KR0164243B1 - Production of polyolefin - Google Patents

Abstract

An object of the present invention is to provide a catalyst system capable of producing a polyolefin that is highly active, has excellent comonomer reactivity, and has a high molecular weight by a solution polymerization method or a high temperature and high pressure polymerization method in a temperature range higher than the melting point of a polymer.

In the present invention, polyolefins are prepared by homopolymerizing ethylene or copolymerizing ethylene with at least one α-olefin in the presence of a catalyst composed of a transition metal compound and an organometallic compound, at a reaction temperature above the melting point of the polymer.

Description

Method for producing polyolefin

The present invention relates to an extremely highly active Ziegler catalyst and a process for producing polyolefin using the same. More specifically, the present invention relates to a method for producing polyolefin, characterized by homopolymerization of ethylene or copolymerization of ethylene and α-olefin using a catalyst component having extremely high catalytic activity under temperature conditions above the melting point of the polymer.

Conventionally, as one of the methods for producing an ethylene (co) polymer, a method of polymerizing ethylene in the presence of a so-called Ziegler-type catalyst combining a transition metal compound and an organometallic compound, or a method of copolymerizing ethylene and α-olefin is known. Among them, as a Ziegler-type catalyst, it is advantageous to combine a compound of titanium, zirconium and vanadium with an organoaluminum compound in terms of catalytic activity and molecular weight, molecular weight distribution, copolymerization composition of the resulting polyethylene, and is widely used industrially. .

In addition, if the production method is classified by process, the slurry polymerization method which polymerizes the polymer while keeping the polymer in the particle state under the temperature of melting point of polyethylene, the gas phase polymerization method, the solution polymerization method which polymerizes under the temperature condition above melting point, and the high temperature high pressure polymerization method This is known.

The solution polymerization method and the high temperature and high pressure polymerization method of these comprehensive processes can effectively utilize the heat of polymerization by exothermic reaction and are advantageous in terms of energy. On the other hand, the slurry polymerization method and the gas phase polymerization method keep the copolymer particles in a stable state due to the low crystallinity of the copolymer in low density polyethylene produced by copolymerization with α-olefin. There are limitations on the range of products that can be industrially produced, such as low reactivity, making it difficult to produce higher α-olefin copolymers having excellent physical properties. On the other hand, the solution polymerization method and the high temperature and high pressure polymerization method do not take a particulate state or the reactivity of the α-olefin is increased by the high temperature reaction, so that the high-quality low-density polyethylene can be produced in a wide range without the above limitations.

However, since the transition metal compound commonly used as a Ziegler catalyst is a solid, it is suspended in an inert solvent. Therefore, when the transition metal compound is continuously supplied to the polymerization reactor, the transition metal compound is easily settled in the transport pipe and is quantitatively and uniformly supplied. . In the case where it is not possible to supply constantly, it is difficult to stably perform the polymerization reaction, and thus the quality of the resulting polyethylene is also nonuniform. Therefore, in order to refine catalyst particles and suppress sedimentation, it was necessary to react α-olefins such as hexene in advance.

An object of the present invention is that the polyolefin has excellent comonomer reactivity and high molecular weight in the temperature range higher than the melting point of the polymer, i.e., it does not require the catalyst removal step by the melt polymerization method or the high temperature and high pressure polymerization method. It is to provide a catalyst system that can be prepared. In addition, the present invention provides a catalyst system capable of making the polymerization reaction stable and further producing a polyolefin having a uniform quality without requiring a process for miniaturizing catalyst particles.

In order to solve the above problems, the inventors of the present invention have made diligent studies to develop a high activity polymerization catalyst utilizing the advantages of the solution polymerization method and the high temperature and high pressure polymerization method. As a result, a uniform solution containing a specific transition metal and a halogen are used. A catalyst system using an organoaluminum compound containing or a component containing a homogeneous solution containing a transition metal and an organoaluminum compound containing a halogen exhibits amazing catalytic activity in carrying out (co) polymerization of ethylene. It has been found that the present invention has been completed. That is, the gist of the present invention is to prepare a polyolefin by homopolymerizing ethylene or copolymerizing at least one α-olefin at a reaction temperature above the melting point of the polymer in the presence of a catalyst composed of a transition metal compound and an organometallic compound. In

(Requirement 1) (Ⅰ) Metal magnesium

(II) Oxygen-Containing Organic Compounds in Titanium

(Ⅲ) alcohol

Titanium-magnesium-containing homogeneous solution (component (A)) and halogen-containing organoaluminum compound (component (B)) obtained by reacting the same, and the carbon number in the alcohol of component (III) A catalyst for producing polyolefin, wherein 6 or more alcohols are contained in an amount of 1 mol / mol or more with respect to the metal magnesium of the component (I).

