KR20030055637A - Method of polymerization and copolymerization of ethylene using carbodiimde ligand chelated catalyst - Google Patents

Abstract

PURPOSE: A method for polymerizing and copolymerizing ethylene by using a catalyst chelated with a carbodiimide-based ligand is provided, to obtain an ethylene polymer or copolymer having a large bulk density and the narrow distribution of molecular weight. CONSTITUTION: The method comprises the step of polymerizing or copolymerizing ethylene in the presence of a transition metal compound catalyst component of group IV chelated with a carbodiimide-based ligand, a magnesium-containing support and an organometallic compound cocatalyst of group II or III. The transition metal compound catalyst component of group IV chelated with a carbodiimide-based ligand, is prepared by reacting a Grignard compound of dialkyl magnesium with an alkoxy aluminum to obtain an alkoxy aluminum-magnesium compound; reacting the obtained alkoxy aluminum-magnesium compound with a carbodiimide-based ligand; and reacting the obtained one with a transition metal of group IV. Preferably the carbodiimide-based ligand is represented by the formula 1, wherein W, Y and Z are independently an alkyl group, a phenyl group or a heteroatom-containing alkyl group.

Description

Ethylene Polymerization and Copolymerization Method Using Chelating Compound Catalyst of Carbodiimide-Based Ligand {METHOD OF POLYMERIZATION AND COPOLYMERIZATION OF ETHYLENE USING CARBODIIMDE LIGAND CHELATED CATALYST}

The present invention relates to a polymerization method of ethylene and a copolymerization method of ethylene and alpha-olefin, and more particularly, ethylene polymerization and ethylene using a Group IV transition metal compound chelate-bonded with a carbodiimide-based ligand as a catalyst. / Alpha-olefin copolymerization method.

In olefin polymerization reactions in which olefins are polymerized using a transition metal compound as a catalyst, efforts have been made to improve the properties of polymers produced by changing the reaction environment of transition metal compounds. In particular, efforts to control the reaction environment in which the transition metal compound reacts with the olefin using the metallocene compound obtained by converting the ligand of the transition metal compound into the cyclopentadiene ligand have made significant progress.

In the 1980s, homogeneous catalysts using metallocene compounds started to get the spotlight due to their excellent (co) polymerization properties with alpha-olefins, such as impact strength and transparency.

In particular, by synthesizing a metallocene compound having special substituents such as indenyl, cycloheptadiene, and fluorenyl, which controls an electronic or steric spatial environment in a cyclopentadienyl group, Metallocene catalysts that can regulate the regularity and molecular weight size of polymers have been developed and are expanding their applications.

In recent years, by developing a metallocene compound on an inorganic carrier to produce a non-uniform catalyst, development of a catalyst capable of controlling the particle properties of a polymer while producing an excellent copolymer has been actively progressed. For example, U. S. Patent No. 5,439, 995 and U. S. Patent No. 5,455, 316 disclose that the zirconocene and titanocene compounds are supported on magnesium or silica compounds to produce non-uniform catalysts having excellent particle properties and excellent copolymerization properties. It was.

However, metallocene catalysts known to date have the disadvantage of requiring complex organometallic synthesis and using expensive methylaluminoxane (MAO) or boron compounds as cocatalysts in the polymerization of olefins. Desire continues, and on the other hand, the polymer produced by the metallocene catalyst has a narrow molecular weight distribution (Mw / Mn = 2 to 5), which has disadvantages in terms of processing of the polymer.

Recently, a transition metal compound called a non-metallocene catalyst or a supermetallocene catalyst or an organometallic catalyst is a bidentate or tree as a catalyst component. Efforts have been made to develop catalysts that use dentated chelate compounds to produce polymers with narrow molecular weight distributions, while not as complex as metallocene compounds.

For example, Japanese Patent Application Laid-Open No. 63-191811 reports a result of polymerizing ethylene and propylene using a compound in which a halide ligand of a titanium halide compound is substituted with a TBP ligand (6- tert- butyl-4-methylphenoxy) as a catalyst component. The polymerization of ethylene and propylene using MAO as a cocatalyst resulted in the formation of a polymer with high activity and high molecular weight (average molecular weight = 3,600,000 or more).

U.S. Patent No. 5,134,104 discloses a catalyst for olefin polymerization using a dioctylaminetitanium halide (C ₈ H ₁₇ ) ₂ NTiCl ₃ compound as a catalyst component in which a halide ligand of TiCl ₄ is replaced with a bulky amine ligand.

In addition, American J. Am. Chem. Soc No. 117 3008 is a chelating compound that can limit the steric space of transition metals and is a 1,1'-bi-2,2'-naphthoxy ligand (1,1'-bi) to titanium or zirconium transition metal -2,2'-naphthol) and a catalyst for olefin polymerization using a chelate-linked compound and derivatives thereof are disclosed. Japanese Unexamined Patent Publication No. Hei 6-340711 and EP 0606125A2 disclose titanium and halide compounds A catalyst for chelating olefin polymerization having a narrow molecular weight distribution while producing a high molecular weight polymer by replacing a halide ligand with a chelated phenoxy group was disclosed.

