KR100353120B1 - Method for Preparing a Supported Metallocene Catalyst - Google Patents

Abstract

The present invention relates to a method for preparing a supported metallocene solid catalyst for olefin polymerization by semi-recrystallization, wherein recrystallization is performed in a non-uniform solution state in which a part of a magnesium halide carrier, which is a solid component, is partially dissolved in a catalyst manufacturing process. A method of preparing a supported metallocene catalyst which is used to copolymerize various olefins and styrenes by carrying a metallocene derivative on a modified carrier by modifying a magnesium carrier, and polyethylene and ethylene / α-olefins, in particular ethylene / styrene It relates to a method of producing a copolymer. More specifically, as the supported metallocene solid catalyst system for olefin polymerization, a compound containing an electron donor such as an alcohol derivative, an amine and phosphorus derivative, an ether and a sulfide derivative or an acid derivative composed of elements of Groups VA and VIA of the periodic table (A ) And a metal compound (B) and magnesium halides (C) in combination with alkoxy and a metal of Groups IB to IVB of the periodic table cause a catalytic reaction, and the general formula M (R) _n (M = Mg, B, Al And olefin polymerization or copolymerization with a supported metallocene catalyst obtained by treating an alkyl metal compound (D) represented by Zn) and reacting a metallocene derivative (E). The present invention does not require a separate process for removing residual catalyst due to high polymerization activity, and the post-treatment process after the preparation of the catalyst is simple, thereby reducing manufacturing costs.

Description

Method for preparing supported metallocene solid catalyst for olefin polymerization {Method for Preparing a Supported Metallocene Catalyst}

The present invention relates to a method for producing a solid catalyst for olefin polymerization on which metallocene is supported by semi-recrystallization and a method for producing polyolefin using the same. More specifically, the supported metallocene solid for olefin polymerization using the method of preparing a solid catalyst for polymerization by a semi-recrystallization method in which a solid component, which is one of the catalyst components, is not completely dissolved but is partially dissolved in the catalyst manufacturing process. It relates to a method for producing a catalyst. The supported metallocene catalyst of the present invention is ethylene polymerization and homopolymerization of propylene, 1-butene, 1,3-butadiene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, styrene, etc. And a catalyst system capable of copolymerization.

The existing Ziegler-Natta catalyst system refers to a heterogeneous catalyst system composed of a combination of a main catalyst composed mainly of transition metal compounds, a cocatalyst composed of an organic metal compound, and an electron donor. More specifically, the Ziegler-Natta type polymerization catalyst is basically composed of titanium halide supported on magnesium compound complexed with alkylaluminum. Magnesium compounds used as carriers include, for example, dialkyl magnesiums such as dichloromagnesium, dibromo magnesium, diaiod magnesium, chloroethoxymagnesium, diethoxy magnesium, and dibutoxymagnesium, such as dialkoxymagnesium, diemagnesium and dibutylmagnesium. Magnesium, and chlorohydroxymagnesium and dihydroxymagnesium. Among the most widely used among them, dichloromagnesium, diethoxymagnesium, chlorohydroxymagnesium, dialkylmagnesium, and the like are variously used. Examples of synthesizing a catalyst using such various magnesium carriers include US Pat. No. 4,218,339; 4,439,540; 4,115,319, European Patents: 0,412,696; It was announced a lot at 0,412,750. In particular, dichloromagnesium and diethoxy magnesium not only vary the shape and size of the synthesized catalyst depending on the shape and size of the particles, but also determine the shape, size and particle size distribution of the polymerized polymer. , Shape, porosity, etc. determine the size and shape of the polymer after polymerization. That is, when the carrier particles are close to the spherical shape, the bulk density (g / ml) of the polymer may increase after polymerization, which is directly related to the production capacity of commercial scale polyolefins, and having a uniform particle size distribution It is a very important problem from the point of view of post-processing such as production capacity and transportation of the device. Therefore, these magnesium compounds have been tried to have a uniform, fine, spherical uniform particle shape by milling, recrystallization, or semi-crystallization.

Since the method of pulverization depends on the type and size of magnesium compounds according to variables such as the type of pulverizer and the pulverization time, it is appropriate for the type of olefin and the type of polymerization adopted by the skilled technicians in consideration of these conditions. Can be chosen. Examples of catalytic synthesis through such grinding are disclosed in US Pat. Nos. 4,777,216, 4,487,845 and the like.

In general, magnesium compounds can be obtained by recrystallization by a solvent method, temperature difference, and drying under reduced pressure by solubility difference. In this case, the choice of solvent plays an important part, and at the same time, US Patent 4,469,648 recrystallizes the solution obtained by reacting chloromagnesium and ethanol.The temperature, flow rate, and flow rate must be well controlled to obtain the desired shape and size (diameter 1). It is reported that magnesium compounds having spherical particles in the range of -5,000 microns can be obtained. However, this recrystallization method has problems such as separation and drying of solid magnesium compounds from the liquid phase, and other examples are disclosed in US Pat. No. 3,308,221.

The semirecrystallization method provides a lot of information for particle control by partially crystallizing the heterogeneous solution rather than the complete homogeneous solution. Compared to recrystallization and anti-recrystallization, the recrystallization method is highly affected by external conditions (eg temperature, velocity, solvent, etc.) because it precipitates solids from the complete homogeneous solution, but the semi-recrystallization method is used for some homogeneous solutions. Precipitates the solid from the heterogeneous solution containing, but is not significantly affected by the external conditions, but in order to obtain a solid with the particles controlled from the heterogeneous solution, a component or a factor capable of controlling the particles is required. The inventor has already filed a Korean patent (Korean Patent Application Publication No. 1999 75692, 1999. 10. 15).

