KR20060042562A - Method for preparing cyclic olefin polymer having a high bulk density and cyclic olefin polymer prepared thereby - Google Patents

Abstract

The present invention relates to a method for preparing a cyclic olefin polymer having a high bulk density and a cyclic olefin polymer prepared by the above, and the method for preparing the cyclic olefin polymer includes a) cyclic olefin monomers or cyclic olefin monomers. Polymerizing ethylene to prepare a cyclic olefin polymer solution, b) diluting the cyclic olefin polymer solution with a solvent containing ketones, c) adding a nonsolvent to the diluted cyclic olefin polymer solution. Adding in a slow dropwise manner to precipitate the cyclic olefin polymer, and d) filtering and drying the precipitated cyclic olefin polymer.

The method of the present invention can provide a cyclic olefin polymer having a high bulk density and easy to precipitate the polymer.

Cyclic olefin polymer, ketone, diluent solvent, azeotrope, nonsolvent

Description

METHODS FOR PREPARING CYCLIC OLEFIN POLYMER HAVING A HIGH BULK DENSITY AND CYCLIC OLEFIN POLYMER PREPARED THEREBY}

1 is an electron micrograph (magnification 100 times) of the cyclic olefin polymer particles of Example 1. FIG.

Figure 2 is a polymer micrograph of the fiber form of Comparative Example 3 (magnification 10 times).

The present invention relates to a method for producing a cyclic olefin polymer and a cyclic olefin polymer prepared thereby, and more particularly, to a method for producing a cyclic olefin polymer having a high bulk density and an olefin polymer prepared thereby.

Until now, inorganic materials such as silicon oxide and silicon nitride have been mainly used in the information electronics industry. As the demand for small size and high efficiency devices increases, the need for high functional new materials increases. Due to these high functional properties, there is increasing interest in polymers having low dielectric constant and hygroscopicity, excellent metal adhesion, strength, thermal stability and transparency, and high glass transition temperature (Tg> 250 ° C.).

Such high functional polymers include insulating films of semiconductors or TFT-LCDs, polarizer protective films, multichip modules, integrated circuits (ICs), printed circuit boards, encapsulants or flat panel displays of electronic materials. It can be used as a material for optics such as a flat panel display.

For example, the cyclic olefin polymer is a polymer produced by polymerization of a cyclic monomer such as norbornene, and has excellent transparency, heat resistance, and chemical resistance, and has low birefringence and water absorption rate as compared with the existing olefin polymer. Therefore, it can be applied to various medical materials such as optical materials such as CD, DVD, Plastic Optical Fiber (POF), capacitor film, information and electronic materials such as low dielectric, low absorbing syringe, blister packaging, etc. Can be.

Steam stripping has been used as a method of obtaining a polymer from the polymer solution during the manufacturing process of the polymer having a high glass transition temperature as described above. In addition, it is difficult to dry the water used, it is difficult to remove the included monomers or metal catalysts, and enormous amounts of steam are used, resulting in inefficiency and high energy consumption.

As another method, US Pat. No. 4,400,501 describes a process of mixing a polymer solution and a nonsolvent with a high shear stirrer to precipitate the polymer, followed by filtration and drying. However, the polymer particles produced by this method are irregular fluffy fibers and have a very small bulk density of 0.06 g / ml to 0.08 g / ml, which is a non-solvent for discharging, conveying and washing the slurry from the settling tank. High usage and difficult to dry In addition, US Pat. No. 6,455,650 describes a process of pouring a polymer solution into a non-solvent to precipitate the polymer, filter and dry it. However, the polymer produced by this method also has a very small bulk density as an irregular fluffy fiber. U.S. Patent No. 4,414,386 describes a process for precipitating a polymer by mixing a non-solvent comprising alcohol and water in a constant composition with a polymer solution. By this process, polymers of elongated particles were obtained and the bulk density was increased to 0.16 g / ml. However, since the mixture of water and alcohol is used, their separation is difficult and the bulk density needs to be further improved.

The present inventors, in the step of precipitating and separating the polymer from the polymer solution in the manufacturing method of the cyclic olefin polymer, as in the prior art, without mixing the polymer solution and the non-solvent or pouring the polymer solution into the non-solvent, When the nonsolvent is slowly added dropwise to the polymer solution by diluting it with a solvent of ketones, the method of slowly dropping the nonsolvent into the polymer solution solves the problem that the precipitation of the polymer is difficult. Edo also revealed that it is possible to precipitate cyclic olefin polymers with high bulk density.

Accordingly, an object of the present invention is to provide a method for preparing a cyclic polymer having a high bulk density from a cyclic olefin polymer solution, and a cyclic olefin polymer prepared thereby.