On the other hand, recently, a catalyst for non-metallocene-based olefin polymerization using an amine-based chelate transition metal compound has been attracting attention. Organanometallics 1996, 15, 2672 and Chem. Commun. 1996 and 2623 show examples of synthesizing titanium compounds chelate-bonded with various types of diamide compounds and using them as catalysts for olefin polymerization. J. Am. Chem. Soc., 1998, 120, 8640 introduce propylene polymerization using titanium and zirconium compounds chelate-bonded by diamide. Organometallics 1998, 17 and 4795 also introduced catalysts for polymerization using titanium or zirconium chelated by [(aryl-NCH ₂ CH ₂ ) ₂ O] and [(aryl-NCH ₂ CH ₂ ) ₂ S]. In addition, Organometallics 1998, 17, 4541 introduce a catalyst for olefin polymerization using titanium, vanadium, and chromium compounds chelate bonded by [N, N-diphenyl-2,4-pentadiimine] ligand. See also J. Am. Chem. Soc., 1996, 118, 10008 introduce a titanium compound chelate-bonded by (aryl NCH ₂ CH ₂ CH ₂ Naryl) as a catalyst for olefin polymerization. U.S. Patent No. 5,502,128 also discloses a sPS polymerization method using a titanium zirconium compound chelate-bonded by an amidinate ligand. Highly active nonmetallocene catalysts using titanium or zirconium compounds bound by compounds have been introduced.

However, the catalyst for the non-metallocene series olefin polymerization using the chelated titanium and zirconium compounds has been developed as a homogeneous catalyst using expensive MAO or boron compounds as cocatalysts. Therefore, there is a problem in that it is difficult to directly apply to a non-uniform catalyst activated by an inorganic support, a process requiring a catalyst having excellent particle properties such as most of the existing polymerization process, especially gas phase polymerization process. Therefore, there is a demand for the development of a polymerization method using a catalyst which can be easily activated by an inorganic carrier such as MgCl _{2 that} is applied to most existing processes while using a nonmetallocene compound or a metallocene compound as a catalyst component.

The present invention has solved the above problems, using a metal compound chelate-bonded by a carbodiimide-based ligand produced by a unique synthesis method as a catalyst component, inorganic support such as magnesium halide and general organometallic compound It is an object to provide an ethylene polymerization and copolymerization method having a narrow molecular weight distribution and a uniform copolymer composition distribution using a catalyst.

Ethylene polymerization and copolymerization method of the present invention;

(1) a) an alkoxyaluminum-magnesium compound is obtained by reacting a Grignard compound in the form of a dialkyl magnesium with an alkoxy aluminum,

Ii) reacting the compound obtained in iii) with a carbodiimide ligand,

Iii) a periodic table Group IV transition metal compound catalyst component cheated by a carbodiimide-based ligand obtained by a method of reacting a product with a Group IV transition metal compound of the periodic table;

(2) magnesium-containing carriers; And

(3) Periodic Table The composition is made in the presence of a Group II or Group III organometallic compound promoter.

In the ethylene polymerization and copolymerization method of the present invention, the periodic table group IV transition metal compound catalyst component chelate-bonded with the carbodiimide-based ligand of (1) is further reacted with the alkoxyaluminum-magnesium compound after reaction of i)). It is characterized by being obtained through reaction.

The ethylene polymerization and copolymerization method of the present invention is also characterized in that the carbodiimide-based ligand is represented by the following formula (1).

(One)

Wherein each of W, Y, and Z independently represents an alkyl group including alkyl, phenyl or heteroatoms.

The present invention is also characterized in that the carbodiimide-based ligand is dimethylcarbodiimide, dicyclohexylcarbodiimide, or 1,3-bistrimethylsilylcarbodiimide.

On the other hand, the magnesium-containing support in the ethylene polymerization and copolymerization method of the present invention is MgPh ₂ · nMgCl ₂ · mR ₂ O (wherein Ph is phenyl, n = 0.37 to 0.7, m ≧ 1, R ₂ O is And an organic magnesium compound and an organic chlorine compound represented by each of the ethers) are produced by reacting the molar ratio of the organic chlorine compound and magnesium to 0.5 or more.

Furthermore, in the present invention, the Group IV transition metal compound of the periodic table is a general formula M (OR) _a X _4-a , wherein M is Ti, Zr or Hf, R is a hydrocarbon group, X is a halogen atom, and a is It is a compound which satisfy | fills the integer of 0 <= a <= 2).

In the ethylene polymerization and copolymerization method of the present invention, the organometallic compound promoter component is MR _n (wherein M represents a periodic table group II or IIIA metal atom, R represents an alkyl group having 1 to 20 carbon atoms, n is The valence of the metal atom).

Hereinafter, the present invention will be described in more detail.

The periodic table Group IV transition metal compound catalyst chelated by a carbodiimide-based ligand used in the ethylene polymerization and copolymerization method of the present invention is

Iii) an alkoxyaluminum-magnesium compound obtained through the reaction of a Grignard compound in the form of a dialkyl magnesium with alkoxyaluminum,

Ii) react with a carbodiimide family of chelate ligands,

V) reacted with a Group IV transition metal compound of the Periodic Table.

The alkoxyaluminum compound used to prepare the alkoxyaluminum-magnesium compound in the process of step iii) is R _3-n Al (OR ') _n (wherein R, R' is alkyl and n is 1, 2 or 3). It can be represented by the general formula of), for example, it can be produced by reacting an alkyl aluminum and an alcohol compound.

