TWI327575B - Method of producing styrene 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

(3) / 575 19721 pj f IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to the preparation of a styrene polymer: the present invention relates to the preparation of a stupid [previous technique] with high syndiotacticity . The ruthenium polymerization reaction causes the ruthenium metal catalyst to prepare a benzene bismuth catalyzed by a olefinic compound such as methylaluminoxane. The Group 4 transition metal prepared by the combination of 匕3 with the mother alkadienyl group or a derivative thereof is accompanied by gelation, and because: the bee is prevented from growing into a whole gel, It is well known in the art. For example, U.S. Patent No. 5, No. 37,9,7, discloses a vertical trough type reactor including a mixer for scraping the reaction into an inner wall and a method for preparing a styrene polymer using the reactor. According to U.S. Patent No. 5,037,907, by using a reactor as a polymerization medium, a large amount of poly-containing particles are dispersed in a liquid monomer to induce polymerization on the surface of the particles, and thus it is theoretically possible to prevent rapid formation of polymer blocks. However, it is not possible to prevent the formation of such large particles or blocks in a low conversion region. Especially when the polymer is not sufficiently mixed, the polymer is more likely to agglomerate. A scraped surface reactor for preparing a styrene polymer is disclosed in U.S. Patent No. 5,254,647. The scraped surface reactor uses two pairs of conventional propellers to mix the monomers to prevent agglomeration at low conversion ranges where the particle growth begins to rapidly. The stirred styrene polymer was then transferred to a powder bed type 1327575 19721pif reactor (powder bed type reactor). Therefore, a high conversion ratio can be obtained. Although the powder bed type reactor exhibits low mixing efficiency, a relatively uniform product can be obtained. Furthermore, by using a scraped surface reactor', rapid aggregation is prevented and thus it is possible to easily control the polymerization. However, the rotation of the reactor is limited according to the structure in which the reaction is 'circle; I: the paddle to be installed in the main body. Therefore, there is insufficient residence time for the reaction, and the reactant charged into the cylinder. In addition, the use of the propeller structure results in reduced processing capacity and increased manufacturing costs. No. Reverse mixing reactor. However, a conventional method of preparing a styrene polymer having a syndiotacticity is accompanied by a formation of 2 wins, and a large-sized one having a mean purity of 2 mm or more is attached to the reaction (4) by a method of (iv). It is difficult for the silk reactant to ride on the teeth and it is difficult to mix in the subsequent reaction. ^ Therefore, the preparation of styrene polymerization according to the above-mentioned patents takes eight expensive means' and thus the prepared styrene polymer has a low port productivity. In addition, there is a risk that the deterioration of gel properties cannot be prevented. SUMMARY OF THE INVENTION The present invention provides a method for preparing a phenethyl hydrazine polymer having high activity, high stereoregularity, and uniform molecular f distribution by preventing gelation occurring during polymerization. The invention also provides styrenic polymers prepared using the methods described. 1327575 )972lpif

According to one aspect of the invention, there is provided a method of preparing a stupid ethylene polymer. The method comprises: uniformly mixing styrene monomer (styie monomers), a supplement using a high speed homogenizing mixer A cocatalyst mixture and a catalyst mixture 'to obtain a well mixed and fine-homogenized mixture, wherein the secondary catalyst mixture comprises a Group 13 metal-containing An organometallic compound auxiliary catalyst and an inert organic solvent, and the catalyst, the θ character comprises a metallocene catalyst and the inert organic, six doses, and the homogenized mixture is further provided To the reactor to initiate polymerization. Another aspect of the invention is a styrene polymer. [Embodiment] It is provided by the method of preparation

