KR100998025B1 - Method for preparing cyclic olefin polymer - Google Patents

Abstract

The present invention provides a method of polymerizing a cyclic olefin monomer by Ring Opening Metathesis Polymerization (ROMP) method to prepare a cyclic olefin polymer without producing gel in high yield.

Cyclic Olefin, Ring Opening Polymerization, Gel Formation

Description

Method for preparing cyclic olefin polymer {Method for preparing cyclic olefin polymer}

The present invention relates to a method for preparing a polymer of cyclic olefins by polymerizing the cyclic olefin monomers by a ring opening metathesis polymerization (ROMP) method.

Currently, polymers generally used where optical properties are required include polycarbonate (hereinafter referred to as PC) or poly (methyl methacrylate) (hereinafter referred to as PMMA). However, PMMA has a limitation in being used as a precision optical device or a flat panel display material because of its high water absorption and high glass transition temperature (T _g ) of 100 ° C., which is poor in dimensional stability. In addition, the PC has a relatively high T _g of 150 ° C., but its light transmittance is lower than PMMA, its dielectric constant is high, and its birefringence is poor after injection molding.

On the other hand, the polymer obtained by hydrogenation after the ring-opening polymerization of the cyclic olefin has a low water absorption and dielectric constant, excellent optical properties, low birefringence, low density, high dimensional stability and excellent chemical resistance, in particular according to the temperature Due to the small change in refractive index, the scope of application is becoming very wide for optical and medical applications such as next-generation high-density information storage media (HD-DVD), camera lenses, optical fibers, and flat panel displays.

Methods of polymerizing a polymer using a cyclic olefin monomer can be broadly classified into Ring Opening Metathesis Polymerization (ROMP), copolymerization by Addition Polymerization with ethylene, and cationic polymerization. When using a double ROMP catalyst, it is essential to increase the thermal stability and the oxidation stability through the reaction of saturating the double bond formed after the polymerization by a hydrogenation reaction. Compared to the polymerization, there is an advantage that a high molecular weight product is produced which has high activity and excellent mechanical properties.

Examples of the main catalyst constituting the ROMP-based catalyst include metal compounds such as titanium (Ti), molybdenum (Mo), tungsten (W), rhenium (Re), and ruthenium (Rum). Various ligands or alterations of cocatalysts and other additives can control the activity of the catalyst and inhibit the formation of gels during polymerization.

As an example of a polymerization method using a ROMP-based catalyst, U.S. Patent No. 5,034,482 uses a cyclic olefin using TiCl _{4 as a} main catalyst and triethylaluminum (Et ₃ Al) and triethylamine (Et ₃ N) as cocatalysts. A method of ring-opening polymerization of phosphorus methyl tetracyclododecene (hereinafter referred to as 'MTD') is disclosed. The method has the disadvantage of using an excessive amount of catalyst and cocatalyst while suppressing gel formation and having a low polymer polymerization yield of about 60%.

Japanese Patent Application Laid-Open No. 01-197460 discloses a method of polymerizing norbornene-based monomers using WCl ₆ as a main catalyst, isobutylaluminum (i-Bu ₃ Al) as a promoter, and paraaldehyde as an additive. However, the above method has a disadvantage in that it is difficult to produce a high molecular weight polymer due to the progress of gelation during polymerization.

U.S. Patent No. 4,002,815 discloses cyclopentene (hereinafter referred to as 'CP') and dicyclopentadiene (hereinafter referred to as WCI ₆ as the main catalyst and Et ₂ AlI and Et ₂ AlCl or Et ₃ Al and I ₂ as promoters). , A method of controlling the content of a gel when forming a copolymer of " DCPD " However, according to the method, the gel content in the resulting polymer was high, 17-62%, and the polymerization yield was relatively low, 70% or less.

