JP2001278910A - Catalyst for olefin polymerization and production method of olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst for an olefin polymerization which can produce an olefin polymer with little content of a low molecular-weight component, and to provide a production method of the olefin polymer with little content of a low molecular-weight component. SOLUTION: The catalyst for olefin polymerization is provided by making a solid catalyst component (I) containing at least a titanium atom, a magnesium atom and a halogen atom contact with an organoaluminum compound (II) and a cyclic ketone compound (III). A method of producing an olefin polymer includes using the catalyst for olefin polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an olefin polymerization catalyst and a method for producing an olefin polymer.

[0002]

2. Description of the Related Art The presence of a low molecular weight component in an olefin polymer is not preferable for the transparency, impact resistance, blocking property, etc. of a film made of the olefin polymer. desirable.

In recent years, catalytic performance has been improved by using a solid catalyst component obtained by combining a specific magnesium compound and a specific titanium compound (JP-B-46-34092, JP-B-47-41676). JP, JP-B-55-23561, JP-B-57-24
361).

Further, in the polymerization of propylene, it has been disclosed that a highly crystalline propylene polymer can be obtained by using an oxygen-containing electron donor such as an ester as an internal donor of a solid catalyst component (Japanese Patent Publication No. Sho 52). -3
No. 9431, Japanese Patent Publication No. 52-36786, Japanese Patent Publication No. 1-28049, Japanese Patent Publication No. 3-43283, etc.).

[0005]

However, the olefin polymer obtained by the former catalyst (Japanese Patent Publication No. 46-34092, etc.) is not satisfactory in terms of blocking properties, and the latter catalyst (Special Features) No.52-39431
In the case where the olefin polymer is used for copolymerization of ethylene and an α-olefin, the obtained olefin polymer is not satisfactory in terms of blocking properties. JP-A-11-80
JP-A-234, JP-A-11-322833 and the like disclose an olefin polymerization catalyst capable of producing an olefin polymer having a low content of a low-molecular-weight component, which is an index of blocking property. However, in order to further improve the quality of the olefin polymer, it is required to further reduce the content of low molecular weight components. Under these circumstances, the problem to be solved by the present invention, that is, an object of the present invention is to provide an olefin polymerization catalyst capable of producing an olefin polymer having a low low molecular weight component content, and an olefin having a low low molecular weight component content. An object of the present invention is to provide a method for producing a polymer.

[0006]

That is, the present invention comprises contacting a solid catalyst component (I) containing at least a titanium atom, a magnesium atom and a halogen atom, an organoaluminum compound (II) and a cyclic ketone compound (III). The present invention relates to an olefin polymerization catalyst obtained by the above.
The present invention also relates to a method for producing an olefin polymer using the olefin polymerization catalyst. Hereinafter, the present invention will be described in detail.

[0007]

DETAILED DESCRIPTION OF THE INVENTION [Cyclic Ketone Compound] The cyclic ketone compound (III) used in the present invention is a cyclic compound having a carbonyl group in its ring system (cyclic structure). The ring system may be a saturated or unsaturated aliphatic or aromatic ring. The ring system may be a monocyclic ring or a polycyclic ring. The ring system is preferably a 3- to 10-membered ring, more preferably a 5- to 8-membered ring. The cyclic ketone compound (III) is preferably a compound having at least two carbonyl groups in the ring system, and more preferably a compound having two to three carbonyl groups in the ring system.

Specifically, compounds represented by the following general formula are mentioned. X in the above formula is a hydrogen atom, a hydrocarbon group, a hydrocarbon oxy group or a disubstituted amino group (an amino group substituted with two hydrocarbon groups), and each X in the molecule is bonded to each other. May be. Further, these plural compounds may be compounds having a crosslinked structure at each X.

The cyclic ketone compound (II) used in the present invention
I) includes 1,4-cyclohexanedione, 1,3
-Cyclohexanedione, 1,2-cyclohexanedione or 1,4-benzoquinone is particularly preferred.

The amount of the cyclic ketone compound (III) to be used is usually based on 1 mol of titanium atom in the solid catalyst component (I).
You can choose from a wide range of 1 mol to 2000 mol,
Particularly, the range of 5 mol to 1000 mol is preferable. Further, the organoaluminum compound (I) of the cyclic ketone compound (III)
The amount used for (I) is usually the organoaluminum compound (I
It can be selected from a wide range of 0.001 mol to 10 mol per 1 mol of the aluminum atom in I), but particularly preferably 0.03 mol to 10 mol.
A range from 1 mol to 5 mol is preferred.

[Solid Catalyst Component] As the solid catalyst component (I) containing at least a titanium atom, a magnesium atom and a halogen atom used in the present invention, any known solid catalyst containing a titanium atom, a magnesium atom and a halogen atom is used. Ingredients can be used.

Examples of such a solid catalyst component containing a titanium atom, a magnesium atom and a halogen atom include, for example, JP-B-46-34092 and JP-B-47-41.
676, JP-B-55-23561, JP-B-57-24361, JP-B-52-39431, JP-B-52-36786, and JP-B1-280.
No. 49, Japanese Patent Publication No. 3-43283, Japanese Unexamined Patent Publication No.
80044, JP-A-55-52309, JP-A-58-21405, JP-A-61-18180
7, JP-A-63-142008, JP-A-5-142008
-339319, JP-A-54-148093, JP-A-4-227604, JP-A-6-293
No. 3, JP-A-64-6006, and JP-A-6-1
JP-A-79720, JP-B-7-116252, JP-A-8-134124, JP-A-9-31119, JP-A-11-228628, JP-A-11-112
Examples thereof include solid catalyst components described in JP-A-80234 and JP-A-11-322833. Among them, a solid catalyst component containing an electron donor in addition to a titanium atom, a magnesium atom and a halogen atom is preferred.