(Requirement 2) (Ⅰ) Metal magnesium

(II) oxygen-containing organic compounds of titanium and

(III) alcohols, and

(IV) halogen-containing organoaluminum compound

It consists of all the catalyst components ((C component) obtained by reacting

A catalyst for producing polyolefin, wherein the alcohol having 6 or more carbon atoms is contained in the alcohol of the component (III) with respect to the metal magnesium of the component (I).

(Requirement 3) (Ⅰ) Metal magnesium

(II) oxygen-containing organic compounds of titanium and

(III) alcohols, and

(IV) halogen-containing organoaluminum compound

All catalyst components ((C) component) obtained by reacting

Consists of at least one compound ((D) component) selected from organoaluminum compounds,

A catalyst for producing polyolefin, wherein the alcohol having 6 or more carbon atoms is contained in the alcohol of the component (III) with respect to the metal magnesium of the component (I).

(Requirement 4) The polyolefin may be prepared by homopolymerizing ethylene or copolymerizing ethylene with at least one α-olefin at a reaction temperature above the melting point of the polymer by using a catalyst composed of a transition metal compound and an organometallic compound. It is in the manufacturing method of the polyolefin characterized by manufacturing.

As the metal magnesium of the above-mentioned (I) which is a reaction agent used in this invention, various forms, ie, powder, particle | grains, foil, or any form, such as a ribbon, can be used.

As the oxygen-containing organic compound of titanium which is the reactive agent of (II), a compound represented by the general formula [TiO _a (OR ¹ ) _b X ¹ _c ] _n and the like are used.

In this general formula, R ¹ represents a hydrocarbon group such as an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, a cycloalkyl group, an aryl group, X ¹ represents a halogen atom, and F, Cl, Br or I to be. a, b and c are a g0 and b> 0, 4> c g0 is the valence of titanium and an acceptable number, n is an integer. Among them, a is 0 fa f1, n is 1 fn It is preferable to use an oxygen-containing organic compound of f6.

Specific examples include Ti (OC ₂ H ₅ ) ₄ , Ti (O-n-C ₃ H ₇ ) ₄ , Ti (O-i-C ₃ H ₇ ) ₄ , Ti (O-n -C ₄ H ₉ ) ₄ , Ti ₂ O (O-I-C ₃ H ₇ ) ₆ , Ti (OCH ₂ H ₅ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₃ Cl, and the like. Moreover, you may use the oxygen containing organic compound containing several other hydrocarbon groups.

These oxygen-containing organic compounds of titanium are used alone or as a mixture of two or more thereof.

As said alcohol of (III), the alcohol which has hydrocarbon groups, such as the alkyl group and cycloalkyl group which have 1-18 carbon atoms, can be used. Examples include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, n-hexanol, 1-ethylhexanol, 2-ethylhexanol, n-octanol, 1-ethyloctanol, n -Styryl alcohol, cyclopentanol, cyclohexanol, ethylene glycol, etc. are mentioned.

These alcohols are used alone or as a mixture of two or more kinds. In the present invention, at least one alcohol selected from alcohols having 6 or more carbon atoms in the alcohol used as the component (III) is used as the metal magnesium of the component (I). It should be included at least 1mol / mol.

If this amount is smaller than that, sufficient activity cannot be obtained or a uniform titanium-magnesium-containing solution cannot be obtained.

Although there is no restriction | limiting in particular in the usage-amount of the above-mentioned reactive agent (I) (II) (III), The molar ratio of the magnesium atom in (I) and the titanium atom in (II) is 1: 0.01-1: 5 Preferably It is preferable to select the amount of use so that 1: 0.02-1: 2 becomes. If it is out of this range, it may cause a problem such as low polymerization property or coloring of the product.