The inventors of the present invention have found that in order to prepare a syndiotactic ethylene polymer, 'suppression should be substantially prevented from occurring when the conversion ratio is in the range of 10-20%, and this prevention can be corrected as in the catalyst activity. Initially obtained by completely homogenizing the mixture of the auxiliary catalyst medium. If the initial polymerization __, the mixture of the media is not completely homogenized, the viscosity of the monomer increases rapidly as the polymerization proceeds. Therefore, the catalyst is difficult to disperse and thus the locally non-uniform dispersed catalyst initiates polymerization and forms a gel. Eventually, the entire reaction product is condensed into a large gel. Thus, by discovering the cause of gel formation, the present invention = the inventors propose to prepare a method of syndiotactic styrene polymer having high quality and excellent molecular weight distribution, in which the gelation is prevented on the beauty 1327575 19721pif. For this purpose, a polymer polymerization system according to an embodiment of the present invention includes a homogenization mixer for forming a homogenized monomer, a secondary catalyst and a catalyst for forming a polymer in a short time, and a homogenization mixture thereof A reactor formed from a polymer powder.

According to an embodiment of the present invention, the T25 series batch high-speed homogenizing mixer (S25KV-25F, IKA) and the T50 series batch type high-speed homogenizing mixer (S50KV-50F, IKA) are used to transfer the monomer and the auxiliary at a high speed. The mixture of catalyst and catalyst is homogenized. In addition, the T25 series continuous high-speed homogenization mixer (S25KV-F-IL, IKA) was used to continuously homogenize the mixture of monomer and auxiliary catalyst and the catalyst mixture. These high speed homogenizing mixers are commercially available, and their types and structures are not limited to the present invention. According to one embodiment of the invention, a styrene polymer is prepared using a plurality of high speed homogenization mixers. Various methods can be used depending on the type of connection of the high speed homogenizing mixer. For example, the styrene monomer and the auxiliary catalyst mixture are homogenized using a first high speed homogenization mixer, and then the homogenized product and the catalyst mixture are homogenized using a second high speed homogenization mixer. Alternatively, the styrene monomer and the auxiliary catalyst mixture are homogenized using a pair of first high speed homogenization mixers to form a first homogenized product and homogenize the styrene monomer and the catalyst mixture to form a second homogenized product. And then homogenizing the first and second homogenized products using a second high speed homogenization mixer. The rotational speed of the high speed homogenizing mixer can be in the range of 0-]00,000 revolutions per minute (rpm), for example 100-50,000 rpm. When high-speed homogenization is mixed with /575 l972|pif ^ ^, the rotation speed is lower than 】Q rpm, the dispersion and mixture homogenization are not suitable: only present! The effect of the Ming. On the other hand, when the high speed homogenization mixer has a rotation speed equal to 1 Torr, 〇〇〇 rpm, excessive dispersion and homogenization of the mixture are obtained, which can affect the mechanical components of the mixer. When the rotational speed of the high-speed homogenization mixer reaches 100 φηΜ〇〇, 〇〇〇 rpm, the appropriate speed of the mixer may be selected according to the conditions and scale of the combination. Effective homogenization is achieved especially when the high-speed baton mixing is performed at a rotational speed of 4000 _5 〇〇. (V) Dispersion and homogenization according to the present invention are similar to conventional premixing because the reaction is promoted by increasing the degree of dispersion between the monomer and the catalyst. However, the dispersion and homogenization according to the present invention are different from the conventional premixing, and the catalyst is uniformly dispersed in the early body for polymerization in a short time using an idling homogenization mixer. In general, premixing means that the reactants are mixed under moderate conditions and slowly mixed for two long days to prepare a mixture for thorough mixing of the reaction. However, as in the case of styrene-butadiene conjugates, if the catalyst starts to polymerize Φ, the catalyst is not uniformly dispersed in a short time using a high-speed homogenizer, and the shell j-angle*] Mix evenly and disperse in it. Therefore, the catalyst has a non-uniform concentration level, and thus gelation of the polymer starts rapidly and further promotes internal polymerization between the gel particles. Therefore, all of the reactants condense into one piece and polymerization cannot proceed. Furthermore, when the dispersion and loading are carried out slowly, the polymerization can be carried out during the mixing, and thus the homogenization mixer and the reactant inlet can be clogged. In addition, the gel formed from the initial mixture used as a gel species due to the difference in the polymerization rate of the monomer used in the initial dispersion, the monomer mixture and the monomer-catalyst mixture used in the later dispersion, 1327575 Cohesion of 19721pif gel particles. Therefore, all of the reactants can also coagulate into a gel block. Due to these problems, rapid mixing and dispersion of the monomer and the catalyst are necessary for the polymerization, which is the difference when compared with the conventional premixing. The McCorm's drawing will now describe a homogenization process for a poor embodiment according to the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a process for preparing a syndiotactic styrene polymer according to an embodiment of the present invention, wherein a mixture of monomer 1 and auxiliary catalyst mixture 2 and catalyst mixture 4 is loaded with a high-speed homogenization mixer (S25KV- The reactor of 25F-IL, IKA) was rapidly homogenized and the homogenized product was charged to reactor c connected in series with the reactor & 2 is a process for preparing a syndiotactic styrene polymer according to another embodiment of the present invention, wherein the monomer 1 and the auxiliary catalyst mixture 2 are homogenized using a first high-speed homogenization mixer W, using a second high-speed homogenization The mixer W homogenizes the resulting homogenized mixture fluid 3 and the catalyst mixture 4, and loads the final homogenization mixture fluid 5 into the reactor c in series. 3 is a view illustrating a method of preparing a syndiotactic styrene polymer according to another embodiment of the present invention, in which a mixture of a monomer prepared using a reactor and a secondary catalyst mixture 2 is used and used using a homogenization mixer 6. The mixture of monomer 1 and catalyst mixture 4 prepared in reactor β was homogenized, and the resulting homogenized mixed fluid 5 was charged into reactor c. Figure 4 is a view illustrating a method of preparing a syndiotactic styrene polymer in accordance with another embodiment of the present invention, in which a plurality of high-speed homomixers 6 connected in parallel and in series are used, and a reactor α is replaced. According to an embodiment of the invention, the reactor is constructed such that high shear properties

