KR20120077528A - Catalysts for polymerization or copolymerization of olefins, its preparing method and olefins polymerization or copolymerization method - Google Patents

Abstract

PURPOSE: An olefine polymerization or catalyst for copolymerization, olefin polymerization using the same, and a polymerization method of olefin are provided to use for molding materials including a plate, a film, a container, and fiber. CONSTITUTION: An olefine polymerization or catalyst for copolymerization comprises porous magnesium compound as a support, transition metal compound which is dipped in the porous magnesium compound, and cyclic diol diester compound. The transition metal compound shows catalyst activation. The cyclic diol diester compound is an internal electron donor and is selected from compound groups which are represented by chemical formula 2 and 3. In the chemical formula 2 and 3, R1 and R2 are identical or different from each other and are alkyl aryl which includes hydrogen pr C1-C20 linear or branched alkyl, alkenyl, cycloalkyl, aryl or aryl substituent, and hetero atom. n indicates 1-11.

Description

Catalyst for olefin polymerization or copolymerization, preparation method thereof, and polymerization or copolymerization method of olefin using the same {CATALYSTS FOR POLYMERIZATION OR COPOLYMERIZATION OF OLEFINS, ITS PREPARING METHOD AND OLEFINS POLYMERIZATION OR COPOLYMERIZATION METHOD}

The present invention relates to a catalyst for olefin polymerization or copolymerization having a wide molecular weight distribution, a method for preparing the same, and a method for polymerization or copolymerization of olefins 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. Although many improvements have been made to improve the catalytic activity and stereoregularity which are the basic elements in this system, due to the diversification of polyolefin applications, not only catalytic activity and stereoregularity but also improvement of molecular weight distribution is currently required.

Therefore, there is a need for development of a new Ziegler-Natta catalyst for olefin polymerization having a relatively simple polymerization method and a high polymerization activity and a wide molecular weight distribution.

While the present inventors have studied Ziegler-Natta catalyst for olefin polymerization having a wide molecular weight distribution, the solid catalyst produced shows high activity, and the polyolefin produced using this solid catalyst in the olefin polymerization reaction has a wide molecular weight distribution. It confirmed that the appearance and completed the present invention.

The present invention is to provide a catalyst for olefin polymerization or copolymerization having a wide molecular weight distribution, a method for preparing the same and a method for polymerization or copolymerization of olefins using the same.

The catalyst for olefin polymerization or copolymerization according to the present invention includes a transition metal compound exhibiting catalytic activity and a cyclic diol diester compound selected from the group of compounds represented by the following formulas (2) to (3) as an internal electron donor. It is characterized by being supported on the compound.

Method for producing a catalyst for olefin polymerization or copolymerization according to the present invention comprises the steps of (a) reacting a porous magnesium compound and a nonpolar solvent; (b) reacting the transition metal compound with the resultant obtained in step (a); (c) reacting the resultant obtained in step (b) with a cyclic diester compound selected from the group of compounds represented by formulas (2) to (3).

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 polyolefin prepared using the Ziegler-Natta catalyst for olefin polymerization according to the present invention can be usefully used in molding materials such as plates, films, containers, and fibers, because the particle size is large, uniform and shows a wide molecular weight distribution.

The catalyst for olefin polymerization or copolymerization according to the present invention includes a transition metal compound exhibiting catalytic activity and a cyclic diol diester compound selected from the group of compounds represented by the following formulas (2) to (3) as an internal electron donor. It is supported on the compound.

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, 0.5-15 wt% of transition metal, 5-40 wt% of magnesium, and halogen based on the total weight of the catalyst. It is preferred to comprise 40 to 80% by weight and 2.5 to 30% by weight of the internal electron donor. The production process of the Ziegler-Natta catalyst comprises the steps of preparing a magnesium carrier (a), supporting a transition metal compound on the carrier (b), and adding an internal electron donor (c). In the case of steps (b) and (c), the steps need not be performed in order, and the steps can be executed simultaneously or repeatedly.

There is no particular limitation on the source of magnesium included in the main catalyst component in step (a). Therefore, any magnesium compound used in the preparation 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, and among these, anhydrous magnesium chloride carrier Preference is given to a method using (manufactured by US Pat. No. 4,399,054 Example 2 method).

Representative compounds in step (b) are as follows.

