KR20120077690A - Catalysts for polymerization or copolymerization of olefins, its preparing method and olefins polymerization or copolymerization method - Google Patents

Abstract

PURPOSE: A catalyst for olefin polymerization or copolymerization, a manufacturing method thereof, a method of olefin polymerization or copolymerization using the same are provided to manufacture olefin copolymer which shows a high melt flow index. CONSTITUTION: A catalyst for olefin polymerization or copolymerization comprises a porous magnesium compound as a carrier, transition metal compound showing catalyst activities, two or more cyclic diester compounds having one or more hetero atoms represented by chemical formulas 1-4, and a derivative thereof. In the chemical formulas 1 -4, R1 and R2 are identical or different and include hydrogen, C1-C20 linear or branched alkyl, alkenyl, cyclocalkyl, aryl or aryl substituent, alkylaryl or alkylaryl substituent, and alkylaryl including hetero atom. n and m are integers of 0-10, A indicates oxygen or sulfur, and the magnesium compounds is selected from a group consisting of magnesium chloride, dialkyl magnesium and alkoxy magnesium chloride.

Description

Catalyst for olefin polymerization or copolymerization, preparation method thereof and polymerization or copolymerization method of olefin using same {CATALYSTS FOR POLYMERIZATION OR COPOLYMERIZATION OF OLEFINS

The present invention relates to a catalyst for olefin polymerization or copolymerization having high hydrogen reactivity, a method for preparing the same, and a method for polymerizing or copolymerizing olefin using the same.

The catalyst for olefin polymerization, generally called a Ziegler-Natta catalyst, refers to a catalyst system composed of a combination of a main catalyst composed mainly of a transition metal compound, a cocatalyst composed of an organometallic compound, and an electron donor. It has been extensively researched in order to improve and many related technologies have been proposed.

The Ziegler-Natta catalyst directly affects the properties and properties of the polyolefin produced according to its constituents, structure, and preparation method. Therefore, in order to change the properties of the resulting polyolefin, a change in the constituents of the catalyst, the structure of the carrier and the preparation method of the catalyst should be accompanied during the preparation of the catalyst. The activity of and the molecular weight, stereoregularity, etc. of the polymerized polymer should also be studied.

Conventional Ziegler-Natta catalysts consist of a solid catalyst component centered on titanium, magnesium and halogen compounds and an organoaluminum compound system that is a promoter. Many improvements have been made to improve the catalytic activity and stereoregularity, which are the basic elements in this system, but due to the diversification of the use of polyolefins, further improvement of catalytic activity and stereoregularity is currently required.

In order to solve the stereoregularity problem, U.S. Patent No. 4,544,717 describes a method of adding an electron donor, and U.S. Patent No. 4,226,741 relates to a high stereoregularity catalyst having a stereoregularity of 94 to 95 or more. It is described. EP 045,977 also describes the technology of solid Ziegler-Natta catalysts which are characterized by high activity, high stereoregularity, and derivatives of certain carboxylic acid ester compounds, preferably phthalate derivatives, are solid catalysts as internal electron donors. Coordination to the compound produces a Ziegler-Natta catalyst with the titanium compound. In addition, these main catalysts have been proposed to improve the polymerization activity and stereoregularity by alpha-olefin polymerization using an aluminum alkyl compound and a silicon compound having at least one silicon-ether bond as an external electron donor.

However, when the catalyst disclosed by the above patents is used, it is practically difficult to produce polypropylene having a melt flow index of 50 g / 10 minutes or more because of insufficient reactivity of hydrogen as a molecular weight regulator. In other words, if a large amount of hydrogen is added to the polymerization reactor to compensate for insufficient hydrogen reactivity when applied to the actual commercial process, there is a risk of explosion due to the limitation of the device design pressure. Constraints exist. Therefore, in the actual commercial process, there is a problem in that hydrogen can not be added to the pressure required to produce a polypropylene having a high melt flowability.