10 1327575 19721ρίΓ is reserved to prevent particle cohesion when the homogenized monomer is grown into a polymer. The reactor includes: a body having an internal space including an inlet for the homogenization mixture input; and an outlet from which the reaction product is taken out; a mixer (4) (10).) installed in the main body to neutralize the mixture with the mixture; and Connected to the temperature control unit with a 0_j reaction temperature by circulating heating or cooling oil plus QHefrjge]. Mixer: There is an anchor mixer connection and the spacing between the slaves in the reactor is minimized and the heating or cooling oil is circulated along the anchor. The mixer is a vertical tank type reactor - t ^ (anch〇r blade) ^ii and removes its central axis to prevent the polymer from adhering to the mixer due to a decrease in line speed during mixing. . In addition, the mixing "(the distance between the inner walls of the mixing semi-reactor is reduced as much as possible to the minimum appendage so that the polymerization can be additionally prevented). The oil will be described along the mixing blade. The invention will be described in detail with reference to Figure 1. The chemical mixer uniformly mixes and refines the organometallic compound of the Group 3 metal, the auxiliary catalyst mixture of the agent and the metallocene catalyst and the inert organic medium, and the homogeneous mixture The product is charged with a rhodium sigma styrene monomer represented by PhCH=CH2, wherein the quinone-substituted phenyl group has 4 atoms which are selected from the group consisting of c, 0, p, s and sn. Examples of benzoic monomers include succinyl ether (called y kiss t ene), halogemzed styrene, halogen-substituted alkyl stupid ethylene 1327575 I972lpif (halogen-substituted alkyJslylene) ), a丨koxystyrene, vinylbiphenyl, vinylphenyl naphthalene, vinylphenypyrene, ethylene phenyl蒽(vinylphenylanthracene), three: ): Teralkylsilylvinylbiphenyl, ;): alkylsilylstyrene, alkylesterstyrene,

