KR100785187B1 - A preparing method of cyclic olefin copolymer having controlled gel contents - Google Patents

Abstract

The present invention relates to a method of preparing a copolymer in which the production of a gel is controlled by polymerizing a cyclic olefin compound by a ring opening metathesis polymerization (ROMP) method, and the presence or absence of a compound acting as a molecular weight regulator. Under the following conditions, a complex prepared by mixing the W salt compound and the organoaluminum halide compound is used as a catalyst, and the composition of the cyclic olefin monomer constituting the copolymer is maintained at a constant ratio as in the following Formula 1 to form a reaction rate regulator or gel. A method for controlling the production of gels without the use of inhibitors and at the same time producing cyclic olefin copolymers in high yield.

(Composition 1)

Norbornene = 30 to 70% by weight

Cyclic olefin compounds = 70 to 30% by weight

At this time, the cyclic olefin compound specified in the formula 1 is one or more compounds selected from dicyclopentadiene (Dicyclopentadiene) and the compound represented by the following formula (1).

(Formula 1)

In Chemical Formula 1, m is an integer of 0 to 1, R ₁ is an alkyl group having 1 to 5 carbon atoms, and R ₂ is hydrogen or an alkyl group having 1 to 10 carbon atoms.

Ring-opening polymerization, gel formation, control, cyclic olefins, copolymers, preparation method

Description

A preparation method of cyclic olefin copolymer having controlled gel contents

The present invention relates to a method for preparing a copolymer of a cyclic olefin compound, and more particularly, in the presence or absence of a compound which acts as a molecular weight regulator in preparing a copolymer of a cyclic olefin compound, a W salt compound and an organic compound. The complex prepared by mixing the aluminum halide compound is used as a catalyst, but the composition of the cyclic olefin monomer constituting the copolymer is maintained at a constant ratio as in the following Formula 1, thereby producing gel without using a reaction rate regulator or gel formation inhibitor. To control and simultaneously produce a cyclic olefin copolymer in high yield.

(Composition 1)

Norbornene = 30 to 70% by weight

Cyclic olefin compounds = 70 to 30% by weight

At this time, the cyclic olefin compound specified in Formula 1 is one or more compounds selected from dicyclopentadiene and the compound represented by the following formula (1).

(Formula 1)

In Chemical Formula 1, m is an integer of 0 to 1, R ₁ is an alkyl group having 1 to 5 carbon atoms, and R ₂ is hydrogen or an alkyl group having 1 to 10 carbon atoms.

In general, when preparing a copolymer of a cyclic olefin compound, formation of a gel can be observed during or after completion of the reaction.

The resulting gel not only significantly increases the solution viscosity of the polymer, but also accumulates in the reactor walls or pipelines, thereby inhibiting the flow of reactants or products, which may act as a serious obstacle in the commercialization process. In addition, the polymer containing a predetermined amount or more of the gel may be poor in solubility in organic solvents and difficult to melt uniformly by heat may reduce the processing performance. In addition, if the polymer contains a predetermined amount of gel after the polymerization reaction, the efficiency of the hydrogenation reaction, which is the next step, may be greatly reduced. In this case, the double bonds remaining in the polymer chain may be decomposed by external factors such as heat and UV. It may cause deterioration of properties. Therefore, the presence or absence of gel in the ring-opening polymerization reaction of the cyclic olefin compound can be said to be an important factor in determining the success or failure of the reaction.

Copolymers of ethylene, propylene, and cyclic olefin compounds have been introduced to rigid polymers such as norbornene into the polymer backbone. I got it. Accordingly, single and copolymers of cyclic olefin compounds replace optical polycarbonate (PC) or polymethyl methacrylate (PMMA) resins, which are currently used for information recording, and are optical materials with transparency and low hygroscopicity. The possibility of being used for a variety of applications, such as lenses, optical fibers, etc. has opened up.

