Solid catalyst for propylene polymerization and method for producing propylene polymer using the same

Abstract

To provide: a method for producing a solid catalyst for propylene-based copolymerization which makes it possible to produce a polypropylene having high stereoregularity and excellent melt flowability in high yield, and also to produce a copolymer having a high comonomer content through copolymerization with an alpha-olefin, and may further dramatically reduce an agglomeration phenomenon of polymer particles during the copolymer production; and a method for producing a propylene-based polymer using the same.SOLUTION: A method for producing a solid catalyst for propylene-based polymerization comprises steps of: a step (1) of reacting a dialkoxy magnesium with a metal halide compound in the presence of an organic solvent; a step (2) of reacting the reaction product of the step (1) with at least one internal electron donor while increasing the reaction temperature; and a step (3) of reacting the reaction product of the step (2) with a titanium halide.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a solid catalyst for propylene polymerization and a method for producing a propylene polymer using the same. [Background technology]

[0002] Polypropylene is a very useful material in daily life and commerce, and is widely used in a wide range of applications, from everyday items such as food containers to automobiles and electronic products. To improve the performance of various polypropylene products, it is important to improve the rigidity of polypropylene by increasing its crystallinity. Meanwhile, the impact strength required for automobile interior and exterior materials can be met by producing propylene-based block copolymers with a high rubber content, but to achieve this, the role of the polymerization catalyst is of utmost importance. That is, the catalyst system must be designed to improve the stereoregularity of the resulting polymer and achieve high copolymerizability with alpha olefins. In addition, for the economical sake of polymer production, the higher the polymerization activity of the catalyst, the more advantageous it is.

[0003] Meanwhile, catalyst systems used in gas-phase, slurry, and bulk polymerization of polypropylene generally consist of Ziegler-Natta catalyst components, alkylaluminum, and external electron donors. These catalyst components are known as solid catalysts containing magnesium, titanium, internal electron donors, and halogens as essential components. In particular, the internal electron donor is known to have a significant impact on the activity and stereoregularity of the catalyst depending on its molecular structure.

[0004] The use of aromatic dicarboxylic acid diesters as internal electron donors is a widely known method (e.g., U.S. Patent Nos. 4,562,173, 4,981,930, and Korean Patent No. 72844) to reduce costs by increasing catalyst activity and improve catalyst performance, such as stereoregularity, to improve polymer properties. These methods introduce catalyst production methods that exhibit high activity and high stereoregularity using aromatic dialkyl diesters or aromatic monoalkyl monoesters. However, this method is not sufficiently satisfactory for obtaining high-stereoregularity polymers in high yields, and improvements are needed.

[0005] Meanwhile, Korean Patent No. 491387 introduces a catalyst manufacturing method using a non-aromatic diether substance as an internal electron donor, and Korean Patent No. 0572616 introduces a non-aromatic substance that simultaneously has ketone and ether functional groups as an internal electron donor. However, both of these methods have room for significant improvement in terms of both activity and stereoregularity.

[0006] In addition, U.S. Patent Application No. 2011 / 0040051 proposes a method for preparing a catalyst using a mixture of diethyl-2,3-diisopropyl-2-cyanosuccinic acid and 9,9-bismethoxyfluorene as an internal electron donor, but the catalyst is very poor in both activity and stereoregularity, and improvements are required. Summary of the Invention [Problem to be solved by the invention]

[0007] One embodiment of the present invention provides a method for producing a solid catalyst for propylene-based copolymerization, which can not only produce polypropylene with high stereoregularity and excellent melt flowability in high yield, but also produce a copolymer with a high comonomer content through copolymerization with an alpha olefin, and further, can dramatically improve the agglomeration phenomenon of polymer particles during copolymer production, and a method for producing a propylene-based polymer using the same. [Means for solving the problem]

[0008] One embodiment of the present invention comprises the steps of (1) reacting a dialkoxymagnesium with a metal halide compound in the presence of an organic solvent; (2) reacting the reaction product of step (1) with one or more internal electron donors while increasing the reaction temperature; and (3) reacting the reaction product of step (2) with titanium halide; In step (1), the dialkoxy magnesium is prepared by reacting metallic magnesium, an alcohol, and a reaction initiator; The metallic magnesium is divided into n divided portions and injected separately. When the total number of divided portions is n (n is an integer greater than 2), the total amount of metallic magnesium injected from the first to n-1 times is represented as N (N is a positive integer), and the amount (number of moles) of metallic magnesium injected last in n times is represented as W (W is a positive integer), the amount of metallic magnesium injected is adjusted to satisfy the following formula 1. 0.1≦N / W(α)≦1.2 ··· Formula 1

[0009] Another embodiment of the present invention provides a method for producing a propylene-based polymer, which comprises polymerizing polypropylene, copolymerizing propylene with other alpha-olefins, or terpolymerizing propylene to obtain a propylene copolymer, in the presence of the prepared solid catalyst for propylene-based polymerization and an external electron donor comprising an alkylaluminum compound and one or more alkoxysilane compounds as a co-catalyst. [Effects of the Invention]

[0010] According to an embodiment of the present invention, a method for preparing a solid catalyst for propylene polymerization and a method for preparing a propylene polymer using the same can produce polypropylene having high stereoregularity and excellent melt flowability in a high yield, as well as significantly improving the agglomeration of polymer particles during copolymer production. Furthermore, a propylene copolymer having a high comonomer content can be produced. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 is a photograph of a propylene-ethylene-1-butene terpolymer according to a comparative example. [Figure 2] FIG. 2 is a photograph of the propylene-ethylene-1-butene terpolymer according to Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0012] Some embodiments of the present disclosure will be described in detail below with reference to the accompanying drawings. When assigning reference numerals to components in each drawing, identical components may have the same numerals as much as possible, even if they appear in different drawings. Furthermore, when describing the present embodiments, if a detailed description of related known structures or functions is deemed to obscure the gist of the present technical concept, such a detailed description may be omitted. When terms such as "comprise," "have," and "consist" are used in this specification, other parts may be added unless "only" is used. When a component is expressed in the singular, the plural may also be included unless otherwise expressly specified.

[0013] Furthermore, when describing components of the present disclosure, terms such as first, second, A, B, (a), (b), etc. are used to distinguish the component from other components, and the term does not limit the essence, order, sequence, or number of the component.

[0014] In describing the positional relationship of components, when two or more components are described as being "coupled," "coupled," or "connected," it should be understood that the two or more components may be directly "coupled," "coupled," or "connected," but that the two or more components may also be "coupled," "coupled," or "connected" to other components through further "intervening" connections. Here, the other components may be included in one or more of the two or more components that are "coupled," "coupled," or "connected" to each other.

[0015] In describing temporal flow relationships relating to components, methods of operation, methods of making, etc., when a temporal or flow sequence is described using, for example, "after," "next to," "next to," or "before," non-consecutive sequences may be included unless "immediately" or "directly" is used.

[0016] On the other hand, when a numerical value or its corresponding information (e.g., level, etc.) for a component is mentioned, the numerical value or its corresponding information may be interpreted as including an error range that may occur due to various factors (e.g., process factors, internal or external impact, noise, etc.) even if there is no other explicit description.

[0017] As used herein, a propylene-based polymer can include polypropylene or a propylene copolymer, or a combination thereof.

[0018] In one embodiment of the present invention, there is provided a method for producing polypropylene using a solid catalyst for propylene polymerization, the solid catalyst comprising, as a main catalyst component, a solid catalyst prepared by a method for preparing a solid catalyst for propylene polymerization, an alkylaluminum compound as a co-catalyst component, and one dialkoxysilane compound and two different trialkoxysilane compounds as external electron donors, wherein the solid catalyst may be a Ziegler catalyst.

