KR20230067142A - Method for Alkyation of Norbornene Alcohol Compounds - Google Patents

Abstract

The present invention relates to a method for alkylating norbornene alcohol compounds, and more specifically, to a method for alkylating norbornene alcohol compounds, wherein norbornene alcohol compounds having a hydroxy group at the terminal are alkylated in the presence of a solid catalyst to produce 5-(alkoxyalkyl)bicyclo[2,2,1]hepta-2-ene at a high conversion rate. The method for alkylating norbornene alcohol compounds comprises a step of preparing a norbornene-based compound represented by chemical formula 2 by reacting a norbornene alcohol compound represented by chemical formula 1 with an alkylating agent in the presence of solid sodium hydroxide and/or solid potassium hydroxide.

Description

Alkylation method of norbornene alcohol compounds {Method for Alkyation of Norbornene Alcohol Compounds}

The present invention relates to a method for alkylating a norbornene alcohol compound, and more particularly, to a method for alkylating a norbornene alcohol compound in the presence of a solid catalyst to obtain 5-(alkoxyalkyl)bicyclo[2,2,1]hepta-2 with high conversion rate. -It relates to a method for alkylating norbornene alcohol compounds to produce ene.

The cyclic olefin polymer is a polymer produced by polymerization of cyclic olefin monomers such as norbornene, and has excellent transparency, heat resistance and chemical resistance, and very low birefringence and water absorption compared to existing olefin polymers. Therefore, it is a semiconductor or TFT-LCD insulating film, polarizer protective film, multichip modules, integrated circuits (IC), printed circuit boards, printed circuit boards, electronic material encapsulants or flat panel displays. Alternatively, it can be used as a low dielectric coating agent for optical use, film, packaging, etc., and can also be used as a material for a plastic substrate for implementing a flexible display.

In order to use the cyclic olefin polymer for such purposes, it must have excellent thermal stability and adhesion to metal. That is, adhesion to metal materials such as silicon, nitride, alumina, copper, aluminum, gold, silver, platinum, titanium, and nickel should be excellent. When the cyclic olefin monomer contains a polar functional group such as an alkoxy group or an ester group, the polar functional group serves to increase intermolecular packing and adhesion to a metal substrate or other polymers. Polymerization or copolymerization of norbornene containing an alkoxy group or an ester group has been receiving steady interest (European Patent No. 0445755, U.S. Patent No. 5705503, U.S. Patent No. 6455650) because it can be usefully used in information and electronic materials. like).

Norbornene-based monomers used in the preparation of such cyclic olefin polymers were mainly prepared by a Diels-Alder reaction between cyclopentadiene and alkyl acrylate. At this time, Lewis acids were mainly used as catalysts to promote the reaction, that is, ZnX ₂ (X=Cl, Be, etc.), BF ₃ (OEt ₂ ), EtAlCl ₂ , Et ₂ AlCl, TiCl ₄ , AlCl ₃ , SnCl ₄ , SbCl ₅ and the like. In the case of norbornene monomers containing polar functional groups such as alkoxy and ester groups prepared in this way, endo isomers are mainly present rather than exo isomers, and these endo isomers reduce the activity of the catalyst used during polymerization. shows a tendency to decline. Therefore, it is not easy to introduce a polar functional group into a polymer composed of hydrocarbons.

Accordingly, when the present inventors perform an alkylation reaction of a hydroxyl group using a norbornene alcohol compound in the presence of a solid catalyst having a controlled shape, 5-(alkoxyalkyl)bicyclo[2,2,1 It was confirmed that hepta-2-ene could be produced, and the present invention was completed.

European Patent No. 0445755 (published date: 1991.09.11) US Patent Registration No. 575503 (registration date: 1998.01.06) US Patent Registration No. 6455650 (Publication date: 2002.05.02)

The main object of the present invention is to solve the above problems, and to provide a norbornene alcohol compound capable of increasing the yield and conversion rate to 5-(alkoxyalkyl)bicyclo[2,2,1]hepta-2-ene. It is to provide an alkylation method.