Various norbornene derivatives with various alkyl and polar functional groups are currently used for the preparation of cyclic olefin polymers, and these norbornene derivatives can be used for the preparation of homopolymers as well as for copolymers.

Recently, some advanced cyclic olefin polymer manufacturers have copolymerized styrene, cyclic olefin, methyl methacrylate and ethylene to produce next-generation new materials with breakthrough thermal, mechanical and optical properties that cannot be reached with conventional polyolefins. Developing. Particularly, polymers prepared by copolymerization reaction between cyclic olefin compound and ethylene have excellent optical and thermal properties, and thus are attracting attention as next generation materials for information recording such as CD and DVD.

Norbornene-based polymers can not only replace polycarbonates currently used for these applications, but also can reduce the space between CD tracks, thereby enabling high integration, and thus being applicable to next-generation DVDs (HD-DVD). In addition, due to the characteristics such as optical properties, dimensional stability, moisture resistance, low density, the scope of application of the lens of a camcorder or an automatic camera has become very wide.

Polymerization catalysts for preparing polymers using cyclic olefin compounds can be broadly classified into ROMP catalysts (Ring Opening Metathesis Polymerization), addition polymerisation catalysts, cationic catalysts, and radical initiators.

Among them, a common feature of the ROMP catalyst, the addition reaction catalyst, and the cationic catalyst is that all cyclic olefin polymers having high transparency can be produced. When using a ROMP-based catalyst, the step of saturating the double bonds contained in the polymer after the polymerization is essential through the hydrogenation reaction, but the polymerization activity for the monomer containing a hetero atom is superior to other catalyst systems. In the case of using an addition reaction catalyst, there is an advantage in that the final polymer can be prepared immediately after the polymerization reaction, but generally has a disadvantage in that the polymerization activity is low for the monomer containing a hetero atom.

Representative metals of the ROMP-based catalyst include Mo, W, Ru, Re, etc., and the activity of the catalyst can be controlled by variously modifying ligands coordinated around the metal or by changing cocatalysts and additives.

Representative metals constituting the addition reaction catalyst include Ti, Zr, Cr, Co, Ni, and Pd. Among them, Ni and Pd are representative metal catalysts for preparing cyclic olefin polymers.

The main advantages of cyclic olefin polymers are low density, high transparency, low hygroscopicity and heat resistance, which could replace glass, acrylic polymer, polycarbonate and polyvinylidene chloride (PVDC). It is becoming.

As a method of controlling the amount of gel produced in the ring-opening polymerization of the cyclic olefin compound, US Pat. Nos. 4,002,815 and 4,069,376 disclose non-porous non-porous forms containing at least one hydrogen atom in a W salt compound and a double bond carbon. Disclosed is a method for controlling gel formation of a polymer using a complex formed by mixing a liquid olefin (non-conjugated olefin) compound and then adding AlR ₂ I, AlRI ₂ , or a mixture of AlR ₃ and I ₂ as a polymerization catalyst. have. However, in the former case, a relatively low polymerization yield of 70% or less was observed, and in the latter case, the polymerization activity was greatly changed according to polymerization conditions with a polymerization yield of 6 to 100%.

Meanwhile, US Patent Nos. 6,020,443 and 5,939,504 disclose methods for controlling the formation of gels by controlling the rate of polymerization using Lewis base compounds. The compounds used are phosphine, Compounds such as phosphite, ether, amine, amide, sulfoxide, nitrile or furan. However, these methods not only complicate the reaction process by using reaction rate regulators but also in some cases imply the possibility that the polymerization yield may be lowered due to the use of these additives.

As an example of a method for preparing a cyclic olefin polymer by using the Reaction Injection Molding process, U.S. Patent No. 4,400,340 discloses a mixture of a W salt compound and a dialkylaluminum halide or an alkylaluminum dihalide compound as a reaction rate controlling agent such as ether, ester, Or a method for producing a cyclic olefin polymer using a complex formed by adding a ketone compound is disclosed. Similarly, US Pat. No. 4,882,401 also discloses a ring using a complex formed by adding a dialkyl zinc or alkyl zinc halide compound as a catalyst activator to a W salt or Mo salt compound and an ether, phosphine or phosphite compound as a reaction rate regulator. A method for producing a type olefin polymer is disclosed. However, these methods also have a problem in that the reaction process is complicated by using a catalyst activator and reaction rate regulator.