On the other hand, as an example of the ring-opening polymerization method of the cyclic olefin using the Reactive Injection Molding (RIM) process, Japanese Patent Laid-Open No. 2002-121266 uses a Ru carbene compound as a catalyst and extends the gel-time. In order to use a polarizing compound such as amine, phosphine, Lewis base, or alcohol or ketone as a reaction retardant, a copolymer of DCPD and ethyl norbornene (ENB) is used. A method of polymerization is disclosed. U.S. Pat.Nos. 5,939,504 and 6,020,443 also use Ru carbene compounds as catalysts for ring-opening polymerization of DCPD by RIM process, and include phosphines, phosphites, ethers, amines, amides and carbonyls. A method of inhibiting the formation of a gel by using a Lewis base compound such as pyridine or sulfoxide is disclosed. However, in these methods, the overall process is complicated by using a polymerization rate regulator, and in some cases, the polymerization yield may decrease.

US Patent No. 6,310,160 uses tungsten-based, molybdenum-based and rhenium-based compounds as main catalysts and organic aluminum compounds such as Et ₃ Al and i-Bu ₃ Al as co-catalysts and contains oxygen such as alcohols and aldehydes. A method of ring-opening polymerization of MTD is disclosed using an organic substance as an additive. The method has the advantage of high yield, high gel suppression, and high molecular weight of polymers, while polymerizing a certain amount of the main catalyst and monomer in one step during polymerization, and then the remaining main catalyst and monomer in two steps. Slowly introduced over a long period of time has the disadvantage that the entire process is complex and the continuous process is difficult.

In one embodiment of the present invention, a tungsten-based compound, which is a main catalyst, is prepared as a lean solution, which is used as a ring-opening polymerization catalyst, and the amount of alcohol used as an additive in polymerization is controlled to inhibit the formation of the gel in a simple manner and To yield a cyclic olefin polymer in yield.

In one embodiment of the present invention is a method for producing a cyclic olefin polymer by ring-opening polymerization of the cyclic olefin compound in the presence of alcohols as a polymerization catalyst system, a molecular weight regulator and an additive comprising a tungsten-based compound and an organoaluminum compound Tungsten-based compound is 1: 300 It is added in a mixed solution at a ratio of 1: 10,000 by weight, and used to 1 × 10 ^-5 to 1 × 10 ^-3 for 1 mole of the cyclic olefin compound, alcohols 0.01 to 0.03 for 1 mole of the cyclic olefin compound Used in molar ratio, the molecular weight modifier is selected from the group consisting of 1-butene, 1-hexene, 1-pentene, 1-octene and 1-dekene, alcohols are ethanol, propanol, isopropanol, butanol, isobutanol, At least one selected from pentanol, hexanol and octanol, and the solvent is selected from toluene, benzene, xylene, ethylbenzene, cyclohexane, cyclopentane, cyclooctane, hexane, heptane, octane and decane Provided are methods for preparing the cyclic olefin polymer.

Method for producing a cyclic olefin polymer according to an embodiment of the present invention comprises the steps of preparing a monomer-containing solution by stirring the entire amount of the cyclic olefin compound and the solvent; Adding and mixing a molecular weight regulator, an organoaluminum compound and alcohols to the monomer-containing solution; It may include a step of polymerization by adding a tungsten-based compound in a solution state.

In the method for producing a cyclic olefin polymer according to one embodiment of the present invention, the cyclic olefin compound may be selected from compounds represented by the following Chemical Formula 1.

Wherein R ₁ -R ₄ are the same as or different from each other and are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a halogen atom, or an alkoxycarbonyl, cyano group or hydroxyl group having 1 to 3 carbon atoms.

In the preparation method according to an embodiment of the present invention, the tungsten-based compound is WCl ₆ , WCl ₅ , WCl ₄ , WCl ₂ , WOCl ₄ , W (CO) ₆ , W (OC ₆ H ₅ ) ₆ , WCl ₂ ( OC ₆ H ₅ ) ₄ , W (CO) ₃ And W (OEt ₂ ) Cl ₃ It may be selected from the group consisting of.

In the production method according to an embodiment of the present invention, the organoaluminum compound is triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-i-butylaluminum, trihexylaluminum, trioctylaluminum, Dimethylaluminum chloride, methylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, dipropylaluminum chloride, propylaluminum dichloride, di-n-butylaluminum chloride, n-malbutyl aluminum dichloride, di-i-butyl It may be selected from the group consisting of aluminum chloride and i-butyl aluminum dichloride.

In the production method according to an embodiment of the present invention, the organoaluminum compound may be used in 1 to 50 molar ratio with respect to 1 mole of the tungsten compound.

