a cyclic olefin copolymer with increased stretching ability due to weakened interchain attraction. was developed. However, this chemical structure has a weakness in mechanical properties because it causes a loss in the strength of the material.

Therefore, in order to maintain the strength of cyclic olefin polymers while solving their unique brittleness, physical cross-linking is introduced into the polymer chain instead of the previous plasticization method to toughen the polymer chain to prevent fracture. Improving tolerance is fundamentally necessary. There are various methods of physical crosslinking, such as chain entanglement, hydrophobic interaction, ionic bonding, hydrogen bonding, and crystallization, but network formation through chain entanglement is the most basic.

Meanwhile, cyclic olefin polymers have a fairly low chain entanglement density due to their rigid chain backbone, so a high molecular weight is required to form an entanglement network.

Accordingly, while conducting research to increase the molecular weight of the polymer in order to improve stretching ability without loss of mechanical strength by forming an entanglement network for the cyclic olefin polymer, the present inventors discovered that phosphine and imine formed a chelate structure. By adding and polymerizing cyclic olefin monomers using a palladium catalyst, an ultrahigh-molecular-weight cyclic olefin polymer (UHMWCOP) with a number-average molecular weight (M _n ) of 1000 kDa or more is produced. It was confirmed that it could be done, and the present invention was completed.

Macromolecules 2021, 54, 14, 6762-6771

The purpose in terms of work is

The object is to provide a composition for producing a cyclic olefin polymer and a method for producing a cyclic olefin polymer.

In order to achieve the above purpose,

In terms of work,

norbornene monomer; and

A composition for producing a cyclic olefin polymer is provided, including a catalyst comprising a compound represented by Formula 1 below:

<Formula 1>

(Here, R ¹ , R ² , and R ³ are each independently alkyl of C ₁ -C ₆ ).

The norbornene-based monomer may be a norbornene-based monomer represented by Chemical Formula 2 below:

<Formula 2>

(Where R ⁴ and R ⁵ are each independently hydrogen or C ₁ -C ₃₀ alkyl).

Additionally, the norbornene-based monomer may be a mixture of two or more types of norbornene-based monomer.

The catalyst may further include one or more of an ionic aluminum compound and an ionic boron compound.

At this time, the ionic aluminum compound is,

Methylaluminoxane (MAO), modified methylaluminoxane (MMAO), trimethyl aluminum (TMA), triethyl aluminum (TEA), triiso-butyl aluminum (TIBAL) ), dimethylchloro aluminum (DMCA), and diethylchloro aluminum (DECA).

In addition, the ionic boron compound is,

Triphenylmethylium tetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, Triphenylcarbenium tetrakis(2,4,6-trifluorophenyl)borate, triphenylcarbenium tetraphenylborate, tributylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis (pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diphenylaniliniumtetrakis(pentafluorophenyl)borate and lithium tetrakis(pentafluorophenyl)borate. It may be one or more types selected from the group consisting of lophenyl)borate.

On the other side

A catalyst for producing a cyclic olefin polymer is provided, comprising a compound represented by Formula 1 below:

<Formula 1>

(Here, R ¹ , R ² , and R ³ are each independently alkyl of C ₁ -C ₆ ).

In another aspect,

In a method for producing a cyclic olefin polymer from a norbornene monomer, a method for producing a cyclic olefin polymer is provided, using a catalyst containing a compound represented by the following formula (1):

<Formula 1>

(Here, R ¹ , R ² , and R ³ are each independently alkyl of C ₁ -C ₆ ).

The catalyst may further include one or more of an ionic aluminum compound and an ionic boron compound.

In addition, the method for producing the cyclic olefin polymer is

The norbornene-based monomer may be added and polymerized by mixing a first solution containing the norbornene-based monomer and an ionic aluminum compound and a second solution containing the compound represented by Formula 1 and an ionic boron compound.

In another aspect

A cyclic olefin polymer prepared by the above production method and having a number average molecular weight (M _n ) of 1000 kDa or more is provided.

In another aspect

A cyclic olefin polymer film comprising the cyclic olefin polymer is provided.

The present invention can produce an ultrahigh-molecular-weight cyclic olefin polymer (UHMWCOP) having a number average molecular weight (M _n ) of 1000 kDa or more.

The cyclic olefin polymer of the present invention has the advantage of exhibiting excellent mechanical strength and increased stretching ability.

The cyclic olefin polymer of the present invention has superior fracture resistance compared to low molecular weight cyclic olefin polymers of the same composition, and is used in various application fields where cyclic olefin polymers are used, such as packaging, medical plastics, diagnostic materials, optical lens electronic device substrates, and antenna materials. It can be useful.

The effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description below.

Figure 1 is a Kelen-Tudos graph of a cyclic olefin copolymer prepared according to an example.
Figure 2 is a graph showing the results of measuring the number average molecular weight (M _n ) of a cyclic olefin copolymer prepared according to an example using a size exclusion chromatography (SEC) system.
Figure 3 is a graph showing the results of measuring the glass transition temperature of a cyclic olefin copolymer prepared according to an example using differential scanning calorimetry (DSC).
Figure 4 is a graph showing the results of measuring transmittance using an ultraviolet-visible (UV-Vis) spectrophotometer for a cyclic olefin copolymer prepared according to an example.
Figure 5 is a graph showing the results of one-dimensional wide-angle X-ray scattering (1D WAXS) analysis on a cyclic olefin copolymer prepared according to an example.
Figure 6 is a graph of Young's modulus according to molecular weight measured using a universal testing machine (UTM) for a cyclic olefin copolymer prepared according to an example.
Figure 7 is a graph of tensile strength according to molecular weight measured using a universal testing machine (UTM) for a cyclic olefin copolymer prepared according to an example.
Figure 8 is a graph of elongation at break according to molecular weight measured using a universal testing machine (UTM) for a cyclic olefin copolymer prepared according to an example.
Figure 9 is a graph of tensile toughness according to molecular weight measured using a universal testing machine (UTM) for a cyclic olefin copolymer prepared according to an embodiment.

Hereinafter, preferred embodiments of the present invention will be described with reference to the attached drawings. However, the embodiments of the present invention may be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below. Additionally, the following examples are provided to more completely explain the present invention to those with average knowledge in the relevant technical field.

Throughout the specification, “including” an element means that other elements may be further included rather than excluding other elements, unless specifically stated otherwise.

In terms of work

norbornene monomer; and

A composition for producing a cyclic olefin polymer is provided, including a catalyst comprising a compound represented by Formula 1 below:

<Formula 1>

(Here, R ¹ , R ² , and R ³ are each independently alkyl of C ₁ -C ₆ ).

