JP2006274160A - METHOD FOR PRODUCING ULTRAHIGH MOLECULAR WEIGHT ETHYLENE-alpha-OLEFIN COPOLYMER - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an ultrahigh molecular weight ethylene-α-olefin copolymer having a low melting point and excellent balance between transparency and mechanical strength. <P>SOLUTION: The method for producing the ultrahigh molecular weight ethylene-α-olefin copolymer satisfying the following essential conditions (i) and (ii) involves copolymerizing ethylene and an α-olefin in the presence of a polymerization catalyst obtained by bringing the following component (A) into contact with the component (B): component (A): a solid catalytic component containing a titanium atom, a magnesium atom, a halogen atom and an ester compound, and having ≤80 m<SP>2</SP>/g specific surface area by a BET method; component (B): an organoaluminum compound; (i) having 5-30 dl/g intrinsic viscosity [η]; and (ii) having 110-130°C melting point measured by differential scanning calorimetry. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing an ultrahigh molecular weight ethylene-α-olefin copolymer.

Ultra-high molecular weight polyethylene is excellent in strength, wear resistance, impact resistance, self-lubrication, solvent resistance, electrical insulation, etc., but is a highly crystalline polymer having a relatively high density, and therefore has a melting point. It was high and the transparency was low. As an improvement of this point, for example, Patent Document 1 discloses an ultrahigh molecular weight ethylene system excellent in transparency and impact resistance by copolymerizing ethylene and an α-olefin having 3 to 6 carbon atoms. Copolymers are described.
As a method for producing an ultrahigh molecular weight ethylene polymer described in Patent Document 1, for example, a catalyst component formed from a highly active titanium catalyst component, an organoaluminum compound, and an organosilicon compound catalyst component is described.

Japanese Patent Publication No. 5-86803

However, in the production method using the above catalyst component, in order to obtain an ultra-high molecular weight polyethylene polymer having a lower melting point, the content of α-olefin is increased when the content of α-olefin in the copolymer is increased. There is a problem that the mechanical strength is lowered because the amount of by-product of the low molecular weight component having a large amount is remarkably increased.
Under such circumstances, the problem to be solved by the present invention, that is, the object of the present invention is to provide a method for producing an ultrahigh molecular weight ethylene-α-olefin copolymer having a low melting point and excellent balance between transparency and mechanical strength. It is to provide.

That is, the present invention relates to an ultrahigh molecular weight ethylene-α-obtained by copolymerizing ethylene and α-olefin in the presence of a polymerization catalyst obtained by contacting the following component (A) and component (B). A method for producing an olefin copolymer, which provides a method for producing an ultrahigh molecular weight ethylene-α-olefin copolymer that satisfies the following requirements (a) and (a).
(A) A solid catalyst component containing a titanium atom, a magnesium atom, a halogen atom and an ester compound and having a specific surface area of 80 m ² / g or less by BET method (B) Organoaluminum compound (A) Intrinsic viscosity [η] is 5 ~ 30dl / g
(B) Melting point of 110 to 130 ° C. by differential scanning calorimetry

  According to the present invention, there is provided a method for producing an ultrahigh molecular weight ethylene-α-olefin copolymer having a low melting point and an excellent balance between transparency and mechanical strength.

Hereinafter, the present invention will be specifically described.
The ultrahigh molecular weight ethylene-α-olefin copolymer produced by the present invention is a copolymer obtained by copolymerizing ethylene and α-olefin. The α-olefin is preferably an α-olefin having 3 or more carbon atoms. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1 Examples include linear monoolefins such as decene, branched monoolefins such as 3-methyl-1-butene, 3-methyl-1-pentene, and 4-methyl-1-pentene, vinylcyclohexane, and the like. One type of these α-olefins may be used, or two or more types may be used in combination.