As described above, the molar ratio of the carbon atom having 6 or more carbon atoms contained in the magnesium atom in (I) and the component (III) is 1: 1 or more, and the molar ratio of the magnesium atom and the entire alcohol (III) in (I). Is preferably selected from 1: 2 to 1:10.

Preparation of the titanium-magnesium-containing homogeneous solution,

(1) a method of suspending metal magnesium (I) in an oxygen-containing organic compound (II) of titanium and dropping alcohol (III) thereto;

(2) a method of supplying metal magnesium (I) to a solution of an oxygen-containing organic compound (II) and alcohol (III) of titanium;

It can be carried out by, but the method of (1) is particularly preferable.

Further, for the purpose of facilitating the reaction, a substance which reacts with the metal magnesium or generates an addition compound, for example, by adding one or two or more polar substances such as oxo, mercury chloride, alkyl halide, organic acid ester and organic acid, etc. It is preferable.

These catalyst preparation reactions may be carried out in the presence or absence of an inert organic solvent, but inert organic solvents may be used when these reactants themselves are not liquid under the operating conditions or when the amount of the liquid reactive agent is insufficient. It is preferable to carry out in the presence of a solvent. As the inert organic solvent, any one commonly used in the art may be used, but examples thereof include aliphatic, alicyclic or aromatic hydrocarbons, halogen derivatives thereof or mixtures thereof. For example, isobutane, hexane, heptane, cyclohexane, Benzene, toluene, xylene, monochlorobenzene and the like are preferably used.

The reaction conditions when obtaining a homogeneous solution by the above-mentioned reactants (I), (II) and (III) are usually 0.5 to 50 hours at a temperature in the range of -50 to 300 ° C, preferably 0 to 200 ° C. Preferably, it is performed under normal pressure or pressurization in inert gas atmosphere for 1 to 6 hours.

The titanium-magnesium-containing homogeneous solution thus obtained may be used as it is, but is usually diluted in an inert organic solvent and used for the polymerization reaction or the following reaction.

As the catalyst component (B) used in the present invention, for example, general formula AIR ² mX ² _3-m (wherein R ² represents an alkyl group having 1 to 20 carbon atoms, X ² represents a halogen atom, and m is Halogen-containing organoaluminum compounds are used. Specifically, diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesqui chloride, ethyl aluminum dichloride, diethyl aluminum monopromide, diisopropyl aluminum monopromide, etc. are mentioned. These halogen containing organoaluminum compounds are used individually or as a mixture of 2 or more types.

The amount and amount of catalyst component (B) used are such that the molar ratio of halogen atoms to titanium atoms contained in the catalyst is 30 or more and the molar ratio of organic groups to titanium atoms is 30 or more and 80 or less. It is desirable to choose.

If it is out of this range, there is a possibility that the polymerization activity is lowered.

As the halogen-containing organoaluminum which is the reactive agent of (IV), general formula AIR ² mX ² _3-m (wherein R ² represents an alkyl group having 1 to 20 carbon atoms, X ³ represents a halogen atom and m is 0 m ³ ) A halogen-containing organoaluminum compound represented by is used. Specifically, diethyl aluminum monochloride, diiso butyl aluminum monochloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, diethyl aluminum monopromide, diisopropyl aluminum monopromide, etc. are mentioned.

These halogen-containing organoaluminum compounds are used individually or as a mixture of 2 or more types. When m is in the range of 0 m 3 by mixing, trialkyl aluminum or aluminum trihalogenated may be used as one of the components to be mixed.

In the present invention, a compound in which m is represented by 1 m 2 or a mixture of halogen-containing organoaluminum compounds having a composition after mixing in a range of 1 m 2 is suitably used.

The reactant (IV) has a molar ratio of halogen atoms to 5 titanium atoms in (II), particularly 10 or more, and a molar ratio of organic groups to titanium atoms in (II) of 5 to 80, in particular 10 It is preferable to select the kind and usage-amount so that it may become more than 80.

In the reaction of the reaction agent (IV), the reaction is carried out at a temperature ranging from -50 to 200 ° C, preferably 0 to 150 ° C for 1 minute to 10 hours, preferably 10 minutes to 5 hours, in an inert gas atmosphere or under pressure. Is done.