In addition, an object of the present invention is a cyclic olefin polymer characterized in that it is polymerized by including 5- (alkoxyalkyl) bicyclo [2,2,1] hepta-2-ene prepared from the alkylation method of the norbornene alcohol compound It is to provide a manufacturing method of.

In order to achieve the above object, one embodiment of the present invention is a norbornene-based compound represented by Chemical Formula 2 by reacting a norbornene alcohol compound represented by Chemical Formula 1 with an alkylating agent in the presence of solid sodium hydroxide and/or solid potassium hydroxide. A method for alkylating a norbornene alcohol compound characterized in that the compound is prepared is provided.

[Formula 1]

In Formula 1, L is a single bond or an alkylene group having 1 to 10 carbon atoms,

[Formula 2]

In Formula 2, L is a single bond or an alkylene group having 1 to 10 carbon atoms, and R is an alkyl group having 1 to 10 carbon atoms.

In a preferred embodiment of the present invention, the solid sodium hydroxide and solid potassium hydroxide are one or more selected from the group consisting of a bead shape, a flake shape, a power shape, and a pellet shape. It can be characterized as having a shape.

In a preferred embodiment of the present invention, the solid sodium hydroxide and solid potassium hydroxide may be characterized in that they have a bead shape.

In a preferred embodiment of the present invention, the solid sodium hydroxide and solid potassium hydroxide may be used in an amount of 1 to 8 moles based on 1 mole of the norbornene alcohol compound represented by Formula 1.

In a preferred embodiment of the present invention, the alkylating agent is dialkyl sulfate selected from the group consisting of dimethyl sulfate, diethyl sulfate, dipropyl sulfate, dibutyl sulfate, dipentyl sulfate and dihexyl sulfate; dialkyl carbonates selected from the group consisting of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate and dihexyl carbonate; and an alkyl halide selected from the group consisting of alkyl chloride, alkyl bromide, alkyl fluoride and alkyl iodide.

In a preferred embodiment of the present invention, the alkylating agent may be used in an amount of 0.5 to 6 moles based on 1 mole of the norbornene alcohol compound.

In a preferred embodiment of the present invention, the reaction may be characterized in that it is carried out at 0 ℃ ~ 80 ℃ under normal pressure ~ 5 atm pressure.

Another embodiment of the present invention provides a method for producing a cyclic olefin polymer comprising polymerization of a norbornene-based compound represented by Formula 2 prepared by the alkylation method of a norbornene alcohol compound.

According to the present invention, by carrying out the alkylation reaction of norbornene alcohol compounds in the presence of a solid catalyst with a controlled shape, the alkylation reaction of norbornene alcohol compounds is promoted in a simple way to form 5-(alkoxyalkyl)bicyclo[2,2,1 ] has the effect of significantly improving the yield and conversion rate of hepta-2-ene.

In addition, according to the present invention, by preparing a cyclic olefin polymer using 5-(alkoxyalkyl)bicyclo[2,2,1]hepta-2-ene into which an alkoxy group is introduced, transparency, heat resistance and chemical resistance are excellent and There is an effect that can provide a cyclic olefin polymer having a low refractive index and water absorption.

1 is a H-NMR measurement graph of 2-bicyclo[2,2,1]hepta-5-enylmethanol as a reaction starting material.
2 is an H-NMR measurement graph of a norbornene-based compound prepared in Example 1-1 according to the present invention.
3 is a mass-spectrum measurement graph of the norbornene-based compound prepared in Example 1-1 according to the present invention.

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

Terms such as “comprise”, “include” or “having” described in this specification indicate that there is a feature, numerical value, step, operation, component, part, or combination thereof described in the specification. It does not rule out the possibility that other features, figures, steps, operations, components, parts, or combinations thereof may exist or be added that have not been described.

In one aspect, the present invention includes a step of preparing a norbornene-based compound represented by Formula 2 by reacting a norbornene alcohol compound represented by Formula 1 with an alkylating agent in the presence of solid sodium hydroxide and/or solid potassium hydroxide. It relates to a method for alkylating a norbornene alcohol compound.