U.S. Patent No. 3,997,471 discloses a method for preparing a cyclic polymer using a complex formed by adding an alcohol compound containing a nitrile group or a halogen element as a reaction rate regulator to a mixture of a W salt compound and a dialkylaluminum halide as a catalyst. The polymerization yield has been observed to be 80% or less. Similarly, U. S. Patent No. 6,511, 756 discloses a cyclic olefin using a complex formed by adding a compound containing a nitrile group, a ketone group, an ether group or an ester group as a reaction rate regulator to a mixture composed of a W salt or a Mo salt compound and an organoaluminum compound. A method for producing a polymer is disclosed. However, there is a problem that the reaction process is complicated by the use of a reaction regulator.

As another example, US Patent No. 4,060,468 discloses a method for preparing catalytically active species by irradiating UV to a complex formed by adding a phenolic derivative to a W salt or a Mo salt compound. As such, there is a limit to applying it to the mass production process.

US Pat. No. 5,840,820, on the other hand, uses a complex formed by using a Ru carbene complex as a single catalyst or by adding an organoaluminum halide compound or an organoalkyl tin compound to the W salt complex as a catalyst, but using CO ₂ as a polymerization solvent. A method for preparing a cyclic olefin polymer using the same has been disclosed. A polymerization yield of 80% or less has been reported even when the polymerization reaction is performed at a high pressure (1000 psi or more) for a long time (10 hours or more).

  U.S. Patent No. 6,433,113 discloses a method for preparing a cyclic olefin polymer by adding α-olefin as a chain transfer agent to a mixture composed of a Mo salt compound and an organoaluminum compound. This large change has been observed (polymerization yield = 10-100%).

Meanwhile, a series of methods using organoalkyl tin compounds instead of organoaluminum halide compounds which have been used as a component of the catalyst system in the preparation of cyclic olefin polymers have been published. US Patent No. 4,810,762 discloses W salt compounds substituted with phenol derivatives. A method for producing a cyclic olefin polymer using a complex formed by adding a R ₃ SnH or Ph ₃ SnH compound to a catalyst is disclosed. US Pat. No. 5,081,208 discloses a R ₃ SnH compound in a mixture composed of a W salt compound and a phenolic compound. Disclosed is a method for preparing a cyclic olefin polymer using the complex formed as a catalyst. However, these two methods have been pointed out by using a Sn compound known as a harmful substance.

Accordingly, the present inventors have diligently researched to improve the conventional problems as described above, and as a result, a complex prepared by mixing the W salt compound and the organoaluminum halide compound as the ring-opening polymerization catalyst of the cyclic olefin compound is used. By maintaining the composition of the norbornene and cyclic olefin compound represented by the above formula 1 as a constituent monomer at a constant ratio, the formation of the gel is controlled without the use of a reaction rate modifier or a gel formation inhibitor and at the same time a cyclic olefin copolymer with high yield It was found that can be prepared to complete the present invention.

That is, the present invention is to provide a method for producing a cyclic olefin copolymer in a high yield while suppressing the formation of the gel by maintaining the ratio of the monomer constituting the copolymer in a certain range without using a reaction rate regulator or gel production inhibitor Its purpose is to.

The present invention for achieving the above object is to use a complex prepared by mixing a W salt compound and an organoaluminum halide compound as a catalyst, the composition of the norbornene and cyclic olefin compound constituting the copolymer as shown in the following formula It is characterized by producing a copolymer of the cyclic olefin compound in high yield while controlling the formation of the gel without the use of a reaction rate modifier or gel production inhibitor by maintaining at a constant ratio.

