KR20060105494A - Method of producing styrenic polymers using high speed catalytic dispersion technology - Google Patents

Abstract

An ethylene-based copolymer prepared using a supported hybrid metalloene catalyst is provided. The ethylene-based copolymer is prepared using a supported hybrid metalloene catalyst in which two different metalloene catalysts are supported on a support and has a bimodal or multimodal molecular weight distribution. Accordingly, the ethylene-based copolymer has superior processability, sanitation, and internal pressure creep resistance at high temperature. A supported hybrid metallocene catalyst used to prepare the ethylene-based copolymer is also provided.

Description

Method for producing styrenic polymers using a high speed catalytic dispersion method {Method of producing styrenic polymers using high speed catalytic dispersion technology}

1 is a schematic diagram of a method for producing a styrenic polymer using a high speed homogenization mixing apparatus and a reactor according to the present invention.

Figure 2 is a schematic diagram of a method for producing a styrenic polymer in series with a plurality of high speed homogenization mixing apparatus according to the present invention.

Figure 3 is a schematic diagram of a method for producing a styrene-based polymer using a plurality of high speed homogenization mixing apparatus and a reactor according to the present invention.

4 is a schematic diagram of a method for producing a styrene-based polymer in which a plurality of high speed homogenization mixing apparatuses according to the present invention are connected in parallel or in series.

<Explanation of symbols for the main parts of the drawings>

1. monomer 2. promoter mixture

3. 5. Homogenized Mixed Flow 4. Catalyst Mixture

6. Polymer a. c. Reactor

b, b1, b2, b3. High speed homogenization mixing device

The present invention relates to a process for producing a styrene-based polymer, and more particularly to a method for producing a styrene-based polymer having a high level of syndiotactic structure.

Generally, a styrene polymer having a syndiotactic structure is obtained by a polymerization reaction using a metallocene catalyst. This metallocene catalyst is activated with an alkylaluminum compound, in particular methylaluminoxane, and has a structure associated with a ligand composed of a cycloalkanedinyl group or a derivative thereof based on a Group 4 transition metal.

As is known, in order to prepare a styrenic polymer having a syndiotactic structure, it is necessary to overcome the gel phenomenon generated during the polymerization of the styrene monomer. In this regard, U. S. Patent No. 5,037, 907 discloses a vertical tank reactor equipped with a stirrer in the form of scraping an inner wall, and a method for producing a styrene polymer using the reactor.

The reactor of the preceding patent claims that as a polymerization medium, a large amount of polymer particles are dispersed in the monomer liquid phase to induce polymerization at the particle surface, thereby theoretically preventing rapid formation of polymer masses, but in reality, large particles or masses in a low conversion region The formation of agglomerates does not prevent the formation of lumps and tends to be noticeable when the polymer is not sufficiently stirred.

U. S. Patent No. 5,254, 647 also discloses a washed surface reactor as a reaction device for producing styrenic polymers. The reactor uses two pairs of screws to smoothly mix the monomers, avoiding the formation of agglomerates in the low conversion region where particles begin to form rapidly, and transferring the styrene-based polymer back to the powder bed reactor You can get a conversion rate.

Therefore, the prior patent has the advantage of obtaining a relatively uniform product in spite of the low mixing efficiency of the powder bed reactor, this type of reactor despite the advantage of suppressing the rapid polymerization reaction to facilitate the operation of the reactor Due to the structure of the paddle provided inside the cylinder is limited in its rotation it is difficult to give a sufficient reaction residence time to the reactant introduced into the cylinder, and the use of screws to limit the processing capacity and increase the manufacturing cost have.

In addition, US Pat. No. 5,484,862 discloses an improved liquid powder bed type reactor in relation to the preparation of styrene polymer, and US Pat. No. 6,242,542 discloses a reaction apparatus in which a reverse mixing reactor is connected in series or in parallel.

However, the conventional method for producing a styrene-based polymer having a syndiotactic conformation generates large particles of 2 mm or more due to the gel phenomenon generated during the polymerization process, and is attached to the reactor inner wall or the stirrer in large lumps. The reaction also provides a cause for making stirring difficult.

Therefore, the above-mentioned prior patents substantially lower the polymerization productivity due to relatively excessive device cost in manufacturing the styrene-based polymer, and there is a concern that the physical properties of the product may be reduced by not preventing the generation of the gel.