  The intrinsic viscosity of the ultrahigh molecular weight ethylene-α-olefin copolymer produced according to the present invention measured in tetralin at 135 ° C. is 5-30 dl / g. Preferably it is 6-25 dl / g, More preferably, it is 7-20 dl / g. When the intrinsic viscosity is less than 5 dl / g, sufficient mechanical strength may not be obtained, and when it exceeds 30 dl / g, workability may be deteriorated.

  The ultrahigh molecular weight ethylene-α-olefin copolymer produced by the present invention has a melting point (hereinafter referred to as DSC melting point) of 110 to 130 ° C. by differential scanning calorimetry. Preferably it is 112-129 degreeC, More preferably, it is 114 degreeC-128 degreeC. The DSC melting point tends to decrease as the α-olefin content in the copolymer increases.

  The content of the cold xylene soluble part (hereinafter referred to as CXS) of the ultrahigh molecular weight ethylene-α-olefin copolymer produced by the present invention is preferably from the viewpoint of the mechanical strength of the copolymer. Is 4% by weight or less, more preferably 0.1 to 3.4% by weight, and still more preferably 0.2 to 2.8% by weight. In the present invention, CXS is a low molecular weight component having a large content of α-olefin, and tends to increase as the content of the α-olefin in the copolymer increases. By using the polymerization catalyst of the present invention, if the α-olefin content in the copolymer is the same, the copolymer having a lower CXS content can be produced.

  The component (A) used in the present invention is a solid catalyst component containing a titanium atom, a magnesium atom, a halogen atom and an ester compound.

BET specific surface area of the solid catalyst component (A) is not more than 80 m ² / g, preferably 0.05~50m ² / g, more preferably 0.1~30m ² / g.
The specific surface area can be reduced by adding a sufficient amount of the ester compound to the solid catalyst component (A), and can be a solid catalyst component suitable for the present invention.

  The content of the ester compound in the solid catalyst component (A) is preferably 15 to 50% by weight when the total amount of the dried solid catalyst component is 100% by weight. More preferably, it is 20-40 weight%, More preferably, it is 22-35 weight%.

Examples of the ester compound in the solid catalyst component (A) include mono- or polyvalent carboxylic acid esters, and examples thereof include saturated aliphatic carboxylic acid esters, unsaturated aliphatic carboxylic acid esters, alicyclic carboxylic acid esters, and aromatic compounds. Group carboxylic acid esters can be mentioned. Specific examples include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, methyl toluate, toluyl Ethyl acetate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl phthalate Ethyl, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dipentyl phthalate, di-n-hexyl phthalate, diheptyl phthalate, di-n-octyl phthalate, Diphthalic acid (2 Ethylhexyl), diisodecyl phthalate, dicyclohexyl phthalate, may be mentioned diphenyl phthalate. Among these, from the viewpoint of polymerization activity, dialkyl phthalate is preferable, and dialkyl phthalate having a total of 9 or more carbon atoms of two alkyl groups bonded to each ester bond is more preferable.
As will be described later, the ester compound is mainly a compound derived from an ester compound or a compound capable of forming an ester compound in the reaction system in the process of adjusting the solid catalyst component (A).

  The content of titanium atoms in (A) in the solid catalyst component is preferably 0.6 to 1.6 wt%, more preferably 100 wt% when the dried solid catalyst component (A) is 100 wt%. 0.8 to 1.4% by weight.

  Examples of the method for producing the solid catalyst component (A) include, for example, Japanese Patent Publication No. 46-34092, Japanese Patent Publication No. 47-41676, Japanese Patent Publication No. 55-23561, Japanese Patent Publication No. 57-24361, Japanese Patent Publication No. 52. -39431, JP-B-52-36786, JP-B-1-28049, JP-B-3-43283, JP-A-4-80044, JP-A-55-52309, JP-A-58 No. 21405, JP 61-181807, JP 63-142008, JP 5-339319, JP 54-148093, JP 4-227604, JP No. 6-2933, JP-A No. 64-6006, JP-A No. 6-179720, JP-B No. 7-116252, JP-A No. 8-134124. In the process of preparing the solid catalyst component described in Japanese Patent Application Laid-Open No. 9-31119, Japanese Patent Application Laid-Open No. 11-228628, Japanese Patent Application Laid-Open No. 11-80234, and Japanese Patent Application Laid-Open No. 11-322833, an ester compound or a reaction system It can be obtained by coexisting a compound capable of forming an ester compound.