The present invention is to solve the problems of the prior art as described above, the object of the present invention, in the process of preparing a Ziegler-Natta catalyst for olefin polymerization, through the method of using a specific compound as an internal electron donor, In addition to being high enough for commercial use, the reactivity of hydrogen, the molecular weight regulator, is improved to provide a method for easily preparing an olefin polymer having a much higher melt flow index even when the same amount of hydrogen is introduced into the reactor. The purpose is.

The present invention is to provide a catalyst for olefin polymerization or copolymerization having high hydrogen reactivity, a method for preparing the same and a method for polymerizing or copolymerizing olefin using the same.

The catalyst for olefin polymerization or copolymerization according to the present invention is a dicyclic di-type having at least one of a porous magnesium compound as a carrier, a transition metal compound constituting an active site, and a hetero atom represented by the following Chemical Formulas 1 to 4 below. Ester compounds and derivatives thereof.

Method for producing a catalyst for olefin polymerization or copolymerization according to the present invention comprises the steps of (a) preparing a porous support with a magnesium compound; (b) reacting the transition metal compound representing the active site of the catalyst; (c) reacting the cyclic diester compound selected from the group of compounds represented by the formulas (1) to (4) with an internal electron donor, and proceeding to steps (b) and (c) Steps (b) and (c) are repeated one or more times regardless of the order.

The polymerization or copolymerization method of the olefin according to the present invention is to polymerize or copolymerize the olefin in the presence of a catalyst system composed of the olefin polymerization or copolymerization described above as a main catalyst and an alkylaluminum compound as a cocatalyst and a silane compound as an external electron donor. It features.

The Ziegler-Natta catalyst for olefin polymerization according to the present invention not only has high activity for commercial use, but also improves the reactivity of hydrogen, a molecular weight regulator, so that even when the same amount of hydrogen is introduced into the reactor, a much higher melt flow index is achieved. The olefin polymer shown can be manufactured easily.

The catalyst for olefin polymerization or copolymerization according to the present invention is a dicyclic di-type having at least one of a porous magnesium compound as a carrier, a transition metal compound constituting an active site, and a hetero atom represented by the following Chemical Formulas 1 to 4 below. Ester compounds and their derivatives include internal electron donors.

On the other hand, the present invention provides a method for producing an olefin polymer using a Ziegler-Natta catalyst comprising magnesium, transition metals, halogens and internal electron donors. The Ziegler-Natta catalyst prepared by the present invention is not particularly limited in the catalyst composition ratio, but considering the catalyst activity, 5 to 40% by weight magnesium, 0.5 to 15% by weight transition metal, and 2.5 to 30% by weight of the internal electron donor, and preferably 40 to 80% by weight of other halogen-like materials.

The representative formula of the internal electron donor included in the component is as follows.

[Formula 1]

[Formula 2]

(3)

[Formula 4]

R ¹ and R ² in each formula may be the same or different, and may be linear or branched alkyl, alkenyl, cycloalkyl, hydrogen (H) or an alkyl group having 1 to 20 carbon atoms (C ₁ to C ₂₀ ), Alkylaryl including aryl or aryl substituents, alkylaryl or alkylaryl substituents, heteroatoms.

n and m are the numbers of carbons, and are an integer from 0 to 10, Preferably 0-3 are suitable.

A is a hetero atom which represents oxygen (O), sulfur (S) and the like.