[0019] The method for producing a solid catalyst for propylene polymerization may include the following steps. (1) reacting a dialkoxymagnesium with a metal halide compound in the presence of an organic solvent; (2) reacting the reaction product of step (1) with one or more internal electron donors at an elevated reaction temperature; and (3) Step (3) of reacting the reaction product of step (2) with titanium halide. In this case, step (1) is reacted at a relatively lower temperature than step (3), and step (3) is reacted at a higher temperature than step (1).

[0020] In the above-mentioned method for preparing a solid catalyst, diethoxymagnesium used in step (1) is produced by reacting metallic magnesium, alcohol, and a reaction initiator. Here, metallic magnesium and alcohol are added in two or more divided portions in an amount of 1:4 to 1:20 (total moles of metallic magnesium:total moles of alcohol). The reaction initiator can be initially added to the reaction system at the start of the reaction, and then added in one or more divided portions during the reaction as needed.

[0021] In the above-described method for producing a solid catalyst, the form of the magnesium metal particles used is not particularly limited, but in terms of size, a powder form with an average particle size of 10 to 500 μm is preferred, and a powder form with an average particle size of 50 to 300 μm is more preferred. If the average particle size of the magnesium metal is less than 10 μm, the average particle size of the support product will be too fine, while if it exceeds 500 μm, the average particle size of the support will be too large, making it difficult for the support to have a uniform spherical shape, and making it difficult to maintain a uniform particle shape during subsequent catalyst production.

[0022] As the alcohol, it is preferable to use one or more alcohols selected from aliphatic alcohols represented by the general formula ROH (where R is an alkyl group having 1 to 6 carbon atoms), such as methanol, ethanol, normal propanol, isopropanol, normal butanol, isobutanol, normal pentanol, isopentanol, neopentanol, cyclopentanol, and cyclohexanol, or aromatic alcohols such as phenol, either alone or in combination. It is more preferable to use one or more alcohols selected from methanol, ethanol, propanol, and butanol, either alone or in combination, and it is most preferable to use ethanol.

[0023] Meanwhile, the ratio of alcohol to metallic magnesium is preferably 1:4 to 1:50 (moles of metallic magnesium:moles of alcohol) at each stage, and more preferably 1:10 to 1:40. If the ratio is less than 1:10, the viscosity of the slurry increases rapidly, making uniform stirring difficult and producing a large amount of fine particles, while if it exceeds 1:50, the particle surfaces of the produced support become rough or particle formation becomes impossible.

[0024] As a reaction initiator used in the reaction of metallic magnesium with alcohol, a nitrogen halide compound can be used.

[0025] The nitrogen halide compound used as the reaction initiator is not particularly limited, but one or more compounds selected from the group consisting of compounds represented by the following formulas 1 to 4 can be used. [ka] The compound represented by Formula 1 is an N-halide succinimide compound, where X is a halogen, and R1, R2, R3, and R4 are each independently hydrogen, C1-C12 alkyl, or C6-C20 aryl.

[0026] [ka] Formula 2 is a trihaloisocyanuric acid compound, and each X is independently a halogen.

[0027] [ka] Formula 3 is an N-halophthalimide compound, where X is a halogen, and R1, R2, R3, and R4 are each independently hydrogen, C1-C12 alkyl, or C6-C20 aryl.

[0028] [ka] Formula 4 is a hydantoin-based compound, where X is independently a halogen, and R1 and R2 are independently a hydrogen atom, a C1-C12 alkyl, or a C6-C20 aryl.

[0029] On the other hand, a halogen compound or a magnesium halide compound can be used as the reaction initiator. Specific examples of the halogen compound include compounds containing Br2 or I2, and magnesium halide compounds include MgCl2, MgBr2, and MgI2.

[0030] The amount of the reaction initiator is preferably 0.05 to 0.5 moles per part by weight of the total magnesium metal used. If the amount of the reaction initiator used is less than 0.05 moles, the reaction rate will be too slow, and if it exceeds 0.5 moles, the particle size of the product may become too large or a large amount of fine particles may be produced.

[0031] In the method for preparing a solid catalyst for propylene polymerization according to one embodiment of the present invention, in the reaction of metallic magnesium with alcohol in step (1), metallic magnesium and alcohol can be added in 3 to 7 divided portions, and the reaction initiator is preferably injected at the start of the reaction and then added in 2 to 7 divided portions as needed during the reaction. If the number of divided portions of metallic magnesium and alcohol and the number of injections of the reaction initiator are limited to two or less, there are drawbacks such as limitations on particle size control, difficulty in forming spherical particles, and increased generation of fine particles.

[0032] On the other hand, if the total number of divided magnesium products is n, the total amount of magnesium from the first to n-1 times is expressed as N, and the amount of magnesium (number of moles) injected in the last divided injection is expressed as W, it is preferable to adjust the amount of magnesium injected so as to satisfy the following formula 1. 0.1≦N / W(α)≦1.2 ··· Formula 1

[0033] If the value is outside this range, not only will it be difficult to adjust the particle size, but the increase in the amount of fine polymer particles produced during catalytic polymerization may make the polymerization process unstable and cause process problems.

[0034] The stirring speed during the reaction is preferably 50 to 300 rpm, more preferably 70 to 250 rpm. A stirring speed that is too slow or too fast can result in non-uniform particles. The reaction between metallic magnesium and alcohol is preferably carried out in the presence of a reaction initiator at a temperature of 25 to 110°C, more preferably 50 to 100°C. The subsequent aging treatment is preferably carried out at a temperature of 60 to 110°C. The reaction may be carried out under reflux at the boiling point of the alcohol. If the reaction temperature and aging treatment temperature are outside the temperature range, the reaction rate becomes very slow at temperatures below 50°C, and the reaction proceeds very rapidly at temperatures above 110°C, which is undesirable because this can lead to the formation of fine particles and clumping of particles.

[0035] On the other hand, the bulk specific gravity of the dialkoxymagnesium produced in step (1) is preferably 0.20 to 0.40 g / ml, more preferably 0.20 to 0.30 g / ml. If the bulk specific gravity is less than 0.20 g / ml, particle formation becomes difficult or the differential content increases, making it impossible to produce a high-stereoregularity polyolefin in high yield. On the other hand, if the bulk specific gravity exceeds 0.40 g / ml, it will have an undesirable effect on the particle properties of the resulting polyolefin. Furthermore, the pore volume of the dialkoxymagnesium is preferably 0.01 to 0.2 ml / g, more preferably 0.06 to 0.1 ml / g. When a solid catalyst component produced using porous dialkoxymagnesium having such a relatively small pore volume within a specific range is used in the polymerization of olefins, polymers with high stereoregularity and excellent particle properties can be obtained in high yield. Furthermore, copolymers with high copolymer content and excellent particle properties, with a low proportion of rubbery polymers, can be obtained in high yield.

[0036] The organic solvent used in step (1) is not particularly limited in type, and may be an aliphatic hydrocarbon or aromatic hydrocarbon having 6 to 12 carbon atoms, a halogenated hydrocarbon, or the like, more preferably a saturated aliphatic hydrocarbon, an aromatic hydrocarbon, or a halogenated hydrocarbon having 7 to 10 carbon atoms, and specific examples thereof include a mixture of one or more selected from heptane, octane, nonane, decane, toluene, xylene, chlorohexane, chloroheptane, and the like.

[0037] Furthermore, the ratio of the organic solvent to the diethoxymagnesium is preferably 1:5 to 1:50, and more preferably 1:7 to 1:20, in terms of weight of diethoxymagnesium to volume of organic solvent. However, if the ratio is less than 1:5, the viscosity of the slurry increases rapidly, making uniform stirring difficult, and if it exceeds 1:50, the apparent density of the resulting carrier decreases rapidly and the particle surface becomes rough, which is undesirable.