[Formula 1]

[Formula 2]

In Formulas 1 and 2, L is independently a single bond or an alkylene group having 1 to 10 carbon atoms, and R is an alkyl group having 1 to 10 carbon atoms.

In the alkylation method of the norbornene alcohol compound, the norbornene alcohol compound used as a reaction starting material is a compound in which a norbornene terminal is substituted with hydroxy and may be represented by Chemical Formula 1 above. In Formula 1, L is a single bond or an alkylene group having 1 to 10 carbon atoms, preferably a single bond, a methylene group, an ethylene group, a propylene group, and a butylene group, and more preferably a single bond and a methylene group. .

The norbornene alcohol compound can carry out alkylation of the terminal hydroxyl group in the presence of solid sodium hydroxide and/or solid potassium hydroxide, and the solid sodium hydroxide and/or solid potassium hydroxide promotes the alkylation reaction of the norbornene alcohol compound to produce novo It may have a specific shape to improve the conversion rate and yield of the nene alcohol compound.

The shape of the solid sodium hydroxide and solid potassium hydroxide may be at least one shape selected from the group consisting of a bead shape, a flake shape, a power shape, and a pellet shape, and norbornene. Solid sodium hydroxide in the form of beads is preferred in terms of the conversion rate of the alcohol compound and the agitation.

At this time, the bead shape may be spherical with an average diameter of 0.1 mm to 10 mm, preferably 0.1 mm to 5 mm in average diameter, and the flake shape has an average particle diameter of 2 mm to 50 mm and an average thickness of 0.5 mm. It may be in the form of an irregular plate of mm to 2 mm, the powder shape may be in the form of an irregular powder with an average particle diameter of 5 mm or less, and the pellet shape may have an average particle diameter of 2 mm to 30 mm and an average center thickness of 1 mm to 5 mm It may be in the form of a disk.

The solid sodium hydroxide and solid potassium hydroxide can be used without limitation as long as they are solid sodium hydroxide or solid potassium hydroxide, and the solid sodium hydroxide and solid potassium hydroxide can be easily prepared by a known method such as an electrolytic method or a causticization method. and solid sodium hydroxide and solid potassium hydroxide, which can be controlled in shape and have controlled shapes, which are commercially available.

The solid sodium hydroxide and solid potassium hydroxide content may be used in an amount of 1 to 8 moles, preferably 2 to 5 moles, based on 1 mole of the norbornene alcohol compound. If less than 1 mole of norbornene alcohol compound is used with respect to 1 mole of norbornene alcohol compound, the conversion rate of norbornene alcohol compound is low, and if it is used in excess of 8 moles, the conversion rate of norbornene alcohol compound is excellent, but economic problems and after reaction Neutralization may cause problems such as increased wastewater.

Meanwhile, the alkylating agent capable of alkylating the terminal hydroxy group of the norbornene alcohol compound represented by Formula 1 is dimethyl sulfate, diethyl sulfate, dipropyl sulfate, dibutyl sulfate, dipentyl sulfate and dihexyl sulfate. selected dialkyl sulfates; dialkyl carbonates selected from the group consisting of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate and dihexyl carbonate; and an alkyl halide selected from the group consisting of alkyl chloride, alkyl bromide, alkyl fluoride and alkyl iodide; preferably dimethyl sulfate, diethyl sulfate, dialkyl sulfate selected from the group consisting of dipropyl sulfate, dibutyl sulfate, dipentyl sulfate and dihexyl sulfate.

In addition, the content of the alkylating agent may be 0.5 to 6 moles, preferably 0.6 to 5 moles, based on 1 mole of the norbornene alcohol compound. When used in less than 0.5 mol with respect to 1 mol of the norbornene alcohol compound, the conversion rate of norbornene alcohol compound is low, and when used in excess of 6 mol, the conversion rate of norbornene alcohol compound is excellent, but the decomposition of the alkylating agent increases. As a result, a problem of lowering economic efficiency may occur.