Hereinafter, a composition for producing a cyclic olefin polymer according to an embodiment will be described in detail.

More specifically, the composition for producing a cyclic olefin polymer according to an embodiment is for producing an ultrahigh-molecular-weight cyclic olefin polymer (UHMWCOP) having a number-average molecular weight (M _n ) of 1000 kDa or more. It is a composition.

A composition for producing a cyclic olefin polymer according to an embodiment includes a norbornene-based monomer.

At this time, the norbornene-based monomer may be represented by the formula 2 below:

<Formula 2>

(Where R ⁴ and R ⁵ are each independently hydrogen or C ₁ -C ₃₀ alkyl).

The norbornene-based monomer may be a mixture of two or more types of norbornene-based monomers, and preferably may be a mixture of two or more types of norbornene-based monomers represented by Chemical Formula 2.

Accordingly, the composition for producing a cyclic olefin polymer according to an embodiment can produce a homopolymer of norbornene-based monomers and a copolymer of two or more types of norbornene-based monomers.

As an example, the composition for producing a cyclic olefin polymer can produce a copolymer of norbornene (NB) and 5-alkyl-substituted norbornene (NBCX: Can prepare a copolymer where the molar ratio of norbornene and 5-alkyl-substituted norbornene is 0.6:0.4 to 0.1:0.9.

The norbornene-based monomer of Formula 2 is chemically stable on the catalyst, and does not undergo chain transfer reactions such as beta-hydride elimination, which are commonly experienced with ethylene and alpha-olefin monomers, and at the same time alkyl Because of the excellent chemical inertness of the substituent, it has the advantage of being more suitable for achieving living polymerization, that is, polymerization without irreversible chain transfer reaction and termination reaction.

A composition for producing a cyclic olefin polymer according to an embodiment includes a catalyst containing a compound represented by Formula 1 below:

<Formula 1>

(Here, R ¹ , R ² , and R ³ may each independently be alkyl of C ₁ -C ₆ )

The compound represented by Formula 1 contains palladium (Pd) as a transition metal, and is a palladium (II) complex in which phosphine (P) and imine (N) form a chelating structure, and the phosphine ( The phosphine (P) and imine (N) ligands can stabilize palladium by acting as strong electron donors that reduce the electrophilicity of palladium, the central metal, and also create a significantly open coordination space when the metal catalyst is activated. It has a structure that can be induced to react well with the norbornene monomer.

Accordingly, the compound represented by Formula 1 is an ultrahigh-molecular-weight cyclic olefin polymer having a number average molecular weight (M _n ) of 1000 kDa or more, preferably 1500 kDa or more, to achieve living polymerization of norbornene-based monomers. polymer, UHMWCOP) can be produced, and the produced ultra-high molecular weight cyclic olefin polymer has the advantage of increased stretching ability without loss of mechanical strength due to the formation of an entanglement network.

The compound represented by Formula 1 may contain less than 1 × 10 ^-4 moles of palladium (Pd) relative to 1 mole of the norbornene monomer, and preferably contains 1 × 10 ^-3 to 9 × 10 ^-3 moles. It can be done, and more preferably, it can be included in the amount of 1×10 ^-3 to 5×10 ^-3 moles.

The catalyst may further include one or more of an ionic aluminum compound and an ionic boron compound as a co-catalyst for activating the palladium catalyst represented by Formula 1, and more preferably all of them.

The ionic aluminum compounds include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), trimethyl aluminum (TMA), triethyl aluminum (TEA), and triisobutyl aluminum ( It may be one or more selected from the group consisting of triiso-butyl aluminum (TIBAL), dimethylchloro aluminum (DMCA), and diethylchloro aluminum (DECA).

At this time, the ionic aluminum compound may be included so that the molar ratio of aluminum to palladium (Pd) ([Al] ₀ / [Pd] ₀ ) is 10 to 20, preferably 15 to 25. It can be included, and more preferably, it can be included to be 18 to 22.

In addition, the ionic boron compound is triphenylmethylium tetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis[3,5-bis(trifluorophenyl)borate, Romethyl)phenyl]borate, triphenylcarbeniumtetrakis(2,4,6-trifluorophenyl)borate, triphenylcarbeniumtetraphenylborate, tributylammoniumtetrakis(pentafluorophenyl)borate, N, N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diphenylaniliniumtetrakis(pentafluorophenyl)borate and lithium tetrakis(pentafluorophenyl)borate.

At this time, the ionic boron compound has boron (B) of 1.5 × 10 ^-3 mol or more, 2 × 10 -3 mol or more, 2 × ^{10 -3 to} 5 × 10 ^-3 mol, 2 based on 1 mol of the norbornene-based monomer. It may be included in the amount of ×10 ^-3 to 3 × 10 ^-3 moles.

On the other hand, since the ionic boron compound can be used to remove impurities as a scavenger when mixed with norbornene-based monomer during polymer production, the ionic boron compound is included so that boron is contained in a large amount compared to palladium. This may be desirable.

In one example, the catalyst is a palladium catalyst represented by Formula 1 and includes PdCl ₂ (MesN=CHC ₆ H ₄ PPh ₂ ) (Mes = 2,4,6-Me ₃ C ₆ H ₂ ), and an ionic aluminum compound It may include triisobutyl aluminum (iBu ₃ Al), and [Ph ₃ C] [B(C ₆ F ₅ ) ₄ ] as an ionic boron compound. During the polymerization reaction, the catalyst may be [Pd ⁱ Bu. (MesN=CHC ₆ H ₄ PPh ₂ )][B(C ₆ F ₅ ) ₄ ] can form an active species.

On the other side

A catalyst for producing a cyclic olefin polymer is provided, comprising a compound represented by Formula 1 below:

<Formula 1>

(Here, R ¹ , R ² , and R ³ are each independently alkyl of C ₁ -C ₆ ).

The compound represented by Formula 1 is an ultrahigh-molecular-weight cyclic olefin polymer having a number average molecular weight (M _n ) of 1000 kDa or more, preferably 1500 kDa or more, to achieve living polymerization of norbornene-based monomers. UHMWCOP) can be produced, and the produced ultra-high molecular weight cyclic olefin polymer has the advantage of increased stretching ability without loss of mechanical strength due to the formation of an entanglement network.

The catalyst may further include one or more of an ionic aluminum compound and an ionic boron compound as a cocatalyst for activating the palladium catalyst represented by Formula 1, and preferably includes both of them.