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The production method according to one embodiment of the present invention is economical and can be produced in a high yield cyclic olefin polymer without the formation of a gel using a relatively inexpensive tungsten-based compound as a catalyst is a one-step rather than a multi-step reaction The polymer can be produced by the reaction, so the polymerization conditions and the device configuration have simple advantages.

Hereinafter, the present invention will be described in detail.

In one embodiment of the present invention, as the ring-opening polymerization catalyst of the cyclic olefin compound, a tungsten-based compound is used as a main catalyst, an organoaluminum compound is used as a promoter, and alcohols are used as additives. By dissolving the tungsten-based compound into a lean solution and introducing it during polymerization, a high molecular weight polymer can be produced by a simple method and the formation of a gel can be suppressed. In particular, when the ring-opening polymerization of the cyclic olefin compound according to an embodiment of the present invention, the gel content can be adjusted to 0.1 wt% or less with respect to the amount of the polymer produced with a high polymerization yield of 90% or more.

Cyclic olefin compound according to an embodiment of the present invention may include one or more of the compounds represented by the following formula (1).

Formula 1

Wherein R ₁ -R ₄ are the same as or different from each other and are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a halogen atom, or an alkoxycarbonyl, cyano group or hydroxyl group having 1 to 3 carbon atoms.

In the polymerization catalyst system for ring-opening polymerization of such a cyclic olefin compound, a tungsten-based compound is used as a main catalyst. Specific examples thereof include WCl ₆ , WCl ₅ , WCl ₄ , WCl ₂ , WOCl ₄ , and W (CO). ₆ , W (OC ₆ H ₅ ) ₆ , WCl ₂ (OC ₆ H ₅ ) ₄ , W (CO) ₃ and W (OEt ₂ ) Cl ₃ , and the like. ₆ Exemplary tungsten compounds may be used alone or in combination.

The amount of the tungsten compound may be used in an amount of 1 × 10 ⁻⁶ to 1 × 10 ⁻² , more preferably ¹ × 10 ⁻⁵ to 1 × 10 ⁻³ mole per one mole of the monomer. If the amount of the catalyst is outside the above range and less than 1x10 ^-6 moles per mole of monomer, it may lead to a decrease in the polymerization yield, and if used in excess of 1x10 ^-2 moles per mole of monomer, the coloring of the product and the use of excess catalyst and As much effort is required to remove the catalyst after polymerization, it may lead to economic deterioration.

According to one embodiment of the present invention, when adding a tungsten-based compound to the reaction system in the above-described amount, the catalyst solution is prepared by dissolving it in a solvent and adding the same in the above-described amount. The amount of solvent used is weight ratio with respect to the amount of tungsten compound 1: 300 to 1: 10,000, preferably 1: 500 to 1: 5,000 by weight. If the amount of solvent used in the preparation of the catalyst solution is out of the above range and less than 100 parts by weight based on 1 part by weight of the tungsten compound may promote the formation of the gel, if the amount exceeds 10,000 parts by weight based on 1 part by weight of the tungsten compound The use of a solvent may worsen the economics.

Meanwhile, in one embodiment of the present invention, an organoaluminum compound is used as a cocatalyst to activate a tungsten-based compound as a main catalyst, and specific examples thereof include triethylaluminum and tri-n-propylaluminum (try-n). -propylaluminum, tri-n-butylaluminum, tri-i-butylaluminum, trihexylaluminum, trioctylaluminum, dimethyl aluminum chloride chloride, methyl aluminum dichloride, diethyl aluminum chloride, ethyl aluminum dichloride, dipropyl aluminum chloride, propyl aluminum dichloride ( propyl aluminum dichloride, di-n-butyl aluminum chloride, n-butyl aluminum dichloro And n-butyl aluminum dichloride, di-i-butyl aluminum chloride, and i-butyl aluminum dichloride. Of these, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloride, diisobutylaluminum chloride and isobutyl aluminum dichloride are particularly suitable. The amount of the organoaluminum compound may be preferably 1: 1 to 1:50 in molar ratio with respect to tungsten compound, preferably 1: 2 to 1:20 in molar ratio in consideration of polymerization yield and economic efficiency.