The alkyl aluminum used in the preparation of the alkoxy aluminum compound preferably satisfies the general formula R _n AlX _3-n (R is alkyl having 1 to 20 carbon atoms, X is halogen or hydride, and n is 1, 2 or 3). For example, trialkylaluminum having an alkyl group having 1 to 20 carbon atoms such as triethylaluminum and triisobutylaluminum and mixtures thereof are more preferable. In some cases, an organoaluminum compound having one or more halogen or hydride groups, such as ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride, diisobutylaluminum hydride, may be used.

As the alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, 2-ethylhexanol, octanol and the like having 3 or more carbon atoms of an alkyl group are suitable.

In this reaction, the reaction molar ratio of the alcohol and the alkyl aluminum is preferably 1: 0.2 to 1: 5.0, and more preferably 1: 0.5 to 1: 2.5.

Meanwhile, the Grignard compound of the dialkyl magnesium form is represented by the general formula MgR ₂ (R is an alkyl group having 1 to 30 carbon atoms), for example, dibutyl magnesium, butyl ethyl magnesium, butyl octyl magnesium, and the like.

In addition, the reaction ratio of the dialkylmagnesium-type Grignard compound and the alkoxyaluminum compound is preferably 1: 0.2 to 1: 5.0, more preferably 1: 0.5 to 1: 2.5 as the molar ratio.

The reaction is carried out in an aliphatic hydrocarbon solvent that satisfies the general formula RH (R is an alkyl group having 1 to 20 carbon atoms), and proceeds particularly smoothly in solvents such as hexane and heptane.

As reaction temperature in manufacture of said alkoxy aluminum-magnesium compound, normal temperature-less than 50 degreeC which is a mild reaction condition is preferable. And the reaction time is suitably between 1 hour and 3 hours, if more than 1 hour is sufficient reaction.

In the reaction of step ii), the alkoxyaluminum-magnesium compound obtained in the reaction of step iii) is reacted with a ligand of carbodiimide series.

Carbodiimide-based ligands are compounds that satisfy the following general formula, and compounds such as dimethyl carbodiimide, dicyclohexylcarbodiimide, and 1,3-bistrimethylsilylcarbodiimide are particularly suitable.

Wherein each of W, Y, and Z independently represents an alkyl group including alkyl, phenyl or heteroatoms.

The reaction between the alkoxyaluminum-magnesium compound and the carbodiimide-based ligand proceeds smoothly in a nonpolar solvent such as aliphatic hydrocarbons such as hexane and heptane, and the reaction temperature is lower than room temperature to 50 ° C, which is a mild reaction condition. desirable.

On the other hand, the reaction ratio of the alkoxyaluminum-magnesium compound and the carbodiimide-based ligand is preferably 1: 0.2 to 1: 5.0 as a molar ratio, and more preferably 1: 0.5 to 1: 2.5.

The reaction time is suitably between 1 and 3 hours, and more than 1 hour is sufficient reaction.

In step iii), the alkoxyaluminum-magnesium compound containing the carbodiimide-based ligand prepared by the above method is reacted with a Group IV transition metal compound of the periodic table, and in some cases, by addition of the alkoxyaluminum-magnesium compound Liquid chelated transition metal compounds are prepared.

That is, the alkoxyaluminum-magnesium compound containing the carbodiimide-based ligand prepared in step ii) is added dropwise to the transition metal compound of Group IV of the periodic table at room temperature, and then reacted at 65 ° C to 70 ° C for at least 1 hour. A chelated periodic table Group IV transition metal compound is prepared.

The molar ratio of the alkoxyaluminum-magnesium compound containing the carbodiimide-based ligand and the Group IV transition metal compound used at this time is preferably a ratio of 0.5 to 2.0 mol of the transition metal compound per mol of magnesium in the alkoxyaluminum-magnesium compound. Do.

The periodic table Group IV transition metal compound used is a general formula M (OR) _a X _4-a (wherein M is Ti, Zr or Hf, R is a hydrocarbon group, X is a halogen atom, and a is 0 ≦ a). And a transition metal halide compound such as MCl ₄ , MBr ₄ , MCl ₂ (OR) ₂ , MCl ₃ (OR), MBr ₂ (OR) ₂ , MBr ₃ (OR And a transition metal compound containing at least two or more halide groups.

For a smooth reaction, it is preferable to use an adduct-type transition metal halide compound such as MCl ₄ (THF) ₂ obtained by reacting the transition metal compounds with an ether-based solvent such as THF.

In the preparation of the chelated transition metal compound, a magnesium halide compound is produced as a reaction by-product, which is not dissolved in a hydrocarbon solvent and thus can be easily separated.

Chelated transition metal compounds dissolved in non-polar solvents such as heptane and hexane are very stable and can be used directly in a hydrocarbon solvent without a separate separation process. That is, the chelated transition metal compound may be used as a catalyst component for olefin polymerization together with the cocatalyst component in the form of a liquid dissolved in a nonpolar solvent such as hexane and heptane.

On the other hand, in order to make up for the alkoxyaluminum-magnesium component contained in the magnesium halide generated during the reaction of the reaction of iii), the chelated transition metal compound produced in the reaction is again alkoxyaluminum-prepared in iii). What reacted with a magnesium compound can also be used as a catalyst component of ethylene polymerization and copolymerization.