Representative compounds include diisobutyl 7-oxo-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylate (diisobuty 7-oxa-bicyclo [2.2.1] hept-5- ene-2,3-dicarboxylate), diisobutyl 7-oxo-bicyclo [2,2,1] hepta-2,5-diene-2,3-dicarboxylate [diisobuty 7-oxa-bicyclo [ 2.2.1] hepta-2,5-diene-2,3-dicarboxylate), diisobutyl 7-oxo-bicyclo [2,2,1] heptene-2,3-dicarboxylate (diisobuty 7-oxa) -bicyclo [2.2.1] heptene-2,3-dicarboxylate), diisobutyl 7-thia-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylate (diisobutyl 7 -thia-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate), diisobutyl 2-thia-bicyclo [2,2,1] hept-5-ene-5,6-di Carboxylate (diisobutyl 2-thia-bicyclo [2.2.1] hept-5-ene-5,6-dicarboxylate), diisobutyl 8-thia-bicyclo [3,2,1] oct-6-ene -6,7-dicarboxylate (diisobutyl 8-thia-bicyclo [3.2.1] oct-6-ene-6,7-dica rboxylate), diisobutyl 5-thia-bicyclo [2,1,1] hexa-2-ene-2,3-dicarboxylate (diisobutyl 5-thia-bicyclo [2.1.1] hex-2ene- 2,3-dicarboxylate).

There is no particular limitation on the source of magnesium included in the above components. Therefore, any magnesium compound used in the production of the Ziegler-Natta catalyst for olefin polymerization, such as magnesium chloride, dialkoxymagnesium, alkoxymagnesium chloride, etc., can be used for the preparation of the catalyst component without limitation. Among these, the method of recrystallization after melt | dissolving in alcohol is preferable. This acts as a carrier having a spherical particle shape, and the spherical particle shape is maintained even in the polymer of the olefin.

In addition, there is no particular limitation on the source of the transition metal included in the component, and therefore, any transition metal compound used in the production of the Ziegler-based catalyst for olefin polymerization can be used for the preparation of the catalyst component without limitation. Particularly preferred representative compounds can be represented as follows.

[Chemical Formula 5]

MX _n (OR ¹ ) _4-n

In formula (5), M is a metal, X is halogen, R1 is C1-C10 hydrocarbylaoxy, n is the oxidation number of the metal 0-4. Preferably, in formula (5), M is Ti, Zr, Hf, Rf, etc. Group IVB; VB group, such as V, Nb, Ta, and Db; Or VB groups such as Cr, Mo, W, Sg, X is Cl, Br, I, and R1 is C1-C4 alkoxy or phenoxy. More preferably, in the above formula, M is group IVB such as Ti, Zr, Hf, Rf, X is Cl, R1 is ethoxy, butoxy, chlorotriethoxy, dichlorodiethoxy, trichloroethoxy to be. Most preferably, in Chemical Formula 1, M is Ti and R 1 is Cl.

Method for producing a catalyst for olefin polymerization or copolymerization according to the present invention comprises the steps of (a) preparing a porous support with a magnesium compound; (b) reacting the transition metal compound representing the active site of the catalyst; (c) reacting the cyclic diester compound selected from the group of compounds represented by the formulas (1) to (4) with an internal electron donor, and proceeding to steps (b) and (c) after step (a); Steps (b) and (c) are repeated one or more times regardless of the order.

When the prepared solid catalyst is applied to olefin polymerization, the prepared catalyst is used as the main catalyst, the organoaluminum compound as the promoter, and an external electron donor is used. There is no particular limitation on the organoaluminum compound, and preferably, the material of the following Chemical Formula 6 is used.

[Formula 6]

R ⁴ _n AlX _{3- n}

In the above formula, R ⁴ is C ₁ ~ C ₂₀ alkyl, X is halogen, n is 0-3. In addition, there is no particular limitation on the external electron donor applied to the olefin polymerization, and any compound that can be used as an external electron donor for the production of a Ziegler-Natta catalyst for general olefin polymerization may be used for the olefin polymerization without limitation. It is preferable to use a silane-based compound such as.

[Formula 7]

R ⁵ _n Si (OR ⁶ ) _4-n

In Formula 7, R ⁵ C ₁ to C ₂₀ Hydrocarbon, preferably C ₁ -C ₁₀ Alkyl, C ₅ -C ₁₂ Cycloalkyl, C ₆ -C ₂₀ Aryl _, C ₁ to C ₁₀ Alkenyl, A ₁ to C ₁₀ Haloalkyl or C ₁ to C ₁₀ Aminoalkyl, chlorine, R ⁶ C ₁ ~ C ₂₀ hydrocarbon, preferably C ₁ ~ C ₁₀ Alkyl, C ₅ -C ₁₂ Cycloalkyl, C ₆ -C ₂₀ Aryl _, C ₁ to C ₁₀ Alkenyl, C ₂ ~ C ₁₀ Alkoxy alkyl.