In order to achieve the above object, the present invention

a) polymerizing cyclic olefin monomers or cyclic olefin monomers with ethylene to produce a cyclic olefin polymer solution,

b) diluting the cyclic olefin polymer solution with a solvent containing ketones,

c) adding a nonsolvent in a dropwise manner to the diluted cyclic olefin polymer solution to precipitate the cyclic olefin polymer, and

d) filtering and drying the precipitated cyclic olefin polymer.

It provides a method for producing a cyclic olefin polymer comprising a.

The present invention also provides a cyclic olefin polymer having a bulk density of 0.1 to 0.6 g / ml.

Hereinafter, the present invention will be described in more detail.

In the present invention, the cyclic olefin polymer means a polymer produced by polymerization of cyclic olefin monomers or polymerization of cyclic olefin monomer and ethylene.

Examples of the cyclic olefin polymer in the present invention include a homopolymer of norbornene-based monomers of Formula 1 and a copolymer made of different monomers of Formula 1; There is a polymer selected from the group consisting of a copolymer of ethylene norbornene-based monomer of the formula (1).                     

(Formula 1)

,

, -(CH₂)_nPR _⁵ R _⁶ , -(CH₂) _nP(OR _⁵ )(OR _⁶ ), -(CH₂)_nP(R⁵)(OR _⁶ )(OR _⁷ ), -(CH₂)_nP(=O)R _⁵ R _⁶ , -(CH₂) _nP(=O)(OR _⁵ )(OR _⁶ ) 및 -(CH₂)_nP(=O)(R⁵)(OR⁶)로 이루어진 극성 작용기로 구성된 군으로부터 선택되고, 상기 극성 작용기 중 n 은 0 내지 10의 정수이며, R⁵, R _⁶ , 및 R _⁷ 은 각각 독립적으로 수소, 탄소수 1 내지 20인 직쇄 또는 분지쇄의 알킬 또는 탄소수 2 내지 20의 알케닐; 탄소수 1 내지 20의 탄화수소로 치환되거나 치환되지 않은 탄소수 5 내지 12의 시클로알킬; 탄소수 1 내지 20의 탄화수소로 치환되거나 치환되지 않은 탄소수 6 내지 20의 아릴; 탄소수 1 내지 20의 탄화수소로 치환되거나 치환되지 않은 탄소수 7 내지 15의 아랄킬; 탄소수 3 내지 20의 알키닐로 이루어진 군에서 선택되고,In Formula 1, m is an integer of 0 to 4, R ¹ , R ² , R ³ , and R ⁴ is straight or branched chain alkyl of 1 to 20 carbon atoms, alkenyl or vinyl of 2 to 20 carbon atoms; Cycloalkyl having 5 to 12 carbon atoms which may be substituted or unsubstituted with a hydrocarbon having 1 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms, unsubstituted or substituted with hydrocarbons having 1 to 20 carbon atoms; Aralkyl having 7 to 15 carbon atoms, unsubstituted or substituted with hydrocarbons having 1 to 20 carbon atoms; Alkynyl having 3 to 20 carbon atoms; -(CH ₂ ) _n C (O) OR _⁵ ,-(CH ₂ ) _n OC (O) R _⁵ ,-(CH ₂ ) _n OC (O) OR _⁵ ,-(CH ₂ ) _n C (O) R _⁵ ,-(CH ₂ ) _n OR _⁵ ,-(CH ₂ O) _n -OR _⁵ ,-(CH ₂ ) _n C (O) -OC (O) R _⁵ ,-(CH ₂ ) _n C (O) NH ₂ ,-(CH ₂ ) _n C (O) NHR _⁵ ,-(CH ₂ ) _n C (O) NR _⁵ R _⁶ ,-(CH ₂ ) _n NH ₂ ,-(CH ₂ ) _n NHR _⁵ ,- (CH ₂ ) _n NR _⁵ R _⁶ ,-(CH ₂ ) _n OC (O) NH ₂ ,-(CH ₂ ) _n OC (O) NHR _⁵ ,-(CH ₂ ) _n OC (O) NR _⁵ R _⁶ ,-(CH ₂ ) _n C (O) Cl,-(CH ₂ ) _n SR ⁵ ,-(CH ₂ ) _n SSR ⁵ ,-(CH ₂ ) _n SO ₂ R ⁵ ,-(CH ₂ ) _n SO ₂ R ⁵ ,-(CH ₂ ) _n OSO ₂ R ⁵ ,-(CH ₂ ) _n SO ₃ R _⁵ ,-(CH ₂ ) _n OSO ₃ R ⁵ ,-(CH ₂ ) _n BR _⁵ R _⁶ ,-(CH ₂ ) _n B (OR _⁵ ) (OR _⁶ ),-(CH ₂ ) _n B (R ⁵ ) (OR ⁶ ),-(CH ₂ ) _n N = C = S,-(CH ₂ ) _n NCO,- (CH ₂ ) _n N (R ⁵ ) C (= O) R ⁶ ,-(CH ₂ ) _n N (R ⁵ ) C (= O) (OR ⁶ ),-(CH ₂ ) _n CN,-(CH ₂ ) _n NO ₂ ,