The magnesium containing carrier of (2) used in the ethylene polymerization and copolymerization method of this invention is demonstrated.

The magnesium-containing carrier used in the present invention can be produced by the known method described in Patent Application No. 2000-85050.

The magnesium-containing carrier according to the above known method is an organic magnesium compound complex [MgPh _{2 ·} nMgCl ₂ · mR ₂ O] prepared by reacting magnesium with aryl or alkyl halide in the presence of an electron donor as an organic chlorine compound in a hydrocarbon solvent. Prepared by chlorination.

The reaction is preferably carried out at a temperature of -20 ° C to 80 ° C, and the molar ratio of organochlorine compound / Mg is 0.5 or more.

The magnesium-containing carrier thus prepared may be used after reacting with an alkylaluminum represented by the general formula of AlR ₃ (R represents an alkyl group having 1 to 20 carbon atoms).

The prepared magnesium compound has a spherical particle shape, a large particle size, and a uniform particle size distribution, which is suitable for activating a chelated transition metal compound according to the present invention to prepare a polymer having excellent particle properties. An example of a detailed manufacturing method was demonstrated through the Example.

On the other hand, the ethylene polymerization and copolymerization according to the present invention is carried out in the presence of a periodic table of Group II or Group III organometallic compound promoter.

As the promoter component used in the method of the present invention, MR _n (where M is a periodic table group II or IIIA metal component such as magnesium, calcium, zinc, boron, aluminum, gallium, and R is methyl, ethyl, The organometallic compound represented by the general formula of a C1-C20 alkyl group such as butyl, hexyl, octyl, decyl, and n represents the valence of the metal component is preferable, and among these, particularly preferred organometallic compounds are Trialkylaluminum having alkyl groups of 1 to 6 carbon atoms such as ethylaluminum and triisobutylaluminum, and mixtures thereof.

In some cases, an organoaluminum compound comprising at least one halogen or hydride group such as ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride, diisobutylaluminum hydride may also be used.

The olefin polymerization catalyst components may be injected sequentially or simultaneously with each catalyst component in the polymerization process, or a mixture thereof without undergoing a separate reaction.

In the ethylene polymerization and copolymerization method of the present invention, a periodic table group IV transition metal compound catalyst component chelate-bonded with a carbodiimide-based ligand prepared by the above method, the magnesium-containing support and the periodic table group II or III Using an organometallic compound promoter, homopolymerization of ethylene and copolymerization of ethylene and alpha-olefins are carried out.

As said alpha olefin copolymerized with ethylene in this invention, a C3-C10 alpha-olefin is suitable, For example, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1- pentene, 1 Alpha olefins, such as octene, are mentioned.

The olefin polymerization method according to the present invention is suitable to be carried out by a slurry or a gas phase polymerization method.

The slurry polymerization is preferably performed at a temperature of 50 ° C. to 120 ° C. using aliphatic and aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, toluene, and the like as a solvent. In slurry polymerization, the dosage of the catalyst may vary, preferably about 0.005 mmol to about 1 mmol of catalyst per liter of hydrocarbon solvent, and more preferably 0.01 mmol to 0.1 mmol per liter of solvent. desirable.

On the other hand, the control of the molecular weight size can be made through the control of temperature and olefin pressure, the control of hydrogen pressure and the like. The pressure of ethylene at the time of ethylene polymerization is suitably 2-50 kg / cm <2>.

The ethylene / alpha olefin copolymer produced by the method of the present invention has a uniform copolymer composition distribution, has a narrow molecular weight distribution, has a very high impact strength, and does not contain a sticky low molecular weight polymer. It is suitable for high impact LLDPE, such as super hexene grade.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following examples.

(Example)

In the following examples, the hydrocarbon solvent used for preparing the catalyst was removed by distillation in the presence of sodium, and the halogenated hydrocarbon was distilled in the presence of calcium hydride. In addition, all the following reactions for catalyst preparation were performed in nitrogen atmosphere.

(Example 1)

[Preparation of Titanium Compound (A-1) Chelated with Dicyclohexylcarbodiimide Ligand]

After diluting 800 mmol of triethylaluminum in hexane to make 800 ml, it was placed in a 1 L flask, and the temperature of the flask was kept at room temperature by cooling water at room temperature, while 2400 mmol of 2-ethylhexanol was kept for 1 hour. After slowly dropping over, it was stirred for 1 hour to prepare a colorless transparent solution. It was observed that gas was generated by the dropwise addition of 2-ethylhexanol.

400 ml of 1.0M heptane solution of dibutylmagnesium was injected into the solution prepared above, and stirred for 1 hour to prepare an alkoxyaluminum-magnesium compound.

82.4 g of dicyclohexylcarbodiimide (400 mmol) was added to the solution, followed by stirring at room temperature for 1 hour.

The compound thus prepared was reacted with 133.684 g of TiCl ₄ (THF) ₂ (400 mmol) for 6 hours at room temperature. By reaction, TiCl ₄ (THF) ₂ solid, which was initially light yellow, gradually turned red, producing a white magnesium halide solid.

The alkoxyaluminum-magnesium compound (Mg 400 mmol) was further injected and reacted at room temperature for 6 hours.