(Composition 1)

Norbornene = 30 to 70% by weight

Cyclic olefin compounds = 70 to 30% by weight

At this time, the cyclic olefin compound specified in Formula 1 is one or more compounds selected from dicyclopentadiene and the compound represented by the following formula (1).

(Formula 1)

In Chemical Formula 1, m is an integer of 0 to 1, R ₁ is an alkyl group having 1 to 5 carbon atoms, and R ₂ is hydrogen or an alkyl group having 1 to 10 carbon atoms.

Hereinafter will be described in more detail with respect to the configuration of the present invention.

In the present invention, in the polymerization of the cyclic olefin compound, the composition of the norbornene and the cyclic olefin compound constituting the copolymer is maintained at a constant ratio as in the above Formula 1 to produce a gel without using a reaction rate regulator or a gel formation inhibitor. The present invention relates to a method for producing a cyclic olefin copolymer in a high yield while controlling. When the composition of the norbornene and the cyclic olefin compound constituting the copolymer according to the present invention is maintained as in Formula 1, the amount of gel produced can be controlled to 1% by weight or less based on the amount of the monomer used.

In the ring-opening polymerization of such norbornene and cyclic olefin compounds, the catalyst used in the present invention consists of a W salt compound and an organoaluminum halide compound. First, the W salt compound is WCl ₆ , WCl ₄ , WOCl ₄ , W (CO) ₆ , W (OC ₆ H ₅ ) ₆ , WCl ₂ (OC ₆ H ₅ ) ₄ , W (CO) ₃ (CH ₃ CN) ₃ , and W (OEt ₂ ) Cl ₃ compounds. ₆ And WOCl ₄ Compounds and the like are particularly suitable. Such salt compounds W 1 X 10 ^-5 ~ 1 X 10 per 10g of the ^monomer-to use to ³ molar is preferred generally.

On the other hand, the organoaluminum halide compound is, for example, dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dioctylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, Isobutylaluminum dichloride, octylaluminum dichloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, butylaluminum sesquichloride compounds and the like. Particularly suitable are diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum dichloride, isobutylaluminum dichloride, ethylaluminum sesquichloride compounds. When the alkylaluminum compound (AlR ₃ ), which is a polymerization catalyst component of the conventional diene compound, is used instead of the organoaluminum halide compound, the reaction yield is extremely low, which is very disadvantageous in terms of economics in commercial production, and the molecular weight of the polymer is fixed. It is difficult to raise abnormalities, so there may be a limit to improvement of physical properties.

Compounds that can act as molecular weight modifiers in accordance with the present invention include, for example, 1-butene, 1-pentene, 1-hexene, 1-octene, 2-butene, 2-pentene, 1,4-hexadiene compounds, etc. , 1-butene, 1-hexene, 1-octene and the like are particularly suitable.

A ring-opening polymerization catalyst for preparing a cyclic olefin copolymer is prepared by mixing the W salt compound and the organoaluminum halide compound as described above. As the solvent for preparing the catalyst, a nonpolar solvent which is not reactive with the catalyst should be used. , Hexane, benzene, toluene, chlorobenzene, o -dichlorobenzene and the like.

The W salt compound and the organoaluminum halide compound may be used in a molar ratio of 1:30 to 1: 100, preferably in a molar ratio of 1:40 to 1:80. If the use ratio is out of the above range and the organoaluminum halide compound is used in less than 30 molar ratio with respect to the W salt compound, the polymerization yield may be lowered. On the contrary, the organoaluminum halide compound is used in excess of 100 molar ratio with respect to the W salt compound. Doing so can lead to discoloration of the product and a decrease in efficiency in economic terms.

The order of the input of each component for preparing the catalyst is put the W salt compound solution into the reactor in a nitrogen atmosphere, and then the organoaluminum halide compound is added. In this case, the order of addition of the compounds constituting the catalyst may be as described above, or in some cases, the catalyst may be prepared by changing the order of addition.