,

,-(CH ₂ ) _n PR _⁵ R _⁶ ,-(CH ₂ ) _n P (OR _⁵ ) (OR _⁶ ),-(CH ₂ ) _n P (R ⁵ ) (OR _⁶ ) (OR _⁷ ),-( CH ₂ ) _n P (= 0) R _⁵ R _⁶ ,-(CH ₂ ) _n P (= 0) (OR _⁵ ) (OR _⁶ ) and-(CH ₂ ) _n P (= 0) (R ⁵ ) ( OR ⁶ ) is selected from the group consisting of a polar functional group consisting of n is an integer of 0 to 10, and R ⁵ , R _⁶ , and R _⁷ are each independently hydrogen, straight or branched carbon atoms 1 to 20 Alkyl of the chain or alkenyl having 2 to 20 carbon atoms; Cycloalkyl having 5 to 12 carbon atoms which may be substituted or unsubstituted with a hydrocarbon having 1 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms, unsubstituted or substituted with hydrocarbons having 1 to 20 carbon atoms; Aralkyl having 7 to 15 carbon atoms, unsubstituted or substituted with hydrocarbons having 1 to 20 carbon atoms; Selected from the group consisting of alkynyl having 3 to 20 carbon atoms,

When R ¹ , R ² , R ³ and R _⁴ are not hydrogen, halogen or a polar functional group, R ¹ and R ² or R ³ and R ⁴ may be connected to each other to form an alkylidene group having 1 to 10 carbon atoms. R ¹ or R ² may be linked to any one of R ³ and R ⁴ to form a saturated or unsaturated cyclic group having 4 to 12 carbon atoms or an aromatic cyclic compound having 6 to 17 carbon atoms.

The method for preparing the cyclic olefin polymer by precipitating the polymer from the polymer solution according to the present invention is carried out by diluting with a solvent of ketones to the polymer solution by dropwise addition of a non-solvent so that precipitation of the polymer occurs gradually. Except that, as in the conventional method, the precipitation method of the polymer according to the present invention is the carbon of the hydrocarbon contained in R ¹ , R ² , R ³ and R ⁴ of the compound of Formula 1 as in the conventional method It is not affected by the number or type of aryl groups.

Hereinafter, the manufacturing method of the cyclic olefin polymer of this invention is demonstrated more concretely.

The cyclic olefin polymer may have a cyclic olefin monomer and prepare a cyclic olefin polymer solution using a conventional polymerization method known in the art, and then separate the polymer from the polymer solution by a method such as precipitation. It can manufacture.

Generally, polymerization is performed by dissolving the monomers to be polymerized in a solvent and then adding a catalyst and adjusting the temperature, wherein the type and temperature of the solvent or catalyst are different depending on the polymerization method applied. Polymerization methods that can be used to prepare the cyclic olefin polymer solution in the present invention include, for example, ring opening metathesis polymerization (ROMP), addition polmerization as illustrated in Scheme 1 below, as well as cationic polymerization ( cationic polymerization) and ring opening metathesis polymerization followed by hydrogenation (HROMP), but are not limited thereto, and polymerization methods known in the art may be used.

(Scheme 1)

In the above polymerization method, a transition metal catalyst such as a metallocene compound, Ni, or Pd-compound may be used, and these catalysts exhibit different polymerization characteristics and polymer structures through changes in the composition of the core metal, ligand, and catalyst.

In the method of the present invention, the concentration of the cyclic olefin polymer solution prepared as described above can be up to the limit at which the polymer can be dissolved, but in terms of economics, the concentration of the cyclic olefin polymer is advantageously 5% by weight or more, and 80 It is difficult to melt | dissolve more than weight%. Therefore, in the present invention, the concentration of the cyclic olefin polymer solution is 5 to 80% by weight, preferably 10 to 60% by weight.                     

The solvent used in the preparation of the polymer solution in the present invention is selected from the group consisting of toluene, mixed xylene, o, m, p-xylene, aromatic compounds including ethylbenzene, chlorobenzene, benzene, and mixtures thereof. Can be.

