KR100270512B1 - The precess for the preparation of solid catalysts for olefin polymerization - Google Patents

Abstract

PURPOSE: A solid catalyst useful in the olefine polymerization process is provided to accomplish high polymerizing activity without requiring alternative treatment for removing residual catalysts by reacting the compounds including electron donor, in combination with metal and alkoxyl group, magnesium halide, alkyl metal compound, titanium halide derivative. CONSTITUTION: A solid catalyst used in the polymerization of olefins comprises the compound A having the VA or VIA family elements on the periodic table as the electron donor; the compound B having the combined material of IB-IVB family metals and the alkoxy group and magnesium halide C. The three compounds react together to form a semi-product under the semi-recrystallization process. The semi-product is added with the alkyl metallic compound D of formula M(R)n (wherein M=Mg, B, Al, Zn) to be fully semi-recrystalized and react with the titanium halide derivative E. The resultant product is washed with any suitable solvent to form the final solid catalyst product. Both of the compounds A and B is contained in an amount of 1x10¬-4 to 30 moles and 1x10¬-2 to 10 moles in terms of 1 mole of the compound C.

Description

[Name of invention]

Method for preparing solid catalyst for olefin polymerization

Detailed description of the invention

[Purpose of invention]

[Technical field to which the invention belongs and the prior art in that field]

The present invention relates to a method for producing a solid catalyst for olefin polymerization using semirecrystallization. In more detail, the present invention relates to a method for preparing a solid catalyst for olefin 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 so that recrystallization occurs. The olefin polymerization catalyst is roughly classified into a heterogeneous catalyst remaining as a solid in the reaction solution and a homogeneous catalyst dissolved in the reaction solution, and the present invention is limited to the heterogeneous catalyst.

The composition of the olefin polymerization catalyst consists of a polymerization catalyst in the form of Ziegler-Natta, an electron donor and an olefin monomer. Conventional techniques for such catalyst systems are disclosed in US Pat. Nos. 4,107,413, 4,294,721, 4,439,540, 4,115,319, 4,220,554, 4,460,701, 4,562,173, and many patents relating to catalyst systems for the polymerization of propylene and ethylene have been published.

Ziegler-Natta type polymerization catalysts consist essentially of titanium halides supported on magnesium compounds 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 catalysts using various magnesium carriers are disclosed in US Pat. In particular, dichloromagnesium and diethoxy magnesium are not only varied in shape and size of the synthesized catalyst depending on the shape and size of particles, but also in shape, size and particle size distribution of the polymerized polymer. In other words, in the heterogeneous catalyst system, the size, shape, and porosity of the carrier particles determine the size and shape of the polymer after polymerization. As the carrier particles become spherical, the bulk density (g / ml) of the polymer after polymerization may increase. It is also important to have a uniform particle size distribution, which is directly connected to the production capacity of polyolefins of scale, from the standpoint of post-treatment such as production capacity and transfer of the polymerization apparatus. Therefore, these magnesium compounds have been tried to have a fine and nearly spherical uniform particle shape by grinding or recrystallization.

Since the type and size of magnesium compounds depend on variables such as the type of grinder and the grinding time, the method of milling is appropriate for the type of olefin and the type of polymerization adopted by those skilled in the art. Can be chosen. Examples of catalytic synthesis through such grinding are disclosed in US Pat. Nos. 4,777,216, 4,487,845, 4,156,063, 4,576,994 and the like.

In general, magnesium compounds can be obtained by crystallization by solvent method, temperature difference, and drying under reduced pressure by solubility difference. In this case, the choice of solvents plays an important part, and at the same time, U.S. Patent 4,469,648 recrystallizes a solution obtained by reacting chloromagnesium and ethanol. It is reported that magnesium compounds with spherical particles in the micron range 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.