After stopping the stirring for 20 minutes, the white solid at the bottom settles, and the red solution of the upper layer is separated from the white solid at the bottom and transferred to another flask to remove the liquid chelated titanium compound catalyst component (A-1). Got it.

[Production of Magnesium-Containing Carrier (B)]

In a 1 liter glass reactor equipped with a stirrer and a thermostat, 29.2 g of magnesium powder (in the presence of 307 ml (1.8 mol) of dibutyl ether and 0.29 g of iodine dissolved in 4 ml butyl chloride as an activator) 1.2 mol) and 436 ml of chlorobenzene (4.3 mol) were reacted. The reaction proceeded with stirring for 10 hours under an inert gas (nitrogen) atmosphere at a temperature of 80 ~ 100 ℃.

Then, the reaction mixture was left for 12 hours without stirring, and then the liquid phase was separated from the precipitate. A: liquid phase _{MgPh 2 · 0.5MgCl 2 · 2 (} C 4 H 9) is an organomagnesium compound having the composition ₂ O dissolved in chlorobenzene solution (0.92㏖ Mg / ℓ concentration).

120 mL (Mg 0.11 mol) of the obtained solution was added to a reactor equipped with a stirrer, and 10.6 mL CCl ₄ (CCl ₄ 0.11 mol) dissolved in 42 mL of n-hexane was added to the reactor at a temperature of 50 ° C. over 1 hour. Was added. The reaction mixture was stirred at the same temperature for 60 minutes, then the solvent was removed, and the precipitate was washed four times with 100 ml of n-hexane at a temperature of 60 ° C. As a result, 11.8 g of a powdered organic magnesium carrier was obtained in a suspended state in n-hexane.

[Ethylene polymerization reaction]

To a fully nitrogen-substituted 2 liter autoclave, 1000 ml of hexane as a polymerization solvent was added at room temperature, and then nitrogen in the autoclave was substituted with ethylene.

3 mmol of trioctyl aluminum were injected at room temperature, and 0.05 mmol of the chelated titanium compound catalyst component (A-1) prepared above and 0.2 g of a magnesium-containing carrier component (B) were injected.

Hydrogen was added at 1.5 kg / cm 2 at 60 ° C., the temperature was raised to 80 ° C., and then pressurized with ethylene to maintain the total pressure at 6 kg / cm 2.

The polymerization proceeded for 1 hour.

After the polymerization was completed, the polymerized polymer was separated from hexane and dried.

As a result of polymerization, 310 g of polyethylene was recovered, and the obtained polymer had M.I. (g / 10min) of 0.7 and MFRR of 25.1, indicating that a polymer having a narrow molecular weight distribution was obtained.

[Ethylene / 1-hexene copolymerization reaction]

To a 2 liter autoclave, a vacuum pump was connected to remove oxygen and moisture and then charged with ethylene gas. The vacuum pump connection and ethylene gas purge were repeated three more times to purge the reactor interior with ethylene gas.

900 ml of hexane was injected into the autoclave as a polymerization solvent, 90 ml of 1-hexene was added and stirred for 10 minutes.

Again, 3 mmol of trioctyl aluminum was injected at room temperature, and 0.05 mmol of the chelated titanium compound catalyst component (A-1) prepared above and 0.1 g of a magnesium-containing carrier (B) were injected.

Hydrogen was added at 1.5 kg / cm 2 at 60 ° C. and the temperature was raised to 80 ° C., and then pressurized with ethylene to maintain the total pressure at 6 kg / cm 2.

The polymerization proceeded for 20 minutes.

After the polymerization, the reaction was stopped by adding an ethanol solution, and an acidic alcohol solution was added to separate the prepared polymer.

The isolated polymer had a M.I. of 1.2 and an MFRR of 23.1.

The properties of the separated polymers are shown in Table 1.

The low MFRR values in Table 1 mean that the molecular weight distribution of the polymer produced is narrow, and from the Tm values obtained by DSC analysis of polymers containing the same amount of copolymer and from the results of temperature rising elution fractionation (TREF) It was confirmed that a uniform copolymer composition distribution was obtained.

(Example 2)

[Production of Titanium Compound (A-2) Chelated by Dimethylcarbodiimide Ligand]

A chelated titanium compound catalyst component (A-2) was prepared in the same manner as in Example 1 except that a dimethylcarbodiimide ligand was used instead of dicyclohexylcarbodiimide.

[Production of Magnesium-Containing Carrier (B)]

A magnesium-containing carrier (B) was prepared in the same manner as in Example 1.

[Ethylene Polymerization and Copolymerization Reaction]

Ethylene polymerization and copolymerization of ethylene / 1-hexene were carried out in the same manner as in Example 1, except that the chelated titanium compound catalyst component (A-2) prepared above was used. The polymerization results are shown in Table 1.

(Example 3)

[Preparation of Titanium Compound (A-3) Chelated with 1,3-Bistrimethylsilylcarbodiimide]

A chelated titanium compound catalyst component (A-3) was prepared in the same manner as in Example 1 except that the 1,3-bistrimethylsilylcarbodiimide ligand was used instead of the dicyclohexylcarbodiimide.

[Production of Magnesium-Containing Carrier (B)]

A magnesium-containing carrier (B) was prepared in the same manner as in Example 1.