The method of the present invention uses a method of diluting a non-solvent after dilution with a solvent of ketone to the polymer solution to separate the polymer from the cyclic olefin polymer solution prepared as described above, even when the alkylnorbornene content is low. It is characterized by providing a polymer having a bulk density. Here, the nonsolvent means a material that can be mixed with the solvent of the polymer solution and has low solubility of the cyclic olefin polymer to be separated.

Therefore, in the present invention, after further diluting the polymer solution with a solvent of ketones, a non-solvent is slowly added dropwise thereto so that the bulk density is eliminated even if there is no monomer containing linear or branched alkyl. It is possible to produce polymer particles having a high and homogeneous form.

The diluting solvent may be selected from the group consisting of ketones of the formula (2), a mixture of ketones, and a mixture of the ketones and non-solvents.

(Formula 2)

(Wherein R ⁸ and R ⁹ are each independently hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms.)

Examples of the ketone compounds include acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, benzophenone and the like.

In the present invention, when the amount of the dilution solvent is small, the polymer particles are not normally produced, and when used in an excessive amount, it is economically disadvantageous, so 30 wt% to 1000 wt% of the solvent usage is preferable.

As said nonsolvent, Alkanes, such as hexane and cyclohexane; Ethers such as dimethyl ether and tetrahydrofuran; And economically advantageous to use those selected from the group consisting of, but are not limited to these.

In this case, alcohols such as methanol and ethanol may be used as the nonsolvent, but alcohols react with ketones used as the diluting solvent to generate acetal, as shown in Scheme 2 below. There is a problem that is difficult to recover.

(Scheme 2)

In addition, ketones and non-solvents used as diluent solvents are difficult to recover and reuse because they form azeotropes as shown in Table 1 below.                     

TABLE 1

Dilute solvent Non-solvent Azeotropic composition (mol% diluent solvent) Azeotropic temperature (℃) Acetone Normal hexane 63 49.0 Acetone Cyclohexane 75 53 Methyl ethyl ketone Normal hexane 32.7 64.2 Methyl ethyl ketone Cyclohexane 47.7 71.4 Methyl Isopropyl Ketone Cyclohexane 14.7 78.5

Therefore, in the present invention, the dilution solvent is preferably used in the azeotropic composition of the ketones and the non-solvent, so that the solvent can be easily recovered.

In the method of the present invention, the rate of adding the diluting solvent to the cyclic olefin polymer solution has no significant effect on the process, but the rate of adding the non-solvent to the diluted polymer is important. If the non-solvent is added to the diluted polymer solution too quickly, fibrous particles other than spherical particles may be produced, or even spherical particles may be produced, which makes it difficult to filter because the fine powder does not sink when the solution is left. However, determining the appropriate dropping rate of the nonsolvent is influenced by the size of the reactor, the dropping method, the amount of the total polymer solution, and the like. For example, when the reaction tank is large, it is preferable that the dropping rate is low because there is a limit in that the non-solvent added is rapidly dispersed throughout the polymer solution as compared with the case where the reaction tank is small. In addition, in the case of using a method of spraying the non-solvent so as to evenly contact the polymer solution, it is possible to slightly increase the dropping speed of the non-solvent than otherwise. Therefore, it is difficult to collectively limit the dropping rate of the non-solvent, and the dropping rate of the non-solvent may be determined in consideration of various conditions as described above.

When the dropping rate of the non-solvent is represented by the dropping speed per total polymer solution amount as shown in Equation 1 below, in the present invention, the dropping rate of the non-solvent is preferably 2000 (kg / hr / kg) or less. However, as described above, the present invention is not limited thereto.

(Equation 1)

Non-solvent dropping rate (kg / hr / kg) = {added drop of cost (kg) / dropping time (hr)} / total polymer solution (kg)

The amount of the non-solvent added is preferably in the range of 1 to 30 times the solvent in the polymer solution, and more preferably in the range of 2 to 20 times the solvent in the polymer solution in order to minimize product loss.

In addition, in this invention, when temperature is added dropwise to a polymer solution dropwise, economic efficiency will become low. In other words, if the temperature is too low, the solubility of the polymer is lowered and the amount of solvent used is increased. If the temperature is too high, the solvent is boiled, and thus a high pressure precipitation tank is required. Therefore, in this invention, it is preferable that the dropping temperature of a nonsolvent is -30 degreeC to 150 degreeC, and it is more preferable that it is -5 degreeC to 110 degreeC.

The cyclic olefin polymer precipitated by the above method can be separated by a method such as filtration and drying. The filtration and drying method is not particularly limited and can be carried out by methods well known to those skilled in the art.