[Technical problem to be achieved]

The modification method of the magnesium compound used as a carrier in the present invention is a semi-recrystallization method, which can diversify particle control by partially crystallizing a heterogeneous solution rather than a complete homogeneous solution. The recrystallization method is highly influenced by temperature, velocity, solvent, etc. because it precipitates solids from the complete homogeneous solution, but the anti-crystallization method of the present invention recrystallizes solids from heterogeneous solution containing some homogeneous solution. In order to obtain a solid in which the catalyst particles are controlled from the heterogeneous solution as described above, the components or factors capable of controlling the particles are required. The first component is an alcohol derivative (ROH, RSH, etc.) consisting of elements containing electron donors (groups VA and VIA elements of the periodic table), amine and phosphorus derivatives (RNH ₂ , R ₂ NH, R ₃ N, R ₃ P and the like), ether derivatives (ROR, RSR, etc.) or acid derivative (RCOOH, RCOSH) as the compound (a), such as R is a having 1 to 20 carbon atoms, preferably an alkyl aryl group having from 1 to 10 Or a cycloalkyl group. The second component is a metal compound (B) of group IB-IVB of the periodic table containing an alkoxy group, represented by the general formula M (OR) _n (M represents a metal of group IB-IVB of the periodic table, R is 1-16 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 solid catalyst by reacting a compound containing an electron donor, a metal compound having a metal and an alkoxy group, a magnesium halide, an alkyl metal compound, and a titanium halide derivative, which is used to prepare a polyolefin, and thus the particle shape and size of the polymer. And to improve bulk density and simplify the manufacturing process.

[Configuration and Function of Invention]

A brief description of the process of preparing the solid catalyst and the polyolefin of the present invention is as follows.

In the present invention, the compound (A) containing the electron donor that can control the catalyst particles and the metal compound (B) containing the alkoxy group do not act independently of each other, but control the catalyst particles while taking a covalent relationship, that is, complex form. The typical reaction is as follows.

These alkoxy metal compounds (B) and electron donor compounds (A) react with the halo magnesium carrier (C) used as a solid catalyst while maintaining equilibrium as in the above formula to modify the carrier. Can be displayed as

The solid catalyst for olefin polymerization according to the present invention is prepared by the combination and reaction of the following components.

(A) a compound containing an electron donor

Alcohol derivatives composed of elements of Groups VA and VIA (ROH, RSH, etc.), amine and phosphorus derivatives (RNH ₂ , R ₂ NH, R ₃ N, R ₃ P, etc.), ether 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, preferably 1 to 10, carbon atoms. For example, alcohols include methanol, methanethiol, ethanol, ethanethiol, isopropanol, isopropanethiol, normal propanol, normal propane thiol, normal butanol, normal butane thiol, isobutanol, isobutanthiol, hexanol and hexanethiol , Octanol, octane thiol, 2-ethylhexanol, ethylene glycol, glycerol, and the like.Amine and phosphorus derivatives include methylamine, dimethylamine, trimethylamine, trimethylphosphine, trimethylphosphite, ethylamine, diethylamine and triethyl Amine, triethylphosphine, triethylphosphite, butylamine, dibutylamine, tributylphosphine, tributylphosphite and the like, and ether and sulfide derivatives include dimethyl ether, dimethyl sulfide, diethyl ether, diethyl sulfide, Diisoamyl ether, diisoamyl sulfide and the like, and acid derivatives include acetic acid, butanoic acid and thiobenzene acid.

(B) a metal compound containing an alkoxy group

A compound in which a metal of Groups IB to IVB of the periodic table is combined with various alkoxy groups is represented by the general formula M (OR ') _n (M represents a metal of Groups IB to IVB of the periodic table, and R' is 1 to 16 carbon atoms, preferably Represents an alkyl, aryl or cycloalkyl group having 1 to 10, and n represents the valence of the metal (M). For example, diethoxy zinc, tetramethoxy titanium, tetraethoxy titanium, tetraisopropoxytitanium, tetranormal butoxytitanium, tetra (2-ethylhexyloxy) titanium, chlorotriethoxytitanium, dichlorodiethoxytitanium And dibromo diethoxy titanium, dibromodiaisopropoxytitanium, tetraethoxy zirconium, tetranormal butoxy zirconium and the like.

(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, difluoromagnesium, dichloromagnesium, dibromomagnesium, diaiod magnesium, chlorohydroxymagnesium, chloroethoxymagnesium, chloromethoxymagnesium, etc. are mentioned.

(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, methyl aluminoxane, diethyl aluminum bromide, diethyl aluminum chloride, diethyl aluminum iodide, diethyl aluminum ethoxide, diethyl aluminum hydride, di Ethyl zinc, triethyl borane, ethyl aluminum sesquichloride, diisobutyl aluminum chloride, diisobutyl aluminum ethoxide, diisobutyl aluminum hydride, triisobutyl borane, triisobutyl aluminum, trinormal hexyl aluminum, tri Normal octyl aluminum, and trinormal mal octyl borane.