For example, the catalyst uses triisobutyl aluminum (iBu ₃ Al) and triphenylmethylium tetrakis(pentafluorophenyl)borate ([Ph ₃ C][B(C ₆ F ₅ ) ₄ ]) as cocatalysts. It can be included.

In another aspect

In a method for producing a cyclic olefin polymer from a norbornene monomer, a method for producing a cyclic olefin polymer is provided, using a catalyst containing a compound represented by the following formula (1):

<Formula 1>

(Here, R ¹ , R ² , and R ³ are each independently alkyl of C ₁ -C ₆ ).

Hereinafter, the method for producing a cyclic olefin polymer according to an embodiment will be described in detail in each step.

A method for producing a cyclic olefin polymer according to an embodiment includes the step of producing a cyclic olefin polymer by addition polymerizing a norbornene-based monomer in a solution containing a catalyst containing a norbornene-based monomer and the compound represented by Formula 1.

At this time, the norbornene-based monomer may be represented by the formula 2 below:

<Formula 2>

(Where R ⁴ and R ⁵ are each independently hydrogen or C ₁ -C ₃₀ alkyl).

The norbornene-based monomer may be a mixture of two or more types of norbornene-based monomers, and preferably may be a mixture of two or more types of norbornene-based monomers represented by Chemical Formula 2.

Accordingly, the method for producing a cyclic olefin polymer according to an embodiment can produce a homopolymer of norbornene-based monomers and a copolymer of two or more types of norbornene-based monomers.

As an example, the method for producing the cyclic olefin polymer can produce a copolymer of norbornene (NB) and 5-alkyl-substituted norbornene (NBCX: Can prepare a copolymer where the molar ratio of norbornene and 5-alkyl-substituted norbornene is 0.6:0.4 to 0.1:0.9.

The catalyst includes a compound represented by Formula 1, and preferably may further include one or more of an ionic aluminum compound and an ionic boron compound, and more preferably all of them.

For example, the catalyst is a palladium catalyst represented by Formula 1 and includes PdCl ₂ (MesN=CHC ₆ H ₄ PPh ₂ ) (Mes = 2,4,6-Me ₃ C ₆ H ₂ ), and an ionic aluminum compound It may include triisobutyl aluminum (iBu ₃ Al), and [Ph ₃ C] [B(C ₆ F ₅ ) ₄ ] as an ionic boron compound. During the polymerization reaction, the catalyst may be [Pd ⁱ Bu. (MesN=CHC ₆ H ₄ PPh ₂ )][B(C ₆ F ₅ ) ₄ ] can form an active species.

The solution includes a solvent, the solvent being toluene, 1,2-dichlorobenzene, n-pentane, n-hexane, n-heptane, chlorobenzene, dichloromethane, chloroform, 1,2-dichloroethane and 1, One or more species selected from the group consisting of 1,2,2-tetrachloroethane may be used, but are not limited thereto.

On the other hand, the compound represented by Formula 1, the ionic aluminum compound, and the ionic boron compound are dissolved in the solvent, while the active species in which the compound represented by Formula 1, the ionic aluminum compound, and the ionic boron compound are combined shows low solubility in the solvent.

Accordingly, when the catalyst includes a compound represented by Formula 1, an ionic aluminum compound, and an ionic boron compound, the solution is a first solution containing an ionic aluminum compound and a norbornene-based monomer and a compound represented by Formula 1. It may be formed by mixing a second solution containing a compound and an ionic boron compound, and as soon as an active species combining the compound represented by Formula 1, an ionic aluminum compound, and an ionic boron compound is formed by the mixing, Polymerization can be performed, and polymerization initiation efficiency can be further increased.

In one example, the cyclic olefin polymer is a first solution of iBu ₃ Al, PdCl ₂ (MesN=CHC ₆ H ₄ PPh ₂ ) (Mes = 2,4,6-Me ₃ C ₆ H ₂ ) mixed with toluene solvent, It can be prepared by preparing a second solution by mixing [Ph ₃ C][B(C ₆ F ₅ ) ₄ ], norbornene, and toluene, and then mixing the first solution and the second solution.

A method for producing a cyclic olefin polymer according to an embodiment involves producing an ultra-high molecular weight cyclic olefin polymer or copolymer with an average molecular weight (M _n ) of 1000 kDa or more, and forming an entanglement network, rather than plasticizing, the cyclic olefin polymer. By improving this ability, it is possible to produce cyclic olefin polymers with improved stretching ability without loss of mechanical strength.

In another aspect

A cyclic olefin polymer prepared by the above production method and having a number average molecular weight (M _n ) of 1000 kDa or more is provided.

The cyclic olefin polymer prepared by the above-described method is an ultra-high molecular weight cyclic olefin polymer or copolymer with a number average molecular weight (M _n ) of 1000 kDa or more. The ultra-high molecular weight cyclic olefin polymer or copolymer produced is not plasticized but is formed by entanglement network. It improves the stretching ability of cyclic olefin polymer by forming a network, and has the advantage of improved stretching ability without loss of mechanical strength.

In another aspect

A cyclic olefin polymer film comprising the cyclic olefin polymer is provided.

The film exhibits excellent mechanical strength and strain rate, and can be useful in a variety of applications where cyclic olefin polymers are used, such as packaging, medical plastics, diagnostic materials, optical lens electronic device substrates, and antenna materials.

Hereinafter, the present invention will be described in detail through examples and experimental examples.

However, the following examples and experimental examples only illustrate the present invention, and the content of the present invention is not limited to the following examples.

<Material preparation>

Reagents used for polymerization, namely norbornene (NB: >99.0%, Tokyo Chemical Industry), 1-hexene (HX: 97%, Sigma-Aldrich), 5-Octyl-2-norbornene (NBC8), triisobutylaluminum. Solution (iBu ₃ Al: hexane solvent, 1.0 M, Sigma-Aldrich), triphenylmethylium tetrakis(pentafluorophenyl)borate ([Ph ₃ C][B(C ₆ F ₅ ) ₄ ]: >98.0% , Tokyo Chemical Industry), toluene (anhydrous, 99.8%, Sigma-Aldrich) was placed in a glove box (KK-011AS: Korea Kiyon) filled with nitrogen (99.9999%, DIG Airgas) under dry conditions (O ₂ : <0.1 ppm, H ₂ O: <0.1 ppm).

The iBu ₃ Al solution was maintained at -30°C, and hydrochloric acid solution (HCl: deionized water solvent, 35-37%, Samcheon Chemical) and methanol (99.8%, Duksan) were prepared for termination and product precipitation processes. Tetrahydrofuran (THF: stabilized with butylated hydroxytoliene, greater than 99.5% by high-performance liquid chromatography (HPLC), JTBaker) and chloroform-d (CDCl ₃ : 99.8% D, 0.05% v/v trimethylsilane ( TMS) (including Cambridge Isotope Laboratories) was prepared as a solvent for instrumental analysis. Various other chemicals not mentioned above were purchased from appropriate suppliers and used without further purification.