Specifically, a method of contact-treating a magnesium halide compound and a titanium compound, a method of contact-treating a magnesium halide compound, an electron donor and a titanium compound, and a method of treating a magnesium halide compound and a titanium compound with an electron-donating solvent , A method of impregnating the carrier substance with a carrier material, a method of contact-treating a dialkoxymagnesium compound with a titanium halide compound and an electron donor, a solid catalyst component precursor containing a magnesium atom, a titanium atom and a hydrocarbyloxy group And a solid catalyst component obtained by, for example, a method of subjecting the catalyst to a contact treatment with a halogen compound having a halogenating ability and an electron donor.

In particular, a method of contacting a solid catalyst precursor (C) containing a magnesium atom, a titanium atom and a hydrocarbyloxy group with a halogen compound (A) having a halogenating ability and an electron donor (B). Are preferred. The solid catalyst component precursor (C) referred to here is a solid component containing a magnesium atom, a titanium atom and a hydrocarbyloxy group. Specifically, an organosilicon compound having a Si-O bond () disclosed in JP-A-11-80234
Is represented by the general formula Ti (OR ¹ ) _a X _4-a (wherein R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, and a is 0 <a ≦ 4 A solid product obtained by reducing a titanium compound () represented by the formula (1) with an organomagnesium compound (), or a Si—O bond disclosed in Japanese Patent Publication No. 4-57685. Organosilicon compound () and porous carrier ()
Is represented by the general formula Ti (OR ¹ ) _a X _4-a (wherein R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, and a is 0 <a ≦ 4 And a solid product obtained by reducing the titanium compound () represented by the formula (1) with an organomagnesium compound ().

Specific examples of R ^{1 in} the general formula Ti (OR ¹ ) _a X _4-a include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl and the like. , An alkyl group such as heptyl group, octyl group, decyl group, dodecyl group, an aryl group such as phenyl group, cresyl group, xylyl group, naphthyl group, a cycloalkyl group such as cyclohexyl group and cyclopentyl group, and an allyl group such as propenyl group. And an aralkyl group such as a benzyl group. It is also possible to use a titanium compound having two or more different (OR ¹ ) groups. Among these groups, an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms is preferable. Especially 2 carbon atoms
~ 18 linear alkyl groups are preferred.

Examples of the halogen atom represented by X include a chlorine atom, a bromine atom and an iodine atom. Particularly chlorine atoms give favorable results.

The value of a in the general formula Ti (OR ¹ ) _a X _4-a is a number satisfying 0 <a ≦ 4, preferably 2 ≦ a.
It is a number satisfying ≦ 4, and particularly preferably a = 4.

As _a method for synthesizing the titanium compound represented by the general formula Ti (OR ¹ ) _a X _4-a , _a known method can be used. For example, a method of reacting Ti (OR ¹ ) ₄ and TiX ₄ at a predetermined ratio, or a method of reacting TiX ₄ with a corresponding alcohol (eg, R ¹ OH) in a predetermined amount can be used.

The organosilicon compound () having a Si--O bond is preferably represented by the general formula Si (OR ³ )
_{^{b R 4 4-b, R}} 5 (R 6 2 SiO) c SiR 7 3 or (R ⁸ ₂ Si
O) Those represented by _d can be exemplified. Here, R ³ is a hydrocarbon group having 1 to 20 carbon atoms, and R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. , B is a number satisfying 0 <b ≦ 4, c is an integer of 1 to 1000, and d is 2 to 10
It is an integer of 00.

Specific examples of such organosilicon compounds include tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, tetra-isopropoxysilane, and di-isopropoxy-silane. Di-isopropylsilane, tetrapropoxysilane, dipropoxydipropylsilane, tetrabutoxysilane, dibutoxydibutylsilane, dicyclopentoxydiethylsilane, diethoxydiphenylsilane, cyclohexyloxytrimethylsilane, phenoxytrimethylsilane, tetraphenoxysilane, triphen Ethoxyphenylsilane, hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, octaethyltrisiloxane, Le polysiloxane, diphenyl polysiloxane, methyl hydropolysiloxane, phenyl hydropolysiloxane like.

[0021] a preferred general formula _{^{Si (OR 3) b R 4}} 4-b alkoxysilane compound represented among these organic silicon compounds, in which case b is preferably 1 ≦
The number satisfies b ≦ 4, and a tetraalkoxysilane compound with b = 4 is particularly preferable.

As the organomagnesium compound (),
Any type of organomagnesium compound having a magnesium-carbon bond can be used. In particular, the general formula R
A Grignard compound represented by ⁹ MgX (where Mg represents a magnesium atom, R ⁹ represents a hydrocarbon group having 1 to 20 carbon atoms, and X represents a halogen atom) or a compound represented by the general formula R
(Wherein, Mg is a magnesium atom, respectively R ¹⁰ and R ¹¹ represents a hydrocarbon group having a carbon number of 1 to 20) ¹⁰ R ¹¹ Mg dihydrocarbyl magnesium compound represented by is preferably used. Wherein R ¹⁰ and R ¹¹ may be the same or different. Specific examples of R ^{9 to} R ¹¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an isoamyl group, a hexyl group, an octyl group, and a 2-ethylhexyl group. , A phenyl group, a benzyl group and the like, an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group and an alkenyl group. In particular, it is preferable to use a Grignard compound represented by R ⁹ MgX in an ether solution from the viewpoint of catalytic performance.

A hydrocarbon-soluble complex of the above-mentioned organomagnesium compound and an organic metal that solubilizes the organomagnesium compound in hydrocarbon can also be used. Examples of organometallic compounds include Li, Be, B, Al or Z
n.