Therefore, the present invention is to solve the above problems, the first technical problem of the present invention is to fundamentally prevent the gel phenomenon occurring during the production of syndiotactic styrene-based polymers, high activity and excellent stereoregularity and uniform molecular weight distribution It is to provide a method for producing a styrene polymer having.

The second technical problem of the present invention is to provide a styrene-based polymer prepared using the above method.

In order to achieve the first task,

The present invention provides a high-speed homogenizing and mixing apparatus for a styrene-based monomer, a cocatalyst mixture comprising an organometallic compound containing a Group 13 metal and an inert organic solvent, and a catalyst mixture comprising a metallocene catalyst and an inert organic solvent. Finely homogenizing using; And

It provides a method for producing a styrene-based polymer comprising supplying the homogenized mixture to the reactor to initiate the polymerization.

In order to achieve the second task,

The present invention provides a styrene-based polymer prepared using the above method.

The above and other objects of the present invention can be achieved by the present invention described below. Hereinafter, the content of the present invention will be described in detail.

In order to prepare the syndiotactic styrene-based polymer, it is necessary to fundamentally block the gel phenomenon occurring between 10 to 20% of the conversion rate. It was found that the dispersion should be dispersed in a completely homogeneous state to initiate the polymerization. Otherwise, as the polymerization proceeds rapidly, the viscosity of the monomers increases in a short time, which makes the dispersion of the catalyst more difficult and the polymerization starts from each of the locally heterogeneously dispersed catalysts, and the gel forms and eventually clusters as a whole. The phenomenon of hardening into one mass occurs. Therefore, through the identification of the cause of the gel phenomenon, the present invention has proposed a method for producing a high quality syndiotactic styrene polymer having a fundamental block of the gel production and excellent particle distribution through this.

Accordingly, the system for preparing a polymer according to the present invention is provided with a homogenizing mixing device and a homogenized mixture from which a monomer, a promoter, a catalyst and the like for producing a polymer are uniformly mixed within a short time to produce a powder of the polymer. It includes a reactor.

In the present invention, in order to homogenize the monomer, the promoter and the catalyst mixture at high speed

A T25 series batch high speed homogenizing mixer (S25KV-25F, IKA) and a T50 series batch high speed homogenizing mixer (S50KV-50F, IKA) were used. In addition, the T25 series continuous high speed homogenization mixing unit (S25KV-F-IL, IKA) was applied to continuously homogenize the monomer / catalyst mixture and the catalyst mixture. These high speed homogenizing mixing apparatuses can be easily purchased on the market, and the type and structure of the high speed homogenizing mixing apparatus for this does not limit the content of the present invention.

In addition, in the present invention, a styrene-based polymer may be manufactured using a plurality of high speed homogenization mixing apparatuses, and according to the connection method, the homogenization step of the present invention may include

Homogenizing the styrenic monomer and the promoter mixture in the first high speed homogenization mixing apparatus, and then homogenizing the catalyst mixture in the second high speed homogenizing mixing apparatus, or the styrene monomer and the promoter mixture, and the styrene monomer and the catalyst mixture, respectively. It is also possible to independently homogenize in the first high speed homogenization mixing apparatus and then homogenize the homogenized mixture together in the second high speed homogenization mixing apparatus.

The rotational speed of the high speed homogenization mixing device is preferably 10 to 100,000 rpm, more preferably 100 to 50000 rpm. If the rotational speed is less than 10 rpm, the degree of dispersion and mixing homogenization is insufficient to realize the effects of the present invention. There is a possibility of influence, which is not preferable. On the other hand, when the rotational speed is 100rpm to 100,000rpm it can also be selected and used according to the reaction conditions and scale. Especially in the case of 4000rpm to 50,000rpm, effective homogenization is possible.