(E) titanium halide derivatives

General formula Ti (OR) _4-n X _n wherein R is an alkyl group having 1 to 10 carbon atoms, X is a halogen atom and n is 0 <n satisfying the valence of titanium 4 Some examples include tetrabromotitanium, tetrachlorotitanium, trichloroethoxytitanium, dichlorodiethoxytitanium, chlorotetraethoxytitanium, chloronormaltributoxytitanium, tribromoethoxytitanium, dichloroethoxybutoxytitanium Etc.

In the present invention, the catalyst is prepared by selecting a suitable hydrocarbon having 5 to 12 carbon atoms as a solvent, an electron donor compound (A) composed of magnesium halide (C) and elements of Groups VA and VIA of the periodic table, and IB to IVB of the periodic table. As the metal alkoxide (B) in which the alkoxy group is combined with the metal of the group is subjected to a semirecrystallization by chemical reaction in the appropriate temperature range (30 ° C. to 150 ° C.), the particles of the magnesium halide (C) are deformed. When a mixture of alkyl metal compound (D) or alkyl metal compound (D) is added dropwise to the mixture (a) of (A), (B), and (C) above, Crystals precipitate. The modified magnesium halide solid may be washed with the appropriate hydrocarbons until the impurities are free and then reacted with the titanium halide derivative (E) to obtain the final solid catalyst.

The monomer used for the polymerization in the present invention is an α-olefin having the general formula RC ₂ H ₃ and R has hydrogen or 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, etc. are mentioned. In addition, homopolymerization of the α-olefin monomers as well as copolymerization using a monomer mixture of two or more components is possible. 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. That is, the polymerization is carried out in a continuous or batch type (temperature of 20 ℃ ~ 200 ℃, especially in the slurry phase 50 ℃ ~ 100 ℃, in the solution phase 120 ℃ ~ 160 ℃. The polymerization pressure is in the range of 1 to 100 kg / cm 2, preferably in the range of 1 to 40 kg / cm 2.

The polymerization in the present invention is a solid magnesium-titanium catalyst prepared by the process of semi-recrystallization, after sufficiently replacing the 2 L stainless steel high pressure reactor with nitrogen, the solvent is normal hexane under a nitrogen stream (slurry polymerization method) and a cocatalyst. The furnace is suitably selected from alkyl aluminum, and the pressure of the monomer is carried out between 1 to 15 kg / cm 2 and the temperature between 20 ° C and 100 ° C. 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 1 liter four-necked round bottom flask equipped with a magnetic stirrer, a condenser, and a temperature sensor under nitrogen stream, 100 ml of decane and 4 g of magnesium chloride were stirred for several minutes, followed by 5.8 g of ethanol and 28.7 g of titanium tetraethoxide. After raising the temperature to 95 ° C., the reaction was carried out for 2 hours. After completion of the reaction, the heterogeneous reaction mixture was cooled to room temperature, 15.2 g of diethylaluminum chloride was diluted in 100 ml of normal hexane, and added dropwise for 2 hours to completely precipitate some dissolved solids. To complete the reaction, the mixture was slowly heated at room temperature and refluxed for about 1 hour. The supernatant was removed under nitrogen pressure, 200 ml of normal hexane was added, the solids were washed in the order of stirring, standing, and removing the supernatant, followed by 200 ml of normal hexane. 20 g of titanium tetrachloride was added thereto, and the mixture was heated to 70 ° C. and refluxed for 2 hours. After refluxing, the mixture was left to stand under pressure under nitrogen to remove the supernatant, washed with normal hexane until no chlorine ion was detected in the supernatant, and dried at 30 to 40 ° C. to obtain a solid catalyst.