Carboxymethylstyrene, vinylbenzene sulfonic acid ester, vinylbenzyl dichloride;): vinylbenzyl dialkoxyphosphate, such as p-diethylene Diphenylbenzene, trivinylbenzene, and styrene, and the like, and bis-phenylene benzene. Examples of the styrene styrene include stylene, methylstylene, ethylstylene 'butylstylene', and p-methylstylene. ), p-tertiary-butylstylene, dimethyl stylene, cyclohexylstylene and the like. Examples of the halogenated styrene include fluorostylene, chlorostylene, 'bromostylene, and the like. Examples of the halogenated substituted alkylstyrene include chloromethyl stylene, bromoethylstyjene, and the like. Examples of the alkoxystyrene include methoxystylene, etoxystylene, butoxystylene, and the like. Examples of the vinylbiphenyl include 12 1327575 1972 ] pif 4-vinyl diphenyl, 3-vinylbiphenyl, and the like. Examples of the vinyl phenylnaphthalene include: 1-(4-vinylbiphenyl naphthalene), 2-(4-ethylenebiphenylnaphthalene) (2-(4-vinylbiplienyl) (2-(4-vinylbiplienyl)) Naphthalene)), 1-(3-vinylbiphenyl naphthalene), 1-(2-vinylbiphenyl naphthalene) and its Examples of the vinyl stupid base include 1-(4-vinylphenyl) fluorene (1-(4-vinylphenyl)pyrene), 2-(4-vinylphenyl)fluorene (2-(4) -vinylpheny])pyrene) and its analogs. Examples of vinylphenyl hydrazine include 1-(4-ethlylphenyl)anthracene (]-(4-vinylpheny丨)anthracene), 2-(4-ethylene 2-(4-vinylphenyl)anthracene and its analogs. Examples of trialkylsulfonylalkylbiphenyl include 4-vinyl-4-triterpene • sulphur-based biphenyl (4) -vinyl-4-trimethylsiIy丨biphenyl) and the like. Examples of alkyl fluorenyl alkyl styrene include o-tri methylsilylstylene, m-triethyl sulphate; Styrene (m-triethyl silylstylene) > triethyl stellate;): complete benzene acetonitrile p-t〗, iethy] silylstylene) and the like. Metallocene catalysts are used to prepare styrene polymers having a high degree of syndiotacticity and can be any metallocene catalyst well known in the art. In general, the metallocene catalyst is a bonding product of a Group 4 transition metal compound with a ligand selected from one or two cycloalkyldienyl groups and derivatives thereof. The Group 4 transition metal compound shown in the periodic table may be a compound of Ti, Zr, Hf, V, Nb or D, such as a Ti compound. In an embodiment of the invention

13 1327575 The metallocene catalyst for I9721pif may be pentamethylcyclopentadienyltitanium trimethoxide or pentamethylcyclopentadiadiyll (itanhimtrichloi.ide) or analog.