The concept of dispersion and homogenization according to the present invention is similar to the conventional premixing in that it promotes the reaction by increasing the degree of dispersion between the monomer and the catalyst, but reacts by finely dispersing the catalyst on the monomer in a short time by a high speed homogenizer. It differs from conventional general premixing in that it is performed. Premixing is generally used to slow the mixing of reactants for a long period of time in mild conditions to make them well mixed beforehand. However, in the case of the styrenic polymer of the present invention, if the catalyst is not dispersed finely in a short time by a high-speed homogenization device immediately before the polymerization is started, the catalyst cannot be uniformly mixed and dispersed in the monomer, resulting in uneven concentration gradient. The rapid formation of the polymer by the catalyst and the further promotion of the mutual coagulation between the gel particles result in the solidification of the entire reactant, making further polymerization impossible. On the other hand, if the dispersion and input is not made in a short time and a considerable time is required in the dispersion process, the polymerization may proceed in the mixing process itself, thereby clogging the homogenizer and the input of the reactant. In addition, due to the difference in the polymerization reaction rate between the monomer-catalyst mixture introduced at the beginning of the dispersion and the monomer-catalyst mixture introduced at the late stage of dispersion, the gel first generated in the initially added mixture acts as a gel seed, which also causes agglomeration between the gel particles. Since the whole can be solidified into a single gel mass, it is different from the conventional general premixing in that monomer-catalyst mixed dispersion at high speed is essential for polymerization.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific embodiments of the present invention, in which the homogenization method is changed, will be described with reference to the accompanying drawings.

1 is a homogenized rapidly by supplying monomer (1), cocatalyst mixture (2) and catalyst mixture (4) to a well stirred reactor (b) to which a high speed homogenization mixing apparatus (S25KV-25F-IL, IKA) is attached. Here, a method of producing a syndiotactic styrene-based polymer by feeding the reactor (c) connected in series is shown.

FIG. 2 shows a second homogenization mixing unit (1) and cocatalyst mixture (2) homogenized in a first high speed homogenization mixing unit (b1) and this homogenized mixing flow (3) connected in series with the catalyst mixture (4) The process for producing a syndiotactic styrene-based polymer is shown by homogenizing in b2) and also feeding the finally homogenized mixing flow 5 to a reactor connected in series as well.

FIG. 3 shows homogenization of the monomer (1) and the promoter mixture (2) and the monomer (1) and catalyst mixture (4) mixed through a well stirred reactor (a) using a homogenization mixing device (b). A method of producing a syndiotactic styrene polymer by supplying a homogenized mixing flow 5 to the reactor c is shown.

4 can efficiently produce a styrenic polymer by connecting a plurality of high speed homogenization mixing apparatuses b1, b2, b3 in series or in parallel instead of a well stirred reactor (a).

The reactor in the present invention is designed to maintain high-shear in order to maximize the suppression of the particles from agglomerating with each other as the homogenized monomers grow into polymers.

The reactor has an inner space and a main body having an inlet through which the mixture is introduced and an outlet through which the reaction product is discharged, a stirrer installed inside the main body and connected to the main body to agitate the mixture, and is disposed outside the main body. It comprises a temperature control unit for controlling the reaction temperature by circulating the heat medium oil and the refrigerant oil. At this time, the stirrer was a well-stirred vertical tank type reactor equipped with anchor blades, which eliminated the central axis, thereby preventing the polymer from adhering to the stirrer due to a decrease in the linear velocity during stirring. It also prevents the reactants from adhering to the reactor inner wall by minimizing the gap between the stirring vanes and the reactor inner wall. In addition, by circulating the fruit oil and the refrigerant oil to the stirring blade it is possible to further reduce the adhesion of the polymer to the stirrer.

The invention can be described in detail with reference to FIG. 1 as follows.

The purified styrene-based monomer may include a cocatalyst mixture including a cocatalyst of an organometallic compound including a Group 13 metal and an inert organic solvent, a catalyst mixture comprising a metallocene catalyst and an inert organic solvent, and a high speed homogenization mixing device. It is finely homogenized and used in the reactor.

Styrene-based monomers of the present invention is a substance having a structure of PhCH = CH ₂ , Ph is hydrogen; halogen; Or a phenyl group having one or two or more substituents including at least one carbon, oxygen, phosphorus, sulfur, tin.