The cyclic olefin polymer obtained by this method has a spherical shape and has a bulk density of 0.1 g / ml or more, preferably 0.2 g / ml to 0.5 g / ml.

Hereinafter, the present invention will be described in detail through examples. However, the following examples are intended to illustrate the invention, and the invention is not limited thereto.

Preparation Example 1

(Preparation of copolymer solution of 5-norbornene-2-methylacetate and 5-norbornene-2-carboxylic acid methyl ester)

5-norbornene-2-methylacetate (1,745 g) and 5-norbornene-2-carboxylic acid methyl ester (685 g) were added to the reactor at room temperature, followed by toluene (3,645 g). The inside of the reactor was replaced with nitrogen, and the reactor was heated to 90 ° C. Subsequently, palladium diacetate (0.33 g), dimethylanilinium tetrakis (pentafluorophenyl) borate (2.4 g), and tricyclohexylphosphine (0.42 g) were added to dichloromethyl. After dissolving, this was added to the reactor, stirred for 18 hours, and the reaction was completed to prepare a polymer solution to which toluene (3,000 g) was added.

Example 1

210 g of a copolymer solution of 5-norbornene-2-methylacetate and 5-norbornene-2-carboxylic acid methyl ester prepared in Preparation Example 1 was added to a reactor, and 450 g of acetone was added thereto to dilute. Subsequently, 750 g of normal hexane was slowly added dropwise to the reactor at room temperature for 2 hours (dripping rate = 1.8 kg / hr / kg). The stirring speed of the reactor was 200 rpm. When about 450 g of normal hexane was added, the polymer began to precipitate slowly. The precipitated polymer sank to the bottom when the stirring was stopped and the top became a clear solution layer. After completing the dropwise addition of normal hexane, the polymer slurry was filtered, washed with normal hexane, and dried under reduced pressure at 70 ° C. to obtain 49.5 g of a white polymer (88 wt% based on the total amount of added monomers). The bulk density of the dried polymer was 0.37 g / ml and the content of palladium was 30 ppm. The molecular weight (Mw) of this copolymer was 143,000, and Mw / Mn was 2.1. An electron micrograph (100 times magnification) of the cyclic olefin polymer particles thus obtained is shown in FIG. 1. In Figure 1, it can be seen that the cyclic olefin polymer particles of Example 1 are spherical in shape.

Example 2

210 g of a copolymer solution of 5-norbornene-2-methylacetate and 5-norbornene-2-carboxylic acid methyl ester prepared in Preparation Example 1 was added to a reactor, and azeotropic composition of 450 g of acetone and 400 g of normal hexane was added thereto. When the mixture was added and diluted, the solution became emulsified. Subsequently, 350 g of normal hexane was slowly added dropwise to the reactor at room temperature for 1 hour (dripping rate = 1.7 kg / hr / kg). The stirring speed of the reactor was 200 rpm. When the stirring was stopped after dropping of normal hexane, the precipitated polymer sank to the bottom and the upper layer became a clear solution layer. The polymer slurry was filtered, washed with normal hexane, and dried under reduced pressure at 70 ° C. to obtain 49.9 g of a white polymer (88 wt% based on the total amount of added monomers). The bulk density of the dried polymer was 0.38 g / ml and the content of palladium was 30 ppm. The molecular weight (Mw) of this copolymer was 143,000, and Mw / Mn was 2.1.

Comparative Example 1

210 g of a copolymer solution of 5-norbornene-2-methyl acetate and 5-norbornene-2-carboxylic acid methyl ester prepared in Preparation Example 1 was charged into a reactor. Subsequently, 750 g of normal hexane was slowly added dropwise to the reactor at room temperature for 2 hours (dripping rate = 1.8 kg / hr / kg). The stirring speed of the reactor was 200 rpm. When about 450 g of normal hexane was added, the polymer began to precipitate slowly. Precipitated polymers were entangled with each other in an aggregated form to obtain dispersed particles. Even when methanol, ethanol, cyclohexane and the like were used instead of normal hexane, the precipitated polymers were entangled with each other to obtain dispersed particles.

Preparation Example 2

(Production of Polymer Solution of 5-norbornene-2-methylacetate)

5-norbornene-2-methyl acetate (2,493 g) was added to the reactor at room temperature, followed by toluene (7,479 g). The inside of the reactor was replaced with nitrogen, and the reactor was heated to 90 ° C. Subsequently, palladium diacetate (0.33 g), dimethylanilinium tetrakis (pentafluorophenyl) borate (2.4 g), and tricyclohexylphosphine (0.42 g) were added to dichloromethyl. After dissolution, this was added to the reactor, stirred for 18 hours, and the reaction was completed to prepare a polymer solution.