In the ring-opening polymerization of the cyclic olefin compound using the catalyst prepared as described above to prepare a copolymer according to the present invention, the non-polar polymerization solvent used in the polymerization includes aliphatic hydrocarbons such as hexane, heptane, octane, isooctane; Cycloaliphatic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane and the like; And aromatic hydrocarbons such as benzene, toluene, chlorobenzene, o -dichlorobenzene and the like. It is preferable that the weight ratio of a polymerization solvent and a monomer is 2: 1-20: 1.

According to the present invention, a cyclic olefin copolymer can be obtained in a yield of 80 to 100% by appropriate polymerization for 1 to 3 hours under suitable catalyst conditions. After the polymerization reaction, the product was obtained by precipitation in methanol or ethanol containing a small amount of HCl.

As described above, according to the present invention, it is possible to prepare the cyclic olefin copolymer in high yield while controlling the formation of the gel.

Although this invention is demonstrated in detail based on an Example, this invention is not limited by an Example.

Example  One

The ring-opening polymerization catalyst used in the reaction is WCl ₆ (1% toluene solution), diethylaluminum chloride (1M toluene solution), and 2.0 × 10 ⁻⁵ mol of WCl ₆ per 10 g of monomer was used.

In the polymerization process, the pressure reactor was sufficiently blown with nitrogen, followed by toluene, monomeric norbornene and dicyclopentadiene (10 g, weight ratio = 70:30), and 1-hexene (molecular weight regulator) (20 wt%). ), WCl _{6 and} a diethylaluminum chloride compound ([Al] / [W] = 60) were added sequentially and reacted at 60 degreeC for 1 hour. At this time, the weight ratio of the polymerization solvent and the monomer was 7: 1, and after the reaction was terminated by adding ethanol to the reaction product.

The gel content of the polymer was measured after leaving the reaction product at room temperature for 15 hours, and then mixed with toluene (60 mL) by taking 8g of the polymerization solution (1g of polymer content and yield of 100%) and then 1 at room temperature. Stir time and vacuum filter using filter paper (pore size: 5 micrometers) (if the yield is not 100%, the polymerization solution is taken so that the polymer content is 1 g considering the yield). The filtered solid was dried and weighed, and the gel content was expressed as a percentage divided by the weight of the polymer used in the measurement test.

Example  2 ~ 11

A cyclic olefin polymer was prepared in the same manner as in Example 1, but polymerization was performed by varying the catalyst composition ratio, the type of the W salt catalyst, the composition ratio of the monomer, the input order of the catalyst, and the amount of 1-hexene used as shown in Table 1 below. The reaction was carried out.

division Polymerization catalyst 1 Molar ratio Monomer 2) W / monomer (mol / g) Yield (%) Gel content (%) Usage of 1-hexene (g) Example 1 WCl6 / AlEt2Cl 1:60 Norbornene: DCPD (70: 30, weight ratio) 2.0X10-5 / 10 100 0.11 2 Example 2 WCl6 / AlEt2Cl 1:60 Norbornene: DCPD (65:35, weight ratio) 2.0X10-5 / 10 100 0 2 Example 3 WCl6 / AlEt2Cl 1:60 Norbornene: DCPD (60:40, weight ratio) 2.0X10-5 / 10 100 0 2 Example 4 WOCl4 / AlEt2Cl 1:80 Norbornene: DCPD (60:40, weight ratio) 2.0X10-5 / 10 100 0 2 Example 5 WCl6 / AlEt2Cl 1:60 Norbornene: DCPD (50:50, weight ratio) 2.0X10-5 / 10 100 0 2 Example 6 AlEt2Cl / WCl6 30: 1 Norbornene: DCPD (50:50, weight ratio) 1.2X10-4 / 60 95.8 0 3 Example 7 AlEt2Cl / WCl6 30: 1 Norbornene: DCPD (50:50, weight ratio) 2.0X10-4 / 100 100 0 10 Example 8 AlEt2Cl / WCl6 30: 1 Norbornene: DCPD (50:50, weight ratio) 2.0X10-4 / 100 100 0 20 Example 9 WOCl4 / AlEt2Cl 1:80 Norbornene: DCPD (50:50, weight ratio) 2.0X10-5 / 10 100 0 2 Example 10 WCl6 / AlEt2Cl 1:80 Norbornene: DCPD (40:60, weight ratio) 2.4X10-5 / 10 100 0 2 Example 11 WCl6 / AlEt2Cl 1:80 Norbornene: DCPD (30:70, weight ratio) 2.4X10-5 / 10 100 0.91 2 Note 1) Sequence of input of components constituting the polymerization catalyst; DCPD = Dicyclopentadiene