In contrast, metallocene catalysts based on two cyclopentadienyl groups are known as homogeneous catalysts as a kind of organometallic compound. Metallocene catalysts generally exhibit high activity and have a single polymerization activity point, which not only has a narrow molecular weight distribution of about 2, but also has a uniform distribution of copolymers. In the conventional Ziegler-Natta catalyst system, the stereospecificity of the catalyst is regulated in the coordination unsaturation of the polymerized active species present on the solid surface, whereas in the metallocene catalyst system, the isotropic (C _2V symmetry) isotropy is changed by changing only the symmetry of the ligand. From tactics (C ₂ symmetry) to syndiotactic (C _S symmetry), various changes in stereospecificity, molecular weight, and catalytic activity of polymers are shown. The metallocene catalyst is largely composed of four parts: a central metal,? Ligand, bridge structure, and? Ligand. The polymerization mechanism of the olefin is affected by the structural change of the metallocene catalyst due to the change of the central metal and the ligand and the subsequent electrical and steric influences, and thus the activity of the catalyst, molecular weight and stereospecificity of the polymerized polymer are changed. . In addition, the copolymerization of the olefin is better than the conventional Ziegler-Natta catalyst, which can greatly increase the content of the comonomer in the polymer and enable the production of a homogeneous copolymer having a high randomness, and cyclo olefins such as cyclopentene and norbornene. Or high polar olefins other than olefins having a bulky substituent such as styrene, 1.3-dienes, and α.ω-dienes. Reports on α-olefin polymerization using such metallocene catalysts have been published in US Pat. Nos. 4,730,071, 4,892,851 and the like.

On the other hand, a half metallocene catalyst having one cyclopentadienyl group exhibits polymerization activity not only in ethylene but also in styrene. In particular, the polymerization is carried out in combination with methyl aluminoxane in cyclopentadienyl titanium trichloride or cyclopentadienyl titanium trialkoxide. Syndiotactic polystyrene (sPP) is synthesized by Idemitsu, Japan, and is disclosed in European Patent Publications 210,615, 312,976 and U.S. Patent 5,037,907. In addition, Constrained Geometry Catalyst, also known as CGC catalyst, has a long side chain structure for ethylene polymerization. Very useful for the preparation of polyethylene (LLDPE) is disclosed in European Patent Publication 416,815.

However, under polymerization conditions in which polymers are formed as solid particles, such as slurries or gas phase polymerization, homogeneous metallocene catalysts form polymer deposits on the reactor walls and stirrers, and these deposits provide efficient heat exchange needed for cooling the reactor contents. They must be removed frequently as they interfere with and cause excessive wear on the rotating parts of the reactor. In addition, polymers formed by metallocene catalysts have a low bulk density, which limits commercial viability for both polymer and polymerization processes. In order to solve these problems in gas phase and slurry processes, and to maintain good polymer particles, it is necessary to carry out metallocene catalyst support.

As a support of the conventional metallocene catalyst, all organic and inorganic materials having pores are used as they are, or in the case of inorganic materials, inorganic materials surface-treated with organic compounds having hydrophobic functional groups are used to increase the carrying efficiency, and silica is mainly used as a support. It is becoming. As a method of supporting a metallocene catalyst, a method of covalently bonding a metallocene catalyst to the surface of a carrier is known, which is a method of bonding a moisture-sensitive organometallic compound to a silanol group (Si-OH) on a silica surface. The supporting method can be largely divided into two types, one is to directly support the metallocene catalyst on the silica carrier, and the other is to support the silica carrier after surface treatment with another compound. However, the supporting method inevitably deforms the form of the metallocene catalyst inevitably during the supporting process, and thus has a disadvantage in that the polymerization activity of the supported catalyst is very small. For example, US Pat. Nos. 4,808,561, 4,912,075 and 4,904,631 disclose methods for preparing supported catalysts that combine metallocenes after surface treatment of silica with methylaluminoxane or surface treatment of silica with alkylaluminum. have. Another example of attempting metallocene support using silica as a support is disclosed in US Pat. Nos. 4,659,685, 5,057,475 and the like. In addition, US Pat. No. 5,308,811 discloses a method for preparing a supported metallocene catalyst using various carriers, that is, clay, clay mineral, ion-exchanged layered compound, or silicate, but this method is also a surface-treated carrier. Since the metallocene catalyst is supported through chemical bonding, the amount of the supported catalyst and the cocatalyst is very small, and when supported, the form of the metallocene catalyst is deformed, thereby rapidly decreasing the activity of the supported catalyst.

Meanwhile, it is disclosed in US Pat. No. 5,075,394 that the production of ultra high molecular polyethylene using alumina (Al ₂ O ₃ ) in a manner similar to that of silica is possible.

Examples using magnesium chloride (MgCl ₂ ) carriers having superior activity by supporting them compared to silica (SiO ₂ ) or alumina (Al ₂ O ₃ ) have been published. For example, in European Patent Publication 412,750, magnesium chloride is disclosed. Supported metallocene was synthesized by reacting a titanocene complex on a modified magnesium chloride carrier obtained by reacting titanium butoxide with a silane compound. In US Pat. No. 5,439,995, dibutylmagnesium, isoamyl ether and t-butylchloride are reacted. The supported metallocene was synthesized by reacting a zirconocene complex on the obtained magnesium chloride. As another example, European Patent 436,328 reports that a polymer having a wide molecular weight distribution can be obtained by preparing and polymerizing a metallocene catalyst without the chemical reaction by magnesium reaction by copulverization. Doing.

The modification method of the magnesium compound used as a carrier in the present invention is a semi-recrystallization method to obtain various information for particle control by partially crystallizing the heterogeneous solution rather than the complete homogeneous solution. In comparison with the recrystallization method and the semi-recrystallization method, the recrystallization method is significantly affected by external conditions (eg, temperature, velocity, solvent, etc.) because it precipitates a solid from a completely homogeneous solution. However, since the semi-recrystallization method of the present invention precipitates a solid from a heterogeneous solution containing some homogeneous solution, it is not significantly affected by the external conditions, but the particles are controlled to obtain a controlled solid from the homogeneous solution. You need ingredients or factors that can be used. The first component is an alcohol derivative (ROH, RSH, etc.) consisting of elements containing electron donors (groups VA and VIA of the periodic table), amine and phosphorus derivatives (RNH ₂ , R ₂ NH, R ₃ N, R ₃ P, etc.), an ether derivative (ROR, RSR, etc.) or an acid derivative (RCO OH, RCOSH), etc. (A) R having 1 to 20 carbon atoms, preferably 1 to 10 Alkyl aryl or cycloalkyl group. The second component is a metal compound (B) of group IB to IVB of the periodic table containing an alkoxy group, and the general formula M (OR) _n (M represents a metal of group IB to IVB of the periodic table, R is 1 to 16 carbon atoms, Preferably an alkyl, aryl or cycloalkyl group having 1 to 10, and n represents the valence of the metal (M). The present invention provides a highly active supported metallocene solid catalyst by reacting a compound containing an electron donor, a metal compound combining a metal and an alkoxy group, magnesium halide, and a metallocene derivative, and using the same to prepare a polyolefin. To simplify the shape and manufacturing process.