In addition, the alkylation reaction of the present invention may be carried out at 0 ° C to 80 ° C under normal pressure to 5 atm. If the pressure is out of the above range, the alkylation reactivity may be lowered due to the high-pressure condition in the reactor, and if the reaction temperature is less than 0 ° C, the alkylation reactivity is lowered and a lot of side-reacted norbornene alcohol compounds may be generated. , when the temperature exceeds 80 ° C., a problem may arise in that norbornene alcohol compound, which is a reaction raw material that rather lowers the conversion rate due to the reverse reaction of the product, may be decomposed during the reaction process.

In the alkylation reaction according to the present invention, one or more reactors filled with solid sodium hydroxide and/or solid potassium hydroxide may be used, and the one or more reactors in which the alkylation reaction is performed are not limited in form, such as a fixed bed reactor, a fluidized bed reactor, or a mobile bed reactor. A known reaction process using a reactor or the like can be applied, and for example, a batch reactor with an agitator attached or a fixed-bed continuous type reactor can be used. In the case of carrying out the fixed-bed continuous process, an appropriate amount of solid sodium hydroxide and/or solid potassium hydroxide is charged into the reactor, and the norbornene alcohol compound and the alkylating agent, which are reactants, are continuously and simultaneously supplied to form solid hydroxide adjusted to the desired reaction temperature and pressure. Sodium is passed continuously. Compounds passing through a reactor set to an appropriate reaction temperature and pressure are separated/purified, and unreacted norbornene alcohol compounds and alkylating agents can be recycled.

The norbornene alcohol compound is alkylated with an alkylating agent in the presence of the above-mentioned solid sodium hydroxide to produce 5-(alkoxyalkyl)bicyclo[2,2,1]hepta-2-ene, a norbornene-based compound represented by Formula 2. there is.

[Formula 2]

In Formula 2, L is a single bond or an alkylene group having 1 to 10 carbon atoms, preferably a single bond, a methylene group, an ethylene group, a propylene group, and a butylene group, more preferably a single bond and a methylene group, R is an alkyl group having 1 to 10 carbon atoms, preferably a methyl group, an ethyl group, a propyl group and a butyl group.

The alkylation method of the norbornene alcohol compound according to the present invention described above can be illustrated by Reaction Scheme 1 below.

[Scheme 1]

In Scheme 1, L and R are as described above.

Meanwhile, the method for alkylating a norbornene alcohol compound according to the present invention may further include conventional steps known in the art before or after each step in addition to the above steps.

In another aspect, the present invention relates to a method for producing a cyclic olefin polymer comprising the norbornene-based compound represented by Chemical Formula 2 prepared by the above-described alkylation method of a norbornene alcohol compound and polymerizing the same.

In the present invention, 5-(alkoxyalkyl)bicyclo[2,2,1]hepta-2-ene, which is a norbornene-based compound represented by Formula 2, may be homopolymerized or other olefinic monomers may be copolymerized. At this time, the olefin-based monomer can be used without limitation as long as it is an olefin-based monomer capable of addition polymerization with the norbornene-based compound represented by Formula 2, and in terms of physical properties of the prepared polymer, cyclic olefin-based monomers such as norbornene and dicyclopentadiene may be a monomer.

In addition, in the present invention, a catalyst and a cocatalyst may be used for polymerization activity, and any catalyst used for polymerization of cyclic olefin monomers may be applied without limitation. For example, nickel-based catalysts, cobalt-based catalysts, palladium-based catalysts, etc. catalysts, or cocatalysts such as modified methylaluminoxane (MMAO), trimethyl aluminum (TMA), triethyl aluminum (TEA), and triiso-butyl aluminum (TIBAL) can be used.

Meanwhile, in the method for preparing a cyclic olefin polymer according to the present invention, polymerization may be performed in a slurry phase, a liquid phase, or a gas phase. When the polymerization is carried out in a liquid or slurry phase, a solvent or olefin itself can be used as a medium. The solvent used at this time is 1,2-dichlorobenzene, toluene, n-pentane, n-hexane, n-heptane, chlorobenzene, dichloromethane, chloroform, 1,2-dichloroethane and 1,1,2,2- It may be one or more solvents selected from the group consisting of tetrachloroethane.