[Ethylene Polymerization and Copolymerization Reaction]

Ethylene polymerization and copolymerization of ethylene / 1-hexene were carried out in the same manner as in Example 1, except that the chelated titanium compound catalyst component (A-3) prepared above was used. The polymerization results are shown in Table 1.

(Example 4)

[Production of Titanium Compound (A-4) Chelated by Dicyclohexylcarbodiimide]

A chelated titanium compound catalyst component (A-4) was prepared in the same manner as in Example 1 except that isopropanol (2400 mmol) was used instead of 2-ethylhexanol.

[Production of Magnesium-Containing Carrier (B)]

A magnesium-containing carrier (B) was prepared in the same manner as in Example 1.

[Ethylene Polymerization and Copolymerization Reaction]

Ethylene polymerization and copolymerization of ethylene / 1-hexene were carried out in the same manner as in Example 1, except that the chelated titanium compound catalyst component (A-4) prepared above was used. The polymerization results are shown in Table 1.

(Example 5)

[Production of Titanium Compound (A-5) Chelated with Dicyclohexylcarbodiimide]

A chelated titanium compound catalyst component (A-5) was prepared in the same manner as in Example 1 except that n-butanol (2400 mmol) was used instead of 2-ethylhexanol.

[Production of Magnesium-Containing Carrier (B)]

A magnesium-containing carrier (B) was prepared in the same manner as in Example 1.

[Ethylene Polymerization and Copolymerization Reaction]

Ethylene polymerization and copolymerization of ethylene / 1-hexene were carried out in the same manner as in Example 1, except that the chelated titanium compound catalyst component (A-5) prepared above was used. The polymerization results are shown in Table 1.

(Example 6)

[Production of Titanium Compound (A-6) Chelated by Dicyclohexylcarbodiimide]

A chelated titanium compound catalyst component (A-6) was prepared in the same manner as in Example 1 except that Ti (O-iPr) ₂ Cl ₂ (400 mmol) was used instead of TiCl ₄ (THF) ₂ .

[Production of Magnesium-Containing Carrier (B)]

A magnesium-containing carrier (B) was prepared in the same manner as in Example 1.

[Ethylene Polymerization and Copolymerization Reaction]

Ethylene polymerization and copolymerization of ethylene / 1-hexene were carried out in the same manner as in Example 1, except that the chelated titanium compound catalyst component (A-5) prepared above was used. The polymerization results are shown in Table 1.

(Example 7)

[Production of Titanium Compound (A-7) Chelated by Dicyclohexylcarbodiimide]

A chelated titanium compound catalyst component (A-7) was prepared in the same manner as in Example 1 except that TiCl ₄ (400 mmol) was used instead of TiCl ₄ (THF) ₂ .

[Production of Magnesium-Containing Carrier (B)]

A magnesium-containing carrier (B) was prepared in the same manner as in Example 1.

[Ethylene Polymerization and Copolymerization Reaction]

Ethylene polymerization and copolymerization of ethylene / 1-hexene were carried out in the same manner as in Example 1, except that the chelated titanium compound catalyst component (A-7) prepared above was used. The polymerization results are shown in Table 1.

(Example 8)

[Production of Titanium Compound (A-8) Chelated with Dicyclohexylcarbodiimide]

After diluting 800 mmol of triethylaluminum in hexane to make 800 ml, it was placed in a 1 L flask, and the temperature of the flask was kept at room temperature by cooling water at room temperature, while 2400 mmol of 2-ethylhexanol was kept for 1 hour. After slowly dropping over, it was stirred for 1 hour to prepare a colorless transparent solution. It was observed that gas was generated by the dropwise addition of 2-ethylhexanol.

400 ml of 1.0M heptane solution of dibutylmagnesium was injected into the solution prepared above, and stirred for 1 hour to prepare an alkoxyaluminum-magnesium compound.

82.4 g of dicyclohexylcarbodiimide (400 mmol) was added to the solution, followed by stirring at room temperature for 1 hour.

The compound thus prepared was reacted with 133.684 g of TiCl ₄ (THF) ₂ (400 mmol) for 6 hours at room temperature. By reaction, TiCl ₄ (THF) ₂ solid, which was initially light yellow, gradually turned red, producing a white magnesium halide solid.

After stopping the stirring for 20 minutes, the white solid at the bottom settles, and the red solution from the upper layer is separated from the white solid at the bottom and transferred to another flask to remove the liquid chelated titanium compound catalyst component (A-8). Got it.

[Production of Magnesium-Containing Carrier (B)]

A magnesium-containing carrier (B) was prepared in the same manner as in Example 1.

[Ethylene Polymerization and Copolymerization Reaction]

Ethylene polymerization and copolymerization of ethylene / 1-hexene were carried out in the same manner as in Example 1, except that the chelated titanium compound catalyst component (A-8) prepared above was used. The polymerization results are shown in Table 1.

(Comparative Example 1)

[Production of Titanium Catalyst Component]

19.2 g of magnesium metal was placed in a 1 L flask, and 20 ml of dibutyl ether was injected.

After raising the temperature to 80 ° C., 5 ml of the solution of 2 g of iodine and 50 ml of chlorobutane was taken and injected to activate the magnesium surface.