[0038] The titanium halide used in the above-mentioned method for producing a solid catalyst is represented by the following formula 5. Ti(OR) n X (4-n) (Formula 5) (Here, R is an alkyl group having 1 to 10 carbon atoms, X is a halogen element, and n is an integer of 0 to 3 for adjusting the valence of the general formula.)

[0039] Specific examples include TiCl4, Ti(OCH3)Cl3, Ti(OC2H5)Cl3, Ti(OC3H7)Cl3, Ti(O(n-C4H9))Cl3, Ti(OCH3)2Cl2, and Ti(OC2H5)2C 12 , Ti(OC3H7)2C 12 , Ti(O(n-C4H9))2C 12, Ti(OCH3)3Cl, Ti(OC2H5)3Cl, Ti(OC3H7)3Cl, Ti(O(n-C4H9))3Cl, etc., of which TiCl4 is preferably used. These tetravalent titanium halide compounds can be used alone or in combination of two or more. The reaction temperature in step (1) is -10 to 60°C.

[0040] The one or more internal electron donors shown in step (2) are preferably diesters, particularly aromatic diesters, more specifically phthalic acid diesters. Suitable examples of phthalic acid diesters include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-pentyl phthalate, di(2-methylbutyl) phthalate, di(3-methylbutyl) phthalate, dineopentyl phthalate, di-n-hexyl phthalate, di(2-methylpentyl) phthalate, di(3-methylpentyl) phthalate, diisohexyl phthalate, dineohexyl phthalate, di(2,3-dimethylbutyl) phthalate, di-n-heptyl phthalate, di(2-methylhexyl) phthalate, di(2-ethylpentyl) phthalate, and di(2-ethylpentyl) phthalate. One or a mixture of two or more compounds selected from the compounds represented by the following Chemical Formula 6 can be used, such as diisoheptyl phthalate, dineoheptyl phthalate, di-n-octyl phthalate, di(2-methylheptyl)phthalate, diisooctyl phthalate, di(3-ethylhexyl)phthalate, dineohexyl phthalate, di-n-heptyl phthalate, diisoheptyl phthalate, dineoheptyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, dineooctyl phthalate, di-n-nonyl phthalate, diisononyl phthalate, di-n-decyl phthalate, and diisodecyl phthalate. [ka] In Formula 6, each R is independently an alkyl group having 1 to 10 carbon atoms.

[0041] On the other hand, as the internal electron donor, it is also very preferable to use 1,3-diethers, and a compound represented by the structure of the following formula 7 is very preferable. R 6 R 7 C(CH2OR 8 )(CH2OR 9 ) (Formula 7) In Formula 7, R 6 and R 7 are the same or different and each independently represent a C1-C18 alkyl, a C3-C18 cycloalkyl, or a C7-C18 aryl radical; R 8 and R 9 are the same or different and are each independently a C1-C4 alkyl radical; the carbon atom at position 2 is a 1,3-diether containing two or three unsaturations and belonging to a cyclic or polycyclic ring of 5, 6 or 7 carbon atoms.

[0042] Specific examples of the 1,3-diether compounds that are internal electron donors include 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-t-butyl-1,3-dimethoxypropane, 2-cumyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexyl)-1,3-dimethoxypropane, 2-(1-naphthyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2-(1-naphthyl)-1,3-dimethoxypropane, 2-(p-fluorophenyl)-1,3-dimethoxypropane, 2-(1-decahydronaphthyl)-1,3-dimethoxypropane, 2-(p-butylphenyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropion 2,2-dibutyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-diethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-diethoxypropane, 2,2-dibutyl-1,3-diethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2 -Cyclohexyl-1,3-dimethoxypropane, 2-methyl-2-methylcyclohexyl-1,3-dimethoxypropane, 2,2-bis(p-chlorophenyl)-1,3-dimethoxypropane, 2,2-bis(2-phenylethyl)-1,3-dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-bis(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-bis(p-methylphenyl)-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropyl, 2,2-diisobutyl-1,3-diene t-butyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dibutoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2,2-di-sec-butyl-1,3-dimethoxypropane, 2,2-di-t-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclohexyl-2- Cyclohexylmethyl-1,3-dimethoxypropane, 9,9-bis(methoxymethyl)fluorene, 9,9-bis(methoxymethyl)-2,3,6,7-tetramethylfluorene, 9,9-bis(methoxymethyl)-2,3,4,5,6,7-hexafluorofluorene, 9,9-bis(methoxymethyl)-2,3-benzofluorene, 9,9-bis(methoxymethyl)-2,3,6,7-dibenzofluorene, 9,9-bis(methoxymethyl)-2,7-diisopropylfluorene fluorene, 9,9-bis(methoxymethyl)-1,8-dichlorofluorene, 9,9-bis(methoxymethyl)-2,7-dicyclopentylfluorene, 9,9-bis(methoxymethyl)-1,8-difluorofluorene, 9,9-bis(methoxymethyl)-1,2,3,4-tetrahydrofluorene, 9,9-bis(methoxymethyl)-1,2,3,4,5,6,7,8-octahydrofluorene, or 9,9-bis(methoxymethyl)-4-t-butylfluorene.

[0043] Furthermore, cyclic ester compounds represented by the structures of the following formulas 8 to 11 are highly preferred. [ka] [ka] [ka] [ka]

[0044] In formulae 8 to 11, R is each independently a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms.

[0045] Examples of internal electron donors include bicyclo[2.2.1]heptane-2,3-dicarboxylic acid diisobutyl ester, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid dibutyl ester, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid diisopropyl ester, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid dipropyl ester, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid diethyl ester, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid dimethyl ester, and bicyclo[2.2.1]hept-5-ene. -2,3-dicarboxylic acid diisobutyl ester, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid dibutyl ester, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid diisopropyl ester, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid dipropyl ester, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid diethyl ester, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid dimethyl ester, bicyclo[2.2.1]hept-2-ene-2,3-dicarboxylic acid Acid diisobutyl ester, bicyclo[2.2.1]hept-2-ene-2,3-dicarboxylic acid dibutyl ester, bicyclo[2.2.1]hept-2-ene-2,3-dicarboxylic acid diisopropyl ester, bicyclo[2.2.1]hept-2-ene-2,3-dicarboxylic acid dipropyl ester, bicyclo[2.2.1]hept-2-ene-2,3-dicarboxylic acid diethyl ester, bicyclo[2.2.1]hept-2-ene-2,3-dicarboxylic acid dimethyl ester, bicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylic acid diisobutyl ester esters, bicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylic acid dibutyl ester, bicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylic acid diisopropyl ester, bicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylic acid dipropyl ester, bicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylic acid diethyl ester, bicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylic acid dimethyl ester, etc., and one or more of these can be used in combination.As another example of the internal electron donor, a cyclic alkyl diester can also be used.

[0046] Specific examples of the internal electron donor include compounds represented by the following formulas 12 to 19.

[0047] In Formulas 12 to 19, R1 and R2 are the same or different and each independently represent a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, an alkenyl group, an aryl group, an arylalkyl group, or an alkylaryl group; and R3 to R12 are the same or different and each independently represent a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, an alkenyl group, an aryl group, an arylalkyl group, or an alkylaryl group.

[0048] [ka] Specific examples of the compound represented by formula 12 include dimethyl cyclohex-1-ene-1,2-dicarboxylate, diethyl cyclohex-1-ene-1,2-dicarboxylate, 1-ethyl 2-methyl cyclohex-1-ene-1,2-dicarboxylate, 1-ethyl 2-propyl cyclohex-1-ene-1,2-dicarboxylate, dipropyl cyclohex-1-ene-1,2-dicarboxylate, and diisopropyl cyclohex-1-ene-1,2-dicarboxylate. cyclohex-1-ene-1,2-dicarboxylate, diethyl 3-methylcyclohex-1-ene-1,2-dicarboxylate, diethyl 3,3-dimethylcyclohex-1-ene-1,2-dicarboxylate, diethyl 3,3,4,4-tetramethylcyclohex-1-ene-1,2-dicarboxylate, diethyl 3,3,4,4,6-pentamethylcyclohex-1-ene-1,2-dicarboxylate 3,3,4,4,6-pentamethylcyclohex-1-ene-1,2-dicarboxylate), dibutyl 4,5-dimethylcyclohex-1-ene-1,2-dicarboxylate, 2-ethyl-1-propyl-5-ethyl-3,3,Examples include 4-trimethylcyclohex-1-ene-1,2-dicarboxylate (2-ethyl1-propyl5-ethyl-3,3,4-trimethylcyclohex-1-ene-1,2-dicarboxylate).