In Formula 1, M is a metal, X is halogen, R1 is C1 ~ C10 hydrocarbylaoxy, n is the number of oxidation of the metal 0-4. There is no particular limitation on the source of the transition metal included in the main catalyst component, and therefore, any transition metal compound used in the production of the Ziegler-Natta catalyst for olefin polymerization can be used for the preparation of the catalyst component without limitation. Preferably, in Formula 1, M is a group IVB, such as Ti, Zr, Hf, Rf; 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 Formula 1, M is a group IVB, such as Ti, Zr, Hf, Rf, X is Cl, R1 is ethoxy, butoxy, chlorotriethoxy, dichlorodiethoxy, trichloro Oxy. Most preferably, in Chemical Formula 1, M is Ti and R 1 is Cl.

Representation of the internal electron donor in step (c) is as follows.

The internal electron donor in Chemical Formulas 2 to 3 provides a method of preparing a Ziegler-Natta catalyst for olefin polymerization comprising the step of necessarily adding during the catalyst manufacturing process. R ¹ and R ² in Formulas 2 to 3 may be the same or different, and hydrogen or C ₁ to C ₂₀ linear or branched alkyl, alkenyl, cycloalkyl, aryl or aryl substituent, alkylaryl or alkylaryl Alkylaryl including a substituent, heteroatom. In the formula (2), n is the number of carbons, 1 to 11, preferably 1 to 2 is appropriate. Specifically, cyclohexane-1,2-diyl-bis (isovalleic acid ester) (Cyclohexane-1,2-diyl-bis (isovalerate)), cyclohexane-1,2-diyl-bis (caproic acid ester) ) (Cyclohexane-1,2-diyl-bis (caproate)), cyclohexane-1,2-diyl-bis (pivalate ester) (Cyclohexane-1,2-diyl-bis (pivalate)), cyclohexane- Compounds such as 1,2-diyl-bis (benzoic acid ester) (Cyclohexane-1,2-diyl-bis (benzoate))

Hydrocarbon solvents used include aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, heptane, octane, nonane, decane, dodecane, hexadecane and octadecane; Alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane and cyclooctane; Aromatic hydrocarbons such as benzene, toluene, xylene and the like may be included, preferably aliphatic hydrocarbons, more preferably decane.

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 3 is used.

In Formula 4, 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 any limitation, It is preferable to use a silane-based compound such as.

In Formula 5, 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 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, C ₂ to C ₁₀ Alkoxy alkyl.

The compound represented by the formula (5) 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.

When the solid catalyst according to the present invention is applied to olefin polymerization, a polyolefin having high activity of a polymer and a wide molecular weight distribution can be prepared.

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.

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.

Example  1-4 and Comparative example  One  : Ziegler - Appear  Preparation of the catalyst

Synthetic example  One  : Internal Electron Donor-1

To 1,2-cyclochlorodiol (7.0 g, 0.06 mol) was added to toluene (25 mL) and isovaleric acid (27 mL, 0.24 mol) and catalytic amount of sulfuric acid was added. Above 120 reaction mixture ^o Heat to C and stir for 12 hours using water to remove the Deanstock device. Next, wash with 75 mL of 1M KOH, and extract the organic layer twice with 50 mL of hexane. The organic layer obtained is dried using anhydrous magnesium sulfate, filtered and the filtered solution is dried under reduced pressure. The filtrate was separated using column chromatography (hexane: ethyl acetate = v / v, 10: 1) to obtain an internal electron donor-1 in 60% yield. The obtained material was analyzed by 400 MHz ¹ H NMR (CDCl ₃ ), and the results are as follows.

¹ H NMR (ppm): δ 0.95 (d, J = 6.4 Hz, 12H, CH ₃ ), 1.36-1.40 (m, 4H, CH ₂ -Cy), 1.72-1.74 (m, 4H, CH ₂ -Cy ), 2.04-2.15 (m, 2H, CH), 2.15 (d, J = 6.0 Hz, 4H, CH ₂ ), 4.82-4.84 (m, 2H, O-CH) ppm.

Synthetic example  2  : Internal electron donor-2

Using the same method as in Synthesis Example 1, internal electron donor-2 was obtained in a yield of 52%. The obtained material was analyzed under the same conditions as in Synthesis Example 1, and the results are as follows.

¹ H NMR (ppm): δ 0.91 (t, J = 6.4 Hz, 12H, CH ₃ ), 1.25-1.47 (m, 6H, CH ₂ ), 1.57-1.88 (m, 4H, CH ₂ ), 2.90 ( t, J = 7.2 Hz, 4H, CH ₂ ), 4.81-4.83 (m, 2H, O-CH) ppm.