<Measurement device and method>

Proton and carbon-13 nuclear magnetic resonance (1H and 13C NMR) spectra of the synthesized compounds were recorded using an Avance Neo spectrometer (Bruker Corporation) at 25°C. At this time, all samples for NMR analysis were dissolved in chloroform-d.

The number average molecular weight (Mn) and dispersion (Ð) of each polymer sample were measured using a 1515 Isocratic HPLC pump (Waters Corporation), a 2707 autosampler (Waters Corporation), and three Shodex HPLC columns (GPC KF-802.5, 804, and 805: It was determined on a size exclusion chromatography (SEC) system equipped with a Showa Denko KK) and a 2414 refractive index detector (Waters Corporation). At this time, the SEC system was operated using tetrahydrofuran as the eluent at a flow rate of 1 mL/min at 40°C, using the Shodex Standard SM-105 kit (molecular weight range = 1.31 × 10 ³ -3.64 × 10 ⁶ Da, Showa Denko KK). A calibration curve was obtained using 10 polystyrene standards. All samples for GPC analysis were dissolved in THF at a concentration of 1 mg/mL, and the resulting solution was polytetrafluoroethylene (PTFE) with a pore size of 5.0 μm. Passed through a membrane filter.

Thermogravimetric analysis (TGA) was performed using a Rigaku Thermo plus EVO II TG8120 series thermogravimetric analyzer in a temperature range of 0-600°C with a heating rate of 10°C/min in a nitrogen atmosphere. The decomposition temperature (T _d,5wt% ) of the copolymer sample was determined as the temperature corresponding to the initial loss of 5 wt%.

Differential scanning calorimetry (DSC) analysis was performed using a Rigaku Thermo plus EVO II DSC 8230 calorimeter in a temperature range of 0-250°C at a heating rate of 10°C/min in a nitrogen atmosphere. The glass transition temperature (T _g ) of the copolymer was determined as the midpoint of the temperature range where the endothermic change in heat capacity occurred.

Ultraviolet-visible (UV-Vis) spectrophotometric analysis was performed to record the transmittance of the copolymer films in the wavelength range of 300-800 nm using a Cary 5000 spectrophotometer (Agilent Technologies).

Wide-angle

MX170-HS 2D CCD detector (Rayonix) detector collected scattering data at a position of 0.38 m from the sample. The 1D intensity profile versus scattering vector, q = (4π/λ)sinθ, was obtained from the recorded 2D pattern. Here, λ = 0.63 A (E = 19.81 KeV) is the wavelength of the X-ray and θ is the scattering angle.

The stress-strain curve of the copolymer film was obtained using a universal testing machine (UTM, LLoyd LR5KPlus, LLoyd Instruments) at a strain rate of 5 mm/min and room temperature. At this time, the copolymer film was cut with a hand press to prepare a dogbone-shaped specimen (gauge length: 10 mm, width: 4 cm, thickness: 161-182 μm). A minimum of four tests were performed for each specimen type.

<Preparation Example 1> (E)-1-(2-(diphenylphosphanyl)phenyl)-N-mesitylmethanimine) (MesN=CHC ₆ H ₄ PPh ₂ , Mes = 2,4,6-Me ₃ C ₆ H ₂ ) Manufacturing

(Diphenylphosphino)benzaldehyde (261 mg, 0.9 mmol) was added to a solution of 2,4,6-trimethylaniline (0.14 mL, 0.99 mmol) using toluene (7 mL) as a solvent, and the reaction mixture was refluxed with stirring for 24 hours. I ordered it. Afterwards, it was cooled to room temperature and unreacted aniline was removed to obtain the crude product in powder form. Pure ligand was obtained by recrystallization from degassed ethanol. The solvent was removed in vacuo, and MesN=CHC ₆ H ₄ PPh ₂ was obtained as a yellow solid.

Yield: 334 mg (91.1%). ^1H NMR (CDCl ₃ , 500 MHz): δ (ppm) 8.89 (d, 1H), 8.27 (m, 1H), 7.49 (t, 1H), 7.39-7.18 (m, 11H), 6.93 (m, 1H) ), 6.80 (s, 2H), 2.25 (s, 3H), 1.84 (s, 6H). ³¹ P NMR (CDCl3, 500 MHz): δ (ppm) -14.46.

<Preparation Example 2> Dichloro-(E)-1-(2-(diphenylphosphanyl)phenyl)-N-mesitylmethanimine)palladium (PdCl ₂ (MesN=CHC ₆ H ₄ PPh ₂ )) Preparation

MesN (0.102g, 0.25mmol) was added to a solution of dichloro(1,5-cyclooctadiene)palladium (PdCl ₂ (cod), 0.102g, 0.25mmol) using dichloromethane (DCM, 2mL) as a solvent, and reacted. The mixture was stirred at room temperature for 4 hours. Afterwards, the solvent was removed in vacuo and the crude product was washed with hexane (10 mL) and dried under reduced pressure. A pale yellow solid of PdCl ₂ (MesN=CHC ₆ H ₄ PPh ₂ ) was obtained and stored in a glove box.

Yield: 0.138 g (97.8%). ¹ H NMR (CDCl ₃ , 500 MHz): δ (ppm) 8.05 (d, 1H), 7.79 (m, 1H), 7.70-7.56 (m, 8H), 7.47 (m, 4H), 7.10 (t, 1H) ), 6.81(s, 2H), 2.25 (s, 3H), 2.09 (s, 6H). ³¹ P NMR (CDCl ₃ , 500 MHz): δ (ppm) -34.45.

<Example 1> Polynorbornene (PNB) polymer production

Polynorbornene (PNB) was prepared according to Scheme 1 by the following method.

[Scheme 1]

In a 20 mL vial in a glove box, norbornene (NB) (0.942 g, 10 ^-2 mol), magnetic stirrer, toluene (4.8 mL) and [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] (1.84 ×10 ^- NB solution solution was prepared by adding ² g, 2.0 × 10 ^-5 mol).

In another 20 mL vial, PdCl ₂ (MesN=CHC ₆ H ₄ PPh ₂ ) (5.85 × 10 ^-3 g, 10 ^-5 mol), magnetic stirrer, toluene (4.0 mL), iBu ₃ Al (hexane solvent, 0.2 mL solution, A Pd(II) solution was prepared by adding 2.0×10 ^-4 mol).