Examples of the styrene monomer having the above structure include alkyl styrene, halogenated styrene, halogen substituted alkyl styrene, alkoxy styrene, vinyl biphenyl, vinyl phenyl naphthalene, vinyl phenylpyrene, vinyl phenyl anthracene, trialkyl silyl vinyl biphenyl, alkyl silyl styrene , Alkyl ester styrene, carboxymethyl styrene, vinyl benzene sulfonic acid ester, vinyl benzyl dialkoxy phosphite, p-divinylbenzene, divinylbenzene such as m-divinylbenzene, trivinylbenzene, and aryl styrene.

Examples of the alkyl styrene include styrene, methyl styrene, ethyl styrene, butyl styrene, p-methyl styrene, p-tertiary-butyl styrene, dimethyl styrene, and cyclohexyl styrene. Halogenated styrene includes fluoro styrene and chloro styrene. And bromostyrene, and halogen-substituted alkyl styrene include chloromethyl styrene and bromoethyl styrene. Examples of alkoxy styrene include methoxy styrene, ethoxy styrene and butoxy styrene. 4-vinyl biphenyl, 3-vinyl biphenyl, and the like, and examples of vinylphenylnaphthalene include 1- (4-vinylbiphenylnaphthalene), 2- (4-vinylbiphenylnaphthalene), and 1- (3-vinylbiphenyl). Naphthalene), 1- (2-vinylbiphenylnaphthalene), and the like, and vinylphenylpyrene includes 1- (4-vinylphenyl) pyrene, 2- (4-vinylphenyl) pyrene, and the like. 1- (4-vinylphenyl) anthracene, 2- (4-vinylphenyl) anthracene, etc. Examples of the trialkylsilyl vinyl biphenyl include 4-vinyl-4-trimethylsilylbiphenyl, and the like, and alkyl silyl styrene include o-trimethylsilyl styrene, m-triethylsilyl styrene, and p-triethyl silyl styrene. There is this.

And the metallocene catalyst is for the production of styrenic polymers having a high syndiotactic steric structure, if known previously is not limited to use.

Generally, the metallocene catalyst is a combination of a ligand selected from the group consisting of i) a Group 4 transition metal compound and ii) one or two cycloalkyldienyl groups, and derivatives thereof. Group 4 metal compounds on the periodic table include titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta) compounds and the like, and particularly titanium-based compounds. . Examples of the metallocene catalyst used in the present invention include pentamethylcyclopentadienyl titanium trimethoxide, pentamethylcyclopentadienyl titanium trichloride, and the like.

The metallocene catalyst is preferably included in 0.00001 to 0.1 mol%, more preferably 0.00005 to 0.02 mol% based on the styrene monomer. If the content is less than 0.00005% by weight, the polymerization activity is significantly lowered, so there is a problem in economic efficiency in the separation and purification of the product. If the content is larger than 0.02 mol%, the molecular weight is lowered and the polymerization is easy due to severe heat generation during the polymerization. It is not desirable because there is a problem that does not.

In the present invention, the metallocene catalyst is preferably used with a cocatalyst, and the cocatalyst may be selected from one group from the group consisting of an alkylaluminoxane, an alkylaluminum compound, and a borate compound as the organometallic compound.

The alkylaluminoxanes include modified methylaluminoxanes (MMAOs) having improved stability by adding methylaluminoxanes (MAO) and alkylaluminum compounds, and trimethylaluminum and triethyl as alkylaluminum compounds. Aluminum, dimethylaluminum chloride, diethylaluminum chloride, triisobutylaluminum, tri (n-butyl) aluminum, tri (m-propyl) aluminum and triisopropylaluminum, and are mainly triisobutylaluminum (TIBAL). This is used. Examples of the borate compounds include borane, triphenylcarbonium tetra (pentafluorophenyl) borate, o-cyano-N-methylpyridium tetra (pentafluorophenyl) borate, tri (pentafluorophenyl) boron, 1,1-dimethylferrocenium-tetra (pentafluorophenyl) borate, benzyldimethylferrocenium tetra (pentafluorophenyl) borate, and the like.

And the amount of the promoter is preferably 1 to 2,000 moles, more preferably 10 to 1,000 moles with respect to 1 mole of the metal contained in the metallocene catalyst based on the metal contained in the promoter. If the amount is less than 1 mole, the absolute amount of the promoter is insufficient, so that the metallocene catalyst is difficult to be activated. If the amount is greater than 2,000 moles, the excess of the promoter remains after the catalyst activation. It is difficult to control and it is not preferable because there is a problem that the average molecular weight of the polymer is reduced.