As the porous carrier (), a known carrier may be used. SiO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , ZrO ₂
And the like, or polystyrene, styrene-divinylbenzene copolymer, styrene-
Ethylene glycol-methyl dimethacrylate copolymer,
Polymethyl acrylate, polyethyl acrylate, methyl acrylate-divinylbenzene copolymer, polymethyl methacrylate, methyl methacrylate-divinylbenzene copolymer, polyacrylonitrile, acrylonitrile-divinylbenzene copolymer, polyvinyl chloride, Organic porous polymers such as polyethylene and polypropylene can be mentioned. Among these, an organic porous polymer is preferably used, and among them, a styrene-divinylbenzene copolymer or an acrylonitrile-divinylbenzene copolymer is particularly preferred.

The porous carrier has a pore radius of 200 to 2000.
細孔 preferably has a pore volume of 0.3 cc / g or more,
More preferably, the pore volume is 0.4 cc / g or more, and the pore volume in the range is preferably 35% or more, more preferably 40% of the pore volume at a pore radius of 35 to 75000 °.
That is all. If the pore volume of the porous material is small, the catalyst component may not be effectively immobilized, which is not preferable. Further, the pore volume of the porous carrier is 0.3 cc / g.
Even if it is above, if it does not sufficiently exist in the pore radius of 200 to 2000 °, it may not be possible to effectively immobilize the catalyst component, which is not preferable.

As a method of the reduction reaction of the titanium compound by the organomagnesium compound, a method of adding the organomagnesium compound () to a mixture of the titanium compound () and the organosilicon compound (), or the reverse method, can be mentioned. At this time, a porous carrier () may coexist.

The titanium compound () and the organosilicon compound () are preferably used after being dissolved or diluted in an appropriate solvent.

Examples of such a solvent include aliphatic hydrocarbons such as hexane, heptane, octane and decane, toluene,
Examples thereof include aromatic hydrocarbons such as xylene, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and decalin; and ether compounds such as diethyl ether, dibutyl ether, diisoamyl ether, and tetrahydrofuran.

The temperature of the reduction reaction is usually -50 to 70 ° C, preferably -30 to 50 ° C, particularly preferably -25 to 35 ° C.
Temperature range. The lowering time is not particularly limited, but is usually about 30 minutes to 6 hours. After completion of the reduction reaction, a post-reaction may be further performed at a temperature of 20 to 120 ° C.

The amount of the organosilicon compound () used is usually Si / Ti = 1 to 500, preferably 1 in terms of the atomic ratio of silicon atoms to titanium atoms in the titanium compound ().
To 300, particularly preferably 3 to 100. The amount of the organomagnesium compound () used is usually represented by the sum of titanium atoms and silicon atoms and the atomic ratio of magnesium atoms (T
i + Si) /Mg=0.1 to 10, preferably 0.2 to
5.0, particularly preferably 0.5 to 2.0.
In the solid catalyst component, the molar ratio of Mg / Ti is 1 to 51, preferably 2 to 31, and particularly preferably 4 to 2.
The amounts of the titanium compound (), the organosilicon compound (), and the organomagnesium compound () may be determined so as to fall within the range of 6.

The solid product obtained by the reduction reaction is usually subjected to solid-liquid separation and washed several times with an inert hydrocarbon solvent such as hexane and heptane. The solid catalyst component precursor (C) thus obtained contains a trivalent titanium atom, a magnesium atom and a hydrocarbyloxy group, and generally shows amorphous or extremely weak crystallinity. From the viewpoint of catalyst performance, an amorphous structure is particularly preferable.

As the halogen compound (A) having a halogenating ability, a compound capable of replacing the hydrocarbyloxy group of the solid catalyst precursor (C) with a halogen atom is preferable. Of these, a halogen compound of a Group 4 element, a halogen compound of a Group 13 element, or a halogen compound of a Group 14 element is preferable. As the halogen compound of the Group 4 element, a halogen compound of titanium is preferable.
Specifically, titanium halide, titanium halide alkoxide, titanium halide amide and the like can be mentioned.

As the halogen compound of the Group 13 element or the Group 14 element, a compound represented by the general formula MR _ma X _a (where M is
R is a Group 3 or 14 atom, and R has 1 to 20 carbon atoms.
X represents a halogen atom, and m represents the valence of M. a represents a number satisfying 0 <a ≦ m). Examples of the group 13 atoms include B, Al, Ga, In, and Tl.
1 is preferred, and Al is more preferred. Examples of Group 14 atoms include C, Si, Ge, Sn, and Pb.
Si, Ge or Sn is preferred, and Si or Sn is more preferred.

M is the valence of M. For example, when M is Si, m = 4. a represents a number satisfying 0 <a ≦ m. When M is Si, a is preferably 3 or 4.
Examples of the halogen atom represented by X include F, Cl, Br and I, and Cl is preferable.

Specific examples of R include methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, decyl and dodecyl. Alkyl groups such as phenyl group, tolyl group, cresyl group, xylyl group, naphthyl group, cycloalkyl group such as cyclohexyl group, cyclopentyl group, allyl group such as propenyl group, and aralkyl group such as benzyl group. No. Preferred R is an alkyl group or an aryl group, and particularly preferred R is a methyl group, an ethyl group, a normal propyl group, a phenyl group or a paratolyl group.