After stirring the two solutions at 25°C for 10 minutes, the Pd(II) solution was transferred to the NB solution and [M] ₀ = 1 mol L ^-1 , [Al] ₀ /[Pd] ₀ = 20; Homopolymerization ^of NB was performed in ^a mixed solution (see Table ^{1 below} ) with [B] ₀ = ₁

The reaction mixture was stirred at 25°C for 24 hours. Afterwards, the vial of reaction mixture was removed from the glove box and 10 vol% HCl solution (diluted with methanol) was added to the reaction mixture to demetalize the polymer chain ends. After stirring for 1 hour, the mixture was poured into methanol. The precipitate was stirred for 1 hour, filtered, and dried under vacuum at 60°C for 24 hours to obtain insoluble polynorbornene (PNB). Yield: 0.820 g (87%).

<Example 2>

Polymerization was carried out in the same manner as in Example 1, except that the mixed solution was [M] ₀ = 1 mol L ^-1 , [Al] ₀ / [Pd] ₀ = 20; ^{[ B} _{] 0} ^{= 2} Norbornene (PNB) was obtained. Yield: 80% (see Table 1 below).

<Example 3> Preparation of poly(5-octyl-2-norbornene) (PNBC8) polymer

Poly(5-octyl-2-norbornene) (PNBC8) was prepared according to Scheme 2 by the following method.

[Scheme 2]

In a 20 mL vial in a glove box, NBC8 (2.06 g, 10 ^-2 mol), toluene (3.6 mL), magnetic stirrer, [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] (1.84 × 10 ^-2 g, 2.0 × 10 ^-5 mol) was added to prepare an NBC8 solution,

In another 20 mL vial, PdCl ₂ (MesN=CHC ₆ H ₄ PPh ₂ ) (5.85 × 10 ^-3 g, 10 ^-5 mol), magnetic stirrer, toluene (4.0 mL), iBu ₃ Al (hexane solvent, 0.2 mL solution, A Pd(II) solution was prepared by adding 2.0×10 ^-4 mol).

After stirring the two solutions at 25°C for 10 minutes, the Pd(II) solution was transferred to the NBC8 solution and [M] ₀ = 1 mol L ^-1 , [Al] ₀ /[Pd] ₀ = 20; Homopolymerization of NBC8 was performed in a mixed solution (see Table 1 below) with [B] ₀ = 2 × 10 ^-3 mol L ^-1 and [Pd] ₀ = 1 × 10 ^-3 mol L ^-1

The reaction mixture was stirred at 25°C for 24 hours. Afterwards, the vial of reaction mixture was removed from the glove box and 10 vol% HCl solution (diluted with methanol) was added to the reaction mixture to demetalize the polymer chain ends. After stirring for 1 hour, the mixture was poured into methanol. The precipitate was stirred for 1 hour, filtered, and dried under vacuum at 60°C for 24 hours. The product was dissolved in toluene, precipitated in methanol, stirred for 1 hour, filtered, and dried at 60°C for 24 hours under vacuum to obtain soluble poly(5-octyl-2-norbornene) (PNBC8). Yield: 1.65 g (80%).

<Example 4>

Polymerization was carried out in the same manner as in Example 3, except that the mixed solution was [M] ₀ = 1 mol L ^-1 , [Al] ₀ / [Pd] ₀ = 20; _[ ^{B ]} ₀ ^{= 2} (5-octyl-2-norbornene) (PNBC8) was obtained. Yield: 87% (see Table 1 below).

<Example 5>

Polymerization was carried out in the same manner as in Example 3, except that the mixed solution was [M] ₀ = 1 mol L ^-1 , [Al] ₀ / [Pd] ₀ = 20; ^{[ B} _{] 0} ^{= 2} (5-octyl-2-norbornene) (PNBC8) was obtained. Yield: 93% (see Table 1 below).

<Example 6>

Polymerization was carried out in the same manner as in Example 3, except that the mixed solution was [M] ₀ = 1 mol L ^-1 , [Al] ₀ / [Pd] ₀ = 20; ^{[ B} _{] 0} ^{= 2} (5-octyl-2-norbornene) (PNBC8) was obtained. Yield: 95% (see Table 1 below).

<Example 7> Preparation of copolymers of NB and NBC8

A copolymer of NB and NBC8 was prepared according to Scheme 3 by the following method.

[Scheme 3]

Add NB/NBC8 at the specified molar composition (mole fraction of NBC8 (f _NBC8 ) = 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9, 10 ^-2 mol) to each of six 20 mL vials in a glove box and stir on a magnetic stirrer. , toluene (appropriate volume of [NB/NBC8] ₀ = 1 mol L ^-2 ) and [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] (1.84 × 10 ^-2 g, 2.0 × 10 ^-5 mol) Each NB/NBC8 solution was prepared by adding.

In a 70 mL vial, [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] (1.84 × 10 ^-2 g, 2.0 × 10 ^-5 mol), magnetic stirrer, toluene (28.0 mL), iBu ₃ Al (hexane solvent) , 1.4 mL solution, 1.4 mL × 10 ^-3 mol) was added to prepare a Pd(II) solution.

After all solutions were stirred at 25 °C for 10 min, 4.2 mL of Pd(II) solution was transferred into each NB/NBC8 solution to perform NB/NBC8 copolymerization of six different feed compositions.

After the reaction mixture was stirred at 25°C for 50 or 60 minutes, the vials of the reaction mixture were removed from the glove box and 10 vol% HCl solution (diluted with methanol) was added to each mixture to terminate the copolymerization. After stirring for 1 hour, the mixture was poured separately into methanol. The precipitate was stirred for 1 hour, filtered, and dried under vacuum at 60°C for 24 hours to obtain 6 NB/NBC8 soluble copolymers in less than 10% yield.

The copolymer composition was characterized by 1H NMR spectroscopy to determine the mole fraction of NBC8 in the copolymer for each sample. Composition information of the feed and each copolymer was applied to the Kelen-Tudos method to determine the monomer reactivity ratios for NB and NBC8 (rNB and rNBC8).

<Example 8> Preparation of a copolymer of NB and NBC8 in the presence of a chain transfer agent

A copolymer of NB and NBC8 was prepared according to Scheme 4 using the following method, depending on the presence or absence of 1-hexene (HX), a chain transfer agent.

[Scheme 4]

NB (0.471 g, 5.0 × 10 ^-3 mol), NBC8 (1.03 g, 5.0 × 10 ^-3 mol), and specific amounts of HX ([HX] ₀ /[NB/NBC8]) in each of four 20 mL vials in a glove box. ₀ = 10, 5, 1 or 0), magnetic stirrer, toluene (3.6 mL) and [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] (1.84 × 10 ^-2 g, 2.0 × 10 ^-5 mol) was added to prepare an NB/NBC8 solution.