Meanwhile, the alcohol used as an additive may be an alcohol having 2 or more carbon atoms, and specific examples thereof may include ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, octanol, and the like. Propanol and butanol are suitable. The amount of alcohol may be 1: 0.01 to 1: 0.03 in molar ratio with respect to the monomer, preferably 1: 0.01 to 1: 0.02 in molar ratio. If the amount of alcohol used is out of the above range of less than 0.01 mole relative to 1 mole of monomer can promote the production of the gel, if it exceeds 0.03 mole relative to 1 mole of monomer can lead to a decrease in the polymerization yield.

Compounds that can be used as the molecular weight regulator according to the present invention may be a compound such as 1-butene, 1-hexene, 1-pentene, 1-octene, 1-dekene, but 1-butene, 1-pentene, 1-hexene, etc. Especially suitable.

The polymerization solvent and the catalyst preparation solvent according to the present invention may be any inert solvent which does not react with the catalyst and may be a solvent capable of dissolving the polymerized polymer. Examples of such a solvent include aromatic hydrocarbons such as toluene, benzene, xylene, ethylbenzene, cycloaliphatic hydrocarbons such as cyclohexane, cyclopentane, cyclooctane, and aliphatic hydrocarbons such as hexane, heptane, octane, and decane. Among them, toluene, benzene, cyclohexane and the like are particularly suitable.

On the other hand, the weight ratio of the monomer and the polymerization solvent is preferably in the range of 1: 2 to 1:30.

The polymerization temperature according to the present invention is not particularly limited and may be selected from -10 to 100 ℃, more preferably 20 to 80 ℃.

According to the present invention, the ring-opening polymerization method of the cyclic olefin is prepared by dissolving the whole amount of monomer in a solvent in an inert gas condition to prepare a homogeneous solution, followed by introducing a molecular weight regulator, introducing an organoaluminum compound, and then introducing an alcohol. can do. After stirring this mixture to make a uniform solution, a tungsten-based compound solution is introduced thereto. Within the range described above, the polymerization proceeds for 30 minutes to 2 hours after the appropriate amount of tungsten compound is introduced. The polymer produced after the polymerization is precipitated using methanol and collected by filtration.

In one embodiment of the present invention it is possible to produce a cyclic olefin polymer by a simple method through such a one-step reaction.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention more specifically, it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples in accordance with the gist of the present invention.

The molecular weight of the polymer prepared in the Examples below is gel permeation chromatography (GPC) manufactured by YOUNG LIN, and 4.6 cm × 30 cm Styragel (HR3) manufactured by Waters as a column. , HR4, HR4E) and toluene were used as the mobile phase. The flow rate of the mobile phase was fixed at 1.0 ml / min. Refractive index detector (YOUNG LIN, RI 750F) was used as a detector. The number average molecular weight (M _n ) and weight average molecular weight (M _w ) were calculated by comparing the residence time of the polymer measured in the detector with that of monodisperse polystyrene.

Polymerization yield, on the other hand, was expressed as a percentage divided by the weight of the polymer produced.

In order to measure the gel content in the polymer, 50 g of toluene was introduced into the polymer produced after the polymerization, and the mixture was stirred and diluted for 2 hours. The diluted solution was filtered through filter paper (pore size; 5 μm), and the filtered solid was dried in a vacuum oven and weighed. Gel content is expressed as a percentage of the weight of the total polymer produced relative to the weight of the filtered solid.

Example 1

Into a 100 mL volumetric glass flask, 6 mmol of a cyclocyclododecene (tetracyclododecene, hereinafter referred to as 'TCD') was introduced in a nitrogen atmosphere, 3 g of toluene was introduced, followed by stirring to prepare a uniform solution. 0.06 mmol of 1-nuxene (1 wt% toluene solution) was introduced into the solution as a molecular weight regulator, and 0.1 mmol of (i-Bu) ₃ Al (25 wt% toluene solution) was introduced into the organoaluminum compound, and ethanol (5 wt%) was used as an additive. 0.1 mmol of toluene solution) was introduced.