[0049] [ka] Specific examples of the compound represented by formula 13 include dimethylcyclohexa-1,4-diene-1,2-dicarboxylate, diethylcyclohexa-1,4-diene-1,2-dicarboxylate, dipropylcyclohexa-1,4-diene-1,2-dicarboxylate, diisopropylcyclohexa-1,4-diene-1,2-dicarboxylate, and diethyl3-methylcyclohexa-1,4-diene-1,2-dicarboxylate. a-1,4-diene-1,2-dicarboxylate, diethyl 3,3-dimethylcyclohexa-1,4-diene-1,2-dicarboxylate, diethyl 3,3,6-trimethylcyclohexa-1,4-diene-1,2-dicarboxylate, diethyl 3,3,6,6 tetramethylcyclohexa-1,4-diene-1,2-dicarboxylate, diethyl 3,3,4,5,6,6-hexamethylcyclohexa-1,4-diene-1,2-dicarboxylate 3,3,4,5,6,6,-hexamethylcyclohexa-1,4-diene-1,2-dicarboxylate), 1-ethyl 2-propyl 4-ethyl-3,5,6-trimethylcyclohexa-1,4-diene-1,2-dicarboxylate (1-ethyl2-propyl4-ethyl-3,5,6-trimethylcyclohexa-1,4-diene-1,2-dicarboxylate), 2-ethyl1-propyl5-ethyl-3,3,4,6-tetramethylcyclohexa-1,4-diene-1,2-dicarboxylate, etc.

[0050] [ka] Specific examples of formula 14 include trans-dimethyl-cyclohexane-1,2-dicarboxylate, trans-1-ethyl 2-methyl-cyclohexane-1,2-dicarboxylate, trans-1-ethyl-2-propyl-cyclohexane-1,2-dicarboxylate, trans-1-ethyl-2-propyl-cyclohexane-1,2-dicarboxylate, trans-2-ethyl-3-propyl-1-methylcyclohexane-1,2-dicarboxylate, trans-1-ethyl-2-propyl-1,2-dimethylcyclohexane-1,2-dicarboxylate carboxylate), trans-1-ethyl2-propyl-1,2,4,4-tetramethylcyclohexane-1,2-dicarboxylate, trans-1-ethyl2-propyl-1,2,4,4,5,5-hexamethylcyclohexane-1,2-dicarboxylate, and trans-1-butyl2-ethyl-1,4,5,5-tetramethylcyclohexane-1,2-dicarboxylate.

[0051] [ka] Specific examples of formula 15 include cis-dimethyl-cyclohexane-1,2-dicarboxylate, cis-1-ethyl 2-methyl-cyclohexane-1,2-dicarboxylate, cis-diethyl-cyclohexane-1,2-dicarboxylate, cis-1-ethyl 2-propyl-cyclohexane-1,2-dicarboxylate, cis-2-ethyl 3-propyl 1-methylcyclohexane-1,2-dicarboxylate, cis-1-ethyl 2-propyl 1,2-dimethyl Examples include cis-1-ethyl2-propyl1,2-dimethylcyclohexane-1,2-dicarboxylate, cis-1-ethyl2-propyl-1,2,4,4-tetramethylcyclohexane-1,2-dicarboxylate, cis-1-ethyl2-propyl-1,2,4,4,5,5-hexamethylcyclohexane-1,2-dicarboxylate, and cis-1-butyl2-ethyl-1,4,5,5-tetramethylcyclohexane-1,2-dicarboxylate.

[0052]

change

[0053] [ka] A specific example of Formula 17 is cis-dimethylcyclohex-4-ene-1,2-dicarboxylate (cis-dimethyl cyclohex-4-ene-1,2dicarboxylate, cis-diethylcyclohex-4-ene-1,2dicarboxylate, cis-dipropylcyclohex-4-ene-1,2dicarboxylate, cis-diisopropylcyclohex-4-ene-1,2dicarboxylate, cis-dibutylcyclohex-4-ene-1,2dicarboxylate, cis-1-ethyl-2-methylcyclohex-4-ene-1,2-dicarboxylate, cis-1-ethyl-2-propylcyclo cis-1-ethyl-2-propylcyclohex-4-ene-1,2-dicarboxylate, cis-1-ethyl-2-propyl3-methylcyclohex-4-ene-1,2-dicarboxylate, cis-1-ethyl-2-propyl3,6-dimethylcyclohex-4-ene-1,2-dicarboxylate cis-1-ethyl-2-propyl3,6-dimethylcyclohex-4-ene-1,2-dicarboxylate, cis-2-ethyl-1-propyl3,4,6-trimethylcyclohex-4ene-1,2-dicarboxylate, cis-2-ethyl-1-propyl4-ethyl3,6-dimethylcyclohex-4-ene-1,2-dicarboxylate2 dicarboxylate (cis-2-ethyl-1-propyl4-ethyl3,6-dimethylcyclohex-4ene-1,2-dicarboxylate), etc.

[0054] [ka] Specific examples of formula 18 include trans-dimethylcyclohexa-3,5-diene-1,2-dicarboxylate, trans-diethylcyclohexa-3,5-diene-1,2-dicarboxylate, trans-dipropylcyclohexa-3,5-diene-1,2-dicarboxylate, cyclohexa-3,5-diene-1,2-dicarboxylate, trans-dibutylcyclohexa-3,5-diene-1,2-dicarboxylate, trans-dimethyl1-methylcyclohexa-3,5-diene-1,2-dicarboxylate, trans-dimethyl1,2-dimethylcyclohexa-3,5-diene-1,2-dicarboxylate, trans-1-ethyl 2-propyl 1, 2-dimethylcyclohexa-3,5-diene-1,2-dicarboxylate (trans-1-ethyl2-propyl1,2-dimethylcyclohexa-3,5-diene-1,2-dicarboxylate), trans-diethyl 4-methylcyclohexa-3,5-diene-1,2-dicarboxylate (trans-diethyl4-methylcyclohexa-3,5-diene-1,2-dicarboxylate), trans-diethyl 4,5-dimethylcyclohexa-3,5-diene-1,2-dicarboxylate (trans-diethyl4,5-dimethylcyclohexa-3,5-diene-1,2-dicarboxylate), trans-diethyl 4-ethyl-3,5,6-trimethylcyclohexa-3,5-diene-1,2-dicarboxylate (trans-diethyl4-ethyl-3,5,6-trimethylcyclohexa-3,5-diene-1,2-dicarboxylate), etc.

[0055] [ka] Specific examples of formula 19 include cis-dimethylcyclohexa-3,5-diene-1,2-dicarboxylate, cis-diethylcyclohexa-3,5-diene-1,2-dicarboxylate, cis-dipropylcyclohexa-3,5-diene-1,2-dicarboxylate, cis-dibutylcyclohexa-3,5-diene-1,2-dicarboxylate, cis-dimethyl ... cis-dimethyl1-methylcyclohexa-3,5-diene-1,2-dicarboxylate, cis-dimethyl1,2-dimethylcyclohexa-3,5-diene-1,2-dicarboxylate, cis-1-ethyl2-propyl1,2-dimethylcyclohexa-3,5-diene-1,2-dicarboxylate, cis-diethyl4-methylcyclohexa-3,5-diene-1,2-dicarboxylate cyclohexa-3,5-diene-1,2-dicarboxylate), cis-diethyl 4,5-dimethylcyclohexa-3,5-diene-1,2-dicarboxylate, cis-diethyl 4-ethyl-3,5,6-trimethylcyclohexa-3,5-diene-1,2-dicarboxylate5-diene-1,2-dicarboxylate), etc.