In addition, the polymerization may be carried out in a batch, semi-continuous or continuous manner, and the reaction conditions are 30 ° C to 150 ° C for 1 to 26 hours, when the reaction is performed at 30 ° C or less than 1 hour. , A problem occurs that the polymerization reaction does not sufficiently proceed, and when carried out at 150 ° C. or over 26 hours, the polymer chain may be decomposed and the molecular weight may decrease or gelation may occur.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited by the following examples.

<Example 1-1: Preparation of 5-(methoxymethyl)bicyclo[2,2,1]hepta-2-ene>

1 mole of 2-bicyclo[2,2,1]hepta-5-enylmethanol (where L is a single bond in Formula 1) and 4 moles of sodium hydroxide in the form of beads with an average diameter of 1 mm are mixed under a nitrogen atmosphere. was put into the reactor. While stirring, 2 mol of dimethyl sulfate was added dropwise using a syringe pump. Inside the reactor, bead-shaped sodium hydroxide and dimethyl sulfate were added four times so as not to exceed 40 ° C. at atmospheric pressure. After reacting for 1 hour, 500 g of distilled water was added and stirred to perform layer separation when sodium hydroxide was dissolved. After washing until the pH of the aqueous layer becomes neutral, magnesium sulfate is added to the separated organic layer and filtered to remove water to obtain 5-(methoxymethyl)bicyclo in Formula 1 where L is a single bond and R is a methyl group. [2,2,1]hepta-2-ene was prepared. The prepared 5-(methoxymethyl)bicyclo[2,2,1]hepta-2-ene was measured using GC (Gas Chromatograph), and 2-bicyclo[2,2,1]hepta-5 - It was found that the conversion rate of enylmethanol was 97.8% and the yield of 5-(methoxymethyl)bicyclo[2,2,1]hepta-2-ene was 99.5%.

<Example 1-2: Preparation of 5-(methoxymethyl)bicyclo[2,2,1]hepta-2-ene>

Flakes having an average thickness of 1 mm and an average particle diameter of 15 mm with 1 mole of 2-bicyclo[2,2,1]hepta-5-enylmethanol (L in Formula 1 is a single bond) under a nitrogen atmosphere. 1 mole of sodium hydroxide in the form was charged into the reactor. While stirring, 0.5 mol of dimethyl sulfate was added dropwise using a syringe pump. Inside the reactor, bead-shaped sodium hydroxide and dimethyl sulfate were added four times so as not to exceed 70 ° C. at atmospheric pressure. After reacting for 1 hour, 500 g of distilled water was added and stirred to perform layer separation when sodium hydroxide was dissolved. After washing until the pH of the aqueous layer becomes neutral, magnesium sulfate is added to the separated organic layer and filtered to remove water to obtain 5-(methoxymethyl)bicyclo in Formula 1 where L is a single bond and R is a methyl group. [2,2,1]hepta-2-ene was prepared. As a result of measuring the prepared norbornene-based compound using GC (Gas Chromatograph), the conversion rate of 2-bicyclo[2,2,1]hepta-5-enylmethanol was 90.0%, and the 5-(methoxymethyl) ratio The yield of cyclo[2,2,1]hepta-2-ene was found to be 99.3%.

<Example 1-3: Preparation of 5-(methoxymethyl)bicyclo[2,2,1]hepta-2-ene>

In a nitrogen atmosphere, 1 mole of 2-bicyclo[2,2,1]hepta-5-enylmethanol (L in Formula 1 is a single bond) and a disk pellet having an average particle diameter of 10 mm and an average center thickness of 3.5 mm ) was added to the reactor in the form of 2.5 moles of sodium hydroxide. While stirring was performed, 2.8 mol of dimethyl sulfate was slowly added dropwise using a syringe pump. The inside of the reactor was not allowed to exceed 40 ° C. at normal pressure. After adding 440 g of distilled water and stirring to separate the layers, 1 mole of sodium hydroxide in a pellet form was added, and 1 mole of dimethyl sulfate was slowly added dropwise and stirred. Sodium hydroxide and dimethyl sulfate were added once more by 1 mole each. After reacting for 1 hour, 440 g of distilled water was added and stirred to separate the layers when sodium hydroxide was dissolved. After washing until the pH of the aqueous layer becomes neutral, magnesium sulfate is added to the separated organic layer and filtered to remove water to obtain 5-(methoxymethyl)bicyclo in Formula 1 where L is a single bond and R is a methyl group. [2,2,1]hepta-2-ene was prepared. As a result of measuring the prepared norbornene-based compound using GC (Gas Chromatograph), the conversion rate of 2-bicyclo[2,2,1]hepta-5-enylmethanol was 90.0%, and the 5-(methoxymethyl) ratio The yield of cyclo[2,2,1]hepta-2-ene was found to be 98.7%.