Example  12-19

A cyclic olefin polymer was prepared in the same manner as in Example 1, but the copolymerization reaction was performed by varying the type of monomer as shown in Table 2 below.

division Polymerization catalyst 1 Molar ratio Monomer 2) W / monomer (mol / g) Yield (%) Gel content (%) Usage of 1-hexene (g) Example 12 WCl6 / AlEt2Cl 1:80 Norbornene: MEN (70:30, weight ratio) 3.0X10-5 / 10 92.1 0 2 Example 13 WCl6 / AlEt2Cl 1:80 Norbornene: MEN (50:50, weight ratio) 4.0X10-5 / 10 93.6 0 2 Example 14 WCl6 / AlEt2Cl 1: 100 Norbornene: MEN (30:70, weight ratio) 5.0X10-5 / 10 86.3 0 2 Example 15 WCl6 / AlEt2Cl 1:80 Norbornene: MMN (50:50, weight ratio) 3.0X10-5 / 10 88.3 0 2 Example 16 WCl6 / AlEt2Cl 1:80 Norbornene: MMN (50:50, weight ratio) 3.0X10-5 / 10 86.5 0 0 Example 17 WCl6 / AlEt2Cl 1: 100 Norbornene: MMN (30: 70, weight ratio) 4.0X10-5 / 10 83.2 0 2 Example 18 WCl6 / AlEt2Cl 1:80 Norbornene: DCPD: MMN (50:40:10, weight ratio) 4.0X10-5 / 10 94.9 0.8 2 Example 19 WCl6 / AlEt2Cl 1:80 Norbornene: DCPD: MMN (30: 35: 35, weight ratio) 5.0X10-5 / 10 97.2 0 2 Note 1) Sequence of input of components constituting the polymerization catalyst; 2) MEN = 5-methylester-2-norbornene; MMN = 5-methyl-5'-methylester-2-norbornene; DCPD = Dicyclopentadiene

Comparative example  1-6

The cyclic olefin copolymer was prepared in the same manner as in Example 1, but the polymerization reaction result obtained by changing the composition range of the monomer from the composition formula 1 according to the present invention is shown in Table 3 below.

division Polymerization catalyst 1) Molar ratio Monomer 2) Mo / monomer (mol / g) Yield (%) Gel content (%) Comparative Example 1 WCl6 / AlEt2Cl 1:60 Norbornene: DCPD (9: 1, weight ratio) 2.0X10-5 / 10 100 29.1 Comparative Example 2 WCl6 / AlEt2Cl 1:80 Norbornene: DCPD (2: 8, weight ratio) 2.4X10-5 / 10 100 50.1 Comparative Example 3 WCl6 / AlEt2Cl 1:80 Norbornene: MMN (8: 2, weight ratio) 3.0X10-5 / 10 94.4 24.9 Comparative Example 4 WCl6 / AlEt2Cl 1:80 Norbornene: DCPD: MMN (8: 1: 1, weight ratio) 3.0X10-4 / 10 98.6 28.9 Comparative Example 5 WCl6 / AlEt2Cl 1: 100 Norbornene: DCPD: MEN (2: 6: 2, weight ratio) 5.0X10-5 / 10 100 8.6 Comparative Example 6 WCl6 / AlEt2Cl 1: 100 Norbornene: DCPD: MMN (2: 7: 1, weight ratio) 5.0X10-5 / 10 99.8 50.8 (Note) 1) Input procedure of components constituting the polymerization catalyst; 2) DCPD = Dicyclopentadiene; MMN = 5-methyl-5'-methylester-2-norbornene; MEN = 5-methylester-2-norbornene