[0056] Step (2) is preferably carried out by gradually increasing the temperature of the product obtained in step (1) to 60 to 150°C, preferably 80 to 130°C, and adding an internal electron donor during the temperature increase, followed by a reaction for 1 to 3 hours. If the temperature is below 60°C or the reaction time is less than 1 hour, the reaction is unlikely to be completed. If the temperature exceeds 150°C or the reaction time exceeds 3 hours, side reactions may occur, reducing the polymerization activity of the catalyst or the stereoregularity of the resulting polymer.

[0057] As long as the internal electron donor is added during the temperature rise process, its addition temperature and number of times are not particularly limited, and two or more different internal electron donors may be added simultaneously or at different temperatures. There is no limitation on the total amount of the two internal electron donors used, but the total number of moles of the two internal electron donors used is preferably 0.001 to 2.0 moles per mole of the dialkoxymagnesium used. However, if the amount is outside this range, the polymerization activity of the resulting catalyst or the stereoregularity of the polymer may be reduced, which is undesirable.

[0058] In the process for producing a solid catalyst, step (3) is a step of reacting the resultant of step (2) with a titanium halide for two or more times at a temperature of 60 to 150° C., preferably 80 to 130° C. Examples of the titanium halide used in this step include the titanium halide of formula 5.

[0059] In the method for producing a solid catalyst, the reaction at each stage is preferably carried out in a nitrogen gas atmosphere in a reactor equipped with a stirrer from which moisture and the like have been thoroughly removed.

[0060] The solid catalyst according to one embodiment of the present invention prepared by the above method comprises magnesium, titanium, a halogen compound, and an internal electron donor. In consideration of catalytic activity, the solid catalyst preferably comprises 5-40 wt % of magnesium, 0.5-10 wt % of titanium, 50-85 wt % of halogen, and 0.01-20 wt % of the internal electron donor.

[0061] As described above, it can be seen from Table 2 below that a catalyst having high apparent density and activity, as well as high hydrogen reactivity and narrow molecular weight distribution, can be obtained through the method for preparing a solid catalyst for propylene polymerization according to an embodiment of the present invention, compared to a general catalyst. The solid catalyst produced by the method for producing a solid catalyst according to one embodiment of the present invention is suitably used for polypropylene polymerization or propylene copolymerization.

[0062] In the method for producing a propylene-based polymer using the solid catalyst prepared according to an embodiment of the present invention, polypropylene can be polymerized in the presence of the solid catalyst, a co-catalyst, and an external electron donor, or propylene can be copolymerized or terpolymerized with other alpha-olefins to produce a propylene copolymer.

[0063] In one embodiment of the present invention, the alpha-olefin used for copolymerization is at least one olefin selected from alpha-olefins having 2 to 20 carbon atoms (excluding polypropylene having 3 carbon atoms), specifically ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, etc., and one or more alpha-olefins can be used, among which ethylene and 1-butene are preferred, and ethylene is particularly preferred.

[0064] The solid catalyst may be prepolymerized with ethylene or an alpha olefin before being used as a component in the polymerization reaction.

[0065] The prepolymerization reaction can be carried out in the presence of a hydrocarbon solvent (e.g., hexane), catalyst components, and an organoaluminum compound (e.g., triethylaluminum) at a sufficiently low temperature and ethylene or alpha-olefin pressure. Prepolymerization helps to maintain the catalyst shape by surrounding the catalyst particles with polymer, thereby improving the shape of the polymer after polymerization. The weight ratio of polymer to catalyst after prepolymerization is preferably about 0.1:1 to 20:1.

[0066] In the method for producing a propylene-based polymer by polypropylene polymerization or propylene copolymerization, an organometallic compound of Group II or III of the periodic table can be used as the co-catalyst component, and an alkylaluminum compound is preferably used as the co-catalyst component. The alkylaluminum compound is represented by the following formula 20: AlR3 (formula 20) In Formula 20, each R is independently an alkyl group having 1 to 6 carbon atoms.

[0067] Specific examples of alkylaluminum compounds include trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, and trioctylaluminum.

[0068] The ratio of the co-catalyst component to the solid catalyst component varies somewhat depending on the polymerization method, but the molar ratio of the metal atom in the co-catalyst component to the titanium atom in the solid catalyst component is preferably in the range of 1 to 1000, more preferably in the range of 10 to 300. If the molar ratio of the metal atom, for example, aluminum atom, in the co-catalyst component to the titanium atom in the solid catalyst component is out of the range of 1 to 1000, there is a problem that the polymerization activity is greatly reduced.

[0069] In the method for producing a propylene-based polymer, one or more alkoxysilane compounds represented by the following formula 21 can be used as the external electron donor. R1mR2nSi(OR3)(4-mn) (Formula 21) In Formula 21, R1 and R2 may be the same or different and each independently represent a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, or an aryl group; R3 represents a linear or branched alkyl group having 1 to 6 carbon atoms; m and n each represent 0 or 1, and m+n represents 1 or 2.

[0070] Specific examples of the external electron donor include normal propyl trimethoxysilane, di-normal propyl dimethoxysilane, isopropyl trimethoxysilane, diisopropyl dimethoxysilane, normal butyl trimethoxysilane, di-normal butyl dimethoxysilane, isobutyl trimethoxysilane, diisobutyl dimethoxysilane, tert-butyl trimethoxysilane, di-tert-butyl dimethoxysilane, normal pentyl trimethoxysilane, di-normal pentyl dimethoxysilane, cyclopentyl trimethoxysilane, and dicyclopentyl dimethysilane. Dimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylpropyldimethoxysilane, cyclohexyltrimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylpropyldimethoxysilane, cycloheptyltrimethoxysilane, dicycloheptyldimethoxysilane, cycloheptylmethyldimethoxysilane, cycloheptylethyldimethoxysilane, cycloheptylpropyldimethoxysilane, Phenyltrimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylethyldimethoxysilane, phenylpropyldimethoxysilane, normal propyltriethoxysilane, di-normal propyldiethoxysilane, isopropyltriethoxysilane, diisopropyldiethoxysilane, normal butyltriethoxysilane, di-normal butyldiethoxysilane, isobutyltriethoxysilane, diisobutyldiethoxysilane, tert-butyltriethoxysilane, di-tert-butyldiethoxysilane, normal Pentyl triethoxysilane, di-normal pentyl diethoxysilane, cyclopentyl triethoxysilane, dicyclopentyl diethoxysilane, cyclopentyl methyl diethoxysilane, cyclopentyl ethyl diethoxysilane, cyclopentyl propyl diethoxysilane, cyclohexyl triethoxysilane, dicyclohexyl diethoxysilane, cyclohexyl methyl diethoxysilane, cyclohexyl ethyl diethoxysilane, cyclohexyl propyl diethoxysilane, cycloheptyl triethoxysilane, dicycloheptyl diethoxysilane,Examples of suitable silanes include cycloheptylmethyldiethoxysilane, cycloheptylethyldiethoxysilane, cycloheptylpropyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, phenylethyldiethoxysilane, and phenylpropyldiethoxysilane. One or more of these silanes may be used alone or in combination.

[0071] Although the amount of external electron donor used relative to the solid catalyst varies somewhat depending on the polymerization method, the molar ratio of silicon atoms in the external electron donor to titanium atoms in the catalyst component is preferably in the range of 0.1 to 500, more preferably in the range of 1 to 100. If the molar ratio of silicon atoms in the external electron donor to titanium atoms in the solid catalyst component is less than 0.1, the stereoregularity of the produced polypropylene will be significantly reduced, which is undesirable, and if it exceeds 500, there is a problem of a significant decrease in the polymerization activity of the catalyst.