<Example 1-4: Preparation of 5-(methoxymethyl)bicyclo[2,2,1]hepta-2-ene>

A norbornene-based compound was prepared in the same manner as in Example 1-1, but instead of bead-shaped sodium hydroxide, needle-shaped powder-shaped sodium hydroxide having an average particle diameter of 2 mm was used, and L in Formula 1 is a single bond, 5-(methoxymethyl)bicyclo[2,2,1]hepta-2-ene in which R is a methyl group was prepared. As a result of measuring the prepared norbornene-based compound using GC (Gas Chromatograph), the conversion rate of 2-bicyclo[2,2,1]hepta-5-enylmethanol was 89.5% and 5-(methoxymethyl)bicyclo The yield of [2,2,1]hepta-2-ene was found to be 99.5%.

<Comparative Example 1-1: Preparation of 5-(methoxymethyl)bicyclo[2,2,1]hepta-2-ene>

Under a nitrogen atmosphere, 1 mol of 2-bicyclo[2,2,1]hepta-5-enylmethanol (L in Formula 1 is a single bond) and 5 mol of 50% sodium hydroxide aqueous solution were introduced into the reactor. While stirring, 1.4 mol of dimethyl sulfate was slowly added dropwise. The temperature inside the reactor did not exceed 40 °C. Once again, 5 moles of a 50% sodium hydroxide aqueous solution and 1.4 moles of dimethyl sulfate were added and stirred overnight, then 700 g of distilled water was added and stirred to separate the layers. After washing until the pH of the aqueous layer becomes neutral, magnesium sulfate is added to the separated organic layer and filtered to remove water to obtain 5-(methoxymethyl)bicyclo in Formula 1 where L is a single bond and R is a methyl group. [2,2,1]hepta-2-ene was prepared. The prepared 5-(methoxymethyl)bicyclo[2,2,1]hepta-2-ene was measured using GC (Gas Chromatograph), and 2-bicyclo[2,2,1]hepta-5 - The conversion of enylmethanol was 78.3%, and the yield of 5-(methoxymethyl)bicyclo[2,2,1]hepta-2-ene was 97.3%.

The above examples and comparative examples are summarized in Table 1 below.

division alkylation catalyst Conversion rate (%) transference number(%) Example 1-1 Bead-shaped Sodium Hydroxide 97.8 99.5 Example 1-2 Sodium hydroxide in flake form 90.0 99.3 Examples 1-3 Sodium hydroxide in pellet form 92.9 98.7 Example 1-4 Sodium hydroxide in powder form 89.5 99.5 Comparative Example 1-1 aqueous sodium hydroxide solution 78.3 97.3

As shown in Table 1, Examples 1-1 to 1-4 were found to have higher conversion rates and yields than Comparative Example 1-1, especially in the case of Example 1-1 using bead-shaped sodium hydroxide. It was confirmed that the conversion rate and yield were much higher than those of Examples and Comparative Examples.