The catalyst component (C) thus obtained is soluble in the solvent used as the diluent, or becomes a soluble component and an insoluble fine particle. In the present invention, all of them are used in the polymerization system. If only fine particles are separated and used by an operation such as washing, sufficient activity is not obtained. Therefore, in the preparation of the catalyst used in the present invention, the washing step for separating the solid component and the miniaturization step for the purpose of constant supply to the polymerization reactor to suppress sedimentation are unnecessary.

Further, when the amount of the reactive agent (IV) is less than the above-mentioned range, that is, the molar ratio of the halogen atom to the titanium atom is less than 30, in particular less than 40, or the titanium atom in (II) When the molar ratio of the device is less than 30, in particular 40, at least one compound ((D) selected from organoaluminum compounds described below in addition to the catalyst component (catalyst component (C)) obtained in the reactants (I) to (IV) It is preferable to add (component) to a polymerization reaction system to perform (co) polymerization.

As the catalyst component (D), an organic compound represented by the general formula AIR ⁴ ₁ mX ⁴ _3-1 (wherein R ⁴ represents an alkyl group having 1 to 20 carbon atoms, X ⁴ represents a halogen atom and 1 is 01f3) Aluminum compounds are used. Specifically, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, diethyl aluminum monopromide And diisopropyl aluminum monopromide and the like.

These organoaluminum compounds are used individually or in mixture of 2 or more types. Another 1 by Mix 01 When it is in the range of f3, aluminum trihalide may be used as one of the components to be mixed.

As said (D) component, the compound in which 1 is represented by 112, or the mixture of the organoaluminum compound in which the composition after mixing becomes the range of 112 is used suitably.

The catalyst component (D) depends on the amount of the reagent (IV) used in the preparation of the catalyst component (C). However, the catalyst component (D) is added to the reagent (II) in the sum of the halogen atoms or organic groups contained in both aluminum compounds. The molar ratio of the halogen atom to the titanium atom in 5, in particular 10 or more, and the molar ratio of the organic group to the titanium atom in the reactive agent (II) is 5 or more and 80 or less, in particular 10 or more and 80 or less, and It is preferable to select the usage amount. If it is out of this range, there is a possibility that the polymerization activity is lowered.

The polymerization of the present invention is homopolymerization of ethylene or copolymerization of ethylene with at least one α-olefin. As an alpha olefin used for copolymerization with ethylene, a C3-C20 thing is preferable, As a specific example, propylene, 1-ptene, 1-pentene, 1-hexene, 4-methyl-1- pentene, 1-octene, 1- Decene and the like and mixtures thereof are used.

The polymerization of ethylene is carried out at a melting point of the polymer or higher, preferably at a temperature in the range of 130 to 300 ° C, and an inert solvent or monomer itself is used as the polymerization medium.

In solution polymerization using an inert solvent, aliphatic hydrocarbons and mixtures such as hexane, heptane, octane, nonane, decane, undecane and dodecane, aromatic hydrocarbons such as benzene and toluene, cyclohexane and methylcyclohexane, etc. Alicyclic hydrocarbons are used. The polymerization conditions are usually 1 to 200, preferably 10 to 50 kg / cm 2, and residence time of 10 minutes to 6 hours, preferably 20 minutes to 3 hours.

In the high temperature and high pressure polymerization in which the monomer itself is used as the polymerization medium, a high-pressure radical polymerization apparatus of ethylene can be generally used, and the polymerization pressure is 200 to 2500 kg / cm 2, preferably 400 to 1500 kg / cm 2, and residence time 5. It is performed in the range of -600 second, Preferably it is 10 to 150 second.

In the present invention, the molecular weight of the polymer can also be controlled by controlling the reaction temperature, but can be easily controlled by the presence of hydrogen in the polymerization zone. Since the amount of hydrogen varies depending on the polymerization conditions, the molecular weight of the desired ethylene polymer, etc., it is necessary to adjust it appropriately.

EXAMPLE

The present invention is shown below by way of examples, and the present invention is not limited at all by these examples unless the gist thereof is exceeded.

In an Example, MI shows a mult index and measured on 190 degreeC and the conditions of 2.16 kg of loads based on JISK-6760.

Density was measured by JIS K-6760. The polymerization activity is expressed by the amount of polymer (Kg) produced per 1 g of titanium in the catalyst component (A).