The results of Tables 1 to 3 clearly show that when the copolymer of norbornene and the cyclic olefin compound is used as a monomer, the formation of the gel is controlled when the composition of the two monomers is according to the formula 1 of the present invention, but the composition is If it is out of the range of Formula 1, as shown in Table 3, it shows that a significant amount of gel is produced.

Experimental Example  One

Hydrogenation reaction was performed on the cyclic olefin copolymer prepared in Example 3 to measure the hydrogenation rate and the molecular weight of the produced polymer, and the results are shown in Table 4 below.

The hydrogenation reaction was carried out in a 1 L high pressure reactor, toluene (the weight ratio of the polymerization solvent and the copolymer was 10.5: 1), the hydrogenation target copolymer, 5 mol% Pd / carbon (10 Wt% by weight of the copolymer) as a reaction solvent. It was added sequentially, and the hydrogenation reaction was performed for 150 minutes under hydrogen pressure of 150 degreeC and 600psi. After adding a small amount of antioxidant to the reaction product, the reaction contents were precipitated in methanol (MeOH) containing HCl to obtain a final polymer. The hydrogenation rate was calculated | required using ¹ H-NMR.

Experimental Example  2 ~ 4

Hydrogenation of the cyclic olefin polymer was carried out in the same manner as in Experimental Example 1, and the hydrogenation rate and the molecular weight of the produced polymer were measured, and the results are shown in Table 4 below.

division Hydrogenated polymer % Of lottery M _w MWD Experimental Example 1 Example 3 99.9 31,000 1.55 Experimental Example 2 Example 6 99.9 225,000 2.50 Experimental Example 3 Example 7 99.5 115,000 1.75 Experimental Example 4 Example 8 99.9 89,500 1.57

In the table, M _w represents the weight average molecular weight (Weight Average Molecular Weight), MWD represents the molecular weight distribution (Molecular Weight Distribution) of the produced polymer.

Experimental Example  5

Hydrogenation reaction was performed on the cyclic olefin copolymer prepared in Example 14 to measure the hydrogenation rate and the molecular weight of the produced polymer, and the results are shown in Table 5 below.

The hydrogenation reaction was carried out in a 100 mL three-necked reactor, toluene (100 mL) as the reaction solvent, 0.5 g of the cyclic olefin copolymer, p-toluenesulfonhydrazide (20 mmol, 3.75 g), the hydrogenated reactant. ) Was added sequentially and reacted for 7 hours while refluxing. After completion of the reaction, the reaction solution was filtered to remove unreacted p-toluenesulfonhydrazide, and a small amount of antioxidant was added to the filtrate. The reaction solution was added to methanol containing HCl to obtain a final polymer, and the hydrogenation rate was calculated using ¹ H-NMR.

Experimental Example  6 ~ 8

Hydrogenation of the cyclic olefin polymer was carried out in the same manner as in Experimental Example 5, and the hydrogenation rate and the molecular weight of the produced polymer were measured, and the results are shown in Table 5 below.

division Hydrogenated polymer % Of lottery M _w MWD Experimental Example 5 Example 14 99.9 34,400 2.50 Experimental Example 6 Example 17 99.9 38,600 2.64 Experimental Example 7 Comparative Example 2 92.5 39,700 2.46 Experimental Example 8 Comparative Example 3 94.8 122,000 3.92

In the table, M _w represents the weight average molecular weight (Weight Average Molecular Weight), MWD represents the molecular weight distribution (Molecular Weight Distribution) of the produced polymer.