PdCl ₂ (MesN=CHC ₆ H ₄ PPh ₂ ) (2.92 × 10 ^-2 g, 5.0 × 10 ^-5 mol) in a 70 mL vial, magnetic stirrer, toluene (20 mL), iBu ₃ Al (hexane solvent, 1.0 mL solution, A Pd(II) solution was prepared by adding 1.0×10 ^-3 mol).

After all solutions were stirred at 25°C for 10 minutes, 4.2 mL of Pd(II) solution was transferred to the NBC8 solution to perform copolymerization of NB/NBC8.

The reaction mixture was stirred at 25°C for 24 hours. Afterwards, the vial of reaction mixture was removed from the glove box and 10 vol% HCl solution (diluted with methanol) was added to the reaction mixture to demetalize the polymer chain ends. After stirring for 1 hour, the mixture was poured separately into methanol. The precipitate was stirred for 1 hour, filtered, and dried under vacuum at 60°C for 24 hours. The crude product was dissolved in toluene, precipitated in methanol, stirred for 1 hour, filtered, and dried under vacuum at 60°C for 24 hours to produce four soluble poly(norbornene-random-5-octyl) with different molecular weights. -2-norbornene) (P(NB-r-NBC8)s) was obtained. Yield: 1.22-1.29 g (81-86%).

<Example 9> Preparation of P(NB-r-NBC8) film

Each of four 70 mL vials was filled with four P(NB-r-NBC8) (0.4 g) and toluene (45.7 mL) having different molecular weights prepared in Example 8 to prepare a 1 wt% copolymer solution, and the solution was was stirred at 60°C for more than 3 hours. Carefully inject each of the four copolymer solutions into a glass dish (diameter = 45 mm, height = 30 mm) placed on a parallel, minimized vibration table using a 50 mL syringe equipped with a PTFE membrane filter with a pore size of 5.0 μm. Added. The four dishes filled with the copolymer solution were covered with a larger volume glass dish and the dishes were left undisturbed until the toluene was completely evaporated. Afterwards, the copolymer film on the plate was dried at 100°C in a vacuum atmosphere for 12 hours. Afterwards, the copolymer film was separated from the dish to obtain films made of poly(norbornene-random-5-octyl-2-norbornene) (P(NB-r-NBC8)s) having different molecular weights.

<Experimental Example 1> Analysis of independent polymerization results

In order to evaluate the cyclic olefin polymer production performance of the composition for producing cyclic olefin polymer according to an embodiment, vinyl addition polymerization of norbornene monomer was performed according to Examples 1 to 6, and molecular weight and dispersion were measured through SEC (size exclusion chromatography). The temperature was measured and the results are shown in Table 1 below.

Example M
(molL ^-1 ) [Pd] ₀
(mol L ^-1 ) [B] ₀
(mol L ^-1 ) hour
(h) transference number
(%) A _1h M _n,theo
(kDa) M _n
(kDa) Ð M _n,theo /M _n One N.B.
One 10 ^-3 10 ^-3 One Not created - - - - - One 24 - - - - - 2 N.B.
l 10 ^-3 2 × 10 ^-3 One 7.8 7.36 × 10 ³ 24 87 3 NBC8 1 10 ^-3 2 × 10 ^-3 One 1.4 2.86 × 10 ³ 2.89 302 2.48 0.00957 24 80 165 1140 1.56 0.145 4 NBC81 5 × 10 ^-4 2 × 10 ^-3 One 2.1 7.27 × 10 ³ 8.67 498 2.22 0.0174 24 87 359 1020 1.70 0.352 5 NBC8
One 2 × 10 ^-4 2 × 10 ^-3 One 2.1 2.12 × 10 ⁴ 21.7 591 2.42 0.0367 24 93 960 1260 1.48 0.762 6 NBC8
One 10 ^-4 2 × 10 ^-3 One 0.78 1.62 × 10 ⁴ 16.1 352 3.88 0.0457 24 95 1960 631 2.41 3.11

- M: Norbornene monomer and content (molL ^-1 ) - [Pd] ₀ : Pd content (mol L ^-1 )

- [B] ₀ : Boron content (mol L ^-1 )

- A _1h : Catalyst activity during the first 1 hour (g _polymer mol _Pd ^-1 h ^-1 )

- M _n,theo : [M] ₀ /[Pd] ₀ × molecular weight of M × polymer yield/100% (kDa)

- M _n : Number average molecular weight measured by SEC (size exclusion chromatography) of tetrahydrofuran at 40°C (PNB polymer cannot be measured due to insolubility in THF) (kDa)

- Ð: Dispersity measured by SEC (size exclusion chromatography) of tetrahydrofuran at 40°C (PNB polymer cannot be measured in THF due to insolubility)

As shown in Table 1, in norbornene (NB) homopolymerization, [M] ₀ = 1 mol L ^-1 , [Al] ₀ /[Pd] ₀ = 20; In Example ₁ ^, where the polymerization was performed in ^a mixed solution ^of [B] ₀ = ¹ While this did not proceed, it can be confirmed that polymerization was achieved with a yield of 87% in the solution added with [B] ₀ = 2 × 10 ^-3 mol L ^-1 . This is because [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] acts as a scavenger in the monomer solution, and in Example 1, most of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] is expected to be sacrificed by removing impurities when mixed with the monomer.

From the above results, it can be confirmed that in order for polymerization to occur, at least 2×10 ^-3 moles of [B] ₀ are required when [M] ₀ is 1 mol L ^-1 .

In addition, through Example 2, the catalytic activity during the initial 1 hour (A _1h ) at [Pd] ₀ = 10 ^-3 mol/L was observed to be less than 10 ^-4 g _polymer mol _Pd ^-1 h ^-1 for 24 hours. After polymerization, it was confirmed that insoluble PNB was polymerized with a high yield of 87%.

In addition, as a result of preparing soluble PNBC8 in the same catalyst system in Example 3, the homopolymerization of NBC8 at [Pd] ₀ = 10 ^-3 mol/L was slower than the homopolymerization of NB, with yields in 1 h and A _1h . Although polymerized, 80% yield was achieved after 24 hours.

As a result of measuring the number average molecular weight (M _n ) of the polymerized PNBC8 at the first 1 hour and 24 hours using size exclusion chromatography (SEC), it was found to be 1140 kDa, which is much larger than the theoretical M _n (M _n,theo ) value of 165 kDa. was obtained, and the dispersion degree Ð was 1.56, confirming that a cyclic olefin polymer with an ultra-high molecular weight of 1000 kDa or more was produced.