The supported metallocene catalyst of the present invention has a high polymerization activity corresponding to the existing Ziegler-Natta polymerization catalyst, while a low polymerization activity polymer is obtained as the existing supported metallocene catalyst. In addition, the present invention shows high polymerization activity in general alkyl aluminum cocatalysts compared to conventional supported metallocene catalysts using expensive aluminoxane cocatalysts, and uses environmentally friendly catalysts by using hexane as a reaction solvent in the catalyst manufacturing process. It provides a method of manufacturing. In addition, it is generally known that it is not easy to support metallocene on a magnesium support, and the polymer particles of the supported catalyst are also known to be poor. However, the polymer particles of the supported catalyst of the present invention are excellent in spherical shape, and the anti-recrystallization method is applied. Therefore, it has the characteristics of simultaneously forming the magnesium compound and the activation reaction of the magnesium carrier for supporting the metallocene. That is, it is characterized in that the metallocene is directly supported on the magnesium compound that has undergone the carrier particle formation and activation.

The present invention briefly describes a process for preparing a supported metallocene catalyst by providing a catalyst for olefin polymerization comprising a component composed of a transition metal complex and a component composed of an alkylating agent.

[Manufacturing process of supported metallocene catalyst]

Hydrocarbon solvent, component (A, B, C) → semirecrystallization and carrier activation (component B) → heating → component (D) → semirecrystallization and carrier activation (component D) → solid component washing (hexane) → Component (E) → heating → washing → supported metallocene catalyst → polymerization → polyolefin

In the present invention, the compound (A) containing the electron donor and the metal compound (B) containing the alkoxy group, which can control the modification of the catalyst carrier and the support of the metallocene compound, do not act independently of each other. The catalyst carrier particles are controlled while taking the form of a covalent relationship, that is, a complex reaction scheme.

M (OR ') _n + ROH ↔ M (OR') _n

M (OR ') _n + R ₂ NH ↔ M (OR') _n (R ₂ NH)

M (OR ') _n + ROR ↔ M (OR') _n

M (OR ') _n + RCOOH ↔ M (OR') _n

These alkoxy metal compounds (B) and electron donor compounds (A) react with the halo magnesium carrier (C) used as a solid catalyst carrier while maintaining an equilibrium as in the above formula to modify the carrier. Here are some of the reactions:

MgX ₂ + ROH ↔ MgX ₂ · (ROH)

MgX ₂ + M (OR ') _n ↔ MgX ₂ · [M (OR') _n ]

MgX ₂ + [M (OR ') _n ] · [ROH] ↔ MgX ₂ · [M (OR') _n ] · [ROH]

MgX ₂ + [M (OR ') _n ] · [ROH] ↔ MgX ₂ · [M (OR') _n ]

MgX ₂ + [M (OR ') _n ] · [ROH] ↔ MgX ₂ · (ROH)

The metallocene derivative of component (E) in the catalyst composition of the present invention may be contacted in any order to obtain a supported metallocene catalyst. Contact of each component can be performed by any method generally known. The feature of the present invention lies in the contact method of each component (A), (B), (C), (D), and (E), and is particularly important when the component (E) is introduced during the carrier particle formation process. There may be a method of contacting in the state before the semi-recrystallization, a method of contacting in the granulated state after the semi-recrystallization. In addition, the degree of activation of the magnesium compound is determined by the type of alkyl metal compound of the component (D) used in the formation of the semi-recrystallization process and the use ratio of the alkyl metal compound, and the support of the metallocene derivative and the polymerization of the supported catalyst Affect performance. The addition amount of (A), (B), (D) with respect to the said component (C) is 1: 0.0001-30, 0.01-10, 0.1-10 in molar concentration ratio, respectively. In addition, the addition amount of (E) with respect to the said component (C) is 1: 0.01-10 in molar concentration ratio.

On the other hand, as the alkylating agent component of the present invention, known aluminoxane cocatalysts are preferable, but organic metals belonging to groups IA, IIA, IIB, IIIB, and IVB on the Periodic Table of the Elements and a small number of straight-chain, branched or cycloalkyl groups having 1 to 20 or Organometallic compounds containing halogen atoms are also possible and include general alkylating agents trimethylaluminum, triethylaluminum and triisobutylaluminum. The catalyst according to the invention can be used particularly effectively for olefin polymerization.

As the polymerization method, any known polymerization method can be used, and examples thereof include solution polymerization, high temperature polymerization, slurry polymerization or gas phase polymerization. The polymerization temperature is usually from 10 ° C to 200 ° C, more preferably in the range from 40 ° C to 140 ° C.

Solid supported metallocene catalyst for olefin polymerization according to the present invention is prepared by the combination and reaction of the following components.

(A) Compound containing electron donor

Alcohol derivatives composed of elements of Groups VA and VI of the periodic table (ROH, RSH, etc.), amine and phosphorus derivatives (RNH ₂ , R ₂ NH, R ₃ N, R ₃ P, etc.), ethers and sulfide derivatives (ROR, RSR, etc.) Or, as acid derivatives (RCOOH, RCOSH, etc.), R represents an alkyl, aryl or cycloalkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Alcohols include linear or branched aliphatic alcohols having 1 to 18 carbon atoms, alicyclic alcohols or aromatics such as methanol, methanethiol, ethanol, ethanethiol, isopropanol, isopropanethiol, normal propanol, normal propanethiol, Normal butanol, normal butane thiol, iso butanol, isobutane thiol, hexanol, hexanethiol, octanol, octane thiol, 2-ethylhexanol, ethylene glycol, glycerol and the like. Amine, trimethylphosphine, trimethylphosphide, ethylamine, diethylamine, triethylamine, triethylphosphine, triethylphosphite, butylamine, dibutylamine, tributylphosphine, tributylphosphite and the like. And sulfide derivatives include dimethyl ether, dimethyl sulfide, diethyl ether, diethyl sulfide, diisoamyl ether, diisoamyl Sulfide or the like acid derivative may include acid, acid, thio acid benzene.