(b) polymerization

After sufficiently replacing the 2 L stainless steel autoclave with nitrogen, 900 mL of normal hexane was added under nitrogen stream, and 0.6 g of triisobutyluminum was added thereto, followed by stirring for several minutes. 4 mg of the solid catalyst prepared in Example (a) was added and the inert gas was removed using a vacuum pump in a reactor filled with nitrogen. Then, the polymerization was carried out while adding 4 kg / cm 2 of hydrogen and raising the temperature to 65 ° C. and adding ethylene. The polymerization is started for 1 hour while the pressure of ethylene is 7 kg / cm 2, the total pressure is 11 kg / cm 2, and the polymerization temperature is 70 ° C. After the polymerization is completed, the unreacted gas is slowly discharged, the reactor is opened, the slurry powder is filtered, and the powder is dried in a vacuum at 40 ° C. for 24 hours. The polymer powder obtained by drying was 182 g, the catalytic activity was 45,500 (g-polymer / g-catalyst), the bulk density was 0.21 (g / ml), and the average particle diameter of the polymer powder was 250 µm. The particle size distribution and polymerization results of the polymer powder are summarized in Table 1.

Example 2

Except for using 7.6 g of isopropanol instead of ethanol in the catalyst preparation process (a), the polymer powder obtained in the same manner as in Example 1 was 172 g, and the catalytic activity was 43000 (g-polymer / g-catalyst), and the bulk density. Was 0.21 (g / ml) and the average particle diameter of the polymer powder was 250 µm.

Example 3

Except for using 9.3 g of normal butanol instead of ethanol in the catalyst preparation process (a), the polymer powder obtained in the same manner as in Example 1 was 176 g, and the catalytic activity was 44000 (g-polymer / g-catalyst), and the bulk density Was 0.23 (g / ml) and the average particle diameter of the polymer powder was 240 µm.

Example 4

Except that 16.4 g of 2-ethylhexanol was used instead of ethanol in the catalyst preparation process (a), the polymer powder obtained in the same manner as in Example 1 was 188 g, and the catalytic activity was 4700 (g-polymer / g-catalyst). The bulk density was 0.23 (g / ml) and the average particle diameter of the polymer powder was 240 µm.

Example 5

In the catalyst preparation process (a), except that 42.9 g of titanium tetrabutoxide was used instead of titanium tetraethoxide, the polymer powder obtained in the same manner as in Example 1 was 168 g, and the catalytic activity was 42000 (g-polymer / g). -Catalyst), the bulk density was 0.23 (g / ml), and the average particle diameter of the polymer powder was 250 µm.

Example 6

In the catalyst preparation process (a), except that 35.8 g of titanium tetraisopropoxide was used instead of titanium tetraethoxide, the polymer powder obtained in the same manner as in Example 1 was 179 g, and the catalytic activity was 44800 (g-polymer). / g-catalyst), bulk density was 0.26 (g / ml), and the average particle diameter of the polymer powder was 270 µm.

Example 7

Except for using 14.4 g of triethylaluminum instead of diethylaluminum chloride in the catalyst preparation process (a), the polymer powder obtained in the same manner as in Example 1 was 129 g, and the catalytic activity was 32200 (g-polymer / g-catalyst). ), The bulk density was 0.22 (g / ml), and the average particle diameter of the polymer powder was 430 µm.

Example 8

In the catalyst preparation process (a), except that 25 g of triisobutylaluminum was used instead of diethylaluminum chloride, the polymer powder obtained in the same manner as in Example 1 was 117 g, and the catalytic activity was 29200 (g-polymer / g-catalyst). The bulk density was 0.26 (g / ml) and the average particle diameter of the polymer powder was 410 µm.

Example 9

Except for using 16 g of ethyl aluminum dichloride instead of diethyl aluminum chloride in preparing the catalyst (a), the polymer powder obtained in the same manner as in Example 1 was 166 g, and the catalytic activity was 41500 (g-polymer / g-catalyst). The bulk density was 0.26 (g / ml) and the average particle diameter of the polymer powder was 350 µm.

Example 10

The polymer powder obtained by performing the same procedure as in Example 1 except for using a mixture of 7.6 g of diethylaluminum dichloride and 12.5 g of triisobutylaluminum instead of diethylaluminum chloride in the preparation of the catalyst (a) was 160 g of catalytic activity. The average particle diameter of silver 40000 (g-polymer / g-catalyst), bulk density was 0.29 (g / ml), and the polymer powder was 400 µm.

Example 11

In the catalyst preparation process (a), except that 7.6 g of normal propanol was used instead of ethanol, the polymer powder obtained in the same manner as in Example 10 was 158 g, and the catalytic activity was 39500 (g-polymer / g-catalyst), and the bulk density was The average particle diameter of 0.28 (g / ml) and polymer powder was 420 micrometers.