For example, the preparation method in any one of (1)-(5) below is mentioned.
(1) A method of contacting a magnesium halide compound, a titanium compound and an ester compound.
(2) A method in which an ester solution is brought into contact with a solid component obtained by bringing an alcohol solution of a magnesium halide compound into contact with a titanium compound.
(3) A method of bringing a halogenated compound and an ester compound into contact with a solid component obtained by bringing a solution of a magnesium halide compound and a titanium compound into contact with a precipitant.
(4) A method of contacting a dialkoxymagnesium compound, a titanium halide compound and an ester compound.
(5) A method of contacting a solid component containing a magnesium atom, a titanium atom and a hydrocarbyloxy group, a halogenated compound and an ester compound.
Among them, (5) is suitable in the present invention, and the solid component (a) containing a magnesium atom, a titanium atom and a hydrocarbyloxy group, a halogenated compound (b) and a phthalic acid derivative (c) are brought into contact with each other. Is preferred. This will be described in more detail below.

（上記一般式［Ｉ］において、ａは１〜２０の数を表し、Ｒ²は炭素原子数１〜２０の炭化水素基を表す。Ｘ²はそれぞれ、ハロゲン原子または炭素原子数１〜２０の炭化水素オキシ基を表し、全てのＸ²は同じであっても異なっていてもよい。） (A) Solid component The solid component (a) used in the present invention comprises a titanium compound (ii) represented by the following general formula [I] in the presence of an organosilicon compound (i) having a Si-O bond. , A solid component obtained by reduction with an organomagnesium compound (iii). At this time, if the ester compound (iv) is present as an optional component, the polymerization activity may be further improved.

(In the above general formula [I], a represents a number of 1 to 20, R ² represents a hydrocarbon group having 1 to 20 carbon atoms. X ² is a halogen atom or a carbon atom having 1 to 20 carbon atoms, respectively. Represents a hydrocarbon oxy group, and all X ² may be the same or different.)

Examples of the organosilicon compound (i) having a Si—O bond include compounds represented by the following general formula.
Si (OR ¹⁰ ) _t R ¹¹ _4-t ,
R ¹² (R ¹³ ₂ SiO) _u SiR ¹⁴ ₃ or
(R ¹⁵ ₂ SiO) _v
In the above general formula, R ¹⁰ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrocarbon group having 1 to 20 carbon atoms. Or represents a hydrogen atom. t represents an integer satisfying 0 <t ≦ 4, u represents an integer of 1 to 1000, and v represents an integer of 2 to 1000.

  Examples of the organosilicon compound (i) include tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, tetraisopropoxysilane, diisopropoxy-diisopropylsilane, Tetrapropoxysilane, dipropoxydipropylsilane, tetrabutoxysilane, dibutoxydibutylsilane, dicyclopentoxydiethylsilane, diethoxydiphenylsilane, cyclohexyloxytrimethylsilane, phenoxytrimethylsilane, tetraphenoxysilane, triethoxyphenylsilane, hexa Methyldisilohexane, hexaethyldisilohexane, hexapropyldisiloxane, octaethyltrisiloxane, dimethylpolysiloxane Rokisan, diphenyl polysiloxane, methylhydropolysiloxane, phenyl hydropolysiloxane like.

Of these organosilicon compounds (i), an alkoxysilane compound represented by the general formula Si (OR ¹⁰ ) _t R ¹¹ _4- t is preferable. In this case, t preferably satisfies 1 ≦ t ≦ 4. A tetraalkoxysilane with t = 4, most preferably tetraethoxysilane.