Example 3

210 g of the polymer solution of 5-norbornene-2-methylacetate prepared in Preparation Example 2 was added to a reactor, and 750 g of acetone was added thereto and diluted. Subsequently, 750 g of normal hexane was slowly added dropwise to the reactor at room temperature for 2 hours (dripping rate = 1.8 kg / hr / kg). The stirring speed of the reactor was 200 rpm. When about 450 g of normal hexane was added, the polymer began to precipitate slowly. The precipitated polymer sank to the bottom when the stirring was stopped and the top became a clear solution layer. After completing the dropwise addition of normal hexane, the polymer slurry was filtered, washed with normal hexane, and dried under reduced pressure at 70 ° C. to obtain 47.0 g of a white polymer (90 wt% based on the total amount of monomers added). The dried polymer was spherical in shape and had a bulk density of 0.30 g / ml and a palladium content of 15 ppm. The molecular weight (Mw) of this copolymer was 189,000, and Mw / Mn was 2.4.

Example 4

210 g of the polymer solution of 5-norbornene-2-methylacetate prepared in Preparation Example 2 was added to a reactor, and 750 g of methyl ethyl ketone was added thereto and diluted. Subsequently, 750 g of normal hexane was slowly added dropwise to the reactor at room temperature for 2 hours (dripping rate = 1.8 kg / hr / kg). The stirring speed of the reactor was 200 rpm. When about 450 g of normal hexane was added, the polymer began to precipitate slowly. The precipitated polymer sank to the bottom when the stirring was stopped and the top became a clear solution layer. After completion of the dropwise addition of normal hexane, the polymer slurry was filtered, washed with normal hexane, and dried under reduced pressure at 70 ° C. to obtain 49.0 g of a white polymer (93 wt% based on the total amount of added monomers). The bulk density of the dried polymer was 0.35 g / ml and the content of palladium was 17 ppm. The molecular weight (Mw) of this copolymer was 201,000, and Mw / Mn was 2.3.

Comparative Example 2

210 g of the polymer solution of 5-norbornene-2-methylacetate prepared in Preparation Example 2 was added to the reactor. Subsequently, 750 g of normal hexane was slowly added dropwise to the reactor at room temperature for 2 hours (dripping rate = 1.8 kg / hr / kg). The stirring speed of the reactor was 200 rpm. When about 450 g of normal hexane was added, the polymer began to precipitate slowly. The precipitated polymer was entangled with each other to obtain dispersed particles. Even when methanol, ethanol, cyclohexane, etc. were used instead of normal hexane, the precipitated polymers were entangled with each other to obtain dispersed particles.

Comparative Example 3

210 g of the polymer solution of 5-norbornene-2-methylacetate prepared in Preparation Example 2 was added to a reactor, and 750 g of acetone was added thereto and diluted. Subsequently, 750 g of normal hexane was rapidly added to the reactor at room temperature for 5 seconds (dripping acceleration = 2,570 kg / hr / kg). The stirring speed of the reactor was 200 rpm. The precipitated polymer was in the form of irregular fibers as shown in Figure 2, and the bulk density was very small, 0.07 g / ml.

Preparation Example 3

(Preparation of terpolymer copolymer solution of 5-butylnorbornene, 5-norbornene-2-methylacetate and 5-norbornene-2-carboxylic acid methyl ester)

5-butylnorbornene (15.6 g), 5-norbornene-2-methyl acetate (81.4 g) and 5-norbornene-2-carboxylic acid methyl ester (16.0 g) were added to the reactor at room temperature, followed by toluene (170). g) was added and the inside of the reactor was replaced with nitrogen and heated to 90 ° C. Subsequently, palladium diacetate (10.5 mg), dimethylanilinium tetrakispentafluorophenyl) borate (74.8 mg) and tricyclohexyl phosphine (13.1 mg) were dissolved in dichloromethyl, which was added to the reactor and stirred for 18 hours. Terpolymer by polymerization of 15 mol% of 5-butylnorbornene, 70 mol% of 5-norbornene-2-methyl acetate and 15 mol% of 5-norbornene-2-carboxylic acid methyl ester A solution was made.

Example 5

340 g of acetone was added to the polymer solution prepared in Preparation Example 3, and diluted. 848 g of normal hexane was slowly added dropwise at room temperature for 90 minutes while stirring the reactor at 150 rpm (dripping rate = 2.0 kg / hr / kg). After dropping, the precipitated polymer sank to the bottom when the stirring was stopped, and the upper part became a clear solution layer. After completion of the dropwise addition of normal hexane, the polymer slurry was filtered, washed with normal hexane, and dried under reduced pressure at 60 ° C. to obtain 104 g of a white polymer (92 wt% based on the total amount of added monomers). The dried polymer was spherical and had a bulk density of 0.35 g / ml. The content of palladium was 30 ppm. The molecular weight (Mw) of this copolymer was 185,000 and Mw / Mn was 2.2.