After preparing a homogeneous solution by stirring the solution to prepare a catalyst solution dissolved in a 0.1 wt% WCl ₆ in the toluene was introduced so that the WCl ₆ 0.038 mmol and polymerization for 2 hours at 30 ℃.

After the polymerization, the polymerization was terminated by precipitating the polymer prepared by adding methanol. The molecular weight, polymerization yield and gel content of the prepared polymer are shown in Table 1 below.

Example 2

In Example 1, the polymer was polymerized using a catalyst solution in which WCl ₆ was dissolved in toluene at a concentration of 0.05 wt% instead of a catalyst solution in which WCl ₆ was dissolved in toluene at a concentration of 0.1 wt%. The prepared polymer was analyzed in the same manner as in Example 1, and the results are shown in Table 1 below.

Example 3

In Example 1, the polymer was polymerized using a catalyst solution in which WCl ₆ was dissolved in toluene at a concentration of 0.01 wt% instead of a catalyst solution in which WCl ₆ was dissolved in toluene at a concentration of 0.1 wt%. The prepared polymer was analyzed in the same manner as in Example 1, and the results are shown in Table 1 below.

Example 4

In Example 1, the polymer was polymerized using a catalyst solution in which WOCl ₄ was dissolved in toluene at a concentration of 0.1 wt% instead of a catalyst solution in which WCl ₆ was dissolved in toluene at a concentration of 0.1 wt%. The prepared polymer was analyzed in the same manner as in Example 1, and the results are shown in Table 1 below.

Example 5

In Example 1, the polymer was polymerized using 0.1 mmol of isobutanol instead of 0.1 mmol of ethanol. The prepared polymer was analyzed in the same manner as in Example 1, and the results are shown in Table 1 below.

Comparative Example 1

In Example 1, the polymer was polymerized using a catalyst solution in which WCl ₆ was dissolved in toluene at a concentration of 0.5 wt% instead of a catalyst solution in which WCl ₆ was dissolved in toluene at a concentration of 0.1 wt%. The gelation was observed after the introduction of WCl ₆ to 0.019 mmol.

The prepared polymer was analyzed in the same manner as in Example 1, and the results are shown in Table 1 below.

Comparative Example 2

In Example 1, the polymer was polymerized using a catalyst solution in which WCl ₆ was dissolved in toluene at a concentration of 1 wt% instead of a catalyst solution in which WCl ₆ was dissolved in toluene at a concentration of 0.1 wt%. The gelation was observed after the introduction of WCl ₆ to 0.01 mmol. The prepared polymer was analyzed in the same manner as in Example 1, and the results are shown in Table 1 below.

Comparative Example 3

In Example 1, instead of introducing 6 mmol of TCD and 3 g of toluene, 19 g of toluene was introduced, and 0.1 wt% of WCl ₆ toluene solution instead of introducing 0.038 mmol of a WCl ₆ toluene solution of 1 wt% WCl ₆ toluene. The polymerization was carried out by introducing a solution to 0.038 mmol, but no polymer was produced.

Comparative Example 4

Example 1 and WCl ₆ (0.1 wt% toluene solution) of 0.005 mmol instead of WCl ₆ (0.1 wt% toluene solution) of 0.038 mmol in the same manner by using as a catalyst, but attempts to polymerization reaction was not polymer is produced.

Comparative Example 5

In Example 1, polymer was polymerized using 0.01 mmol of WCl ₆ (0.1 wt% toluene solution) instead of 0.038 mmol of WCl ₆ (0.1 wt% toluene solution) as a catalyst. The prepared polymer was analyzed in the same manner as in Example 1, and the results are shown in Table 1 below.