[0072] In the method for producing a propylene-based polymer, the polymerization temperature is preferably 20 to 120°C. If the polymerization temperature is lower than 20°C, the reaction does not proceed sufficiently, which is not preferred. If the polymerization temperature is higher than 120°C, the activity drops significantly, which has a negative effect on the physical properties of the polymer, which is not preferred.

[0073] In particular, when producing a propylene block copolymer, multi-stage polymerization is carried out in two or more stages, typically by polymerizing propylene in the presence of a polymerization catalyst in the first stage and copolymerizing ethylene and propylene in the second stage. During the second stage or polymerization after this stage, α-olefins other than propylene can be polymerized either alone or in the presence of other α-olefins. Examples of α-olefins include ethylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, 1-hexene, and 1-octene.

[0074] In particular, the method for producing a propylene polymer or copolymer using the solid catalyst proposed in one embodiment of the present invention not only enables the production of polypropylene with high activity, excellent stereoregularity, and excellent melt flowability, but also enables the production of a propylene copolymer with a high comonomer content more stably without process troubles by copolymerization with an alpha olefin.

[0075] EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited thereto.

[0076] Example 1 [Production of spherical carriers] A 5L glass reactor equipped with a stirrer, oil heater, and reflux condenser was thoroughly ventilated with nitrogen, and then 4g of N-bromosuccinimide, 15g of metallic magnesium (powder product with an average particle size of 100μm), and 300ml of absolute ethanol were added, and the temperature of the reactor was maintained at 60°C while operating at a stirring speed of 200 rpm. After about 10 minutes, the reaction began and hydrogen was generated, so the reactor outlet was opened to allow the generated hydrogen to escape, and the pressure in the reactor was maintained at atmospheric pressure.

[0077] Once hydrogen generation had ceased, the reactor temperature was maintained at 60°C for 1 hour. After 1 hour, 20g of metallic magnesium (powder product with an average particle size of 100μm), 400ml of absolute ethanol, and 3g of reaction initiator were added to the reactor and maintained for 1 hour. Finally, 60g of metallic magnesium (powder product with an average particle size of 100μm), 900ml of absolute ethanol, and 4g of reaction initiator were added and maintained for 30 minutes. After that, an additional 100ml of ethanol was added and the mixture was aged for 3 hours until the reaction was complete. After aging, the resulting product was washed three times at 50°C, using 2,000ml of normal hexane each time.

[0078] The washed product was dried under flowing nitrogen for 24 hours to obtain 415 g (yield 92.8%) of diethoxymagnesium support as a free-flowing white powdery solid product (α=0.6). The particle size of the dried product was measured using a laser particle analyzer (Mastersizer X, manufactured by Malvern Instruments) by the light transmission method, and the average particle size was 42.3 μm. The particle size distribution index (P) (P = (D90 - D10) / D50, where D90 is the particle size corresponding to 90% of the cumulative weight, D50 is the particle size corresponding to 50% of the cumulative weight, and D10 is the particle size corresponding to 10% of the cumulative weight) was 0.43, and the apparent density measured according to ASTM D1895 was 0.26 g / cc. The pore volume of diethoxymagnesium measured by the BET method was 0.061 cc / g.

[0079] [Production of solid catalyst component] A 1 L glass reactor equipped with a stirrer and thoroughly purged with nitrogen was charged with 112 ml of toluene and 15 g of the diethoxymagnesium prepared above. While maintaining the temperature at 10°C, 20 ml of titanium tetrachloride diluted with 30 ml of toluene was added over 1 hour, and then 5 g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was gradually added while the temperature of the reactor was raised to 100°C. After maintaining the temperature at 100°C for 2 hours, the temperature was lowered to 90°C, stirring was stopped, the supernatant was removed, and the mixture was washed once with 200 ml of toluene. To this, 120 ml of toluene and 20 ml of titanium tetrachloride were added, and the temperature was raised to 100°C and maintained for 2 hours. This process was repeated once. After the aging process, the slurry mixture was washed twice with 200 ml of toluene each time, and then washed five times with 200 ml of normal hexane at 40°C to obtain a pale yellow solid catalyst component. After drying for 18 hours under flowing nitrogen, the titanium content of the obtained solid catalyst component was 2.3 wt%.

[0080] [Polypropylene polymerization] 10 mg of the solid catalyst, 10 mmol of triethylaluminum as a cocatalyst component, and 1 mmol of dicyclopentyldimethoxysilane as an external electron donor were placed in a 4 L stainless steel high-pressure reactor. 5,000 mL of hydrogen and 2.4 L of liquid propylene were then added, and the temperature was raised to 70°C to carry out polymerization. Two hours after the start of polymerization, the reactor temperature was lowered to room temperature and the valve was opened to completely degas the polypropylene inside the reactor.

[0081] The resulting polymer was analyzed and is shown in Table 1. The catalytic activity and stereoregularity were determined by the following methods. (1) Catalytic activity (kg-PP / g-cat) = Amount of polymer produced (kg) ÷ Amount of catalyst (g) (2) Stereoregularity (XI): Weight percentage of insoluble components crystallized and precipitated in mixed xylene (3) Melt flow (g / 10 min): Value measured according to ASTM 1238 at 230°C under a load of 2.16 kg

[0082] Example 2 [Production of spherical carriers] After thoroughly ventilating a 10L glass reactor equipped with a stirrer, oil heater, and refrigerant cooler with nitrogen, 4g of N-bromosuccinimide, 20g of metallic magnesium (powder product with an average particle size of 120μm), and 400ml of absolute ethanol were added, and the temperature of the reactor was maintained at 70°C while operating at a stirring speed of 250 rpm. After about 10 minutes, the reaction began and hydrogen was generated, so the reactor outlet was opened to allow the generated hydrogen to escape, and the pressure in the reactor was maintained at atmospheric pressure.

[0083] After hydrogen generation ceased, the reactor temperature was maintained at 70°C for 1 hour. After 1 hour, 60g of magnesium metal (powder product with an average particle size of 120μm) was added to the reactor along with 1000ml of absolute ethanol and 5g of reaction initiator. This was maintained for 1 hour, followed by 30g of magnesium metal (powder product with an average particle size of 120μm) and 1g of reaction initiator along with 1000ml of absolute ethanol. Finally, 100g of magnesium metal (powder product with an average particle size of 120μm), 1000ml of absolute ethanol, and 7g of reaction initiator were added and maintained for 30 minutes. After this, an additional 400ml of ethanol was added and the mixture was aged for 3 hours until the reaction was complete. After aging, the resulting product was washed three times with 3000ml of normal hexane at 50°C.

[0084] The washed product was dried under flowing nitrogen for 24 hours to obtain 941 g (yield 95.5%) of diethoxymagnesium support as a free-flowing white powdery solid product (α=1.1). The average particle size of the support was 40.2 μm, the particle size distribution index was 0.56, and the apparent density was 0.27 g / cc. The pore volume of diethoxymagnesium measured by the BET method was 0.066 cc / g.

[0085] [Production of solid catalyst component] A catalyst was produced in the same manner as in the production of the solid catalyst of Example 1. The titanium content in the solid catalyst component was 2.3 wt %. Polypropylene polymerization was then carried out in the same manner as in Example 1, and the results are shown in Table 1.

[0086] Example 3 [Production of spherical carriers] After thoroughly ventilating a 10L glass reactor equipped with a stirrer, oil heater, and refrigerant cooler with nitrogen, 3g of N-bromosuccinimide, 40g of metallic magnesium (powder product with an average particle size of 130μm), and 800ml of absolute ethanol were added, and the temperature of the reactor was maintained at 70°C while operating at a stirring speed of 250 rpm. After about 10 minutes, the reaction began and hydrogen was generated, so the reactor outlet was left open to allow the generated hydrogen to escape, and the pressure in the reactor was maintained at atmospheric pressure.