The compound represented by the formula (7) is preferably an organic silane compound, specifically triethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, diphenyldimethoxy Silane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyl diethoxysilane, ethyl Trimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane, preferably diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane and dicyclopentyldiethoxysilane.

The external electron donor is used together with the promoter in the polymerization, and may be used if necessary. The concentration of the external electron donor includes 0.001 to 50 mol%, preferably 0.01 to 20 mol%, more preferably 0.02 to 10 mol% per mole of promoter. If the concentration of the external electron donor is less than 0.001 mol%, there is a problem that the improvement of stereoregularity does not occur.

In the present invention, 'polymerization' includes not only homopolymerization but also copolymerization.

The polymerization can be in gas phase, liquid phase, or solution phase. When performing a polymerization reaction in a liquid phase, a hydrocarbon solvent may be used and olefin itself can also be used as a solvent. The polymerization temperature is usually in the range of -50 to 350 ° C, preferably 0 to 200 ° C. If the polymerization temperature is less than -50 ° C, the activity of the catalyst is not good, and if it exceeds 350 ° C, the stereoregularity is poor, which is not good. The polymerization pressure is usually at normal pressure to 250 kg / cm 2, preferably at atmospheric pressure to 200 kg / cm 2, and the polymerization reaction can be carried out by any of batch, semi-continuous and continuous methods. When the polymerization pressure is 250 kg / cm 2 or more, it is not preferable from an industrial and economical point of view.

To the polyolefin prepared using the solid catalyst according to the present invention, a heat stabilizer, a light stabilizer, a flame retardant, carbon black, a pigment, an antioxidant, and the like, which are commonly added, may be added. In addition, the prepared polyolefin may be mixed with linear low density polyethylene (LLDPE), high density polyethylene (HDPE), polypropylene, polybutene, EP (ethylene / propylene) rubber and the like.

The Ziegler-Natta catalyst for olefin polymerization according to the present invention not only has high activity for commercial use, but also improves the reactivity of hydrogen, a molecular weight regulator, so that even when the same amount of hydrogen is introduced into the reactor, a much higher melt flow index is achieved. The olefin polymer shown can be manufactured easily.

Activity is obtained as the amount of polymer (kg) out of the amount (g) of the catalyst put into the reaction.

The melt flow index (MFR) is expressed in units of g / 10 min and is obtained by ASTM1238 by measuring the weight of the polymer released at 230 ° C. and a 2.16 kg load for 10 minutes.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited by the examples.

In a high-purity nitrogen atmosphere, 60 mL of anhydrous magnesium dichloride carrier and toluene were introduced into a double jacketed glass reactor with a stirrer, the temperature was lowered to -10 ^o C, and then 0.2 mol of titanium tetrachloride (TiCl ₄ ) and 60 mL of tutuene were slowly added dropwise. After that, raise the temperature to 110 ℃ constantly. Diisobutyl 7-oxo-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylate (diisobuty 7-oxa-bicyclo [2.2.1] hept-5-ene-2 , 3-dicarboxylate) is added and reacted for 1 hour to obtain a precipitate. After washing the solid component with toluene, titanium tetrachloride (TiCl ₄ ) (0.2 mol) and 100 mL of toluene were added again, and reacted for 1 hour. The solid component is washed with toluene and hexane to give a solid catalyst.