<Example 2-1: Preparation of cyclic olefin polymer>

After adding 130 g of toluene to the reactor at room temperature under a nitrogen atmosphere, the temperature was raised to 120 ° C. to remove moisture. After the toluene boils, the temperature of the reactor is lowered to 90 ° C. Then, 0.0134 g of palladium diacetate as a catalyst, 0.0928 g of dimethyl aniliniumtetrakiss (pentafluorophenyl) borate and tricyclohexyl 0.0168 g of phosphine was dissolved in dichloromethyl, which was charged into the reactor. 56 g of 5-(methoxymethyl)bicyclo[2,2,1]hepta-2-ene prepared in Example 1 was mixed with methyl 2-methylbicyclo[2,2,1]hepta-5-en-2 - It was mixed with 29 g of carboxylate and slowly added dropwise to the reactor. The reaction was terminated after stirring for 3 hours. After lowering the temperature of the reactor to room temperature, a precipitated polymer was obtained using an acetone solvent. The polymer precipitate was filtered, washed with acetone, and dried at 60° C. under reduced pressure to obtain a white cyclic olefin polymer. It was found that the number average molecular weight of the prepared cyclic olefin polymer was 114,499 and the weight average molecular weight was 190,857.

<Comparative Example 2-2: Preparation of Cyclic Olefin Polymer>

120 g of toluene was placed in a reactor at room temperature under a nitrogen atmosphere. The temperature of the reactor was raised to 120° C. to remove moisture. After boiling toluene, the temperature of the reactor was lowered to 90 °C. Subsequently, 0.0134 g of palladium diacetate, 0.0930 g of dimethyl aniliniumtetrakiss (pentafluorophenyl) borate, and 0.0163 g of tricyclohexylphosphine as catalysts were dissolved in dichloromethyl and then introduced into the reactor. did 51 g of 2-bicyclo[2,2,1]hepta-5-enylmethanol was mixed with 29 g of methyl 2-methylbicyclo[2,2,1]hepta-5-ene-2-carboxylate to was added dropwise slowly. The reaction was terminated after stirring overnight. After completion of the reaction, hardly any precipitated polymer could be obtained even when the obtained polymer solution was used with acetone or ethanol.

As described above, specific parts of the present invention have been described in detail, to those skilled in the art, it is clear that these specific descriptions are only preferred embodiments, and the scope of the present invention is not limited thereby. something to do. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (8)

A norbornene alcohol compound comprising the step of preparing a norbornene-based compound represented by Formula 2 by reacting a norbornene alcohol compound represented by Formula 1 with an alkylating agent in the presence of solid sodium hydroxide and/or solid potassium hydroxide. Alkylation method of:
[Formula 1]

In Formula 1, L is a single bond or an alkylene group having 1 to 10 carbon atoms,
[Formula 2]

In Formula 2, L is a single bond or an alkylene group having 1 to 10 carbon atoms, and R is an alkyl group having 1 to 10 carbon atoms.
According to claim 1,
The solid sodium hydroxide and solid potassium hydroxide are norbornene, characterized in that they have at least one shape selected from the group consisting of a bead shape, a flake shape, a power shape, and a pellet shape. A method for alkylation of alcohol compounds.
According to claim 1,
The method of alkylation of norbornene alcohol compounds, characterized in that the solid sodium hydroxide and solid potassium hydroxide are in the form of beads having an average diameter of 0.1 mm to 10 mm.
According to claim 1,
The method of alkylating a norbornene alcohol compound, characterized in that the solid sodium hydroxide and solid potassium hydroxide are used in an amount of 1 to 8 moles based on 1 mole of the norbornene alcohol compound represented by Formula 1.
According to claim 1,
The alkylating agent is a dialkyl sulfate selected from the group consisting of dimethyl sulfate, diethyl sulfate, dipropyl sulfate, dibutyl sulfate, dipentyl sulfate and dihexyl sulfate; dialkyl carbonates selected from the group consisting of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate and dihexyl carbonate; and an alkyl halide selected from the group consisting of alkyl chloride, alkyl bromide, alkyl fluoride and alkyl iodide.
According to claim 1,
The alkylating agent is used in an amount of 0.5 to 6 moles based on 1 mole of the norbornene alcohol compound.
According to claim 1,
The reaction is an alkylation method of a norbornene alcohol compound, characterized in that carried out at 0 ℃ ~ 80 ℃ under normal pressure ~ 5 atm.
A method for producing a cyclic olefin polymer, characterized by polymerizing a norbornene-based compound represented by Formula 2 prepared by the alkylation method of a norbornene alcohol compound according to any one of claims 1 to 7.

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