Synthetic example  3  : Internal Electron Donor-3

Using the same method as in Synthesis Example 1, internal electron donor-3 was obtained in a yield of 46%. The obtained material was analyzed under the same conditions as in Synthesis Example 1, and the results are as follows.

¹ H NMR (ppm): δ 1.17 (s, 18H, CH ₃ ), 1.33-1.42 (m, 4H, CH ₂ -Cy), 1.68-1.73 (m, 2H, CH ₂ -Cy), 2.00-2.03 (m, 2H, CH ₂ -Cy), 4.80-4.83 (m, 2H, O-CH) ppm.

Synthetic example  4  : Internal electron donor-4

To benzoyl chloride (10 mL, 0.08 mol) was added dichloroethane (30 mL), dimethylaminopyridine (10.5 g, 0.8 mol) and triethylamine (30 mL), followed by 1,2-cyclohexanediol (5.0 g, 0.04 mol) is added. The reaction mixture was stirred at room temperature for 2 hours. Next, 25 mL of 2M HCl is added, washed three times with 25 mL of water, and then 50 mL of aqueous sodium hydrogen carbonate solution is added thereto. After adding 60 mL of diethyl ether, the organic layer is dried using anhydrous magnesium sulfate, filtered and the filtered solution is dried under reduced pressure. Internal electron donor-4 was obtained in a yield of 90%. The obtained material was analyzed under the same conditions as in Synthesis Example 1, and the results are as follows.

¹ H NMR (ppm): δ 1.49-1.69 (m, 4H, CH ₂ -Cy), 1.85-1.87 (m, 2H, CH ₂ -Cy), 2.28-2.29 (m, 2H, CH ₂ -Cy) , 5.23-5.29 (m, 2H, O-CH), 7.37 (t, J = 7.8 Hz, 4H, C ₆ H ₅ ), 7.50 (t, J = 7.8 Hz, 2H, C ₆ H ₅ ), 7.98 ( d, J = 7.8 Hz, 4H, C ₆ H ₅ ) ppm.

Example  One  :

In a high-purity nitrogen atmosphere, anhydrous magnesium dichloride carrier (prepared by US Pat. No. 4,399,054 Example 2) (8.0 g, 0.07 mol) and 60 mL of toluene were injected into a double jacketed vitreous reactor with a stirrer and the temperature was -10. ^{o After} lowering to C, slowly add dropwise addition of titanium tetrachloride (TiCl ₄ ) (30 mL, 0.2 mol) and 60 mL of tutuene, and then constantly raise the temperature to 110 ° C. at a rate of 1.0 ° C./min. Then cyclohexane-1,2-diyl-bis (isovalleic acid ester) (Cyclohexane-1,2-diyl-bis (isovalerate)) (2.8 g, 0.01 mol) was added and reacted for 1 hour to obtain a precipitate. . After washing the solid component with toluene, titanium tetrachloride (TiCl ₄ ) (30 mL, 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.

Example  2  :

In Example 1, cyclohexane-1,2-diyl-bis (capro) instead of cyclohexane-1,2-diyl-bis (isovalleic acid ester) (Cyclohexane-1,2-diyl-bis (isovalerate)) A solid catalyst was prepared in the same manner as in Example 1, except that acid ester) (Cyclohexane-1,2-diyl-bis (caproate)) (3.1 g, 0.01 mol) was used.

Example  3  :

In Example 1, cyclohexane-1,2-diyl-bis (P instead of cyclohexane-1,2-diyl-bis (isovaleric acid ester) (Cyclohexane-1,2-diyl-bis (isovalerate)) A solid catalyst was prepared in the same manner as in Example 1 except for using a divergent ester) (Cyclohexane-1,2-diyl-bis (pivalate)) (2.8 g, 0.01 mol).

Example  4  :

Cyclohexane-1,2-diyl bis (benzoic acid ester) instead of cyclohexane-1,2-diyl-bis (isovalleic acid ester) (Cyclohexane-1,2-diyl-bis (isovalerate)) in Example 1 A solid catalyst was prepared in the same manner as in Example 1 except that (Cyclohexane-1,2-diyl-bis (benzoate)) (3.2 g, 0.01 mol) was used.