Specific examples of the chlorine compound of the Group 13 element include trichloroboron, methyldichloroboron, ethyldichloroboron, phenyldichloroboron, cyclohexyldichloroboron, dimethylchloroboron, methylethylchloroboron, trichloroaluminum, and methyldichloroaluminum. , Ethyldichloroaluminum, phenyldichloroaluminum, cyclohexyldichloroaluminum, dimethylchloroaluminum, diethylchloroaluminum, methylethylchloroaluminum, ethylaluminum sesquichloride, gallium chloride, gallium dichloride, trichlorogallium, methyldichlorogallium, ethyldichlorogallium, phenyldichloro Gallium, cyclohexyldichlorogallium, dimethyl chloride Logallium, methyl ethyl chlorogallium, indium chloride, indium trichloride, methyl indium dichloride, phenyl indium dichloride, dimethyl indium chloride, thallium chloride, thallium trichloride, methyl thallium dichloride, phenyl thallium dichloride, dimethyl thallium chloride, and the like. Compounds in which chloro in the compound name is changed to fluoro, bromo, or iodo are also included.

Specific examples of the chlorine compound of the Group 14 element include tetrachloromethane, trichloromethane, dichloromethane, monochloromethane, 1,1,1-trichloroethane, 1,1-dichloroethane, 1,2-dichloroethane, 1,1 , 2,2-tetrachloroethane, tetrachlorosilane, trichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, normal propyltrichlorosilane, normal butyltrichlorosilane, phenyltrichlorosilane, benzyltrichlorosilane, paratolyltrichlorosilane, cyclohexyltrichlorosilane, dichlorosilane Chlorosilane, methyldichlorosilane, ethyldichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, methylethyldichlorosilane, monochlorosilane, trimethyl Chlorosilane, triphenylchlorosilane, tetrachlorogermane, trichlorogermane, methyltrichlorogermane, ethyltrichlorogermane, phenyltrichlorogermane, dichlorogermane, dimethyldichlorogermane, diethyldichlorogermane, diphenyldichlorogermane, monochlorogermane, trimethylchlorogermane, triethylchlorogermane , Trinormalbutylchlorogermane, tetrachlorotin, methyltrichlorotin, normalbutyltrichlorotin, dimethyldichlorotin, dinormalbutyldichlorotin, diisobutyldichlorotin, diphenyldichlorotin,
Examples thereof include divinyldichlorotin, methyltrichlorotin, phenyltrichlorotin, dichlorolead, methylchlorolead, and phenylchlorolead, and compounds in which chloro of these compounds is changed to fluoro, bromo, or iodo.

As the halogen compound (A), particularly, tetrachlorotitanium, methyldichloroaluminum, ethyldichloroaluminum, tetrachlorosilane, phenyltrichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, normal propyltrichlorosilane,
Alternatively, tetrachlorotin is preferred from the viewpoint of polymerization activity. As the halogen compound (A), only one type may be used, or a plurality of types may be used.

As the electron donor (B), alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers,
Examples include oxygen-containing electron donors such as acid amides and acid anhydrides, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates. Among these electron donors, preferably, esters of organic acids or ethers
Ters are used.

The esters of organic acids are preferably mono- or polyvalent carboxylic esters, such as saturated aliphatic carboxylic esters, unsaturated aliphatic carboxylic esters, alicyclic carboxylic esters, and aromatic carboxylic esters. Can be mentioned.

Specifically, methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl benzoate, benzoic acid Butyl, methyl toluate, ethyl toluate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, Dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate,
Examples thereof include di-2-ethylhexyl phthalate, di-n-octyl phthalate, and diphenyl phthalate.

As the ethers, preferred are dialkyl ethers and general formulas (Wherein, each of R ^{22 to} R ²⁵ is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group;
R ²² or R ²³ may be a hydrogen atom). In particular,
Dimethyl ether, diethyl ether, dibutyl ether, methyl ethyl ether, methyl butyl ether, methyl cyclohexyl ether, 2,2-dimethyl-1,
3-dimethoxypropane, 2,2-diethyl-1,3-
Dimethoxypropane, 2,2-dinorbutyl-1,1,
3-dimethoxypropane, 2,2-diisobutyl-1,
3-dimethoxypropane, 2-ethyl-2-butyl-
1,3-dimethoxypropane, 2-normalpropyl-
2-cyclopentyl-1,3-dimethoxypropane,
2,2-dimethyl-1,3-diethoxypropane, 2-
Normal propyl-2-cyclohexyl-1,3-diethoxypropane and the like can be mentioned.

As the electron donor (B), esters of organic acids are particularly preferred, dialkyl esters of aromatic dicarboxylic acids are particularly preferred, and dialkyl esters of phthalic acid are most preferred. As the electron donor (B), only one type may be used, or a plurality of types may be used.

Halogen compound (A) and electron donor (B)
The contact treatment of the solid catalyst component precursor (C) can be carried out by any known method such as a slurry method or a mechanical pulverization means such as a ball mill, which can bring the two into contact with each other. A large amount of fine powder is generated in the catalyst component and the particle size distribution tends to be widened, which is not preferable from an industrial viewpoint. Therefore, it is preferable that both are brought into contact by the slurry method in the presence of the medium. As a medium,
It is preferably inert to the components to be treated, such as aliphatic hydrocarbons such as pentane, hexane, heptane and octane; aromatic hydrocarbons such as benzene, toluene and xylene; and alicyclic carbons such as cyclohexane and cyclopentane. Halogenated hydrocarbons such as hydrogen, 1,2-dichloroethane and monochlorobenzene can be used. Among them, aliphatic hydrocarbons are preferred in terms of polymerization activity. The amount of the medium used is not particularly limited, but the presence of an excessive amount of the medium is not preferable from the viewpoint of catalyst performance and catalyst productivity. Normal,
0.1 ml to 10 g per 1 g of the solid catalyst component precursor (C)
00 ml, preferably 0.5 ml to 20 ml,
Particularly preferably, it is 1 ml to 5 ml.

After the contact treatment, the next treatment can be carried out as it is, but it is preferable to carry out an arbitrary number of washing operations with a detergent in order to remove the unreacted reagent. The detergent is preferably inert to the component to be treated, and the same compounds as those exemplified above as the medium can be used. The amount of the detergent used is usually 0.1 ml to 1000 ml per 1 g of the solid catalyst component precursor (C). It is preferably 1 ml to 100 ml per gram.