Example 6

The azeotropic mixture of 340 g of acetone and 302 g of normal hexane was added to the polymer solution prepared in Preparation Example 3, and diluted. Subsequently, 546 g of normal hexane was slowly added dropwise to the reactor at room temperature for 1 hour (dripping rate = 1.9 kg / hr / kg). The stirring speed of the reactor was 200 rpm. When the stirring was stopped after the addition of normal hexane, the precipitated polymer settled to the bottom and the upper layer became a clear solution layer. The polymer slurry was filtered, washed with normal hexane, and dried under reduced pressure at 70 ° C. to obtain 104 g of a white polymer (92 wt% based on the total amount of added monomers). The dried polymer was spherical in shape and had a bulk density of 0.32 g / ml and a palladium content of 28 ppm. The molecular weight (Mw) of this copolymer was 187,000, and Mw / Mn was 2.1.

Example 7

When the azeotropic mixture of 340 g of acetone and 167 g of cyclohexane was added to the polymer solution prepared in Preparation Example 3, the solution became emulsified. Subsequently, 681 g of cyclohexane was slowly added dropwise to the reactor at room temperature for 1 hour (dropping rate = 2.4 kg / hr / kg). The stirring speed of the reactor was 200 rpm. When the stirring was stopped after the addition of cyclohexane, the precipitated polymer settled to the bottom and the upper part became a clear solution layer. The polymer slurry was filtered, washed with normal hexane, and dried under reduced pressure at 70 ° C. to obtain 102 g of a white polymer (90 wt% based on the total amount of added monomers). The dried polymer was spherical in shape and had a bulk density of 0.40 g / ml and a palladium content of 25 ppm. The molecular weight (Mw) of this copolymer was 184,000, and Mw / Mn was 2.0.

The present invention dilutes a solvent containing ketones before dropping the nonsolvent into a solution of the cyclic olefin polymer, and in particular, by using a mixture of ketones and nonsolvents as a diluent solvent, causing the polymer to gradually precipitate. Even when the alkylnorbornene content having a linear or branched substituent of alkyl is low, there is an effect of providing a cyclic olefin polymer having a spherical shape and a high bulk density.

Claims (12)

a) polymerizing cyclic olefin monomers or cyclic olefin monomers with ethylene to produce a cyclic olefin polymer solution, b) diluting the cyclic olefin polymer solution with a solvent containing ketones, c) adding a nonsolvent in a dropwise manner to the diluted cyclic olefin polymer solution to precipitate the cyclic olefin polymer, and d) filtering and drying the precipitated cyclic olefin polymer. Method for producing a cyclic olefin polymer comprising a. According to claim 1, wherein the cyclic olefin polymer is a homopolymer of norbornene-based monomers of formula (1); And a copolymer consisting of different monomers of formula (1); And Method of producing a cyclic olefin polymer comprising a polymer selected from the group consisting of a copolymer of ethylene norbornene-based monomer of Formula 1: (Formula 1)