This appears to be due to the low catalyst initiation efficiency of the catalyst system according to one embodiment, PdCl ₂ (MesN=CHC ₆ H ₄ PPh ₂ )/iBu ₃ Al/[Ph ₃ C][B(C ₆ F ₅ ) ₄ The reason for the low initiation efficiency of ] is expected to be due to the low solubility of the initial catalytic species in non-polar toluene, resulting in an equilibrium between active species and inactive clusters.

Meanwhile, in order to confirm the effect of the concentration of the palladium catalyst, the polymerization results in Examples 4 to 6 where [Pd] ₀ = 10, 5, 2, 1 × 10 ^-4 molL ^-1 were varied, 1 hour polymerization Although the M _ntheo /M _n value for 24 hours polymerization remained below 0.1, it was confirmed that the M _ntheo /M _n value for 24-hour polymerization tended to increase as [Pd] ₀ decreased. Abnormal results were observed in Example 6 using ₀ = 1 × 10 ^-4 mol/L, which is expected to be due to chain transfer occurring to residual iBu ₃ Al.

From the above results, it can be confirmed that a cyclic olefin polymer having an ultra-high molecular weight of 1000 kDa or more can be produced using a catalyst containing the compound of Formula 1.

<Experimental Example 2> Analysis of copolymerization results

In order to evaluate the cyclic olefin copolymer production performance of the composition for producing cyclic olefin polymer according to an example, vinyl addition copolymerization of norbornene monomer was performed according to Example 7, and proton and carbon-13 nuclear magnetic resonance (1H and 13C NMR) ) The production of the copolymer was confirmed through the spectrum, and the results are shown in Table 2 and Figure 1 below.

Example f _{N.B. fNBC8} F _NB F _NBC8 f F α ξ η 7-1 0.6 0.4 0.644 0.356 1.5000 1.8090 0.0447 0.7835 0.4225 7-2 0.5 0.5 0.523 0.477 1.0000 1.0964 0.0447 0.7263 0.0700 7-3 0.4 0.6 0.446 0.554 0.6667 0.8051 0.0447 0.6163 -0.1802 7-4 0.3 0.7 0.353 0.647 0.4286 0.5456 0.0447 0.4948 -0.5246 7-5 0.2 0.8 0.221 0.779 0.2500 0.2837 0.0447 0.3906 -1.1191 7-6 0.1 0.9 0.115 0.885 0.1111 0.1299 0.0447 0.2165 -1.6956

- f _NB : supplied NB mole fraction (f _NB +f _NBC8 =1)f _NBC8 : supplied NBC8 mole fraction

- F _NB : NB mole fraction in aerial body (F _NB +F _NBC8 = 1)

- F _NBC8 : NBC8 mole fraction in aerial body

- f: Value calculated according to Equation 1 below

- α: Value calculated according to Equation 2 below

- ξ, η: Values calculated according to Equation 3 below

[Equation 1]

[Equation 2]

[Equation 3]

From the results in Table 2, it can be seen that the prepared copolymer was formed with a composition that is almost identical to the supplied composition, and the Kelen-Tudos graph in Figure 1 showed the ratios of rNB = 1.21 and rNBC8 = 0.859. , From this, it can be confirmed that random copolymer P(NB-r-NBC8) was produced through Example 7.

<Experiment Example 3> Characteristic analysis according to molecular weight

In order to analyze the mechanical properties of the cyclic olefin polymer prepared according to one embodiment, a copolymer of NB and NBC8 was prepared with the NBC8 mole fraction (f _NBC8 ) set to 0.5, and the chain transfer agent (CTA) 1 -To analyze the physical properties of the copolymers prepared using hexene (HX) (Examples 8 and 9), size exclusion chromatography (SEC) system, differential scanning calorimetry (DSC), and ultraviolet visible light (UV-Vis) were used. ) was analyzed using a spectrophotometer, wide-angle X-ray scattering (WAXS) analyzer, and universal testing machine (UTM), and the results are shown in Table 3 below and Figures 2 to 9.

[HX] ₀ /[M] ₀ F _NBC8 M _n
(kDa) Ð T _d,5wt%
(℃) T _g
(℃) T
(%) E
(MPa) σ _B
(MPa) ε _B
(%) U _T
(MJ m ^-3 ) One 0.481 504 2.73 395 162 91-100 1144 ± 68 24.3 ± 1.4 13.6 ± 7.5 2.85 ± 1.84 0.5 0.499 874 1.82 393 160 90-100 1113±190 26.5 ± 2.9 17.6 ± 0.4 4.11 ± 0.76 0.1 0.489 1110 1.62 396 163 92-100 1094 ± 28 26.1 ± 0.8 24.3 ± 1.2 5.61 ± 0.13 0 0.471 1530 1.31 389 160 93-100 1058 ± 53 26.2 ± 1.0 23.1 ± 1.3 5.41 ± 0.46

- F _NBC8 : mole fraction of NBC8 in the copolymerT _d,5wt% : decomposition temperature at 5 wt% loss

- T _g : glass transition temperature

- T: Transmittance

- E: Young's modulus.

- σ _B : tensile strength

- ε _B : elongation at break

- U _T : tensile toughness

For the four copolymers P(NB-r-NBC8) prepared in Example 8, Figure 2 is a graph showing the number average molecular weight (M _n ) results measured using a size exclusion chromatography (SEC) system.

As a result of the analysis of Table 3 and Figure 2, the mole fraction of NBC8 (FNBC8) in all four copolymers P (NB-r-NBC8) prepared when the supply ratio of HX was varied as 1, 0.5, 0.1, and 0. It can be seen that the number average molecular weight (M _n ) is maintained at 0.471 to 0.499, while the number average molecular weight (M n ) is 504 to 1530 kDa, and the degree of dispersion (Ð) is formed differently at 2.73 to 1.31, respectively. From the above results, it can be seen that copolymers with different molecular weights can be prepared by adjusting the supply amount of 1-hexene (HX), a chain transfer agent (CTA).

In addition, in order to confirm the thermal properties of the four copolymers P(NB-r-NBC8) (bulk) with different molecular weights prepared in Example 8, the decomposition temperature (T) at 5 wt% loss was measured by thermogravimetric analysis (TGA). _d,5wt% ) was measured and shown in Table 3, and the glass transition temperature was measured using differential scanning calorimetry (DSC), and the results are shown in Table 3 and Figure 3.