Again, 20 ml of chlorobenzene was injected with 200 ml of dibutyl ether, and 400 ml of chlorobenzene was added dropwise at a temperature of 90 deg. The reaction at 90 ° C. was continued for at least 5 hours to complete the preparation of the Grignard reagent.

The liquid Grignard reagent was separated from the solid component, 120 ml (100 mmol Mg) in the separated supernatant portion were placed in a 1 L flask, and 20 ml of carbon tetrachloride was slowly added dropwise at a temperature of 40 DEG C. The spherical magnesium halide was manufactured by heating up at 80 degreeC and making it react for more than 1 hour. The supernatant solution was again decanted and washed three times with hexane to separate the solid magnesium halide carrier component.

300 mL of hexane was injected into the carrier thus prepared, and 30 mL of TiCl ₄ was injected and heated at 60 ° C. for 1 hour. After the reaction was completed, the supernatant solution was decanted at 60 ° C. and washed three times with hexane to complete the preparation of the catalyst.

The titanium loading rate was 3.5%.

[Ethylene polymerization reaction and copolymerization reaction]

Ethylene polymerization and copolymerization of ethylene / 1-hexene by the same method as in Example 1, except that the titanium catalyst component prepared above was used instead of the catalyst component A-1, and no magnesium containing carrier was used. The reaction was carried out. The polymerization results are shown in Table 1. Indicated.

(Comparative Example 2)

[Preparation of Ti Catalyst Component]

After dissolving 82.4 g of dicyclohexylcarbodiimide (400 mmol) in 400 ml of toluene solution, 40 ml (400 mmol) of TiCl ₄ were injected and reacted at 90 ° C for 4 hours. As the reaction progressed, the colorless solution became dark brown. After the reaction, toluene was removed with a vacuum pump, and the remaining solid was sufficiently washed with hexane to remove the unreacted carbodiimide compound and TiCl ₄ to obtain a Ti catalyst component in a brown solution.

[Production of Magnesium-Containing Carrier (B)]

A magnesium-containing carrier (B) was prepared in the same manner as in Example 1.

[Production of Catalyst (C)]

After dissolving the Ti catalyst component in 400 ml of toluene, 20 g of the magnesium-containing carrier (B) was poured into 100 ml of the suspended slurry, followed by stirring at 60 ° C for 1 hour. After stirring was stopped, 20 ml of hexane was injected and washed three times to obtain a catalyst (C) in a state where a powdery solid was suspended in n-hexane.

[Ethylene Polymerization and Copolymerization Reaction]

By the same method as in Example 1, except that the catalyst (C) prepared above was used instead of the chelate titanium compound catalyst component (A-1) and the magnesium-containing carrier in Example 1 Ethylene polymerization and ethylene / 1-hexene copolymerization were carried out. The polymerization results are shown in Table 1.

(Comparative Example 3)

[Production of Titanium Catalyst Component]

After diluting 800 mmol of triethylaluminum in hexane to make 800 ml, it was placed in a 1 L flask, and the temperature of the flask was kept at room temperature by cooling water at room temperature, while 2400 mmol of 2-ethylhexanol was kept for 1 hour. After slowly dropping over, it was stirred for 1 hour to prepare a colorless transparent solution. It was observed that gas was generated by the dropwise addition of 2-ethylhexanol.

400 ml of 1.0M heptane solution of dibutylmagnesium was injected into the solution prepared above, and stirred for 1 hour to prepare an alkoxyaluminum-magnesium compound.

133.684 g of TiCl ₄ (THF) ₂ (400 mmol) was added to the solution and allowed to react for 6 hours at room temperature. As the reaction proceeded, the initially light yellow TiCl ₄ (THF) ₂ solid gradually turned red, producing a white magnesium halide solid.

When the reaction was completed, the stirring was stopped and waited for about 20 minutes. The white solid sank at the bottom, and the red solution of the upper layer was separated from the white solid at the bottom and transferred to another flask to obtain a liquid titanium compound catalyst component.

[Production of Magnesium-Containing Carrier (B)]

A magnesium-containing carrier (B) was prepared in the same manner as in Example 1.

[Ethylene Polymerization and Copolymerization Reaction]

Ethylene polymerization and copolymerization of ethylene / 1-hexene in the same manner as in Example 1, except that the titanium compound catalyst component prepared above was used instead of the chelated titanium compound catalyst (A-1) in Example 1. The reaction was carried out and the polymerization results are shown in Table 1.

(Comparative Example 4)

[Preparation of Titanium Compound (A-1) Chelated with Dicyclohexylcarbodiimide Ligand]

Chelated titanium compound catalyst component (A-1) was prepared in the same manner as in Example 1.

[Ethylene Polymerization and Copolymerization Reaction]

Ethylene polymerization and copolymerization of ethylene / 1-hexene were carried out in the same manner as in Example 1 except that the magnesium-containing carrier component (B) was not used, and the polymerization results are shown in Table 1.

(Comparative Example 5)

[Preparation of Titanium Compound (A-1) Chelated with Dicyclohexylcarbodiimide Ligand]

Chelated titanium compound catalyst component (A-1) was prepared in the same manner as in Example 1.

[Production of Magnesium-Containing Carrier (B)]

A magnesium-containing carrier (B) was prepared in the same manner as in Example 1.