division Polymerization Catalyst
Alcohol/
TCD
W / TCD
yield
(%)
Gel
content
(%)
M _n
(g / mol) TCD /
Toluene
(mmol / g) WCl ₆ or WOCl ₄
(mmol) WCl ₆ /
toluene
(wt%) Example 1 2 0.038 0.1 0.016 6.3X10 ^-3 100 0 2.1 X 10 ⁴ Example 2 2 0.038 0.05 0.016 6.3X10 ^-3 95 0 2.0 X 10 ⁴ Example 3 2 0.038 0.01 0.016 6.3X10 ^-3 98 0 1.8 X 10 ⁴ Example 4 2 0.038 0.1 0.016 6.3X10 ^-3 92 0 1.8 X 10 ⁴ Example 5 2 0.038 0.1 0.016 6.3X10 ^-3 90 0 2.1 X 10 ⁴ Comparative Example 1 2 0.038 0.5 0.016 6.3X10 ^-3 98 7 2.5 X 10 ⁴ Comparative Example 2 2 0.038 One 0.016 6.3X10 ^-3 100 18 - Comparative Example 3 0.3 0.038 One 0.016 6.3X10 ^-3 0 - - Comparative Example 4 2 0.005 0.1 0.016 8.3X10 ^-4 0 - - Comparative Example 5 2 0.01 0.1 0.016 1.6X10 ^-3 9.4 0 5.4 X 10 ⁴

As shown in Table 1, in Example 1, when the polymerization was prepared using 0.01-0.1 wt% of WCl ₆ as a catalyst, the polymerization yield was very high as 95% or more, and the prepared polymer had a very high gel content of 0%. A polymer could be obtained. On the other hand, as in Comparative Examples 1 to 2, the concentration of the catalyst solution was 0.5 wt% and 1 wt%, and the yield was 98-100% higher while the gel content was 7-18%. Therefore, when the concentration of the introduced catalyst solution is high, it can be seen that the gelation proceeds during the polymerization reaction.

On the other hand, in the case of using WOCl ₄ instead of WCl ₆ in Example 4 and isobutanol instead of ethanol in Example 5 to obtain a very good polymer having a yield of 90% or more and a gel content of 0% I could make it.

Meanwhile, in the case of Comparative Example 3, as in Example 1, instead of using 3 g of TCD 6 mmol / toluene and 0.1 wt% WCl ₆ solution, 19 g of TCD 6 mmol / toluene and WCl ₆ in 1 wt% concentration were introduced during polymerization. The total amount of toluene was the same, but in Example 1, the polymerization yield was 100%, whereas in Comparative Example 3, no polymer was produced. Therefore, when the ratio of the solvent to the monomer is increased by using a lean monomer solution for polymer polymerization, the polymerization reaction does not proceed even if the amount of the catalyst and the amount of the solvent as a whole are the same.

On the other hand, when the amount of the WCl ₆ catalyst at a concentration of 0.1 wt% was as low as 1.6X10 ^-3 to 8.3X10 ^-4 in the ratio of W / TCD as in Comparative Examples 4 to 5, gelation did not proceed, but the polymerization yield was Very low, 0-9.4%.

Comparative Example 6

Instead of introducing 0.1 mmol of ethanol in Example 1, the polymer was polymerized without introducing ethanol. In this case, the introduction of 0.001 mmol of WCl ₆ (0.1 wt% toluene solution) was observed to rapidly progress the gelation to terminate the reaction. The prepared polymer was analyzed in the same manner as in Example 1, and the results are shown in Table 2 below.

Comparative Example 7

Instead of introducing 0.1 mmol of ethanol in Example 1, 0.05 mmol of ethanol was introduced to polymerize the polymer. After the introduction of 0.009 mmol of WCl ₆ (0.1 wt% toluene solution), a rapid progress of gelation was observed to terminate the reaction. The prepared polymer was analyzed in the same manner as in Example 1, and the results are shown in Table 2 below.

Comparative Example 8

Instead of introducing 0.1 mmol of ethanol in Example 1, 0.2 mmol of ethanol was introduced to polymerize the polymer. The gelation was observed after 0.038 mmol of WCl ₆ (0.1 wt% toluene solution) was introduced. The prepared polymer was analyzed in the same manner as in Example 1, and the results are shown in Table 2 below.