As a result of the measurement, it can be seen that the decomposition temperature (T _d,5wt% ) at 5 wt% loss is similar to 389°C to 396°C, and the glass transition temperature (T _g ) is similar to approximately 160°C to 163°C. Through the above results, it can be confirmed that the thermal properties of four copolymers P(NB-r-NBC8) with different molecular weights are similar.

In addition, in order to confirm the optical properties of the four copolymers P(NB-r-NBC8) with different molecular weights prepared in Example 8, each was formed into a film (thickness 161-182 μm) (see Example 9). After that, the transmittance was measured using an ultraviolet-visible (UV-Vis) spectrophotometer, and the results are shown in Figure 4.

As a result of the measurement, it was confirmed that all four copolymer P(NB-r-NBC8) films with different molecular weights exhibited a transmittance (T) of about 90% or more in the visible light wavelength (400-800 nm) range. Through the above results, it can be confirmed that the optical properties of the four copolymers P(NB-r-NBC8) with different molecular weights are similar.

In addition, in order to confirm the nanostructure of the four copolymers P(NB-r-NBC8) with different molecular weights, each was formed into a film (thickness 161-182 μm) (see Example 9), and then one-dimensional wide-angle X-ray scattering (1D WAXS) analysis was performed and the results are shown in Figure 5.

As a result of the measurements, the two lattice spacings (d-spacing, d _i = 2πq _i ^-1 ) in all four copolymer P(NB-r-NBC8) films with different molecular weights were 13.66 to 13.96 Å (= d ₁ ) and 4.69 Å, respectively. Two main scattering peaks corresponding to Å(=d ₂ ) from 0.45 to 0.46 Å ^-1 (=q ₁ ) and 1.34 Å ^-1 (=q ₂ ) were obtained, with a d- of 9.67 Å(=d ₁ '). A small peak at 0.65 Å ^-1 (q _1′ ) corresponding to the gap was obtained. From the above results, it can be expected that the four copolymers P(NB-r-NBC8), which have different molecular weights but have almost the same composition, do not have any unique elements that cause differences in mechanical properties in the nanostructure.

In order to confirm the relationship between the molecular weight and tensile properties of the four copolymers P(NB-r-NBC8) with different molecular weights prepared in Example 8, each was formed into a film (thickness 161-182 μm) (Example 9 After this, a tensile test was performed at a strain rate of 5 mm/min and room temperature using a universal testing machine (UTM) to determine Young's modulus, tensile strength, and elongation at break according to molecular weight. ), tensile toughness was measured and the results are shown in Table 3 and Figures 6 to 9.

As shown in Figures 6 and 7, the Young's modulus (E) is 1058 MPa to 1144 MPa, and the tensile strength (σ _B ) is 24.3 MPa to 26.5 MPa, with little difference depending on molecular weight, while as shown in Figure 8, fracture It can be seen that elongation at break significantly increases from 13.6% to 24.3% as the number average molecular weight (M _n ) increases from 504 kDa to 1110 kDa, and then the number average molecular weight (M _n ) further increases to 1530 kDa. You can see that there is no further improvement even if you do this. Meanwhile, the copolymer film with a number average molecular weight (M _n ) of 504 kDa showed a large error in elongation at break compared to the other three films. Considering the high dispersion (Ð = 2.73), it can be expected that a large amount of short chains are irregularly distributed as weak points, resulting in such large errors. In addition, similar to tensile toughness and elongation at break, it can be seen that the number average molecular weight (M _n ) increases up to 1110 kDa. From the above results, in order to increase the tensile strength of cyclic olefin copolymer P (NB-r-NBC8) of similar or identical composition through chain entanglement and at the same time increase elongation at break, a ^number average molecular weight (M _n ) can be confirmed to be necessary.

Claims (12)

norbornene monomer; and
A composition for producing a cyclic olefin polymer, comprising a catalyst comprising a compound represented by Formula 1 below:
<Formula 1>

(Here, R ¹ , R ² , and R ³ are each independently alkyl of C ₁ -C ₆ ).
According to paragraph 1,
The norbornene-based monomer is a composition for producing a cyclic olefin polymer, represented by the formula 2 below:
<Formula 2>

(Where R ⁴ and R ⁵ are each independently hydrogen or C ₁ -C ₃₀ alkyl).
According to paragraph 1,
A composition for producing a cyclic olefin polymer, wherein the norbornene monomer is a mixture of two or more norbornene monomers.
According to paragraph 1,
The composition for producing a cyclic olefin polymer, wherein the catalyst further includes at least one of an ionic aluminum compound and an ionic boron compound.
According to paragraph 4,
The ionic aluminum compound is,
Methylaluminoxane (MAO), modified methylaluminoxane (MMAO), trimethyl aluminum (TMA), triethyl aluminum (TEA), triiso-butyl aluminum (TIBAL) ), a composition for producing a cyclic olefin polymer, which is at least one selected from the group consisting of dimethyl chloro aluminum (DMCA) and diethyl chloroaluminum (DECA).
According to paragraph 4,
The ionic boron compound is,
Triphenylmethylium tetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, Triphenylcarbenium tetrakis(2,4,6-trifluorophenyl)borate, triphenylcarbenium tetraphenylborate, tributylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis (pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diphenylaniliniumtetrakis(pentafluorophenyl)borate and lithium tetrakis(pentafluorophenyl)borate. A composition for producing a cyclic olefin polymer, which is at least one selected from the group consisting of (lophenyl)borate.
Catalyst for producing a cyclic olefin polymer, comprising a compound represented by Formula 1 below:
<Formula 1>

(Here, R ¹ , R ² , and R ³ are each independently alkyl of C ₁ -C ₆ ).
A method for producing a cyclic olefin polymer from a norbornene monomer, using a catalyst comprising a compound represented by Formula 1 below:
<Formula 1>

(Here, R ¹ , R ² , and R ³ are each independently alkyl of C ₁ -C ₆ ).
According to clause 8,
A method for producing a cyclic olefin polymer, wherein the catalyst further includes at least one of an ionic aluminum compound and an ionic boron compound.
According to clause 9,
The method for producing the cyclic olefin polymer is
Mixing a first solution containing the norbornene-based monomer and an ionic aluminum compound and a second solution containing the compound represented by Formula 1 and an ionic boron compound to add the norbornene-based monomer to the polymerization step; cyclic comprising a. Method for producing olefin polymer.
A cyclic olefin polymer produced by the production method of claim 8 and having a number average molecular weight (M _n ) of 1000 kDa or more.
A cyclic olefin polymer film comprising the cyclic olefin polymer of claim 11.