(B) a metal compound containing an alkoxy group

A compound in which metals of Groups IB to IVB of the periodic table and various alkoxy groups are combined, and is a general formula M (OR ') _n or M (OR') _nm X _m (M represents a metal of Groups IB to IVB of the periodic table and R 'is An alkyl, aryl or cycloalkyl group having 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, X represents a halide group, n represents the valence of the metal (M) and m is substituted for M (metal) A halide group number). Examples of the alkoxy group-containing metal compound include alkoxy titanium trihalides such as titanium ethoxy trichloride, titanium normal butoxy trichloride, titanium ethoxy tribromide and titanium isobutoxy tribromide; Dialkoxy titanium dihalides such as titanium dimethoxy dichloride, titanium diethoxy dichloride, titanium dinormal butoxy dichloride, and titanium diethoxy dibromide; Trialkoxy titanium monohalides, such as titanium trimethoxy chloride, titanium triethoxy chloride, titanium tri normal butoxy chloride; Titanium tetraalkoxides, such as titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetra normal butoxide, titanium tetra isobutoxide, and titanium tetra (2-ethylhetoside), and tetraethoxy zirconium , Tetrabutoxy zirconium, tetraethoxy hafnium, tetra tertiary butoxy hafnium and the like. Among these, titanium tetraalkoxides, in particular titanium tetraethoxide, are preferred for the post-treatment process in the preparation of the catalyst. These alkoxymetal compounds may be used alone or in combination of two or more.

(C) magnesium halide

Magnesium halide in the present invention is represented by the general formula MgX ₂ and X is a halogen element and X can be represented by MgX (OR) substituted by another substituent, where R is 1 to 10 carbon atoms, preferably 1 To 5 or R may be hydrogen. For example, magnesium difluoride, dichloro magnesium, dibromo magnesium, diaiod magnesium, chlorohydroxy magnesium, chloroethoxy magnesium, chloromethoxy magnesium, allyloxy magnesium chloride, etc. are mentioned. In particular, magnesium chloride is preferably used.

Magnesium halide compounds may be used with a surface area of 1m ² / g to 300m ² / g, and commercially available magnesium halides of 1m ² / g to 25m ² / g may also be used as they are. It is more preferable to use what made surface area 30m <^2> / g-300m <^2> / g.

(D) alkyl metal compounds

It is represented by the general formula M (R) _n , M is Mg, B, Al, Zn and the like, n is a metal atom and R is an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. There is also an alkoxy form in which oxygen is inserted in R, and in some cases halogen or hydrogen is substituted for R. For example, butyl ethyl magnesium, dinormal hexyl magnesium, trimethyl aluminum, methylaluminoxane, diethyl aluminum bromide, diethyl aluminum chloride, diethyl aluminum iodide, diethyl aluminum ethoxide, diethyl aluminum hydride, di Ethyl zinc, triethylborane, ethylaluminum sesquichloride. Diisobutyl aluminum chloride, diisobutyl aluminum ethoxide, diisobutyl aluminum hydride, triisobutyl borane, triisobutyl aluminum, trinormal hexyl aluminum, trinormal octyl aluminum, trinormal octyl borane, and the like.

(E) metallocene derivatives

The metallocene derivatives usefully used in the present invention may not contain one, in principle, containing at least one cyclopentadienyl ring. The metals are IVB, VB, VIB and Group VIII metals, with Group IVB and VB metals being preferred, preferably titanium, zirconium, hafnium, chromium, vanadium and especially titanium and zirconium. The cyclopentadienyl ring may be unsubstituted or contain a substituent such as a hydrocarbyl substituent. The metallocene derivative may contain zero, one, two or three cyclopentadienyl rings, but one or two rings are preferable and have a structure as shown in the following formula (I).

(C _p ) _m MR _n X _q (Ⅰ)

In the formula (I), C _p is a cyclopentadienyl ring or a cyclopentadienyl ring derivative substituted with 1 to 20 carbon atoms.

M is IVB, VB, VIB or Group VIII transition metal,

R is alkyl having 1 to 10 carbon atoms, arylalkyl, alkoxy, amide, halogenated, sulfide, phosphine group

X is halogen.

(m = 0-2, n = 0-4, q = 0-4, and the sum of m + n + q is the same as the oxidation state of the metal.)

Examples of the metallocene represented by the general formula (I) include bis (cyclopentadienyl) titanium dimethyl, bis (cyclopentadienyl) titanium diphenyl, bis (cyclopentadienyl) zirconium dimethyl and bis (cyclopentadienyl). Titanium diphenyl, bis (cyclopentadienyl) hafnium dimethyl and diphenyl, bis (cyclopentadienyl) titanium diopentyl, bis (cyclopentadienyl) zirconium diopentyl, bis (cyclopentadienyl) titanium Dialkylmetallocenes such as dibenzyl, bis (cyclopentadienyl) zirconiumdibenzyl, bis (cyclopentadienyl) vanadiumdimethyl: bis (cyclopentadienyl) titaniummethylchloride, bis (cyclopentadienyl) titanium Ethyl chloride, bis (cyclopentadienyl) titaniumphenyl chloride, bis (cyclopentadienyl) zirconiummethylchloride, bis (cyclopentadienyl) titanium ethyl chloride, bis (cyclopentadienyl) Titanium pentyl chloride, bis (cyclopentadienyl) titanium methyl bromide, bis (cyclopentadienyl) titanium methyl iodide, bis (cyclopentadienyl) titanium phenyl bromide, bis (cyclopentadienyl) titanium phenyl iodide Such as id, bis (cyclopentadienyl) zirconiummethylblomide, bis (cyclopentadienyl) zirconium iodide, bis (cyclopentadienyl) zirconiummethyl bromide, bis (cyclopentadienyl) zirconiumphenyl iodide Monoalkylmetallocenes: cyclopentadienyl titanium trimethyl, cyclopentadienyl zirconium triphenyl and cyclopentadienyl zirconium trineopentyl, cyclopentadienyl zirconium trimethyl, cyclopentadienyl hafnium triphenyl, cyclopentadienyl hafnium triphenyl Trialkylmetallocenes such as trineopentyl and cyclopentadienylhafniumtrimethyl: cyclopenta Nyl titanium trichloride, cyclopentadienyl zirconium trichloride, cyclopentadienyl hafnium trichloride, pentamethylcyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl zirconium trichloride, pentamethylcyclopentadienyl hafnium trichloride , Trichloride metallocenes such as pentaethylcyclopentadienyl titanium trichloride, pentaethylcyclopentadienyl zirconium trichloride, and pentaethylcyclopentadienyl hafnium trichloride, but are not limited to these.