[0087] Once hydrogen generation ceased, the reactor temperature was maintained at 70°C for 1 hour. After 1 hour, 60g of metallic magnesium (powder product with an average particle size of 130μm), 1200ml of absolute ethanol, and 4g of reaction initiator were added to the reactor and maintained for 1 hour. Finally, 85g of metallic magnesium (powder product with an average particle size of 130μm), 1300ml of absolute ethanol, and 6g of reaction initiator were added and maintained for 30 minutes. After that, an additional 400ml of ethanol was added and the mixture was aged for 3 hours until the reaction was complete. After aging, the resulting product was washed three times at 50°C using 3,000ml of normal hexane each time.

[0088] The washed product was dried under flowing nitrogen for 24 hours to obtain 796 g (yield 91.4%) of diethoxymagnesium support as a free-flowing white powdery solid product (α=1.2).

[0089] The average particle size of the support was 39.2 μm, the particle size distribution index was 0.61, and the apparent density was 0.28 g / cc. The pore volume of diethoxymagnesium measured by the BET method was 0.068 cc / g.

[0090] [Production of solid catalyst component] A catalyst was produced in the same manner as in the production of the solid catalyst of Example 1. The titanium content in the solid catalyst component was 2.2 wt %. Polypropylene polymerization was then carried out in the same manner as in Example 1, and the results are shown in Table 1.

[0091] Example 4 [Production of spherical carriers] A 5L glass reactor equipped with a stirrer, oil heater, and reflux condenser was thoroughly ventilated with nitrogen, and then 2g of N-bromosuccinimide, 10g of metallic magnesium (powder product with an average particle size of 110μm), and 250ml of absolute ethanol were added, and the temperature of the reactor was maintained at 65°C while operating at a stirring speed of 200 rpm. After about 10 minutes, the reaction began and hydrogen was generated, so the reactor outlet was opened to allow the generated hydrogen to escape, and the pressure in the reactor was maintained at atmospheric pressure.

[0092] Once hydrogen generation ceased, the reactor temperature was maintained at 65°C for 1 hour. After 1 hour, 20g of metallic magnesium (powder product with an average particle size of 110μm), 300ml of absolute ethanol, and 2g of reaction initiator were added to the reactor and maintained for 1 hour. Finally, 40g of metallic magnesium (powder product with an average particle size of 110μm), 600ml of absolute ethanol, and 2g of reaction initiator were added and maintained for 30 minutes. After that, an additional 100ml of ethanol was added and the mixture was aged for 3 hours until the reaction was complete. After aging, the resulting product was washed three times, each time using 3,000ml of normal hexane at 50°C.

[0093] The washed product was dried under flowing nitrogen for 24 hours to obtain 312 g (yield 94.7%) of diethoxymagnesium support as a free-flowing white powdery solid product (α=0.8).

[0094] The average particle size of the support was 42.8 μm, the particle size distribution index was 0.47, and the apparent density was 0.26 g / cc. The pore volume of diethoxymagnesium measured by the BET method was 0.070 cc / g.

[0095] [Production of solid catalyst component] A catalyst was produced in the same manner as in the production of the solid catalyst of Example 1. The titanium content in the solid catalyst component was 2.3 wt %. Polypropylene polymerization was then carried out in the same manner as in Example 1, and the results are shown in Table 1.

[0096] Comparative Example 1 [Production of spherical carriers] After thoroughly ventilating a 5L glass reactor equipped with a stirrer, oil heater, and cooling reflux condenser with nitrogen, 2g of N-bromosuccinimide, 10g of metallic magnesium (powder product with an average particle size of 120μm), and 150ml of absolute ethanol were added, and the temperature of the reactor was maintained at 75°C while operating at a stirring speed of 250 rpm. After about 10 minutes, the reaction began and hydrogen was generated, so the reactor outlet was left open to allow the generated hydrogen to escape, and the pressure in the reactor was maintained at atmospheric pressure.

[0097] Once hydrogen generation had ceased, the reactor temperature was maintained at 75°C for 1 hour. After 1 hour, 30g of metallic magnesium (powder product with an average particle size of 120μm), 400ml of absolute ethanol, and 4g of reaction initiator were added to the reactor and maintained for 1 hour. Finally, 20g of metallic magnesium (powder product with an average particle size of 120μm), 200ml of absolute ethanol, and 2g of reaction initiator were added and aged for 3 hours until the reaction was complete. After aging, the resultant was washed three times at 50°C using 3,000ml of normal hexane each time.

[0098] The washed product was dried under flowing nitrogen for 24 hours to obtain 256 g (yield 90.6%) of diethoxymagnesium support as a free-flowing white powdery solid product (α=2.0).

[0099] The average particle size of the support was 38.7 μm, the particle size distribution index was 0.76, and the apparent density was 0.33 g / cc. The pore volume of diethoxymagnesium measured by the BET method was 0.0085 cc / g.

[0100] [Production of solid catalyst component] A catalyst was produced in the same manner as in the production of the solid catalyst of Example 1. The titanium content in the solid catalyst component was 2.3 wt %. Polypropylene polymerization was then carried out in the same manner as in Example 1, and the results are shown in Table 1.

[0101] Comparative Example 2 [Production of spherical carriers] After thoroughly ventilating a 5L glass reactor equipped with a stirrer, oil heater, and cooling reflux condenser with nitrogen, 7g of N-bromosuccinimide, 60g of metallic magnesium (powder product with an average particle size of 120μm), and 700ml of absolute ethanol were added, and the temperature of the reactor was maintained at 70℃, which is the ethanol reflux state, while operating at a stirring speed of 300rpm. After about 5 minutes, the reaction began and hydrogen was generated, so the reactor outlet was opened to allow the generated hydrogen to escape, and the pressure of the reactor was maintained at atmospheric pressure.

[0102] After hydrogen generation was completed, the temperature and stirring speed of the reactor were maintained at reflux for 2 hours for aging. After aging treatment was completed, the resultant was washed three times with 2,000 ml of normal hexane each time at 50°C.

[0103] The washed product was dried under flowing nitrogen for 24 hours to give 328 g (92.8% yield) of diethoxymagnesium support as a free-flowing white powdery solid product.

[0104] Measurements were performed in the same manner as in Example 1. The average particle size of the dried carrier suspended in normal hexane was 20.6 μm, the particle size distribution index was 1.37, and the apparent density was 0.35 g / cc. The pore volume of diethoxymagnesium measured by the BET method was 0.0078 cc / g.

[0105] [Production of solid catalyst component] In Example 1, 1. Preparation of a solid catalyst, 4.7 g of diisobutyl phthalate was used as the internal donor to prepare a catalyst. The titanium content in the solid catalyst component was 2.2 wt%. Next, polypropylene polymerization was carried out in the same manner as in Example 1, and the results are shown in Table 1.

[0106] [Table 1]

[0107] [Propylene-ethylene copolymer] 5 mg of the solid catalyst was placed in a 2.0 L stainless steel reactor equipped with a stirrer and filled with nitrogen, and 3 mmol of triethylaluminum and 0.3 mmol of cyclohexylmethyldimethoxysilane were then injected. 1.2 L of liquefied propylene and 1,000 mL of hydrogen were then injected. Prepolymerization was carried out at 20°C for 5 minutes, followed by polymerization at 70°C for 30 minutes while injecting 200, 300, and 400 sccm of ethylene through an MFC, yielding a propylene-based copolymer. The results are shown in Table 2. As shown in Table 2, (1) Ethylene propylene rubber content (X / S, wt%): The weight percentage of the component precipitated after extracting the copolymer with xylene and removing the xylene. (2) Ethylene content in copolymer (B-C2, B-C4): The ethylene content measured by sampling the copolymer and using an infrared spectrometer (FT-IR) (calculated based on a calibration curve prepared using standard samples). (3) Melting temperature (Tm) Using a differential scanning calorimetry, the sample was maintained at 200°C for 7 minutes, and then cooled to 40°C at a rate of 10°C / min, while the melting temperature was measured.