For the total amount of metallocene catalyst and styrene monomer, the amount of metallocene catalyst can range from 0.00005 to 0.02 mole percent. When the amount of the metallocene catalyst is less than 0.00005 mol%, the polymerization activity is substantially lowered, and thus the purified product is expensive. On the other hand, when the amount of the metallocene catalyst is less than 0.02 mol%, the molecular weight of the polymer is lowered, and it is difficult to control the polymerization due to a large amount of heat generated during the polymerization. The metallocene catalyst may be used in conjunction with an organic compound comprising at least one compound selected from the group consisting of alkylaluminoxane, alky[alumirmm compound, and borate compound. Use together with the media. The alkyl aluminoxane can be a modified MAO (MMAO) having a high stability comprising methylaluminoxane (MAO) and an alkyl iluene compound. Examples of the compound of the compound of the hospital include triterpene | Lu (1; 1, 丨 11161: 11) ^ 111111 丨 111_1111) 'Triethyl | Lu (1; Shi (:) 1} / 1 aluminum), diterpene Dimethylaluminium chloride, diethyl aluminium chloride, triisobutylahiminum (TIBAL), ti,j (n-butyl) aluminium, Tri(n-pmpyl) ahiminium and triisopropylaluminium and the like. For example, 14 1327575 19721pif alkyl aluminum compound is T]BAL. Borate compound Examples include borane, trjphenyl carboniumtetra(pentafluoiOphenyl)borate, ortho-cyano-N_ oxime ratio, and tetrakis(pentafluorophenyl)石-Cyano_N_methylpyi•丨diumtetra (pentafk丨〇r〇Phenyl) b〇rate), tris(pentafluorophenyl) shipen (td(pentaf丨·〇phenyDboron), 1,1-dimethyl Diferrocene·tetrakis(pentafluorophenyl)borate (], 1 - dime th y 1 fer r 〇ce nui m -1 etr a(pe nt afl u ο ό ph εη y 丨)b or ate) and > benzyldimethyl ierrocenium tetra(pentafluorophenyl)borate and its analogs. The amount of the auxiliary catalyst in the amount of the metal contained in the auxiliary catalyst may be in the range of 12, 〇〇〇mol, preferably lO-LOOO. The amount of auxiliary catalyst is lower than that of 丨莫耳. The absolute amount of the auxiliary catalyst is too low and therefore it is difficult to activate the catalyst. On the other hand, • when the amount of the auxiliary catalyst is more than 2,000 moles, even in the auxiliary touch Excessive auxiliary catalyst still exists after the catalyst participates in the activation of the catalyst, and thus it is difficult to control the polymerization rate in the preparation process of the polymer, and the average molecular weight of the polymer decreases. The transition has an apologetic mixture _ Μ Μ metal catalyst, Auxiliary catalysts. Examples of inactive organic solvents include hexahydrate, hexazone, cyclohexyl, heptyl, octyl, oxime, oxime, benzene, pentafluorobenzene, toluene, and the like. = The concentration of the media mixture can be in the range of Q Moss, and the car is good 0 '〇〇〇】_〇" Moer / liter. When the concentration of the oxime mixture is less than 0 0001 mol/liter, the relative amount of 'organic solvent used' increases, and thus the polymerization effect decreases. In addition, I327575 19721 pir - the concentration of the guest catalyst mixture is 0.] Moere / liter, the amount of catalyst mixture used is too small compared to the amount of monomer, and is unlikely to be a rounding ratio. The polymerization can be carried out at a temperature of 0 to 120 ° C, preferably 3 〇 1 〇〇. When the reaction temperature is lower than 〇 ° C, the reactivity is lowered or the conversion ratio is low. On the other hand, when the reaction temperature is still at 120 C, the activity of the catalyst decreases and more single-edge thermal reform.

The reaction time can be in the range of from 〇 minute to 600 minutes, preferably from minute to minute. The styrene polymer having a syndiotactic configuration prepared as described above has a polymerization conversion ratio of 10 to 100%, preferably 30 to 90%, and has a weight average molecular weight of 1,000 to 2,000,000, preferably 10,000. The result of the -l, 000, 00 〇 a C13 NMR analysis is that the stupid ethylene polymer has a stereoregularity of 75% or more, preferably 90% or more. The invention will be described in further detail with reference to the following examples. These examples are for illustrative purposes only and are not intended to limit the scope of the invention. EXAMPLES Example 1 A 5 liter vertical tank type reactor equipped with a high-speed homogenization mixer (S25 KV-25F, IKA) and a 2 liter liter vertical tank type reactor equipped with an anchor mixer were connected in series, and the inside of such reactors The temperature was set to 75 ° C and the reactors were evacuated overnight. The reactor was then purged 3 times with high purity argon. 37. 5 ml of 1.0 mol/liter of triisobutylaluminum bismuth benzene <972 ΐρίΓ solution (Alddch) and 49.2 ml of cerium-based aluminoxane solution (Albemmrl) containing 4 68 wt% of aluminum and 4 , 〇〇〇ml refined styrene monomer is mixed in sequence. 37 5 ml of 0.005 mol/L of pentamethylcyclopentadienyltitanium trioxide (Cp*Ti(0ME)3) ruthenium benzene solution with 24 liters using a high speed homogenization mixer Mix the mixture for a minute. Then, the lower end of the high-speed homogenization mixer was turned on, and the resulting mixture was quickly charged into a 20-liter reactor = then, the reaction was started while the rotational speed X of the mixing blade was maintained at 80 rpm. * The reaction was carried out for 1 hour' and the reactor was evacuated to completely collect unreacted monomers. The valve of the reactor was then opened to obtain a polymer powder. The amount of polymer that was not collected and attached to the inner walls of the reactor and mixer was negligible. The polymerized product was thoroughly washed with an excess of sterol containing a small amount of HCl: dried in an empty furnace f. The resulting product was quantified. As a result, the powder type polymerization yield was 2] 80 g (yield: 6 〇 4%). The polymerization product had a molecular weight distribution of 398, 〇〇〇 Ϊ: average molecular weight and a molecular weight distribution of 2.81, and the results of NMr analysis, and the polymerization product exhibited *93% or more. Example 2 Except for the south speed homogenization mixing, the rotation speed is n, and the second one is the same as the first example. Complete the test, add, dry and quantify the polymer. As a result, the amount of the polymerization product was found to be 21 〇 2 g (yield: plate recognition / enthalpy). The aggregates that are not collected and attached to the inner wall of the reactor and mixer are negligible. The polymerization product has a weight average of '4', a molecular distribution of 2.74, and a syndiotactic stereoregularity of 93% or 1327575, 19721 pif.