In the preparation of the catalyst in the present invention, an electron donor compound (A) composed of magnesium halide (C) and elements of Groups VA and VIA of the periodic table and the periodic table IB to the periodic table are selected by selecting a suitable hydrocarbon having 5 to 12 carbon atoms as a solvent. Particles of magnesium halide (C) are deformed as the metal alkoxide (B) in which the group IVB metal is combined with an alkoxy group is partially recrystallized by a chemical reaction in an appropriate temperature range (30 ° C. to 150 ° C.). . When a mixture of an alkyl metal compound (D) or an alkyl metal compound (D) is added dropwise to the mixture of (A), (B), and (C), a complete semi-recrystallization process occurs and crystals of the modified magnesium halide are precipitated. do. The modified magnesium halide solid may be washed with the appropriate hydrocarbon until the impurities are free and then reacted with the metallocene derivative (E) to obtain the final solid metallocene supported catalyst.

The monomer used for the polymerization in the present invention is an α-olefin having the general formula RC ₂ H ₃ , wherein R is hydrogen or an aliphatic or aromatic hydrocarbon having 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms. For example, ethylene, propylene, 1-butene, 1,3-butadiene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, styrene, 4-methylstyrene, etc. are mentioned. In addition, the α-olefin may be copolymerized using a monomer and homopolymerization as well as a mixture of two or more components of the monomer. It is particularly suitable to use ethylene or a mixture of ethylene and the above α-olefins other than ethylene. Polymerization of alpha -olefins is performed by the general method of what is called a Ziegler method. In other words, the polymerization is carried out in a continuous or batch type at a temperature of 20 ° C. to 200 ° C., especially at a slurry phase of 50 ° C. to 100 ° C. and a solution phase at 120 ° C. to 160 ° C. Although polymerization pressure does not need to be specifically limited, Usually, 1-100 kg / cm <2>, Preferably 1-40 kg / cm <2> range is suitable.

The polymerization in the present invention is a solid magnesium-metallocene catalyst prepared by a semi-recrystallization process, and after the 2L stainless steel high pressure reactor is sufficiently substituted with nitrogen, the solvent is subjected to normal hexane under a nitrogen stream (slurry polymerization method). As the cocatalyst, methylaluminoxane or alkyl aluminum is appropriately selected, and the pressure of the monomer is carried out at 20 ° C to 100 ° C for a temperature of 1 to 15 kg / cm 2. And the molecular weight of the polymer can be adjusted using hydrogen.

The following examples are intended to illustrate the present invention in more detail, and these examples do not limit the technical scope of the present invention.

< Example 1>

(a) Preparation of Catalyst

In a 500 mL four-neck round bottom flask equipped with a magnetic stirrer, condenser and temperature sensor under nitrogen stream, 100 ml of hexane and 1.0 g of magnesium chloride were stirred for several minutes, followed by stirring for 1.45 g of ethanol and 7.2 g of titanium tetraethoxide. It is heated to ℃ and reacted for 1 hour to undergo partial semi-recrystallization process. After the reaction was completed, the reaction mixture was cooled to room temperature, and 37 ml of diethylaluminum dilute (15wt%) diluted in normal hexane was added dropwise for 1 hour. As a result of complete semi-recrystallization, some dissolved solids were completely precipitated. do. The reaction solution was slowly heated at room temperature and refluxed for about 1 hour. The supernatant was removed under nitrogen pressure, 100 ml of normal hexane was added, the solids were washed in the order of stirring, standing and removing the supernatant, and then dissolved in 100 ml of toluene and toluene. 2.3 g of cyclopentadienyl titanium trichloride is added thereto, the temperature is raised to 70 ° C., and refluxed for 2 hours to support the metallocene catalyst. The mixture was left to stand after reflux, the supernatant was removed under nitrogen pressure, washed with toluene until no chlorine ion was detected in the supernatant, and dried at 30 to 40 ° C. to obtain a solid catalyst.

(b) Ethylene Polymerization

A 2 liter stainless autoclave equipped with a magnetic stirrer was sufficiently substituted with nitrogen, and 900 ml of hexane was added thereto. Thereafter, 1 ml of methylaluminoxane toluene solution having an Al weight of 9.5% by weight was added as a catalyst component, followed by stirring for several minutes. Then, 3 mg of the solid catalyst prepared in Example (a) was added and the inert gas was removed from the reactor filled with nitrogen. Then, hydrogen was added to 4 kg / cm 2 and the temperature was raised to 65 ° C. The polymerization starts with the addition of ethylene when the temperature reaches 65 ° C. At this time, the ethylene pressure was 7 kg / cm 2 and the total pressure was 11 kg / cm 2 while the polymerization temperature was maintained at 70 ° C. for 50 minutes. After the completion of the polymerization, the unreacted gas was gradually discharged, the reactor was opened, the slurry powder was filtered, and the powder was dried in a vacuum at 40 ° C. for 24 hours. The polymer powder obtained by drying was 153g, the catalytic activity was 51,000g-polymer / g-catalyst, the density was 0.960g / ml, the melting point was 137 ° C, and the MFR was 0.010g / 10 min. The weight average molecular weight (Mw) was 391,000, and the molecular weight distribution (Mw / Mn) was 7.7.

< Example 2>

The same experiment as in Example 1 was conducted except that 2.7 g of cyclopentadienyl zirconium trichloride was used instead of cyclopentadienyl titanium trichloride in preparing the catalyst. The polymer powder obtained by drying was 96 g, the catalytic activity was 32,000 g-polymer / g-catalyst, the density was 0.959, the melting point was 136 ° C, and the MFR was 0.009 g / 10 min. The weight average molecular weight (Mw) was 411,000 molecular weight distribution (Mw / Mn) was 8.0.