The metallocene catalyst and the cocatalyst are applied to a polymerization reaction as a mixture with an inert organic solvent, wherein the inert organic solvent is pentane, hexane, cyclohexane, heptane, octane, nonane, decane, benzene, pentafluorobenzene, or toluene Etc. can be used.

At this time, the concentration of the catalyst mixture is preferably 0.00001 to 1.0 M, more preferably 0.0001 to 0.1 M.

If the concentration is less than the concentration range, the amount of the inert organic solvent used is increased so that the polymerization effect is reduced. If the concentration is large, the amount of the catalyst mixture to be added is too small compared to the monomer, which is not preferable because it is difficult to maintain a uniform charging ratio. .

The reaction is preferably carried out at a reaction temperature of 0 to 120 ℃, more preferably at a reaction temperature of 30 to 100 ℃. If the reaction temperature is less than 0 ° C, the reactivity is low or the conversion is low, and if the reaction temperature is greater than 120 ° C it is not preferable because the thermal degradation rate of the monomer increases along with the deactivation of the catalyst.

In addition, the reaction time is preferably 10 minutes to 600 minutes, more preferably 30 minutes to 300 minutes.

The styrenic polymer having the syndiotactic stereostructure thus obtained has a polymerization conversion of 10 to 100%, more preferably 30 to 90%, and a weight average molecular weight of 1,000 to 2,000,000, more preferably 10,000 to It has a weight average molecular weight in the range of 1,000,000. C ¹³ NMR analysis showed at least 75% syndiotactic stereoregularity, and more preferably at least 90% syndiotactic stereoregularity.

Example

Example 1

5L vertical tank reactor equipped with a high speed homogenization mixing device (S25 KV-25F, IKA) and 20L vertical tank reactor equipped with an anchor stirrer were connected in series to set the internal temperature of the two reactors to 75 ° C. The inside of the reactor was cleaned by vacuum overnight. Afterwards, the inside of the reactor was purged using high-purity argon gas three times, and 37.5 ml of 1.0 M triisobutylaluminum toluene solution (Aldrich) and toluene solution of 4.68 wt% aluminum in 4,000 ml of purified styrene monomer (4. Albermarl) 49.2 ml were added sequentially and stirred, and after 15 minutes, 37.5 ml of 0.005 M pentamethylcyclopentadienyltitanium trimethoxide (Cp * Ti (OME) ₃ ) toluene solution was added and high speed homogenization was performed. After the device was operated at 24,000 rpm for 1 minute to complete stirring, the reaction was initiated by opening the lower valve to immediately transfer to the 20 L reactor and maintaining the rotation speed of the stirring blade at 80 rpm.

After 1 hour, the reaction was terminated and vacuum was applied to the reactor to completely recover the unreacted monomer, and the valve was opened to obtain a fine powdery polymer. Polymers that were not recovered and adhered to the reactor inner wall and agitator were not negligible. The obtained polymerization product was sufficiently washed with a large amount of methanol containing a small amount of hydrochloric acid, dried in a vacuum oven and quantified to obtain 2180 g of a powder product, which showed a conversion rate of 60.4%. The weight average molecular weight of this polymerization product was 398,000 and the molecular weight distribution was 2.81, and the NMR analysis showed syndiotactic stereoregularity of 93% or more.

Example 2

The stirring rotation speed of the high speed homogenization mixing apparatus was maintained at 11,000 rpm, and the conditions other than that were the same as that of Example 1. After the completion of the reaction, washing, drying and quantification resulted in 2102 g of a powder product, which showed a conversion rate of 58.2%. The polymers that were not attached to the reactor inner wall and the stirrer were also negligible. The weight average molecular weight of the polymerization product was 405,000, the molecular weight distribution was 2.74, and also showed syndiotactic stereoregularity of 93% or more.

Example 3

The high speed homogenization mixing apparatus was replaced with a slightly larger S50 KV-50F, and the stirring speed was maintained at 11,000 rpm for 1 minute, and the other conditions were the same as in Example 1. After the completion of the reaction, washing, drying and quantification resulted in 2230 g of a powder product, which showed a conversion rate of 61.7%. There was no polymer which was not discharged due to the inside wall of the reactor and the stirrer. The weight average molecular weight of the polymerization product was 379,000 and the molecular weight distribution was 2.83 and showed syndiotactic stereoregularity of 93% or more.