Example 1

(A) [Preparation of catalyst component (A)]

Into a 3-liter flask equipped with a stirring device, a reflux condenser, a dropping tube, and a thermometer, 36 g (1.48 mol) of metal magnesium powder and 51.6 g (0.152 mol) of titanium tetra butoxide were added thereto, 1.8 g of oxo and 134.1 g (1.8 mol of butanol). ), 2-ethyl hexane was added to 231.6 g (91.78 mol), and it heated up to 90 degreeC, and stirred for 2 hours under nitrogen sealing, removing hydrogen gas which generate | occur | produces. Then, it heated up to 140 degreeC and made it react for 2 hours, Then, 2450 ml of heptanes were added, and the catalyst component (A) of the homogeneous solution containing magnesium and titanium was obtained.

The obtained catalyst component (A) was diluted with a solvent (IP-1620 manufactured by Idemitsu Petrochemical Co., Ltd., IP-1620, hereafter) having isoparaffin having 10 to 11 carbon atoms as a main component, and used for the following polymerization.

(B) [ethylene polymerization]

A 2 liter stainless steel induction stirrer autoclave was nitrogen-substituted and IP-1620 was added. Thereafter, ethylaluminum sesquichloride (40 µmol) was added as the catalyst component (B), and the temperature was raised to 200 ° C while stirring. When the solvent becomes about 1.0 kg / cm 2 G at the medium pressure of the solvent, ethylene is filled until the total pressure is 60.0 kg / cm 2 G, and 1.0 µmol of the catalyst component (A) is added to the titanium atom equivalent, followed by polymerization. Started. Ethylene was continuously introduced and polymerization was carried out for 4 minutes while maintaining the total pressure constant to obtain 87.6 g of a polymer. The activity of tartan sugar corresponded to 1829 kg / g. MFR was 0.22 g / 10 min.

EXAMPLES 2-4

Comparative Example 1

The polymerization of ethylene was carried out in the same manner as in Example 1 except that the type and the amount of the catalyst component (B) were shown in Table 1. The results are shown in Table 1 together.

Comparative Example 2

Into a 1 liter flask equipped with a stirring device, a reflux condenser, a dropping tube, and a thermometer, 7 g (0.29 mol) of metal magnesium powder and 39.2 g (0.115 mol) of titanium tetrabutoxide were added thereto, 0.35 g of oxo and 42.9 g (0.58 mol of butanol). ) Was added, and the temperature was raised to 90 ° C and stirred for 2 hours under nitrogen sealing while excluding hydrogen gas generated. Then, it heated up to 140 degreeC and reacted for 2 hours, Then, 815 ml of heptanes were added, and the catalyst component (A) of the homogeneous solution containing magnesium titanium was obtained.

The obtained catalyst component (A) was diluted with IP-1620 and used for the following polymerization.

Ethylene was polymerized under the same conditions as in Example 1 using ethylaluminum sesquichloride as the catalyst component (A) and the catalyst component (B).

The results are shown in Table 1, but the activity was insufficient.

ESAC: ethyl aluminum sesquichloride

DEAC: Diethyl Aluminum Chloride

EADC: Ethyl Aluminum Dichloride

TEAL: Triethyl Aluminum

Comparative Example 3

A 2 liter stainless steel induction stirrer autoclave was nitrogen-substituted and 1200 ml of IP-1620 was added. Thereafter, ethyl aluminum sesquichloride (400 µmol) was added as the catalyst component (B), and the temperature was raised to 200 ° C while stirring. When the solution becomes 1.0 kg / cm 2 G at the vapor pressure of the solvent, the ethylene is filled until the total pressure is 60.0 kg / cm 2 G, and 1.0 μmol of titanium tetrabutoxide is added to the heptane solution of titanium atom, and polymerization is carried out. Started. The polymerization was carried out for 4 minutes while continuously introducing ethylene and keeping the total pressure constant, but the activity was quite low, 8.5 kg / g-Ti.