Except using a high-speed homogenization mixer (S50KV-50F) with a larger scale than S25 KV-25F instead of S25KV-25F, and the rotation speed of the high-speed homogenization mixer is 11,000 rpm, the experimental conditions and example 1 the same. After the reaction is completed, the strips are washed, dried and the polymerized product is quantified. As a result, the amount of the obtained polymerization product was 2230 g (yield: 61.7%). No polymer was found on the reactor and on the inner wall of the mixer. The polymerization product had a weight average molecular weight of 379,000, a molecular weight distribution of 2.83, and a syndiotactic stereoregularity of 93% or more. Example 4

The rotational speed of the high-speed homogenization mixer was maintained at 4,000 revolutions per minute for the same experimental conditions as in Example 3, and the other conditions were the same as in Example 1. After the reaction is completed, the product is washed, dried and quantified. As a result, the amount of the obtained polymerization product was 2213 g (yield: 61.3%). No polymer was found on the reactor and on the inner wall of the mixer. The polymerization product had a weight average molecular weight of 381,000, a molecular weight distribution of 2.57, and a syndiotactic stereoregularity of 93% or more. Example 5 A continuously operating high speed homogenization mixer S25 KV-F-IL was installed on the front end of a 20 liter reactor instead of a 5 liter reactor. 37.5 ml of 1.0 mol/L of triisobutylaluminum toluene solution (Aldrich) and 49.2 ml of a solution of 4.68 wt% of aluminum in a solution of cerium-based aluminoxane benzene (Albermarl) were sequentially added to 4,000 ml of refined styrene. The monomers are then thoroughly mixed to prepare a monomer/auxiliary catalyst mixture. Next, a pump was used to separate the mixture with a flow rate of 1327575 I972lpif 817.0 ml/min and a flow rate of 7·5 ml/min, and 37.5 ml of 0.005 mol/liter of a slightly τ丞ί-戌-titanium triterpene oxide ( Cp*Ti(OME)3) Benzene solution continuous loading homogenization mixer. At this time, the high speed homogenization mixer has a speed of 24,000 丨.pm. In addition, the mixing time is extremely short because the reactants are continuously charged and the enthalpy is "丨[, ‘, two speeds of the mixer”. In this experiment, reverse, in/out