The contacting and / or washing temperature is usually
The temperature is 50 to 150 ° C, preferably 0 to 140 ° C, and more preferably 60 to 135 ° C. The contact treatment time is not particularly limited, but is preferably 0.5 to 8 hours, and more preferably 1 to 6 hours. The washing time is not particularly limited, but is preferably 1 to 120 minutes, and more preferably 2 to 60 minutes.

The specific method of bringing the halogen compound (A) and the electron donor (B) into contact with the solid catalyst component precursor (C) is not particularly limited, but (C), (A) and ( A method in which B) is simultaneously subjected to contact treatment, and a method in which (A) and (B) are successively subjected to contact treatment with respect to (C) are exemplified. (C), (A) and (B) can be simultaneously contact-treated by a method in which a mixture obtained by previously mixing (A) and (B) is charged into (C) and subjected to contact treatment; (B) and (A) and (B) are successively charged and (A) and (B) are subjected to contact treatment. A method in which A) and (B) are simultaneously charged and a contact treatment is performed may be exemplified. As a method of sequentially contacting (A) and (B) with (C), (A) is charged into (C), contact treatment is performed, and then cleaning treatment is performed. A method in which (B) is put into an object to perform contact processing, and (B) is applied to (C).
, A cleaning process is performed after the contact process is performed, and a method of performing the contact process by supplying (A) to the cleaned product can be exemplified. Preferably, (C), (A) and (B) are contacted simultaneously.

After the contact treatment of (C), (A) and (B), the resulting treated solid can be further subjected to contact treatment with (A) and / or (B). As a method of bringing the halogen compound (A) and the electron donor (B) into contact with the solid catalyst component precursor (C), particularly preferably,
(A) and (B) are sequentially charged into (C) to perform a contact treatment, and then a cleaning treatment is performed. ) To (A)
After the contact treatment is performed by charging a mixture of (A) and (B), a cleaning process is performed, and (A) is charged into the cleaned product to perform the contact process. After the contact treatment is performed by sequentially charging B), a cleaning treatment is performed, and the contact treatment is performed by sequentially supplying (A) and (B) to the cleaned product. A method in which a mixture of (A) and (B) is charged to perform a contact treatment, followed by a cleaning treatment, and a mixture of (A) and (B) is charged to the washed material to perform a contact treatment. , (A) and (B) are sequentially charged into (C) to carry out the contact treatment. (C) is charged into (A) to carry out the contact treatment, and then the cleaning treatment is carried out. A method in which (B) is charged into the processed material to perform the contact treatment, and a cleaning process is performed after the (B) is charged into (C) and the contact processing is performed, and the cleaned processed material is obtained. After (A) and (B) are successively charged to perform the contact treatment, a further washing treatment is performed, and (A) and (B) are sequentially charged to the washed material to carry out the contact treatment. How to do, or (B) to (C)
, A contact treatment is carried out, a washing treatment is carried out, a mixture of (A) and (B) is put into the washed treatment material, a contact treatment is carried out, and further a washing treatment is carried out. This is a method in which a mixture of (A) and (B) is charged into a cleaning treatment product to perform a contact treatment. As (A) and (B) used a plurality of times by these methods, the same one may be used each time or a different one may be used.

The amount of the halogen compound (A) used in one contact treatment is usually 0.1 to 1000 mmol, preferably 0.3 to 1 g per 1 g of the solid catalyst component precursor (C).
５００500 mmol, particularly preferably 0.5-300 mmol.

The amount of the electron donor (B) used in one contact treatment is usually 0.1 to 1000 mmol, preferably 0.3 to 50 mmol per 1 g of the solid catalyst component precursor (C).
0 mmol, particularly preferably 0.5 to 300 mmol.

Halogen compound (A), electron donor (B)
When the solid catalyst component precursor (C) is brought into contact with the halogen compound (A), the molar ratio of the electron donor (B) to the halogen compound (A) is preferably 0.01 to 200, preferably 0.1 to 200.
100.

The obtained solid catalyst component may be used for polymerization in a slurry state in the presence of an inert diluent, or may be used for polymerization as a free-flowing powder after appropriate drying. .

[Preliminary Polymerization Treatment] In the present invention, the solid catalyst component (I) can be used as it is in the polymerization (main polymerization) reaction. I ') may be prepared first and used in the main polymerization. The prepolymerization treatment is performed, for example, by bringing the solid catalyst component (I) and the organoaluminum compound (II) into contact with an olefin. As the olefin used in the prepolymerization treatment, ethylene, propylene, 1-
Butene. Preliminary polymerization can be either homopolymerization or copolymerization.

In order to obtain a highly crystalline prepolymer (a polymer obtained by the prepolymerization treatment), a known electron donor, hydrogen, or the like may be used together. As such an electron donor, an organic compound having a Si-OR bond (R represents a hydrocarbon group having 1 to 20 carbon atoms) can be preferably used.

When the solid catalyst component of the present invention is preliminarily polymerized, it is preferable that the solid catalyst component is slurried. As the solvent, an aliphatic hydrocarbon such as butane, pentane, hexane, heptane or the like can be used. Examples thereof include aromatic hydrocarbons such as toluene and xylene.

The slurry concentration is usually from 0.001 to 0.
5 g solid catalyst component / ml solvent, especially 0.01 to 0.3 g
Solid catalyst components / ml solvent are preferred. Further, it is preferable to use the organoaluminum compound in such a ratio that the Al / Ti atomic ratio is 0.1 to 100, particularly 0.5 to 50.