Comparative example  One  :

Ethyl Benzoate (1.5 g, 0.01 mol) instead of cyclohexane-1,2-diyl-bis (isovalleic acid ester) (Cyclohexane-1,2-diyl-bis (isovalerate)) in Example 1 A solid catalyst was prepared in the same manner as in Example 1 except that was used.

activation
(kg.PP / g.cat) MFR MWD Mn Mw Example 1 30.0 2.07 5.96 74,259 499,782 Example 2 29.5 2.00 5.91 75,550 503,974 Example 3 18.5 2.37 4.76 82,514 444,059 Example 4 24.0 4.48 5.64 63,248 402,628 Comparative Example 1 24.0 2.84 4.5 76,776 401,557

Property measurement

1. Catalytic Activity

Determination of the weight (Kg) of the polymer produced per weight (g) of the main catalyst used

2. Stereoregularity:

Weight of Insoluble Component Crystallized in Xylene and Precipitated in 100g of Polymer (g)

3. Melt Flow Index (MFR) (g / 10min):

By ASTM D1238, measured at 230 ^° C, 2.16Kg load

4. Molecular Weight Distribution (Mw / Mn):

Measured by high temperature GPC (Pl-220). Column temperature is 160 ^o C, 1,2,4-trichlorobenzene is used for mobile phase, moving speed is 1mL / min, sample concentration is 1mg / mL

As shown in Table 1, the polymer using the Ziegler-Natta catalyst for olefin polymerization according to the present invention was confirmed to exhibit a wide molecular weight distribution.

Claims (9)

Olefin polymerization, characterized in that a transition metal compound exhibiting catalytic activity and a cyclic diol diester compound selected from the group of compounds represented by the following formulas (2) to (3) as internal electron donors are supported on a porous magnesium compound as a carrier; Catalyst for Copolymerization:
(2)

(Formula 3)

In Formulas 2 to 3, R ¹ and R ² may be the same or different, hydrogen or C ₁ ~ C ₂₀ linear or branched alkyl, alkenyl, cycloalkyl, aryl or aryl substituent, alkylaryl or alkyl Aryl substituents, alkylaryls including heteroatoms. n is number of carbon, 1-11. The catalyst for olefin polymerization or copolymerization according to claim 1, wherein the transition metal compound is represented by Chemical Formula 1.
(Formula 1)
MX _n (OR ¹ ) _4-n
In Formula 1, M is a metal, X is halogen, R1 is C1 ~ C10 hydrocarbylaoxy, n is the number of oxidation of the metal 0-4. According to claim 2, wherein in Formula 1, M is Ti, Zr, Hf, Rf IVB; Or C, Group V, Cr, Mo, W, Sg, X is Cl, Br, I, R ¹ is ethoxy, butoxy, chlorotriethoxy, dichlorodiethoxy, trichloroethoxy Or catalysts for copolymerization.
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 method of claim 1, wherein the cyclic diol diester compound is cyclohexane-1,2-diyl-bis (isovalleic acid ester) (Cyclohexane-1,2-diyl-bis (isovalerate)), cyclohexane-1, 2-diyl-bis (caproic acid ester) (Cyclohexane-1,2-diyl-bis (caproate)), cyclohexane-1,2-diyl-bis (pivalic acid ester) (Cyclohexane-1,2-diyl -bis (pivalate)), cyclohexane-1,2-diyl-bis (benzoic acid ester) (Cyclohexane-1,2-diyl-bis (benzoate)) and any one selected from the group consisting of Polymerization or Copolymerization Catalysts A method for preparing a catalyst for olefin polymerization or copolymerization according to any one of claims 1 to 5, comprising the following steps:
(a) reacting the porous magnesium compound with a nonpolar solvent;
(b) reacting the transition metal compound with the resultant obtained in step (a);
(c) reacting the resultant obtained in step (b) with a cyclic diester compound selected from the group of compounds represented by the following formulas (2) to (3);
(2)

(Formula 3)

In Formulas 2 to 3, R ¹ and R ² may be the same or different, hydrogen or C ₁ ~ C ₂₀ linear or branched alkyl, alkenyl, cycloalkyl, aryl or aryl substituent, alkylaryl or alkyl Aryl substituents, alkylaryls including heteroatoms. n is number of carbon, 1-11. The method of claim 6, wherein the non-polar solvent of step (a) is butane, isobutane, pentane, hexane, heptane, octane, nonane, decane, dodecane, hexadecane, octadecane, cyclopentane, methylcyclopentane, cyclohexane , Cyclooctane, benzene, toluene and xylene. The method for producing a catalyst for olefin polymerization or copolymerization, characterized in that selected from the group consisting of.  Composition of the solid catalyst prepared according to claim 6 or 7 is 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, comprising%. 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.