The rate of 5 liters to 10 liters per minute flows through the high-speed homogenization mix and cry. At the same time, the homogenized monomer/auxiliary catalyst/touch 5 = compound discharged from the high-speed homogenization mixer was charged into a 20-liter reactor, and the reaction was started at the same time. At this time, the rotation speed of the mixed two = piece was maintained at 80 rpm. The reaction time was 1 hour. The second emptying reaction is used to completely collect the unreacted monomer and open the reactor to deplete the polymer powder. No sputum was found on the reactor and on the inner wall of the mixer. The resulting mixture was thoroughly washed with an excess of sterol containing a small amount of HCl and allowed to dry in a true furnace. Set the product to be paid. As a result, the amount of the powder polymerization product was 2,300 g (yield: 63.7%). The polymerization product had a molecular weight distribution of 3, 〇 = weight average molecular weight and 2.65. The result of the NMR analysis was that the polymerization product exhibited 93. /. Or larger syndiotactic stereo rules. A comparative example uses a reactor comprising a 45 FIG. pitch blade driven mixer rather than a high speed homogenizing mixer to provide monomer/auxiliary catalyst at 1,200 rpm. The test conditions were the same as in Example 1 except that the mixture and the catalyst mixture were mixed. After the reaction is completely carried out, the reaction product is washed, dried and quantified. As a result, the amount of the obtained polymer powder was,, 57 gram, and the residue attached to the inner wall of the reactor and the mixer was forcibly removed.

19 1327575 19721pif polymer. The amount of residual polymer removed was 233 grams. That is, the total amount of the polymer produced was 1,804 g (yield: 50.0%), but only 87% of the total polymer was collected, and when the high-speed homogenization mixer was used as in Examples 1 to 5, the polymerization was produced. 100% can be collected. The polymerization product had a weight average molecular weight of 388,000, a molecular weight distribution of 2.52, and a stereoregularity of 93% or more.

According to the present invention, the catalyst is rapidly dispersed in the monomer using a high-speed homogenization mixer, so that gel formation which occurs when the syndiotactic styrene polymer is produced can be substantially prevented, and high activity and excellent stereoscopic rules can be prepared. Sexual and uniform molecular distribution of styrene polymers. While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application. [Simple description of the map]

The above and other objects, features, and advantages of the present invention will become more apparent from the aspects of the invention. Figure] is a schematic view showing a method of producing a styrene polymer using a high-speed homogenization mixer and reactor according to an embodiment of the present invention. Fig. 2 is a schematic view showing a method of producing a styrene polymer using a plurality of series-connected high-speed homogenization mixers according to another embodiment of the present invention. 3 is a schematic diagram illustrating a method of preparing a styrene polymer using a high speed homogenizing 20 1327575 1972 lpif mixer and reactor in accordance with another embodiment of the present invention. Fig. 4 is a schematic view showing a process for producing a styrene polymer using a plurality of high-speed homogenization mixers connected in series and in parallel according to another embodiment of the present invention. [Main component symbol description] 1 : Monomer 2 : Auxiliary catalyst mixture

3: Homogenized mixed fluid 4: Catalyst mixture 5: Homogenized mixed fluid a: Reactor b: Reactor bl: First high-speed homogenizer b2: Second high-speed homogenizer b3: High-speed homogenizer c: Reaction Device

i 21

Claims (1)