The polymerization of propylene was carried out using a 2 L polymerization reactor. The reactor was depressurized to 3 torr or less vacuum and charged with nitrogen of high purity three times. After filling 500 g of propylene and 750 cc of hydrogen at room temperature in a reactor, 3 mmol of triethylaluminum, 0.18 mmol of cyclohexylmethyldimethoxysilane, 0.0044 mmol of the catalyst prepared above were added, and the reactor was heated to 70 ° C. for 1 hour. After the reaction, the final polymer was obtained.

Through this polymerization, activity and melt flow index were measured.

Diisobutyl 7-oxo-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylate in Example 1 (diisobuty 7-oxa-bicyclo [2.2.1] hept-5 diisobutyl 7-oxo-bicyclo [2,2,1] hepta-2,5-diene-2,3-dicarboxylate (diisobuty 7-oxa-bicyclo) instead of -ene-2,3-dicarboxylate [2.2.1] Hepta-2,5-diene-2,3-dicarboxylate) A solid catalyst was prepared in the same manner as in Example 1 except that 0.01 mol was used.

Diisobutyl 7-oxo-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylate in Example 1 (diisobuty 7-oxa-bicyclo [2.2.1] hept-5 diisobutyl 7-oxo-bicyclo [2,2,1] heptene 2,3-dicarboxylate (diisobuty 7-oxa-bicyclo [2.2.1] heptene- instead of -ene-2,3-dicarboxylate) 2,3-dicarboxylate) A solid catalyst was prepared in the same manner as in Example 1, except that 0.01 mol was used.

Diisobutyl 7-oxo-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylate in Example 1 (diisobuty 7-oxa-bicyclo [2.2.1] hept-5 diisobutyl 7-thia-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylate (2.2 instead of -ene-2,3-dicarboxylate) .1] Hept-5-ene-2,3-dicarboxylate) A solid catalyst was prepared in the same manner as in Example 1 except that 0.01 mol was used.

Comparative example  One  :

Diisobutyl 7-oxo-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylate in Example 1 (diisobuty 7-oxa-bicyclo [2.2.1] hept-5 A solid catalyst was prepared in the same manner as in Example 1, except that ethyl benzoate (0.01 mol) was used instead of -ene-2,3-dicarboxylate.

Comparative example  2  :

Diisobutyl 7-oxo-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylate in Example 1 (diisobuty 7-oxa-bicyclo [2.2.1] hept-5 A solid catalyst was prepared in the same manner as in Example 1, except that Diisobutyl Phthalate (0.01 mol) was used instead of -ene-2,3-dicarboxylate).

As shown in Table 1, it was confirmed that the Ziegler-Natta catalyst for olefin polymerization according to the present invention has excellent hydrogen reactivity.

Claims (10)

As a carrier, a porous magnesium compound, a transition metal compound constituting the active site, and two cyclic diester compounds having at least one hetero atom represented by the following Chemical Formulas 1 to 4 and an internal electron donor which is a derivative thereof Olefin polymerization or copolymerization catalyst, characterized in that;
[Formula 1]

(2)

(3)

[Chemical Formula 4]

R ¹ and R ² in each formula may be the same or different, and may be linear or branched alkyl, alkenyl, cycloalkyl, hydrogen (H) or an alkyl group having 1 to 20 carbon atoms (C ₁ to C ₂₀ ), Alkylaryl including aryl or aryl substituents, alkylaryl or alkylaryl substituents, heteroatoms.
n and m are carbon numbers, which are integers from 0 to 10.
A is a hetero atom which represents oxygen (O) or sulfur (S).
The catalyst for olefin polymerization or copolymerization according to claim 1, wherein the magnesium compound is selected from the group consisting of magnesium chloride, dialkoxymagnesium and alkoxymagnesium chloride.
The catalyst for olefin polymerization or copolymerization according to claim 1, wherein the transition metal compound is represented by Chemical Formula 5.