< Example 3>

The same experiment as in Example 1 was performed except that 2.6 g of biscyclopentadienyl titanium dichloride was used instead of cyclopentadienyl titanium trichloride in preparing the catalyst. The polymer powder obtained by drying was 145g, the catalytic activity was 48,300g-polymer / g-catalyst, the density was 0.963, the melting point was 137 ° C and the MFR was 0.019g / 10 min. The weight average molecular weight (Mw) was 368,000 molecular weight distribution (Mw / Mn) was 7.2.

< Example 4>

Experiments were carried out in the same manner as in Example 1, except that 3.0 g of biscyclopentadienylzirconium dichloride was used instead of cyclopentadienyl titanium trichloride. The polymer powder obtained by drying was 135 g, the catalytic activity was 45,000 g-polymer / g-catalyst, the density was 0.965, the melting point was 138 ° C, and the MFR was 0.009 g / 10 min. The weight average molecular weight (Mw) was 400,000, and the molecular weight distribution (Mw / Mn) was 7.1.

< Comparative Example 1>

(a) Preparation of Catalyst

In a 500 mL four-neck round bottom flask equipped with a magnetic stirrer, condenser and temperature sensor under nitrogen stream, 2.0 g of silica gel (SiO ₂ ) and biscyclopentadienyl zirconium di calcined sufficiently for 3 hours at 100 ml of toluene and a temperature of 800 ° C. 5.0 g of chloride was added thereto, stirred for several minutes, the temperature was raised to 100 ° C., and reacted for 3 hours to support the metallocene catalyst. After completion of the reaction, the mixture was left to stand, and the supernatant was removed under nitrogen pressure. The supernatant was washed with toluene until no unreacted biscyclopentadienyl zirconium dichloride was detected and dried at 30 to 40 ° C. to obtain a solid catalyst.

(b) Ethylene Polymerization

The polymerization was carried out in the same manner as in the polymerization method of Example 1 (b), except that 30 mg of the silica-supported metallocene catalyst prepared above was used. The polymer powder obtained by drying was 95 g, the catalytic activity was 3,200 g-polymer / g-catalyst, the density was 0.958, the melting point was 134 ° C., and the MFR was 0.06 g / 10 min. The weight average molecular weight (Mw) was 250,000 molecular weight distribution (Mw / Mn) was 4.4.

< Example 5

The polymerization was carried out in the same manner as in Example 1 except that 2 ml of trimethylaluminum diluted in hexane was used instead of methylaluminoxane as a cocatalyst when the catalyst of Example 1 was used. It was. The polymer powder obtained by drying was 92 g, the catalytic activity was 30,700 g-polymer / g-catalyst, the polymer density was 0.961, the melting point was 136 ° C, and the MFR was 0.5 g / 10 min. The weight average molecular weight (Mw) was 176,000, and the molecular weight distribution (Mw / Mn) was 5.4.

< Example 6>

The polymerization was carried out in the same manner as in Example 1, except that 6 ml of triisobutylaluminum diluted in hexane (15 w%) was used as a cocatalyst for the polymerization of the catalyst of Example 1 instead of methylaluminoxane. Was performed. The polymer powder obtained by drying was 65 g, the catalytic activity was 22,700 g-polymer / g-catalyst, the polymer density was 0.961, and the melting point was 137 DEG C. MFR was 0.6 g / 10 min. The weight average molecular weight (Mw) was 180,000, and the molecular weight distribution (Mw / Mn) was 5.7.

< Comparative Example 2>

Except for using unsupported half-metallocene cyclopentadienyl titanium trichloride catalyst, 6 ml of triisobutylaluminum diluted (15 w%) in hexane instead of methylaluminoxane was used as a co-catalyst for polymerization. The polymerization process was carried out in the same manner as in the polymerization example of Example 1, but no polymer was obtained.

< Comparative Example 3>

Except for using unsupported half-metallocene cyclopentadienyl zirconium trichloride catalyst, 6 ml of triisobutylaluminum diluted (15 w%) in hexane instead of methylaluminoxane was used as a co-catalyst in the polymerization. The polymerization process was carried out in the same manner as in the polymerization example of Example 1, but no polymer was obtained.

< Example 7>

The experiment was carried out in the same manner as in Example 1, except that 4.1 g of 2-ethylhexanol was used instead of ethanol. The polymer powder obtained by drying was 155 g, the catalytic activity was 51,700 g-polymer / g-catalyst, the polymer density was 0.963, and the melting point was 137 DEG C. MFR was 0.03 g / 10 min. The weight average molecular weight (Mw) was 330,000, and the molecular weight distribution (Mw / Mn) was 8.1.

< Example 8>

The experiment was carried out in the same manner as in Example 7, except that 2.7 g of cyclopentadienyl zirconium trichloride was used instead of cyclopentadienyl titanium trichloride in preparing the catalyst. The polymer powder obtained by drying was 94 g, the catalytic activity was 31,000 g-polymer / g-catalyst, the polymer density was 0.958, and the melting point was 135 DEG C. MFR was 0.024 g / 10 min. The weight average molecular weight (Mw) was 350,000 molecular weight distribution (Mw / Mn) was 7.6.

< Example 9>

The experiment was carried out in the same manner as in Example 7, except that 3.0 g of biscyclopentadienyl zirconium dichloride was used instead of cyclopentadienyl titanium trichloride in preparing the catalyst. The polymer powder obtained by drying was 125 g, the catalytic activity was 41,600 g-polymer / g-catalyst, the polymer density was 0.960, and the melting point was 135 ° C., MFR was 0.021 g / 10 min. The weight average molecular weight (Mw) was 361,000 molecular weight distribution (Mw / Mn) was 7.9.

< Example 10>

The experiment was carried out in the same manner as in Example 1, except that 61 ml of triisobutylaluminum was used instead of diethylaluminum chloride diluted in normal hexane (15 wt%). The polymer powder obtained by drying was 120 g. The catalytic activity was 40,000 g-polymer / g-catalyst, the polymer density was 0.965, and the melting point was 137 DEG C. The MFR was 0.012 g / 10 min. The weight average molecular weight (Mw) was 388,000 and the molecular weight distribution (Mw / Mn) was 7.1.