Example 12

In the catalyst preparation process (a), except that 9.3 g of normal butanol was used instead of ethanol, the polymer powder obtained in the same manner as in Example 10 was 157 g, and the catalytic activity was 39200 (g-polymer / g-catalyst), and the bulk density was The average particle diameter of 0.29 (g / ml) and polymer powder was 400 micrometers.

Example 13

In the catalyst preparation process (a), heptane was used instead of the solvent decane and the reaction temperature was increased to 75 ° C. for 2 hours. (g-polymer / g-catalyst), bulk density was 0.28 (g / ml), and the average particle diameter of the polymer powder was 480 µm.

Example 14

In the process of preparing the catalyst (a), hexane was used instead of decane as a solvent, and the reaction temperature was increased to 55 ° C. for 2 hours. (g-polymer / g-catalyst), bulk density was 0.28 (g / ml), and the average particle diameter of the polymer powder was 800 µm.

Example 15

In the preparation of the catalyst (a), heptane was used instead of the solvent decane and the reaction temperature was increased to 98 ° C. for 2 hours, except that the polymer powder obtained in the same manner as in Example 13 was 165 g, and the catalytic activity was 41200. (g-polymer / g-catalyst), bulk density was 0.27 (g / ml), and the average particle diameter of the polymer powder was 400 µm.

Example 16

In the catalyst preparation process (a), using a decane solvent, but the reaction temperature was raised to 130 ℃ and reacted for 2 hours except that the polymer powder obtained in the same manner as in Example 10 is 166g, the catalytic activity is 41500 (g- Polymer / g-catalyst), bulk density was 0.26 (g / ml), and the average particle diameter of the polymer powder was 390 µm.

[Effects of the Invention]

The polymer produced using the solid catalyst of the present invention has a uniform particle shape to facilitate separation and filtration in the separation and drying of the polymer in the slurry process, and in particular, the particle size and bulk of the polymer according to the preparation conditions of the catalyst The density can be easily adjusted. In addition, since the solid catalyst has a high polymerization activity, a separate deliming process is not required to remove the residual catalyst, thereby reducing manufacturing costs in the production process.

Claims (8)

In the solid catalyst for olefin polymerization, a compound (A) containing an electron donor, a metal compound (B) and a magnesium halide (C) in which a metal and an alkoxy group are combined with each other cause a semi-recrystallization, and an alkyl metal compound is formed. A method for producing a solid catalyst for olefin polymerization, comprising adding (D) to complete semi-recrystallization and reacting titanium halide derivative (E) to wash with a solvent to obtain a solid catalyst. 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 range of the component (A) per mole of the component (C) is 1 × 10 ^-4 to 30, the method for producing a solid catalyst for olefin polymerization. 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 compound (B) according to claim 1, wherein component (B) is a metal compound (B) in which a metal and an alkoxy group of the group IB to IVB of the periodic table are combined, and the alkoxy metal compound is a compound represented by the following general formula Method for producing a solid catalyst for olefin polymerization, characterized in that the molar range of the component (B) per mole is 1 × 10 ^-2 to 10. Formula: 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). The method for producing a 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 group or an alkoxy group having 1 to 5 carbon atoms.) The alkyl metal compound of the component (D) is a compound represented by the following general formula, and the molar range is 1 × per mole of the component (C) alone or as a mixture of two or more thereof. 10 ^-1 to 10, characterized in that the method for producing a solid catalyst for olefin polymerization. Formula: M (R) _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 solid catalyst for olefin polymerization according to claim 1, wherein the titanium halide derivative of component (E) is a compound represented by the following general formula. Formula: Ti (OR) _4-n X _n (Wherein R represents an alkyl group having 1 to 10 carbon atoms, X represents a halogen element and n represents 0 <n satisfying the valence of titanium) 4). According to claim 1, wherein the components (A), (B), (C) is formed in a semi-recrystallization process with a contact reaction for 10 minutes to 6 hours at a temperature of 0 to 150 ℃ in a non-uniform solution state Method for producing a solid catalyst for olefin polymerization, characterized in that. The semi-recrystallization process according to claim 1 or 5, wherein the component (D) alone or a mixture of two or more components (D) is reacted at a temperature of 0 to 100 ° C. for 5 minutes to 12 hours. Method for producing a solid catalyst for olefin polymerization, characterized in that.