Example 5

The catalyst of the homogeneous solution obtained in Example 1 was used as a catalyst component (A) and a catalyst component (B) in the stirrer type vertical cylindrical reactor, and ethylene, 1-hexane, and hydrogen were continuously supplied, The polymerization was carried out while maintaining the temperature in the polymerization reactor at 180 ° C. and the pressure at 800 kg / cm 2 G. The average residence time in the polymerization reactor is 50 seconds, the molar ratio of ethylene and 1-hexane is 65/35, hydrogen is 30 l / hr, the catalyst supply is 0.25 mmol / hr of catalyst component (A) in titanium equivalent, catalyst component (B) Ethyl aluminum sesquichloride was supplied at 10.2 mmol / hr, and polymerization was carried out for 8 hours. As a result, 20.0 kg of ethylene copolymer was obtained per hour. The polymerization activity of the titanium sugar was 1670 kg / g. MI was 2.4 g / 10min, the melting point of the polymer was 123 占 폚, and the density was 0.923 kg / cm 2 G.

[Examples 6 to 7]

Copolymerization of ethylene and 1-hexane was carried out in the same manner as in Example 5 except that the polymerization conditions were as shown in Table 2.

The results of the polymerization are shown in Table 3.

Example 8

(A) [Preparation of catalyst component (C)]

12 g (0.49 mol) of metal magnesium powder and 17.2 g (0.050 mol) of titanium tetrabutoxide were added to a 1 liter flask equipped with a stirring device, a reflux condenser, a dropping tube, and a thermometer, and 0.6 g of oxo and 44.7 g (0.60 mol) of butanol were added. 77.2g of 2-ethylhexane was added, the temperature was raised to 90 ° C, and the mixture was stirred under nitrogen sealing for 2 hours while excluding hydrogen gas. Then, the mixture was heated up to 140 ° C and reacted for 2 hours. Then, 815 ml of heptane was added thereto to obtain a homogeneous solution containing magnesium and titanium.

Subsequently, 0.10 mol (Mg) of the obtained solution was added to a 500 ml flask separately prepared, and 53 ml (0.03 mol) of 10% heptane solution of ekyllium sesquichloride was added at 45 ° C, and the temperature was raised to 60 ° C and stirred for 1 hour. Catalyst component (C) was obtained. In addition, the catalyst component (C) was a uniform solution phase.

The obtained catalyst component (C) was diluted with the solvent (IP-1620 by Idemitsu Petrochemical Co., Ltd.) which has a C10-C11 isoparaffin as a main component, and used for the following superposition | polymerization.

(B) [ethylene polymerization]

A 2 liter stainless steel induction stirrer base autoclave was nitrogen-substituted and 1200 ml of IP-1620 was added thereto. Thereafter, ethylaluminum sesquichloride (30 µmol) was added as the catalyst component (D), and the temperature was raised to 200 ° C while stirring. When the solvent reaches about 1.0 kg / cm 2 G at medium pressure of the solvent, ethylene is filled until the total pressure is 60.0 kg / cm 2 G, and 1.1 µmol of the catalyst component (C) is added to the titanium atom, and polymerization is started. It was. Ethylene was continuously introduced and polymerization was carried out for 4 minutes while maintaining the total pressure constant to obtain 104.4 g of a polymer. The activity of titanium sugar was equivalent to 1981 kg / g. MFR was 0.35 g / 10 min.

EXAMPLES 9-19

[Comparative Example 4]

The catalyst component (C) was prepared in the same manner as in Example 8 except that the type and amount of halogen-containing organoaluminum and the catalyst component (D) of the reaction agent (IV) were shown in Table 4, and polymerization of ethylene was carried out. It was. In Example 15 to 16, ethylene aluminum sesquichloride and ethyl aluminum dichloride were used as the reactive agent (IV). In Example 17, diethylaluminum chloride and ethylaluminum sesquichloride were mixed in advance and added to a titanium-magnesium homogeneous solution. Component (C) was obtained. In addition, in Examples 9-19 and the comparative example 4, the presence of microparticles | fine-particles were recognized for all the catalyst components (C). The results are shown in Table 4 together.

Comparative Example 2

Into a 1 liter flask equipped with a stirring device, a reflux condenser, a dropping tube, and a thermometer, 7 g (0.29 mol) of metal magnesium powder and 39.2 g (0.115 mol) of titanium tetrabutoxide were added thereto, 0.35 g of oxo and 42.9 g (0.58 mol of butanol). ) Was added, and the temperature was raised to 90 ° C, followed by stirring for 2 hours under nitrogen sealing while excluding hydrogen gas. Then, it heated up to 140 degreeC and reacted for 2 hours, Then, 815 ml of heptanes were added, and the homogeneous solution containing magnesium and titanium was obtained.