< Example 11>

The experiment was carried out in the same manner as in Example 10, except that 2.7 g of cyclopentadienyl zirconium trichloride was used instead of cyclopentadienyl titanium trichloride in preparing the catalyst. The polymer powder obtained by drying was 81 g. The catalytic activity was 27,000 g-polymer / g-catalyst, the polymer density was 0.960, and the melting point was 137 DEG C. The MFR was 0.012 g / 10 min. The weight average molecular weight (Mw) was 390,000, and the molecular weight distribution (Mw / Mn) was 7.4.

< Example 12>

The experiment was carried out in the same manner as in Example 1, except that 8.9 g of titanium tetraisooxide and 2.7 g of cyclopentadienyl zirconium trichloride were used instead of titanium tetraethoxide and cyclopentadienyl titanium trichloride. It was. The polymer powder obtained by drying was 116 g, the catalytic activity was 38,700 g-polymer / g-catalyst, the polymer density was 0.961, and the melting point was 137 ° C.

< Example 13>

The polymerization was carried out in the same manner as in Example 1 except that 4 kg / cm 2 of propylene was added after hydrogen was added during polymerization using the catalyst of Example 1. The copolymer powder obtained by drying was 98 g, the catalytic activity was 33,000 g-polymer / g-catalyst, and the polymer density was 0.936 g / ml.

< Example 14>

The copolymerization was carried out in the same manner as in Example 13, except that the catalyst of Example 2 was used. The polymer powder obtained by drying was 83 g, the catalytic activity was 27,700 g-polymer / g-catalyst, and the density was 0.945 and the melting point was 129 ° C.

< Example 15>

In a 500 ml glass reactor equipped with a magnetic stirrer, 200 ml of toluene and 20 ml of styrene were added, and 1 ml of methylaluminoxane toluene solution having an Al weight of 9.5% was added and stirred for several minutes. 20 mg of the solid catalyst prepared in Example 1 was added and the inert gas was removed using a vacuum pump in a reactor filled with nitrogen. Then, polymerization was started by adding ethylene, flowing ethylene under atmospheric pressure, and the polymerization temperature was maintained at 60 ° C. 2 Polymerize for time. After the polymerization is completed, the unreacted gas is discharged, the reaction is terminated with hydrochloric acid-treated methanol, washed several times, the slurry powder is filtered, and the powder is dried under vacuum for 24 hours. The polymer powder obtained by drying was 45 g, the catalytic activity was 2,200 g-polymer / g-catalyst, and the melting point was 97, 126, and 259 ° C., respectively, and a mixture of ethylene-styrene copolymer, ethylene homopolymer, and syndiotactic styrene polymer was used. Obtained.

< Example 16>

The same process as in Example 15 was carried out except that the catalyst of Example 2 was used. The polymer powder obtained by drying was 31 g, and the catalytic activity was 1,600 g-polymer / g-catalyst, and the melting point was only 134 ° C. In this case, the styrene polymerization or ethylene-styrene copolymerization did not occur, but only ethylene homopolymer was obtained. lost.

< Example 17>

Catalytic synthesis was carried out under the same conditions as in Example 1 (a), except that 2.0 g of cyclopentadienyl titanium triphenoxide was used instead of cyclopentadienyl titanium trichloride in the preparation of the catalyst. It was carried out. The polymer powder obtained by drying was 55 g, and the catalytic activity was 2,800 g-polymer / g-catalyst, and the melting point was 89, 128, and 257 ° C., respectively, and a mixture of ethylene-styrene copolymer, ethylene homopolymer, and syndiotactic styrene polymer was used. Obtained.

< Example 18>

The catalyst synthesis was carried out under the same conditions as in Example 1 (a), except that 1.3 g of cyclopentadienyl titanium trimethoxide was used instead of cyclopentadienyl titanium trichloride in preparing the catalyst, and the copolymerization was the same as in Example 15. It was carried out. The polymer powder obtained by drying was 49 g, and the catalytic activity was 2,500 g-polymer / g-catalyst, and the melting point was 101, 130, and 256 ° C., respectively, and a mixture of ethylene-styrene copolymer, ethylene homopolymer, and syndiotactic styrene polymer was used. Obtained.

< Example 19>

Example 1 except that 20 g of titanium tetrachloride instead of cyclopentadienyl titanium trichloride and 6 ml of triisobutylaluminum diluted (15 w%) in hexane instead of methylaluminoxane were used as a cocatalyst in the polymerization. The same experiment as was performed. The polymer powder obtained by drying was 164 g, the catalytic activity was 54,700 g-polymer / g-catalyst, the density was 0.964, the melting point was 133 ° C, and the MFR was 0.7 g / 10 min. The weight average molecular weight (Mw) was 171,000, and the molecular weight distribution (Mw / Mn) was 5.6.

The polymerization results of the above examples and the physical property analysis of the obtained polymer are summarized in Table 1.

Table 1 Polymerization and Physical Property Results of Examples

Example Polymer production amount (g) Activation (g-polymer / g-catalyst) Density (g / ml) Melting Point (℃) MFR (g / 10min) Molecular Weight (Mw) Molecular Weight Distribution (Mw / Mn) Remarks One 153 51,000 0.960 137 0.010 391,000 7.7 Ethylene Homopolymerization 2 96 32,000 0.959 136 0.009 411,000 8.0 ' 3 145 48,300 0.963 137 0.019 368,000 7.2 ' 4 135 45,000 0.965 138 0.009 400,000 7.1 ' Comparative Example 1 95 3,200 0.958 134 0.06 250,000 4.4 ' 5 92 30,700 0.961 136 0.5 176,000 5.4 ' 6 65 22,700 0.961 137 0.6 180,000 5.7 ' Comparative Examples 2 and 3 Not polymerized 7 155 51,700 0.963 137 0.03 330,000 8.1 ' 8 94 31,000 0.958 135 0.024 350,000 7.6 ' 9 125 41,600 0.960 135 0.021 361,000 7.9 ' 10 120 40,000 0.965 137 0.012 388,000 7.1 ' 11 81 27,000 0.960 137 0.012 390,000 7.4 ' 12 116 38,700 0.961 137 - - - ' 13 98 33,000 0.936 125 - - - Ethylene-propylene Copolymerization 14 83 27,700 0.945 129 - - - Ethylene-propylene Copolymerization 15 45 2,200 - 97,126,259 - - - Ethylene-styrene copolymerization (see claims 9 and 10) 16 31 1,600 - 134 - - - No ethylene-styrene copolymerization 17 55 2,800 - 89,128,257 - - - Ethylene-styrene copolymerization (see claims 9 and 10) 18 49 2,500 - 101,130,256 - - - Ethylene-styrene copolymerization (see claims 9 and 10) 19 164 54,700 0.964 133 0.7 171,000 5.6 See claim 7