Example 4

Under the same conditions as in Example 3, the stirring speed of the high speed homogenization mixing apparatus was maintained at 4,000 rpm for 1 minute, and the other conditions were the same as in Example 1. After the completion of the reaction, washing, drying and quantification resulted in 2213 g of a powder product, which showed a conversion rate of 61.3%. The weight average molecular weight of the polymerization product was 381,000 and the molecular weight distribution was 2.57 and likewise showed syndiotactic stereoregularity of at least 93%.

Example 5

A high-speed homogenizing mixing device S25 KV-F-IL operating continuously instead of a 5L reactor was installed at the front of the 20L reactor. 37.5 ml of 1.0 M triisobutylaluminum toluene solution (Aldrich) and 49.2 ml of methyl aluminoxane toluene solution (Albermarl) of 4.68 wt% aluminum were sequentially added to 4,000 ml of purified styrene monomer. And a homogenizer at a flow rate of 817.0 ml / min and 7.5 ml / min, respectively, using a pump of 37.5 ml of pentamethylcyclopentadienyltitanium trimethoxide (Cp * Ti (OME) ₃ ) toluene solution of 0.005M Are continuously added. At this time, the stirring speed of the high speed homogenizer is 24,000 rpm, and the stirring time is very short because the reactant is continuously introduced and passes through the homogenizing device, and it is usually passed at a speed of about 5 L to 10 L per minute. The homogenized monomer / cocatalyst / catalyst mixture discharged simultaneously from the high speed homogenizer was received in a 20L reactor and the rotation speed of the stirring blade was maintained at 80 rpm and the reaction was started. After the reaction was conducted for 1 hour, the reactor was vacuumed to completely recover the unreacted monomer, and the valve was opened to obtain a fine powdery polymer. There was no polymer that was not recovered and adhered to the reactor inner wall and agitator. The obtained polymerization product was sufficiently washed with a large amount of methanol containing a small amount of hydrochloric acid, dried in a vacuum oven and quantified to obtain 2300 g of a powder product, which showed a conversion rate of 63.7%. The weight average molecular weight of this polymerization product was 367,000 and the molecular weight distribution was 2.65 and NMR analysis showed more than 93% syndiotactic stereoregularity.

Comparative example

The monomer / catalyst mixture and the catalyst mixture were stirred at a high speed of 1,200 rpm for 2 minutes using a reactor equipped with a magnetic drive stirrer with a 45 degree pitch blade instead of the high speed homogenization mixing apparatus, and the other conditions were the same as in Example 1. After completion of the reaction, washing, drying and quantification resulted in the removal of 1,571 g of powder product, the polymer inside the reactor and the agitator, which was not discharged, and quantified by 233 g. Thus, the total reaction conversion was 50.0% at 1,804 g. The product recovery rate of the reactor was 87%, a clear difference from 100% of the above examples using a high speed homogenizer. The weight average molecular weight of the polymerization product was 388,000 and the molecular weight distribution showed 2.52 and greater than 93% syndiotactic stereoregularity.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention and the accompanying drawings. Naturally, it belongs to

According to the present invention, by dispersing the catalyst in the monomer at high speed by using a high speed homogenization mixing device, it is possible to fundamentally prevent the gel phenomenon generated in syndiotactic styrene polymer production, and to have styrene having high activity and excellent stereoregularity and uniform molecular weight distribution. System-based polymers can be provided.

Claims (21)