The temperature of the prepolymerization treatment is usually from -30 to 80.
° C, especially -10 ° C to 50 ° C. The amount of the prepolymer is usually 0.1 to 300 g, preferably 0.5 to 50 g, per 1 g of the solid catalyst component.

The obtained prepolymerized solid catalyst component (I ')
May be used for the polymerization in a slurry state in the presence of an inert diluent, or may be used for the polymerization as a free-flowing powder after appropriate drying.

[Organic Aluminum Compound] The organoaluminum compound (II) used in the present invention has at least one Al-carbon bond in the molecule, and a typical example thereof is a compound represented by the general formula R ¹² _r AlY _{3. -r} and R ¹³ R ¹⁴ Al- (O
—AlR ¹⁵ ) _d R ¹⁶ . here,
^{R 1 2, R 13, R} 14, R 15 and R ¹⁶ each, 1-8 hydrocarbon group carbon atoms, Y represents a halogen atom, a hydrogen atom or an alkoxy group. r is a number satisfying 2 ≦ r ≦ 3. d is a number satisfying 1 ≦ d ≦ 30.

Specific examples of the organoaluminum compound include trialkylaluminums such as triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, and trihexylaluminum, diethylaluminum hydride, dinormal butylaluminum hydride, diisobutylaluminum hydride and the like. Alkyl aluminum dihalides such as dialkyl aluminum hydride, ethyl aluminum dichloride, normal butyl aluminum dichloride, isobutyl aluminum dichloride, dialkyl aluminum halides such as diethyl aluminum chloride, di normal butyl aluminum chloride, diisobutyl aluminum chloride, trialkyl aluminum and dialkyl aluminum Mixtures Umuharaido, tetraethyldialumoxane, tetrabutyl di alumoxane, polymethyl alumoxane, and alkyl alumoxanes of polyethyl alumoxane like. Of these organoaluminum compounds, trialkylaluminum, a mixture of a trialkylaluminum and a dialkylaluminum halide, or an alkylalumoxane is preferable, and particularly, triethylaluminum, tri-n
-Butyl aluminum, triisobutyl aluminum,
Trihexyl aluminum, a mixture of triethyl aluminum and diethyl aluminum chloride, or tetraethyl dialumoxane is preferred.

The amount of the organoaluminum compound (II) is usually 1 to 10 per mole of titanium atom in the solid catalyst component.
Although it can be selected in a wide range such as 000 mol, a range of 5 to 5000 mol is particularly preferable. The organoaluminum compound (II) may be used as it is, or may be used as a solution with an inert diluent.

[Production of Olefin Polymer] The olefin polymerization catalyst of the present invention is a catalyst obtained by contacting the solid catalyst component (I), the organoaluminum compound (II) and the cyclic ketone compound (III). Contact here means
The catalyst components (I) to (III) may be formed by any means as long as the catalyst components (I) to (III) come into contact with each other to form a catalyst.
And a method of separately contacting them in a polymerization reaction tank and bringing them into contact in the polymerization reaction tank.

As for the method of supplying the solid catalyst component (I), the organoaluminum compound (II) and the cyclic ketone compound (III) to the polymerization reactor, an inert gas such as nitrogen or argon, hydrogen or olefin, etc. It is preferable to supply the gas as a gas without moisture. (I),
(II) and (III) may be supplied individually, or may be supplied by contacting two or more in advance.

The polymerization reaction can be carried out by a known method such as ordinary gas phase polymerization or slurry polymerization. The conditions of the polymerization reaction are usually lower than the temperature at which the obtained polymer melts, preferably lower than 130 ° C, more preferably 20 to 110 ° C, particularly preferably 40 to 100 ° C, and normal pressure to 5 MPa.
It is preferable to carry out in the range of the pressure. For the purpose of adjusting the melt fluidity of the obtained polymer, polymerization can be carried out by adding hydrogen as a molecular weight regulator. Further, the polymerization method may be either a continuous type or a batch type.

The process for producing the olefin polymer of the present invention comprises:
This is a method for producing an olefin polymer using the olefin polymerization catalyst. Examples of the olefin polymer include a homopolymer of an olefin and a copolymer of an olefin and an addition-polymerizable monomer other than the olefin, and the like.
It is suitable for producing an ethylene polymer having a polyethylene crystal structure. As the ethylene polymer, ethylene and α
-Copolymers with olefins (linear low density polyethylene) are preferred.

The α-olefin mentioned here includes propylene, 1-butene, 1-pentene, 1-hexene,
-Methyl-1-pentene, 4-methyl-1-pentene, and the like, and 1-butene, 1-hexene, or 4-
Methyl-1-pentene is preferred.

[0067]

The present invention will be described below with reference to examples.
The present invention is not limited by these examples. The properties of solids (hereinafter, sometimes simply referred to as solid components) such as polymers and solid catalyst components in the examples were measured by the following methods.

(1) The content of the repeating unit derived from α-olefin in the copolymer of ethylene and α-olefin was measured by using an infrared spectrophotometer (1600 series, manufactured by PerkinElmer). It was determined from the characteristic absorption of the olefin using a calibration curve and was expressed as the number of short-chain branches per 1000 C (SCB).

(2) The flow rate (FR) is ASTM
It was determined by measuring at 190 ° C. according to D1238.

(3) The outflow ratio (FRR) was adopted as a measure of the melt fluidity. The FRR is a ratio of the outflow amount when a load of 21.60 kg is applied to the outflow amount when a load of 2.160 kg is applied in the method of measuring the flow rate (FR), that is, FRR = (21.60 kg load)
At this time) (outflow at a load of 2.160 kg). Generally, it is known that the FRR value increases as the molecular weight distribution of the polymer increases.

(4) The content of the low molecular weight component was evaluated by a value (CXS) expressed by a weight percentage (wt%) of an amount soluble in cold xylene at 25 ° C. In general, the larger the SCB, the more C
XS also increases.