Subsequently, 0.10 mol (Mg) of the obtained solution was added to a separately prepared 1 L flask, and 177 ml (0.10 mol) of 10% heptane solution of ethyl aluminum sesquichloride was added at 45 ° C., and the mixture was raised to 60 ° C. and stirred for 1 hour to carry out the catalyst component. (C) was obtained. In addition, the catalyst component (C) was recognized for the presence of fine particles.

The obtained catalyst component was diluted with the solvent (IP-1620 by Idemitsu Petrochemical Co., Ltd.) which has a C10-C11 isoparaffin as a main component, and was used for the following polymerizations.

Ethylene was polymerized under the same conditions as in Example 8 using the catalyst component and ethyl aluminum sesquichloride. The results are shown in Table 4, but the activity was insufficient.

* Ratio of halogenated organic aluminum (IV) to thydan atoms of the reagent (I I) (mol / mol)

EASC: Ethyl Aluminum Sesquichloride

EADC: Ethyl Aluminum Dichloride

DEAC: Diethyl Aluminum Chloride

TEAL: Triethyl Aluminum

Example 20

(A) [Preparation of catalyst component (A)]

40 g (1.65 mol) of metal magnesium powder and 56.6 g (1.17 mol) of titanium tetrabutoxide were added to a 3-liter flask equipped with a stirring device, a reflux condenser, a dropping tube, and a thermometer, and 2.0 g of oxo and 141.6 g (1.91 mol of butanol) were added. 249.7g (1.92mol) of 2-ethylhexane were added, and it heated up to 90 degreeC, and stirred for 2 hours under nitrogen sealing, removing hydrogen gas which generate | occur | produces. Then, it heated up to 140 degreeC and made it react for 2 hours, Then, 2000 ml of heptanes were added, and the homogeneous solution containing magnesium and titanium was obtained.

Subsequently, the obtained solution was placed in a separately prepared 10 L reactor, and 4.1 Kg (3.3 mol) of 10% heptane solution of ethylaluminum sesquichloride was added at 45 ° C. of heptane, followed by raising the temperature to 60 ° C. and stirring for 1 hour. ) In addition, the catalyst component (C) was recognized for the presence of fine particles.

The obtained catalyst component (C) was diluted with a solvent (IP-1620, manufactured by Itate Petrochemical Co., Ltd.) containing isoparaffin having 10 to 11 carbon atoms as a main component, and used for the following polymerization.

(B) [ethylene polymerization]

As the catalyst component (C) and catalyst component (D) obtained above, ethylene, 1-hexane, and hydrogen were continuously supplied to the stirrer section type cylindrical reactor, and the temperature in the polymerization reactor was 180 ° C, The polymerization was carried out while maintaining the pressure at 800 kg / cm 2 G. The average residence time in the polymerization reactor was 50 seconds, the molar ratio of ethylene and 1-hexene was 65/35, hydrogen was 301 / hr, and the catalyst supply was 0.15m mol / hr of catalyst component (C) as titanium equivalent, catalyst component (D ) Ethylaluminum sesquichloride was supplied at 1.5 m mol / hr, and polymerization was carried out for 8 hours. As a result, 19.8 Kg of ethylene copolymer was obtained per hour.

The polymerization activity of the titanium sugar was equivalent to 2756 Kg / g. MI was 2.1 g / 10 min, the melting point of the polymer was 123 ° C., and the density was 0.925 g / cm 3.

[Examples 21 to 22]

As the catalyst component (C) and the catalyst component (D) prepared in Example 16, polymerization was carried out using ethylaluminum sesquichloride. The polymerization of ethylene and 1-hexane was carried out in the same manner as in Example 12 except that the polymerization conditions were as shown in Table 5.

The results of the polymerization are shown in Table 6.

Example 16

(A) [Preparation of catalyst component (C)]

30 g (1.23 mol) of metal magnesium powder and 42.5 g (0.12 mol) of titanium tetrabutoxide were added to a 3-liter flask equipped with a stirring device, a reflux condenser, a dropping tube, and a thermometer, and 1.5 g of oxo and 106.2 g (1.43 mol) of butanol were added thereto. 187.3 g (1.44 mol) of 2-ethylhexanol were added, and it heated up to 90 degreeC, and stirred for 2 hours under nitrogen sealing, removing hydrogen gas which generate | occur | produces. Subsequently, the reaction mixture was heated up to 140 ° C and reacted for 2 hours. Then, 1500 ml of heptane was added to obtain a homogeneous solution containing magnesium and titanium.