（上記一般式［Ｉ］において、ａは１〜２０の数を表し、Ｒ²は炭素原子数１〜２０の炭化水素基を表す。Ｘ²はそれぞれ、ハロゲン原子または炭素原子数１〜２０の炭化水素オキシ基を表し、全てのＸ²は同じであっても異なっていてもよい。） The titanium compound (ii) is a titanium compound represented by the following general formula [I].

(In the above general formula [I], a represents a number of 1 to 20, R ² represents a hydrocarbon group having 1 to 20 carbon atoms. X ² is a halogen atom or a carbon atom having 1 to 20 carbon atoms, respectively. Represents a hydrocarbon oxy group, and all X ² may be the same or different.)

R ² is a hydrocarbon group having 1 to 20 carbon atoms. Examples of R ² include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, decyl, and dodecyl. Examples thereof include aryl groups such as phenyl group, cresyl group, xylyl group and naphthyl group, cycloalkyl groups such as cyclohexyl group and cyclopentyl group, allyl groups such as propenyl group, and aralkyl groups such as benzyl group.
Among these hydrocarbon groups, an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms is preferable. More preferably, it is a linear alkyl group having 2 to 18 carbon atoms.

X ² is each a halogen atom or a hydrocarbon oxy group having 1 to 20 carbon atoms. Examples of the halogen atom for X ² include a chlorine atom, a bromine atom, and an iodine atom. Particularly preferred is a chlorine atom. The hydrocarbon oxy group having 1 to 20 carbon atoms in X ² is a hydrocarbon oxy group having a hydrocarbon group having 1 to 20 carbon atoms in the same manner as R ² . X ² is particularly preferably an alkoxy group having a linear alkyl group having 2 to 18 carbon atoms.

  In the titanium compound (ii) represented by the general formula [I], a is a number of 1 to 20, and preferably a number satisfying 1 ≦ a ≦ 5.

  Examples of the titanium compound (ii) include tetramethoxy titanium, tetraethoxy titanium, tetra n-propoxy titanium, tetraiso-propoxy titanium, tetra n-butoxy titanium, tetraiso-butoxy titanium, n-butoxy titanium trichloride, Di-n-butoxytitanium dichloride, tri-n-butoxytitanium chloride, di-n-tetraisopropylpolytitanate (a mixture in the range of a = 2-10), tetra-n-butylpolytitanate (a mixture in the range of a = 2-10) , Tetra n-hexyl polytitanate (a mixture in the range of a = 2 to 10), tetra n-octyl polytitanate (a mixture in the range of a = 2 to 10). Moreover, the condensate of the tetraalkoxy titanium obtained by making a small amount of water react with tetraalkoxy titanium can also be mentioned.

The titanium compound (ii) is preferably a titanium compound in which a is 1, 2, or 4 in the titanium compound represented by the above general formula [I].
Particularly preferred is tetra n-butoxy titanium, tetra n-butyl titanium dimer or tetra n-butyl titanium tetramer.
In addition, a titanium compound (ii) may be used independently and can also be used in the state which mixed multiple types.

The organomagnesium compound (iii) is any type of organomagnesium compound having a magnesium-carbon bond. In particular, a Grignard compound represented by the general formula R ¹⁶ MgX ⁵ (wherein Mg represents a magnesium atom, R ¹⁶ represents a hydrocarbon group having 1 to 20 carbon atoms, and X ⁵ represents a halogen atom), or Dihydrocarbylmagnesium represented by the general formula R ¹⁷ R ¹⁸ Mg (wherein Mg represents a magnesium atom and R ¹⁷ and R ¹⁸ each represent a hydrocarbon group having 1 to 20 carbon atoms) is preferred. Used for. Here, R ¹⁷ and R ¹⁸ may be the same or different. R ^{16 to} R ¹⁸ are, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isoamyl group, hexyl group, octyl group, 2-ethylhexyl group, Examples thereof include an alkyl group having 1 to 20 carbon atoms such as a phenyl group and a benzyl group, an aryl group, an aralkyl group, and an alkenyl group. In particular, the use of a Grignard compound represented by R ¹⁶ MgX ⁵ in an ether solution is preferable from the viewpoint of polymerization activity and stereoregularity.