[0108] [Table 2]

[0109] As described above, it can be seen from Table 2 that a catalyst having high hydrogen reactivity and narrow molecular weight distribution, as well as high apparent density and activity, can be obtained through a catalyst preparation method using a diether compound according to an embodiment of the present invention, compared to a conventional catalyst.

[0110] [Propylene-ethylene-1-butene terpolymer] 5 mg of the solid catalyst was placed in a 2.0 L stainless steel reactor equipped with a stirrer and filled with nitrogen. 3 mmol of triethylaluminum and 0.3 mmol of cyclohexylmethyldimethoxysilane were then injected, followed by 1.2 L of liquefied propylene and 1,000 mL of hydrogen. Prepolymerization was carried out at 20°C for 5 minutes, and then a fixed amount of 1-butene was injected. Polymerization was carried out at 70°C for 30 minutes while injecting 200, 300, and 400 sccm of ethylene through an MFC, yielding a propylene-based terpolymer. The results are shown in Table 3.

[0111] [Table 3]

[0112] As can be seen from Table 3, according to the embodiment of the present invention, when a propylene copolymer is produced using a Ziegler-Natta catalyst consisting of a support generated by reacting dialkoxy magnesium with a metal halide, titanium halide, an organic electron donor, etc., not only is the agglomeration phenomenon of polymer particles during copolymer production significantly improved, but also a propylene copolymer with a high comonomer content can be produced.

[0113] It is clear that the solid catalyst for propylene polymerization and the propylene polymer mentioned in the above examples can be produced by similarly applying the process for producing a spherical carrier, the process for producing a solid catalyst component, the process for polymerizing polypropylene, and the process for copolymerizing propylene-ethylene, which are exemplified in the above examples 1 to 4, but changing only the starting materials.

[0114] For example, in Example 4, ethylene was used as an example of an olefin, but propylene-1-butene copolymerization can be synthesized using other olefins such as 1-butene instead of the olefin.

[0115] As described above, in one embodiment of the present invention, there is provided a method for preparing a solid catalyst for propylene polymerization, which comprises a support prepared by reacting a dialkoxy magnesium with a metal halide, in which the injection amount and injection frequency of metallic magnesium, alcohol, and initiator, reaction temperature, etc. are controlled, a titanium halide, an organic electron donor, etc., and a method for preparing a propylene polymer using the same.

[0116] In particular, the solid catalyst prepared using the dialkoxymagnesium support used in one embodiment of the present invention can be applied to various types of polypropylene polymerization processes, such as slurry polymerization, bulk polymerization, and gas phase polymerization, and has excellent activity and melt flow properties, allowing for stable production of propylene copolymers with high comonomer contents through copolymerization with alpha olefins. Furthermore, the propylene copolymers produced according to one embodiment of the present invention do not exhibit interparticle clumping even at high comonomer contents, allowing for stable production of products with higher comonomer contents without process problems when applied to commercial processes.

[0117] The above description merely exemplifies the technical concept of the present disclosure, and various modifications and variations may be made by a person skilled in the art without departing from the essential characteristics of the technical concept. Furthermore, since the present examples are intended to illustrate, rather than limit, the technical concept of the present disclosure, the scope of the technical concept is not limited by these examples. The scope of protection of the present disclosure should be interpreted by the following claims, and all technical concepts within the scope equivalent thereto should be interpreted as being within the scope of the present disclosure.

Claims

1. Step (0) of preparing dialkoxy magnesium by reacting metallic magnesium, alcohol, and a reaction initiator, wherein the metallic magnesium is divided into n divided portions and injected separately, and the total number of divided portions is n (n is an integer of 4 or more), the total amount of metallic magnesium injected from the first to n-1 times is represented as N, and the amount (number of moles) of metallic magnesium injected last n times is represented as W, and the injection amount of metallic magnesium is adjusted to satisfy the following formula 1: 1.1≦N / W(α)≦1.2 ...Formula 1 Step (1) of reacting the dialkoxymagnesium prepared in step (0) with a metal halide compound in the presence of an organic solvent; (2) reacting the reaction product of step (1) with one or more internal electron donors while increasing the reaction temperature; and The method for preparing a solid catalyst for propylene polymerization comprises the step (3) of reacting the reaction product of the step (2) with a titanium halide.

2. 2. The method for preparing a solid catalyst for propylene polymerization according to claim 1, wherein the reaction initiator is injected into the reaction system at the start of the reaction in the reaction step.

3. The ratio of the alcohol to the metallic magnesium used to produce the dialkoxymagnesium is 1:5 to 1:100 based on the weight of the metallic magnesium to the volume of the alcohol, 2. The method for producing a solid catalyst for propylene polymerization according to claim 1, wherein the reaction temperature of the metallic magnesium and the alcohol is 25 to 110°C.

4. 2. The method for producing a solid catalyst for propylene polymerization according to claim 1, wherein the catalyst contains 5 to 40% by weight of metallic magnesium, 0.5 to 10% by weight of titanium, 50 to 85% by weight of halogen, and 0.01 to 20% by weight of the internal electron donor.

5. 2. The method for producing a solid catalyst for propylene polymerization according to claim 1, wherein the reaction initiator is at least one of a nitrogen halide compound, a halogen compound, and a magnesium halide.

6. 6. The method for producing a solid catalyst for propylene polymerization according to claim 5, wherein the nitrogen halide compound is any one selected from the group consisting of the following formulas 1 to 4: 【Chemistry 1】 In the formula 1, X is a halogen, and R １ , R ２ , R ３ and R ４ are each independently hydrogen, C1-C12 alkyl, or C6-C20 aryl; 【Chemistry 2】 In the formula 2, each X is independently a halogen; 【Transformation 3】 In the formula 3, X is a halogen, and R １ , R ２ , R ３ and R ４ are each independently hydrogen, C1-C12 alkyl, or C6-C20 aryl; 【Chemistry 4】 In the formula 4, each X is independently a halogen; １ and R ２ are each independently hydrogen, C1-C12 alkyl, or C6-C20 aryl.

7. The halogen compound is Br ２ or I ２ The magnesium halide is one of magnesium chloride (MgCl ２ ), magnesium bromide (MgBr ２ ), magnesium iodide (MgI ２ 6. The method for producing a solid catalyst for propylene polymerization according to claim 5, wherein the catalyst is at least one of the following:

8. 3. The method for producing a solid catalyst for propylene polymerization according to claim 2, wherein the internal electron donor is in the form of a diester such as an aromatic diester or a cyclic diester, or a 1,3-diether.

9. 3. The method for producing a solid catalyst for propylene polymerization according to claim 2, wherein the solid catalyst contains 0.01 to 20% by weight of an internal electron donor.

10. (A) producing a solid catalyst by the method for producing a solid catalyst for propylene polymerization according to any one of claims 1 to 9; (B) A method for producing a propylene-based polymer, in which polypropylene is polymerized, or propylene and other alpha-olefins are copolymerized, or terpolymerized in the presence of the solid catalyst produced in step (A), an alkylaluminum compound as a co-catalyst, and R1mR2nSi(OR3)(4-m-n) as an external electron donor (R1 and R2 may be the same or different and each independently represent a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, or an aryl group; R3 represents a linear or branched alkyl group having 1 to 6 carbon atoms; m and n each represent 0 or 1, and m+n represents 1 or 2).

11. The alkylaluminum compound is AlR ３ (wherein R is an alkyl group having 1 to 6 carbon atoms)

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