As can be seen from the results of Tables 4 and 5, the polymer content of the gel is controlled to provide a high hydrogenation rate of 99% or more (Experimental Examples 1 to 6). It can be seen that there is a difficulty in obtaining more than 95% (Experimental Examples 7-8). Since the hydrogenation reaction does not proceed efficiently, polymers having high unsaturated double bond content may be decomposed or discolored by various additives, which are subjected to high heat and pressure or may be used in comparison with polymers having relatively low double bond content. The possibilities are very large. This result may have a fatal effect on the physical properties and transparency of the polymer, resulting in a case where the application field is limited or difficult to apply.

As described above, a complex prepared by mixing the W salt compound and the organoaluminum halide compound according to the present invention is used as a catalyst, and the composition of the cyclic olefin compound constituting the copolymer is maintained at a constant ratio as in Formula 1 above. When the copolymer is prepared, it is possible to prepare the cyclic olefin copolymer in high yield while controlling the formation of the gel without using a reaction rate modifier or a gel production inhibitor.

Claims (10)

In the method of preparing a copolymer by performing ring-opening polymerization of a cyclic olefin compound in the presence of a nonpolar solvent and a catalyst, regardless of the presence or absence of a compound acting as a molecular weight regulator, The catalyst is a complex prepared by mixing the W salt compound and the organoaluminum halide compound, characterized in that to control the formation of the gel by maintaining the composition of the cyclic olefin compound constituting the copolymer at a constant ratio as shown in the following formula Method for producing cyclic olefin copolymer. (Composition 1) Norbornene = 30 to 70% by weight Cyclic olefin compounds = 70 to 30% by weight The method of claim 1, The cyclic olefin compound represented by the formula 1 is a method for producing a cyclic olefin copolymer, characterized in that one or more selected from dicyclopentadiene and the compound represented by the following formula (1). (Formula 1)

In Chemical Formula 1, m is an integer of 0 to 1, R ₁ is an alkyl group having 1 to 5 carbon atoms, and R ₂ is hydrogen or an alkyl group having 1 to 10 carbon atoms. The method of claim 1, The W salt compound is WCl ₆ , WCl ₄ , WOCl ₄ , W (CO) ₆ , W (OC ₆ H ₅ ) ₆ , WCl ₂ (OC ₆ H ₅ ) ₄ , W (CO) ₃ (CH ₃ CN) ₃ Or W (OEt ₂ ) Cl ₃ Method for producing a cyclic olefin copolymer, characterized in that the compound. The method according to claim 1 or 3, The W salt compound is WCl ₆ or WOCl ₄ Method for producing a cyclic olefin copolymer, characterized in that the compound. The method of claim 1, The salt compound is W 1 X 10 ^-5 ~ 1 X 10 per 10g cyclic olefin ^{compound-process} for producing a cyclic olefin copolymer characterized by using to ³ mol. The method of claim 1, The organoaluminum halide compound is dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dioctylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride Method for producing a cyclic olefin copolymer, characterized in that one or more selected from chloride, octyl aluminum dichloride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride or butyl aluminum sesquichloride compound. The method of claim 1, The W salt compound and the organoaluminum halide compound is a method of producing a cyclic olefin copolymer, characterized in that used in a molar ratio of 1:30 ~ 1: 100. The method according to claim 1 or 7, The W salt compound and the organoaluminum halide compound is a method of producing a cyclic olefin copolymer, characterized in that used in a molar ratio of 1:40 ~ 1:80. The method of claim 1, The molecular weight regulator is a cyclic olefin air, characterized in that one or more selected from 1-butene, 1-pentene, 1-hexene, 1-octene, 2-butene, 2-pentene or 1,4-hexadiene compound Process for the preparation of coalescing. The method of claim 1, The nonpolar solvent is one or more selected from hexane, heptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, benzene, toluene, chlorobenzene or o -dichlorobenzene. The manufacturing method of the cyclic olefin copolymer made into.