(5) The Ti content was determined by decomposing a solid component with dilute sulfuric acid, adding an excess of aqueous hydrogen peroxide, and measuring the characteristic absorption at 410 nm using a Hitachi Double Beam Spectrophotometer U-2001. And a calibration curve. The alkoxy group content was determined by decomposing a solid component with water, and then measuring the corresponding alcohol amount using a gas chromatography internal standard method.

Example 1 (1) Synthesis of Solid Catalyst Component Precursor In a reactor equipped with a stirrer purged with nitrogen, hexane 800 was added.
Liter, 349 kg of tetraethoxysilane and tet
38 kg of labutoxy titanium was charged and stirred. next,
Add the butylmagnesium chloride dib
Chill ether solution (concentration: 2.1 mol / l) 852
Liter over 5 hours while maintaining the temperature of the reactor at 5 ° C
And dropped. After completion of the dropping, at 8 ° C. for 1 hour, and further at 20 ° C.
After stirring for 1 hour, the mixture was filtered.
The washing with 100 liters was repeated three times, and toluene was added.
First, it was slurried. Collect 50 ml of the slurry,
Was removed, which contained 8.15 g of a solid component.
I was The precursor of the solid catalyst component was Ti: 2.09 wt.
%, Ethoxy group: 38.8 wt%, butoxy group: 2.9
wt%.

(2) Synthesis of solid catalyst component A 200-ml flask equipped with a stirrer was placed with nitrogen.
After the conversion, the solid catalyst component precursor 2 obtained in the above (1)
A slurry containing 1.0 g was charged into the flask, and the solid-liquid
Released. The obtained solid is washed three times with 100 ml of heptane.
Then, the total volume of the slurry is 122 ml in the solid after washing.
Heptane was added as before. Internal volume 40 with stirrer
After replacing the 0 ml autoclave with nitrogen,
Transfer the heptane slurry of the solid catalyst component precursor,
Tetrachlorosilane (hereinafter, SiCl_FourMay be written
You. ) (11.0 ml) and then di (2-ethylhexyl)
Xyl) phthalate (hereinafter abbreviated as DEHP)
You. ) Add 16.1 ml and 3 hours at 105 ° C
Stirred. After cooling the autoclave to room temperature, stirring
The mixture was transferred to a 200-ml flask purged with nitrogen.
Sent. The stirred mixture was subjected to solid-liquid separation, and the resulting solid
Washing with 105 ml of toluene at 105 ° C three times
Then, 105 ml of toluene was again charged. Heated to 70 ° C
Then, titanium tetrachloride (hereinafter, TiCl_FourMay be written
You. ) Add 10.5 ml and stir at 105 ° C for 1 hour
Was. Next, solid-liquid separation was performed, and the obtained solid was subjected to 105
Washing with 105 ml of toluene at ℃ was repeated 6 times
Thereafter, washing with 105 ml of hexane is further performed twice at room temperature.
Repeatedly, the solid after washing is dried under reduced pressure to obtain a solid catalyst component.
I got The solid catalyst component contains Ti: 1.0 wt%
Was.

(3) Polymerization An autoclave with an internal volume of 3 liters equipped with a stirrer was sufficiently dried, evacuated, charged with 400 g of butane and 350 g of 1-butene, and heated to 70 ° C. Next, the partial pressure of hydrogen was 0.4 MPa, and the partial pressure of ethylene was 1.2 MPa.
Was added. Triethyl aluminum 5.7m
mol, 1,4-cyclohexanedione 0.57 mmol
1) 20.6 mg of the solid catalyst component obtained in the above (2) was injected with argon to initiate polymerization. After that, while continuously supplying ethylene, keeping the total pressure constant, 70 ° C
For 3 hours. After the completion of the polymerization reaction, unreacted monomers were purged to obtain 148 g of a polymer having good powder properties. The polymer hardly adhered to the inner wall of the autoclave and the stirrer. The amount of the polymer produced per unit of catalyst (polymerization activity) was 7180 g polymer / g solid catalyst component. For this polymer, SCB: 1
9.4, FR: 1.01, FRR: 23.1, CXS:
It was 8.2% by weight.

Example 2 (1) Polymerization In Example 1 (3), 1,4-cyclohexanedione was changed to 0.57 mmol of 1,3-cyclohexanedione, and the amount of the solid catalyst component was increased to 19.7 mg. Polymerization was carried out in the same manner as in Example 1 (3), except for changing, to obtain 215 g of a polymer having good powder properties. The polymer hardly adhered to the inner wall of the autoclave and the stirrer. Amount of polymer produced per unit of catalyst (polymerization activity)
Was 10900 g polymer / g solid catalyst component. About this polymer, SCB: 20.8, FR: 0.88,
FRR: 22.4, CXS: 9.8 wt%.

Example 3 (1) Polymerization In Example 1 (3), 1,4-cyclohexanedione was changed to 0.57 mmol of 1,2-cyclohexanedione, and the amount of the solid catalyst component was reduced to 11.6 mg. Polymerization was carried out in the same manner as in Example 1 (3) except for the change, and 111 g of a polymer having good powder properties was obtained. The polymer hardly adhered to the inner wall of the autoclave and the stirrer. Amount of polymer produced per unit of catalyst (polymerization activity)
Was 9570 g polymer / g solid catalyst component. For this polymer, SCB: 21.2, FR: 0.86, F
RR: 23.0, CXS: 10.2 wt%.