Styrene monomers; A promoter mixture comprising a promoter of an organometallic compound comprising a Group 13 metal and an inert organic solvent; And finely homogenizing the catalyst mixture including the metallocene catalyst and the inert organic solvent using a high speed homogenization mixing apparatus; And Supplying the homogenized mixture to a reactor to initiate polymerization. The method of claim 1, wherein the styrene monomer is alkyl styrene, halogenated styrene, halogen-substituted alkyl styrene, alkoxy styrene, vinyl biphenyl, vinyl phenyl naphthalene, vinyl phenylpyrene, vinyl phenyl anthracene, trialkyl silyl vinyl biphenyl, alkylsilyl Preparation of a styrene polymer characterized in that at least one selected from the group consisting of styrene, carboxymethyl styrene, alkyl ester styrene, vinyl benzene sulfonic acid ester, vinyl benzyl dialkoxy phosphide, divinyl benzene, trivinyl benzene and aryl styrene Way. The method of claim 1 wherein the metallocene catalyst i) a Group 4 transition metal compound and ii) A method for producing a styrene polymer, characterized in that a combination of one or two cycloalkyldienyl groups, and a ligand selected from the group consisting of derivatives thereof. The method of claim 1, wherein the metallocene catalyst is included in an amount of 0.00005 to 0.02 mol% based on the styrene monomer. The method according to claim 1, wherein the promoter is at least one selected from the group consisting of alkylaluminoxanes, alkylaluminum compounds and borate compounds. The method of claim 5, wherein the alkylaluminoxane is methylaluminoxane (MAO) or modified methylaluminoxane (MMAO). 6. The compound of claim 5, wherein the alkylaluminum compound is trimethylaluminum, triethylaluminum, dimethylaluminum chloride, diethylaluminum chloride, triisobutylaluminum, tri (n-butyl) aluminum, tri (n-propyl) aluminum, and tri Method for producing a styrene-based polymer, characterized in that selected from the group consisting of isopropyl aluminum. The method of claim 5, wherein the borate compound is borane, triphenylcarbonium tetra (pentafluorophenyl) borate, o-cyano-N-methylpyridium tetra (pentafluorophenyl) borate, tri (pentafluoro Rophenyl) boron, 1,1-dimethylferrocenium-tetra (pentafluorophenyl) borate, and benzyldimethylferrocenium tetra (pentafluorophenyl) borate. Method for producing a styrenic polymer. The method for producing a styrene polymer according to claim 1, wherein the metal contained in the promoter is 10 to 1,000 moles with respect to 1 mole of the metal contained in the metallocene catalyst. The styrene system according to claim 1, wherein the inert organic solvent is selected from the group consisting of pentane, hexane, cyclohexane, heptane, octane, nonane, decane, benzene, pentafluorobenzene, and toluene. Method of Making Polymers. The method of claim 1, wherein the concentration of the catalyst mixture in an inert organic solvent is 0.0001 to 0.1 M method of producing a styrenic polymer. The method for producing a styrene polymer according to claim 1, wherein the polymerization is carried out at a temperature of 0 to 120 ° C. The method of claim 1, wherein the homogenizing step comprises homogenizing the styrene monomer and the promoter mixture in a first high speed homogenization device and then in a second high speed homogenization device with the catalyst mixture. 2. The homogenizing step of claim 1, wherein the homogenizing comprises homogenizing the styrenic monomer and the promoter mixture, and the styrene based monomer and the catalyst mixture, respectively, independently in a first high speed homogenizer, and then combining the homogenized mixture together in a second high speed homogenizer. A method for producing a styrene polymer, characterized in that homogenization. The method for producing a styrene polymer according to claim 1, wherein the high speed homogenization mixing device has a rotation speed of 1,000 to 50,000 rpm. The apparatus of claim 1, further comprising: a main body having an inlet through which the mixture is introduced and an outlet through which the reaction product is discharged while the reactor has an internal space; A stirrer installed inside the main body to stir the mixture; And It is connected to the main body and includes a temperature control unit for controlling the reaction temperature by circulating the heat medium oil and the refrigerant oil to the outside of the main body, Anchor (anchor) wings are attached to the stirrer, the gap between the stirring blade and the inner wall of the reactor is minimized, and the styrene-based polymer production method characterized in that the fruit oil and refrigerant oil is circulated to the stirring blade. The method of claim 1, wherein the reactor is a powder bed reactor. The method of claim 1, wherein the high speed homogenizing device has a rotation speed of 10 to 100,000 rpm. The method for producing a styrene-based polymer according to claim 1, wherein the high speed homogenizing device has a rotation speed of 100 to 50,000 rpm. Styrene-based polymer prepared using the method of any one of claims 1 to 19. 21. The styrene-based polymer of claim 20, wherein the styrene-based polymer has a polymerization conversion of 30 to 90% and a syndiotactic stereoregularity of at least 75%.

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