The yield of the polymer produced using the supported metallocene solid catalyst of the present invention is about 10 or more higher than the conventional supported metallocene catalyst, the molecular weight is about 1.6 times higher and the molecular weight distribution is about 1.6 times wider. Although the conventional unsupported metallocene is hardly active in the general alkylaluminum cocatalyst, the supported metallocene solid catalyst of the present invention exhibits high activity in the general alkylaluminum cocatalyst and has a uniform particle shape and thus the separation of the polymer in the slurry process. Separation and filtration can be facilitated in the drying process. In particular, since solid catalysts have high polymerization activity, no separate deliming process is required to remove residual catalysts, manufacturing costs can be reduced in the production process, and metallocene supported catalysts without additional equipment investment on existing Ziegler-Natta catalyst manufacturing facilities. Manufacturing is possible. In addition, the supported metallocene solid catalyst of the present invention is capable of preparing not only homo (single) polymers of α-olefins but also copolymers, in particular ethylene-styrene copolymers.

Claims (10)

In the supported metallocene solid catalyst for olefin polymerization, a compound (A) containing an electron donor, a metal compound (B) in combination with a metal and an alkoxy group, and a halogen-containing magnesium (C) are partially in contact with each other, causing a reaction. The supported metallocene solid catalyst for olefin polymerization is formed by recrystallization, addition of an alkyl metal compound (D) to complete semi-recrystallization, reaction of the metallocene derivative (E) and washing with a solvent to obtain a solid catalyst. Manufacturing Method The compound (A) is an alcohol derivative, an amine and phosphorus derivative, an ether and sulfide derivative or an acid derivative composed of elements of Groups VA and VIA of the periodic table, and the electron donor compound is represented by the following general formula The molar ratio of the component (C) is in the range of 1 × 10 ⁻⁴ to 30, wherein the supported metallocene solid catalyst for olefin polymerization is used. Formula: ROH, RSH, RNH ₂ , R ₂ NH, R ₃ N, R ₃ P, R ₃ PO, ROR, RSR, RCOOH, RCOSH (Wherein R represents an alkyl group having 1 to 10 carbon atoms) The component (B) is an alkoxy metal compound in which a metal and an alkoxy group of the Groups IB to IVB of the periodic table are combined, and is represented by the following general formula. The molar ratio of the component (C) to the component (C) is 1 × 10. Method for producing a supported metallocene solid catalyst for olefin polymerization, characterized in that from ^-2 to 10 Formula: X _4-n M (OR) _n (Wherein M represents a metal of Groups IB to IVB of the periodic table, and R represents an alkyl group having 1 to 16 carbon atoms. 1 ≦ n ≦ 4) The method for producing a supported metallocene solid catalyst for olefin polymerization according to claim 1, wherein the magnesium halides of the component (C) are compounds represented by the following general formula. Formula: MgXY (Wherein X represents a halogen element and Y represents a halogen element or an alkyl or alkoxy group having 1 to 5 carbon atoms) The method of claim 1, wherein the alkyl metal compound of the component (D) is a compound represented by the following general formula, characterized in that the molar ratio range of the component (C) is 1 × 10 ^-1 to 10 Method for preparing metallocene solid catalyst General formula: R _n MX _3-n (Wherein M represents Mg, B, Al, Zn, etc., R represents an alkyl group having 1 to 16 carbon atoms and n represents a metal valence.) The method for producing a supported metallocene solid catalyst for olefin polymerization according to claim 1, wherein the metallocene derivative of component (E) is a compound represented by the following general formula. Formula: (C _p ) _m MR _n X _q Wherein C _p is a cyclopentadienyl ring or a cyclopentadienyl ring derivative substituted with 1 to 20 carbon atoms, M is a IVB, VB, VIB or group VIII transition metal, and R is 1 to 10 carbon atoms Alkyl, arylalkyl, alkoxy, amide, halogenide, sulfide, phosphine group, X is halogen (m = 0-2, n = 0-4, q = 0-4, m + n + q Sum equals the oxidation state of the metal) 7. The solid catalyst for olefin polymerization according to claim 6, wherein the derivative of component (E) is titanium halide with M = titanium (Ti), m = 0, n = 0, q = 4, in particular titanium tetrachloride. Manufacturing method. The semi-recrystallization process according to claim 1, wherein the components (A), (B) and (C) are partially recrystallized in a non-uniform solution state at a temperature of 0 to 150 DEG C for 10 minutes to 6 hours. A method of preparing a supported metallocene solid catalyst for olefin polymerization, which is formed and complete recrystallization occurs as the component (D) is added, and then the metallocene derivative of the component (E) is supported on the formed carrier. . The supported metallocene solid catalyst for olefin polymerization according to claim 1 or 8, wherein the supported metallocene solid catalyst for olefin polymerization is prepared by homopolymerization or copolymerization of olefins and a copolymer of ethylene-styrene derivatives. Manufacturing Method 10. The metallocene derivative of component (E) according to any one of claims 6, 8, and 9 as a supported metallocene solid catalyst system for preparing a copolymer of ethylene-styrene derivatives. Method for producing a supported metallocene solid catalyst for olefin polymerization, characterized in that the compound represented by the formula Formula: RMX ₃ (Wherein R is a cyclopentadienyl ring or a cyclopentadienyl ring derivative substituted with 1 to 20 carbon atoms, M is a transition metal such as Ti, Zr, Hf, V, Cr, Co, Ni, Pd, etc.). , X is halogen or aliphatic or aromatic alkoxy group having 1 to 10 carbon atoms.)