Subsequently, the obtained solution was placed in a separately prepared 10 L reactor, and 4.6 Kg (3.7 mol) of 10% heptane solution other than ethyl aluminum chloride was added at 45 ° C. of heptane, followed by raising the temperature to 60 ° C. and stirring for 1 hour. Got it. In addition, the catalyst component (C) was recognized for the presence of fine particles.

The obtained catalyst component (C) was diluted with the solvent (IP-1620 by Idemitsu Petrochemical Co., Ltd.) which has a C10-C11 isoparaffin as a main component, and was used for the following polymerizations.

(B) [ethylene polymerization]

Copolymerization of ethylene and 1-hexene was carried out under the same conditions as in Example 16 except that the catalyst component (C) was fed with a catalyst component of 0.20 m mol / hr in titanium equivalent without using the catalyst component (D). The results are shown in Table 6.

First, the effect of the invention is to obtain a polymer having extremely high polymerization activity of the transition metal sugar and which does not require a deliming step for the purpose of catalyst removal. Due to its high activity, there is no fear of coloring or exploitation of the product, and purification of the polymer is also unnecessary, which is extremely economical.

The second effect of the present invention is that the thermal stability of the catalyst is excellent.

Therefore, the active life is relatively long even at high temperatures.

The third effect of the present invention is that the molecular weight of the copolymer obtained can be increased. Therefore, the (co) polymer suitable for blow molding and film molding can be obtained, and the surface molding of a molded article is also favorable.

The fourth effect of the present invention is that the copolymerization rate of the comonomer is higher than that of other catalyst systems because of good copolymerizability to other α-olefins (comonomers) (the amount of co-polymerized α-olefins used is small).

The fifth effect of the present invention is that since components (A), (B), (C) and (D) are all liquid phases, it is easy to constantly supply the polymerization reactor, and the polymerization reaction can be stably performed. Polyolefins of uniform quality can be obtained.

Claims (6)

(I) Metal Magnesium (II) At least one or more compounds selected from titanium-magnesium-containing homogeneous solution (component (A)) and halogen-containing organoaluminum compound by reacting oxygen-containing organic compound of titanium and (III) alcohol (( B) component), wherein the alcohol of 6 or more carbon atoms is contained in the alcohol of the said (III) component with respect to the metal magnesium of the (I) component 1 mol / mol or more. (I) Metal magnesium (II) Titanium Oxygen-containing organic compound (III) Alcohol and (IV) Halogen-containing organoaluminum compound All catalyst components ((C) obtained by reacting, alcohol of said (III) component 1 mol / mol or more of alcohol containing 6 or more carbon atoms is contained with respect to the metal magnesium of (I) component in the catalyst for polyolefin manufacture. (I) metal magnesium (II) titanium-containing oxygen-containing organic compound (III) alcohol and (IV) all catalyst components obtained by reacting halogen-containing organoaluminum compound ((C) and at least one selected from organoaluminum compounds) The catalyst for polyolefin manufacture comprised from the above compound ((D) component), and the alcohol of 6 or more carbon atoms is contained with respect to the metal magnesium of (I) component in the alcohol of the said (III) component. In the presence of a catalyst composed of a transition metal compound and an organometallic compound, a polyolefin is prepared by homopolymerizing ethylene at a reaction temperature above the melting point of a polymer or by copolymerizing ethylene and at least one α-olefin. A method for producing a polyolefin, comprising using the catalyst of claim. In the presence of a catalyst composed of a transition metal compound and an organometallic compound, a polyolefin is prepared by homopolymerizing ethylene at a reaction temperature above the melting point of the polymer or by copolymerizing ethylene with at least one α-olefin. A method for producing a polyolefin, comprising using the catalyst of claim. In the presence of a catalyst consisting of a transition metal compound and an organometallic compound, a polyolefin is prepared by homopolymerizing ethylene at a reaction temperature above the melting point of the polymer or copolymerizing ethylene with at least one α-olefin, A method for producing a polyolefin, comprising using the catalyst of claim.