[Chemical Formula 5]
MX _n (OR ¹ ) _4-n
In Formula 5, M is a metal, X is halogen, R1 is C1-C10 hydrocarbylaoxy, and n is 0-4 oxidation of the metal.
The method of claim 3, wherein in Formula 5, M is TiB, such as Ti, Zr, Hf, Rf; Or any one of Group VB of Cr, Mo, W, Sg, X is any one of Cl, Br, I, and R ¹ is ethoxy, butoxy, chlorotriethoxy, dichlorodiethoxy, trichloroethoxy It is any one of the catalyst for olefin polymerization or copolymerization.
The method of claim 1, wherein the diester compound and its derivatives are diisobutyl 7-oxo-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylate (diisobuty 7-oxa- bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate), diisobutyl 7-oxo-bicyclo [2,2,1] hepta-2,5-diene-2,3-dicar Diisobuty 7-oxa-bicyclo [2.2.1] hepta-2,5-diene-2,3-dicarboxylate, diisobutyl 7-oxo-bicyclo [2,2,1] heptene-2,3 Diisobuty 7-oxa-bicyclo [2.2.1] heptene-2,3-dicarboxylate, diisobutyl 7-thia-bicyclo [2,2,1] hept-5-ene-2 , 3-dicarboxylate (diisobutyl 7-thia-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate), diisobutyl 2-thia-bicyclo [2,2,1] hept -5-ene-5,6-dicarboxylate (diisobutyl 2-thia-bicyclo [2.2.1] hept-5-ene-5,6-dicarboxylate), diisobutyl 8-thia-bicyclo [3 , 2,1] oct-6-ene-6,7-dicarboxylate (dii sobutyl 8-thia-bicyclo [3.2.1] oct-6-ene-6,7-dicarboxylate), diisobutyl 5-thia-bicyclo [2,1,1] hexa-2-ene-2,3 A catalyst for olefin polymerization or copolymerization, characterized in that any one selected from diisobutyl 5-thia-bicyclo [2.1.1] hex-2ene-2,3-dicarboxylate.
(a) preparing a porous support with a magnesium compound;
(b) reacting the transition metal compound representing the active site of the catalyst;
(c) reacting the cyclic diester compound selected from the group of compounds represented by formulas (1) to (4) with an internal electron donor, wherein steps (b) and (c) are performed after step (a) And (b) and (c) are repeated one or more times regardless of the order.
[Formula 1]

(2)

(3)

[Chemical Formula 4]

R ¹ and R ² in each formula may be the same or different, and may be linear or branched alkyl, alkenyl, cycloalkyl, hydrogen (H) or an alkyl group having 1 to 20 carbon atoms (C ₁ to C ₂₀ ), Alkylaryl including aryl or aryl substituents, alkylaryl or alkylaryl substituents, heteroatoms.
n and m are carbon numbers, which are integers from 0 to 10.
A is a hetero atom which represents oxygen (O) or sulfur (S).
Components of the solid catalyst prepared according to claim 6 comprises 0.5 to 6.0% by weight of titanium, 10 to 20% by weight of magnesium, 40 to 70% by weight of halogen and 5 to 25% by weight of internal electron donor based on the total weight of the catalyst. A catalyst for olefin polymerization or copolymerization, characterized in that. Characterized in that the olefin is polymerized or copolymerized in the presence of a catalyst system comprising the catalyst for olefin polymerization or copolymerization according to any one of claims 1 to 5 as a main catalyst and an alkylaluminum compound as a cocatalyst and a silane compound as an external electron donor. The polymerization or copolymerization method of the olefin which makes it. The polymerization or copolymerization of olefins according to claim 9, wherein the polymerization or copolymerization is carried out by any one of batch, semi-continuous, and continuous processes in the gas phase, liquid phase, or solution phase. Copolymerization method.
A thermal stabilizer, light stabilizer, flame retardant, carbon black, pigment, antioxidant, or the like is added to the polyolefin polymer or copolymer prepared according to the method of claim 9, or linear low density polyethylene (LLDPE), high density polyethylene (HDPE), polypropylene, A method for polymerization or copolymerization of olefins, which is mixed with polybutene and EP (ethylene / propylene) rubber.