Example 4 (1) Polymerization In Example 1 (3), 1,4-cyclohexanedione was changed to 0.57 mmol of 1,4-benzoquinone.
Polymerization was carried out in the same manner as in Example 1 (3) except that the amount of the solid catalyst component was changed to 18.2 mg, to obtain 189 g of a polymer having good powder properties. The polymer hardly adhered to the inner wall of the autoclave and the stirrer. The amount of polymer produced per unit of catalyst (polymerization activity) was 104
It was 00 g polymer / g solid catalyst component. For this polymer, SCB: 22.3, FR: 1.31, FRR:
21.8, CXS: 11.7 wt%.

Comparative Example 1 (1) Polymerization Example 1 (3) was repeated except that 1,4-cyclohexanedione was not used and the amount of the solid catalyst component was changed to 9.8 mg. The polymerization was carried out in the same manner as in the above) to obtain 140 g of a polymer having good powder properties. The polymer hardly adhered to the inner wall of the autoclave and the stirrer. The production amount (polymerization activity) of the polymer per catalyst unit amount was 14000 g polymer / g solid catalyst component.
About this polymer, SCB: 20.9, FR: 1.1
2, FRR: 23.0, CXS: 11.1 wt%, and the CXS amount with respect to SCB was larger than that in the case where a cyclic ketone compound was used.

Comparative Example 2 (1) Polymerization In Example 1 (3), the amount of butane was changed to 380 g, the amount of 1-butene was changed to 370 g, and 1,4-cyclohexanedione was not used. , The amount of the solid catalyst component is 1
Polymerization was carried out in the same manner as in Example 1 (3) except that the amount was changed to 1.2 mg, to obtain 222 g of a polymer having good powder properties. The polymer hardly adhered to the inner wall of the autoclave and the stirrer. The amount of the polymer produced per unit of catalyst (polymerization activity) was 19,800 g polymer / g solid catalyst component. For this polymer, SCB: 1
2.3, FR: 1.27, FRR: 24.5, CXS:
The content was 13 wt%, and the CXS amount with respect to SCB was larger than that in the case where the cyclic ketone compound was used.

Comparative Example 3 (1) Polymerization In Example 1 (3), the amount of butane was changed to 450 g, the amount of 1-butene was changed to 300 g, and 1,4-cyclohexanedione was not used. , The amount of the solid catalyst component is 1
Polymerization was carried out in the same manner as in Example 1 (3) except that the amount was changed to 4.3 mg, to obtain 245 g of a polymer having good powder properties. The polymer hardly adhered to the inner wall of the autoclave and the stirrer. The amount of the polymer produced per unit of catalyst (polymerization activity) was 17,100 g polymer / g solid catalyst component. For this polymer, SCB: 1
9.1, FR: 1.34, FRR: 24.5, CXS:
9.1 wt%, and the CXS amount with respect to SCB was larger than that in the case where the cyclic ketone compound was used.

Comparative Example 4 (1) Polymerization In Example 1 (3), the amount of butane was changed to 480 g, the amount of 1-butene was changed to 270 g, and 1,4-cyclohexanedione was not used. , The amount of the solid catalyst component is 7.
Polymerization was carried out in the same manner as in Example 1 (3) except that the amount was changed to 1 mg, to obtain 105 g of a polymer having good powder properties.
The polymer hardly adhered to the inner wall of the autoclave and the stirrer. The amount of polymer produced per unit of catalyst (polymerization activity) was 15000 g polymer / g solid catalyst component. For this polymer, SCB: 15.
9, FR: 0.69, FRR: 25.5, CXS: 5.
4 wt%, and the CXS amount with respect to SCB was larger than that in the case where the cyclic ketone compound was used.

[0083]

As described in detail above, according to the present invention, an olefin polymerization catalyst capable of producing an olefin polymer having a low content of low molecular weight components, and an olefin polymer having a low content of low molecular weight components are provided. A manufacturing method is provided. According to the present invention, there is also provided a method for producing an olefin polymer having good particle properties with almost no adhesion to a polymerization reaction tank. In the production of an olefin polymer, a large amount of adhesion of the olefin polymer or the like to the polymerization reaction tank causes various obstacles in the operation of the production process of the olefin polymer and causes a decrease in operation efficiency. Should be as small as possible. And, regarding the particle properties of the obtained olefin polymer powder, from the viewpoint of operation stability and operation efficiency,
A polymer powder having a high bulk density, a narrow particle size distribution and good fluidity is desirable. Further, according to the present invention, a catalyst for olefin polymerization having a sufficiently high activity and a method for producing a sufficiently efficient olefin polymer are also provided.

[Brief description of the drawings]

FIG. 1 is a flowchart for helping the understanding of the present invention. The flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J028 AA01A AB01A AC06A BA00A BA01B BB00A BB01B BC04A BC15B BC16B BC17B BC25B CB43C CB44C CB45C CB53C EB02 EB03 EB04 EB05 EB07 EB08 EB09 EB10 GA01

Claims (7)

[Claims] An olefin polymerization catalyst obtained by contacting a solid catalyst component (I) containing at least a titanium atom, a magnesium atom and a halogen atom, an organoaluminum compound (II) and a cyclic ketone compound (III). 2. The olefin polymerization catalyst according to claim 1, wherein the cyclic ketone compound (III) is a cyclic ketone compound having a 3- to 10-membered ring. 3. The cyclic ketone compound (III) is a compound having at least two carbonyl groups in a ring system.
Or the olefin polymerization catalyst according to 2. 4. A solid catalyst component (I) containing at least a titanium atom, a magnesium atom and a halogen atom,
The olefin polymerization catalyst according to any one of claims 1 to 3, further comprising an electron donor. 5. The catalyst for olefin polymerization according to claim 4, wherein the electron donor is an ester of an organic acid. 6. A method for producing an olefin polymer using the catalyst for olefin polymerization according to any one of claims 1 to 5. 7. The method for producing an olefin polymer according to claim 6, wherein the olefin polymer is a copolymer of ethylene and an α-olefin.