[Ethylene Polymerization and Copolymerization Reaction]

The copolymerization reaction of ethylene polymerization and ethylene / 1-hexene was carried out in the same manner as in Example 1 except that 3 mmol of PMAO was used instead of 3 mmol of trioctyl aluminum in Example 1 as a cocatalyst. The polymerization results are shown in Table 1.

(Comparative Example 6)

[Preparation of Titanium Compound (A-1) Chelated with Dicyclohexylcarbodiimide Ligand]

Chelated titanium compound catalyst component (A-1) was prepared in the same manner as in Example 1.

[Ethylene Polymerization and Copolymerization Reaction]

Instead of injecting 3 mmol of trioctyl aluminum in Example 1 as a cocatalyst, 3 mmol of PMAO was used, and the same method as in Example 1 was used except that the magnesium-containing carrier component (B) was not used. Copolymerization of ethylene polymerization and ethylene / 1-hexene was carried out, and the polymerization results are shown in Table 1.

Ethylene Polymerization and Ethylene / 1-hexene Copolymerization Results Ethylene polymerization Ethylene / 1-hexene Copolymerization Active ^(a) MI ^(b) (g / 10min) MFRR B / D ^(c) (g / ml) MI ^(b) (g / 10min) MFRR ΔH (J / g) Tm (℃) Example 1 5500 0.7 25.1 0.42 1.2 23.1 105.8 122.1 Example 2 5800 1.0 28.3 0.42 1.5 25.4 106.8 122.3 Example 3 4500 0.90.9 26.3 0.41 1.9 24.4 110.3 123.2 Example 4 4700 0.7 28.3 0.42 1.6 23.8 98.6 122.2 Example 5 5200 1.3 24.3 0.41 1.2 23.4 107.5 122.5 Example 6 4100 0.6 27.3 0.41 1.3 25.2 108.1 123.0 Example 7 4500 0.8 26.3 0.42 1.6 24.8 102.3 123.2 Example 8 3700 0.4 26.7 0.40 1.0 25.4 104.2 122.9 Comparative Example 1 3500 0.6 30.7 0.37 1.2 30.1 105.6 125.0 Comparative Example 2 2500 0.2 30.7 0.37 0.6 30.4 125.8 125.0 Comparative Example 3 2400 0.6 28.7 0.38 0.7 29.8 103.2 125.2 Comparative Example 4 2200 0.6 31.0 - 1.2 30.8 87.5 123.4 Comparative Example 5 2300 0.3 24.7 0.32 0.3 27.5 86.4 123.2 Comparative Example 6 2500 0.6 30.7 - 1.2 30.1 107.1 125.7

(a) Active unit: g-PE / (mmol-Ti × hr)

(b) ASTM D1238, 190 ° C., 2.16 kg

(c) apparent density

According to the method of the present invention, it is possible to polymerize polymers and copolymers of ethylene and ethylene / alpha-olefins having a high apparent density while having a narrow molecular weight distribution and a uniform copolymer composition distribution.

Claims (7)

(1) a) an alkoxyaluminum-magnesium compound is obtained by reacting a Grignard compound in the form of a dialkyl magnesium with an alkoxy aluminum, Ii) reacting the compound obtained in iii) with a carbodiimide ligand, Iii) a periodic table Group IV transition metal compound catalyst component cheated by a carbodiimide-based ligand obtained by a method of reacting a product with a Group IV transition metal compound of the periodic table; (2) magnesium-containing carriers; And (3) A process for ethylene polymerization and copolymerization, characterized in that the presence of a Group II or Group III organometallic compound promoter of the periodic table is present. The process according to claim 1, wherein the periodic table group IV transition metal compound catalyst component chelate-bonded by the carbodiimide ligand of (1) is obtained by reaction with an alkoxyaluminum-magnesium compound after the reaction of i). Ethylene polymerization and copolymerization method characterized by. The ethylene polymerization and copolymerization method according to claim 1 or 2, wherein the carbodiimide-based ligand is represented by the following general formula (1). (One) Wherein each of W, Y, and Z independently represents an alkyl group including alkyl, phenyl or heteroatoms. The method of claim 3, wherein the carbodiimide-based ligand is dimethyl carbodiimide, dicyclohexylcarbodiimide or 1,3-bistrimethylsilylcarbodiimide. The method of claim 1 or 2, wherein the magnesium-containing support, MgPh ₂ · nMgCl ₂ · mR ₂ O (wherein Ph is phenyl, n = 0.37 ~ 0.7, m ≥ 1, R ₂ O is ether, respectively) And an organic magnesium compound and an organic chlorine compound represented by the above formula are reacted with a molar ratio of organic chlorine compound and magnesium of 0.5 or more. 3. The compound of claim 1, wherein the Group IV transition metal compound of the periodic table is a general formula M (OR) _a X _4-a , wherein M is Ti, Zr or Hf, R is a hydrocarbon group, and X is Halogen atom, and a represents an integer of 0 ≦ a ≦ 2). The organometallic compound promoter component of claim 1 or 2, wherein MR _n (wherein M represents a group II or IIIA metal atom of the periodic table, R represents an alkyl group having 1 to 20 carbon atoms, and n represents Ethylene polymerization and copolymerization method characterized by the above-mentioned.