Comparative Example 9

The polymer polymerization reaction was attempted by introducing 0.4 mmol of ethanol instead of 0.1 mmol of ethanol in Example 1, but no polymer was produced.

division Polymerization Catalyst
EtOH / W
W / TCD
yield
(%)
Gel content
(%) M _n
(g / mol) WCl ₆
(mmol) WCl ₆ /
toluene
(wt%) (i-Bu) ₃ Al
(mmol) Example 1 0.038 0.1 0.1 0.016 6.3X10 ^-3 100 0 2.1X10 ^-4 Comparative Example 6 0.001 0.1 0.1 0 1.6X10 ^-4 31 19 - Comparative Example 7 0.009 0.1 0.1 0.008 1.5X10 ^-3 16 15.6 - Comparative Example 8 0.038 0.1 0.1 0.033 6.3X10 ^-3 10 0 - Comparative Example 9 0.038 0.1 0.1 0.067 6.3X10 ^-3 0 0 -

As shown in Table 2, when ethanol was not used as in Comparative Example 6, even if a very small amount of catalyst was introduced, the gelation proceeded rapidly, resulting in a very high gel content of 19% and a low overall polymerization yield of 31%. . As in Comparative Example 7, when ethanol was introduced in a molar ratio of 0.008 to TCD, the gelation proceeded when 0.009 mmol of the catalyst was introduced, and the gel content was high as 15.6%, and the overall polymerization yield was very low as 16%. On the other hand, gelation did not proceed when 0.033 was introduced in a molar ratio compared to TCD using an excess of ethanol in Comparative Example 8, but the polymerization yield was very low as 10%. In Comparative Example 9, when the amount of ethanol was increased to a ratio of 0.067 mole to 1 mole of TCD, it was confirmed that the polymerization did not occur. Therefore, it was confirmed that when the amount of the catalyst of WCl ₆ introduced was constant, an appropriate amount of ethanol was introduced to produce a high yield polymer having a low gel content.

Claims (9)

In the method for producing a cyclic olefin polymer by ring-opening polymerization of the cyclic olefin compound in the presence of alcohols as a polymerization catalyst system, a molecular weight regulator and an additive comprising a tungsten-based compound and an organoaluminum compound, Tungsten compound is 1: 300 with solvent It is added in a mixed solution at a ratio of 1: 10,000 by weight, and is used to 1 × 10 ^-5 to 1 × 10 ^-3 per mole of the cyclic olefin compound, Alcohols are used in a molar ratio of 0.01 to 0.03 per mole of cyclic olefin compound, The molecular weight modifier is selected from the group consisting of 1-butene, 1-hexene, 1-pentene, 1-octene and 1-dekene, Alcohols are at least one selected from ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol and octanol, And a solvent is selected from toluene, benzene, xylene, ethylbenzene, cyclohexane, cyclopentane, cyclooctane, hexane, heptane, octane and decane. The process according to claim 1, further comprising the steps of: stirring a whole amount of cyclic olefin compound and a solvent to prepare a monomer-containing solution; Adding and mixing a molecular weight regulator, an organoaluminum compound and alcohols to the monomer-containing solution; A method for producing a cyclic olefin polymer, comprising the step of polymerizing by adding a tungsten compound in a solution state. The method for producing a cyclic olefin polymer according to claim 1 or 2, wherein the cyclic olefin compound is selected from compounds represented by the following general formula (1). Formula 1

Wherein R ₁ -R ₄ are the same as or different from each other and are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a halogen atom, or an alkoxycarbonyl, cyano group or hydroxyl group having 1 to 3 carbon atoms. The method of claim 1 or 2, wherein the tungsten-based compound is WCl ₆ , WCl ₅ , WCl ₄ , WCl ₂ , WOCl ₄ , W (CO) ₆ , W (OC ₆ H ₅ ) ₆ , WCl ₂ (OC ₆ H ₅ ) ₄ , W (CO) ₃ and W (OEt ₂ ) Cl ₃ method for producing a cyclic olefin polymer, characterized in that selected from the group consisting of. The organoaluminum compound according to claim 1 or 2, wherein the organoaluminum compound is triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-i-butylaluminum, trihexylaluminum, trioctylaluminum, dimethylaluminum chloride , Methylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, dipropylaluminum chloride, propylaluminum dichloride, di-n-butylaluminum chloride, n-malbutyl aluminum dichloride, di-i-butylaluminum chloride and A process for producing a cyclic olefin polymer, characterized in that it is selected from the group consisting of i-butyl aluminum dichloride. The method for producing a cyclic olefin polymer according to claim 1 or 2, wherein the organoaluminum compound is used in an amount of 1 to 50 moles per 1 mole of the tungsten compound. delete delete delete