1327575 19721pif ^ For the Chinese patent scope of No. 95117545, there is no slash correction. 4, Amendment _ Patent Application Range: ~~~~ A method for preparing styrene polymer, including: Period-If using a high-speed homogenization mixer, uniform Mixing a styrene monomer, a secondary catalyst mixture and a catalyst mixture to obtain a well-mixed and fine homogenized mixture, wherein the secondary catalyst mixture comprises a Group 13 metal organometallic compound secondary catalyst and a An inert organic solvent, and the catalyst mixture comprises a metallocene catalyst and the inert organic solvent; Providing the homogenization mixture to a reactor to initiate a polymerization wherein the high speed homogenization mixer is at a speed of 1, 〇〇〇 5 〇, 〇〇〇 rpm, Wherein the styrene monomer comprises at least one material selected from the group consisting of alkylstyrene, halogenated styrene, halogen-substituted alkyl styrene ( Halogen-substituted alkylstylene), alkoxystyrene, vinylbiphenyl, vinylphenyl naphthalene, vinylphenylpyrene, vinylphenylanthracene , trialkylsilylvinylbiphenyl, alkylsilylstyrene, carboxymethylstyrene, alkylesterstyrene, vinyl acid vinegar (vinylbenzenesulfonic acid ester), vinylbenzyldialkoxyphosphate, divinylbenzene, trivinylbenzene, and arylbenzene 22 1327575 19721pif styrene (aryl styrene), Wherein the metallocene catalyst is a Group 4 transition metal compound and is composed of one or two cycloalkyl groups a bonding product of a selected group of cycloalkyldienyl groups and a derivative thereof, wherein for the total amount of the metallocene catalyst and the stupid ethylene monomer The amount of metallocene catalyst is in the range of 0.00005-0.02 mol%, wherein the cocatalyst comprises at least one alkylalmninoxane, an alkylaluminum compound, and a borate compound (borate c 〇mp〇und) The material selected from the group consisting of. 2. The method for preparing a styrene polymer according to claim 1, wherein the alkyl aluminoxane is methylaluminoxane (MAO) or modified mercapto aluminoxane (m〇difled MAO) The method for producing a styrene polymer according to claim 1, wherein the alkylate compound is selected from the group consisting of trimethylaluminum, Triethylaluminum, dimethylaluminium chloride, diethyl aluminium chloride, triisobutylaluminum, tri(n-butyl) sho (tri (N-) Butyl) aluminium), tri(A η· propyl) aluminium, and triisopropylaluminium. The method of preparing a styrene polymer according to claim 1, wherein the borate compound comprises at least one material selected from the group consisting of: boron chamber (b〇) Rane), triphenyl gold carbon tetra(pentafluorophenyl) boranoic acid (tj*i phenylcarboniumtetra(pentaflu〇rophenyl)borate), o-cyano-N-mercaptopurine rust tetrakis(pentafluorophenyl)boronic acid Salt (o-cyano-N-methylpyridium Tetra(pentafluorophenyl)borate) > tn(pentafluorophenyl)boron, 1,1-dimethylferrocene-tetrakis(pentafluorophenyl)borate (l,l- Dimethylferrocenium-tetra(pentafluorophenyl)borate) and benzyidimethyl ferrocemum tetra(pentafluorophenyl)borate. 5. The method of preparing a styrene polymer as described in claim 1 wherein the 1 mole of metal contained in the metallocene catalyst is The amount of the secondary catalyst may range from 10 to 1,000 moles based on the amount of metal contained in the secondary catalyst. 6. The method of preparing a styrene polymer according to claim 1, wherein the inert organic solvent comprises at least one material selected from the group consisting of pentane, hexane, and cyclohexane. Alkane, heptane, octane H, benzene, five «L benzene, and toluene. P. The method of preparing a styrene polymer as described in claim 1 in the method S, wherein the concentration of the catalyst mixture is in the range of 0.0000 I-OJ mol/liter. 24 19721pif 8 soil as described in the scope of patent application 制备 〇 〇 其 其 其 其 其 其 其 其 其 其 其 其 其 其 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 In the step of uniform mixing, in the step of uniform mixing, homogenization is carried out using the first-** homogenous homopolyphenol styrene monomer and the medium mixture, and the first-rain speed homogenizing mixer is connected. The resulting homogenized mixture is homogenized with the vehicle mixture. 10. The styrene polymer is prepared as described in the scope of claim ii, wherein the styrene monomer is separately used in a first-high speed homogenization mixer. (4) homogenizing the medium mixture to form a homogenized product and forming the second homogenized product with the styrene monomer and the catalyst mixture (4) and then using the second high-speed homogenization The homogenization product is homogenized. 11. The method for preparing a styrene polymer according to claim 1, wherein the reactor comprises: a body having an internal space, the body comprising: an inlet to enable The homogenization mixture is put in; An outlet 'to allow the reaction product to be withdrawn therefrom; a mixer installed in the body for mixing the homogenized mixture; and a temperature control unit 'connected to the body by circulating a heating oil and a cooling The oil controls a reaction temperature in which an anchor is connected to the mixer and the spacing between the anchor and the inner wall of the reactor is minimized and the heating oil and the cooling oil are circulated along the paving blade. 25 1327575 19721pif 12. The method of preparing a styrene polymer according to claim 1, wherein the reactor is a powder bed type reactor. 26