In Formula 1, m is an integer of 0 to 4, R ¹ , R ² , R ³ , and R ⁴ is straight or branched chain alkyl of 1 to 20 carbon atoms, alkenyl or vinyl of 2 to 20 carbon atoms; Cycloalkyl having 5 to 12 carbon atoms which may be substituted or unsubstituted with a hydrocarbon having 1 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms, unsubstituted or substituted with hydrocarbons having 1 to 20 carbon atoms; Aralkyl having 7 to 15 carbon atoms, unsubstituted or substituted with hydrocarbons having 1 to 20 carbon atoms; Alkynyl having 3 to 20 carbon atoms; -(CH ₂ ) _n C (O) OR _⁵ ,-(CH ₂ ) _n OC (O) R _⁵ ,-(CH ₂ ) _n OC (O) OR _⁵ ,-(CH ₂ ) _n C (O) R _⁵ ,-(CH ₂ ) _n OR _⁵ ,-(CH ₂ O) _n -OR _⁵ ,-(CH ₂ ) _n C (O) -OC (O) R _⁵ ,-(CH ₂ ) _n C (O) NH ₂ ,-(CH ₂ ) _n C (O) NHR _⁵ ,-(CH ₂ ) _n C (O) NR _⁵ R _⁶ ,-(CH ₂ ) _n NH ₂ ,-(CH ₂ ) _n NHR _⁵ ,- (CH ₂ ) _n NR _⁵ R _⁶ ,-(CH ₂ ) _n OC (O) NH ₂ ,-(CH ₂ ) _n OC (O) NHR _⁵ ,-(CH ₂ ) _n OC (O) NR _⁵ R _⁶ ,-(CH ₂ ) _n C (O) Cl,-(CH ₂ ) _n SR ⁵ ,-(CH ₂ ) _n SSR ⁵ ,-(CH ₂ ) _n SO ₂ R ⁵ ,-(CH ₂ ) _n SO ₂ R ⁵ ,-(CH ₂ ) _n OSO ₂ R ⁵ ,-(CH ₂ ) _n SO ₃ R _⁵ ,-(CH ₂ ) _n OSO ₃ R ⁵ ,-(CH ₂ ) _n BR _⁵ R _⁶ ,-(CH ₂ ) _n B (OR _⁵ ) (OR _⁶ ),-(CH ₂ ) _n B (R ⁵ ) (OR ⁶ ),-(CH ₂ ) _n N = C = S,-(CH ₂ ) _n NCO,- (CH ₂ ) _n N (R ⁵ ) C (= O) R ⁶ ,-(CH ₂ ) _n N (R ⁵ ) C (= O) (OR ⁶ ),-(CH ₂ ) _n CN,-(CH ₂ ) _n NO ₂ ,

,

,-(CH ₂ ) _n PR _⁵ R _⁶ ,-(CH ₂ ) _n P (OR _⁵ ) (OR _⁶ ),-(CH ₂ ) _n P (R ⁵ ) (OR _⁶ ) (OR _⁷ ),-( CH ₂ ) _n P (= 0) R _⁵ R _⁶ ,-(CH ₂ ) _n P (= 0) (OR _⁵ ) (OR _⁶ ) and-(CH ₂ ) _n P (= 0) (R ⁵ ) ( OR ⁶ ) is selected from the group consisting of a polar functional group consisting of n is an integer of 0 to 10, and R ⁵ , R _⁶ , and R _⁷ are each independently hydrogen, straight or branched carbon atoms 1 to 20 Alkyl of the chain or alkenyl having 2 to 20 carbon atoms; Cycloalkyl having 5 to 12 carbon atoms which may be substituted or unsubstituted with a hydrocarbon having 1 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms, unsubstituted or substituted with hydrocarbons having 1 to 20 carbon atoms; Aralkyl having 7 to 15 carbon atoms, unsubstituted or substituted with hydrocarbons having 1 to 20 carbon atoms; Selected from the group consisting of alkynyl having 3 to 20 carbon atoms, When R ¹ , R ² , R ³ and R _⁴ are not hydrogen, halogen or a polar functional group, R ¹ and R ² or R ³ and R ⁴ may be connected to each other to form an alkylidene group having 1 to 10 carbon atoms. R ¹ or R ² may be linked to any one of R ³ and R ⁴ to form a saturated or unsaturated cyclic group having 4 to 12 carbon atoms or an aromatic cyclic compound having 6 to 17 carbon atoms. The method of claim 1, wherein the polymer concentration in the cyclic olefin polymer solution is 5 wt% to 80 wt%. The method for producing a cyclic olefin polymer according to claim 1, wherein the solvent used for preparing the polymer solution is selected from the group consisting of aromatic compounds, and mixtures thereof. The method of claim 1, wherein the diluting solvent is selected from the group consisting of ketones of Formula 2, mixtures thereof, and mixtures of ketones and non-solvents. (Formula 2)

(Wherein R ⁸ and R ⁹ are each independently hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms.) The method of claim 5, wherein the diluent solvent is selected from the group consisting of azeotropic mixtures of ketones and nonsolvents. The method of claim 1, wherein the dilution solvent is used in an amount of 30 wt% to 1000 wt% based on the amount of solvent used. The method for producing a cyclic olefin polymer according to claim 1, wherein the nonsolvent is selected from the group consisting of alkanes, ether compounds, and mixtures thereof. The method for preparing a cyclic olefin polymer according to claim 1, wherein the dropping rate of the non-solvent is 2000 kg / hr or less per total amount of polymer solution (kg). The method of claim 1, wherein the dropwise addition of the nonsolvent is 1 to 30 times the amount of the solvent in the polymer solution. The method of claim 1, wherein the temperature for performing step b) is -30 ° C to 150 ° C. The cyclic olefin polymer having a bulk density of 0.1 to 0.6 g / ml prepared by the method of any one of claims 1 to 11.

Images