  Said organomagnesium compound (iii) can also be used as a complex with another organometallic compound in order to solubilize in a hydrocarbon solvent. Specific examples of the organometallic compound include lithium, beryllium, aluminum or zinc compounds.

  Examples of the optional ester compound (iv) include mono- or polyvalent carboxylic acid esters, and examples thereof include saturated aliphatic carboxylic acid esters, unsaturated aliphatic carboxylic acid esters, alicyclic carboxylic acid esters, aromatic compounds. Group carboxylic acid esters can be mentioned. Specific examples include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, methyl toluate, toluyl Ethyl acetate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl phthalate Ethyl, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dipentyl phthalate, di-n-hexyl phthalate, diheptyl phthalate, di-n-octyl phthalate, Diphthalic acid (2 Ethylhexyl), diisodecyl phthalate, dicyclohexyl phthalate, may be mentioned diphenyl phthalate.

  Of these ester compounds, unsaturated aliphatic carboxylic acid esters such as methacrylic acid esters and maleic acid esters, or aromatic carboxylic acid esters such as phthalic acid esters are preferred, and dialkyl phthalates are particularly preferred.

  The solid component (a) is obtained by reducing the titanium compound (ii) with the organomagnesium compound (iii) in the presence of the organosilicon compound (i) or in the presence of the organosilicon compound (i) and the ester compound (iv). can get. Specifically, a method in which the organomagnesium compound (iii) is introduced into a mixture of the organosilicon compound (i), the titanium compound (ii), and, if necessary, the ester compound (iv) is preferable.

The titanium compound (ii), the organosilicon compound (i) and the ester compound (iv) are preferably used in the form of a solution or slurry in an appropriate solvent.
Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, octane, and decane, aromatic hydrocarbons such as toluene and xylene, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and decalin, diethyl ether, and dibutyl ether. , Ether compounds such as diisoamyl ether and tetrahydrofuran.

The temperature range of the reduction reaction temperature is usually −50 to 70 ° C., preferably −30 to 50 ° C., and particularly preferably −25 to 35 ° C.
The input time of organomagnesium (iii) is not particularly limited, but is usually about 30 minutes to 10 hours. Although the reduction reaction proceeds with the addition of (iii) of organomagnesium, after the addition, a post reaction may be performed at a temperature of 20 to 120 ° C.

In the reduction reaction, a porous carrier such as an inorganic oxide or an organic polymer can be allowed to coexist, and the porous carrier can be impregnated with the solid component. The porous carrier used may be a known one. Specific examples include porous inorganic oxides represented by SiO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , ZrO _2, etc., or polystyrene, styrene-divinylbenzene copolymer, styrene-ethylene glycol-dimethacrylic acid. Methyl copolymer, polymethyl acrylate, polyethyl acrylate, methyl acrylate-divinylbenzene copolymer, polymethyl methacrylate, methyl methacrylate-divinylbenzene copolymer, polyacrylonitrile, acrylonitrile-divinylbenzene copolymer And organic porous polymers such as polyvinyl chloride, polyethylene, and polypropylene. Among these, an organic porous polymer is preferably used, and a styrene-divinylbenzene copolymer or an acrylonitrile-divinylbenzene copolymer is particularly preferable.

The pore volume at a pore radius of 20 nm to 200 nm of the porous carrier is preferably 0.3 cm ³ / g or more, more preferably 0.4 cm ³ / g or more, from the viewpoint of effectively immobilizing the catalyst component. And a carrier having a pore volume in the pore radius range of preferably 35% or more, more preferably 40% or more of the pore volume at a pore radius of 3.5 nm to 7500 nm. The catalyst component may not be effectively immobilized unless it is sufficiently present in the pore radius range of 20 nm to 200 nm, which is not preferable.

The amount of the organosilicon compound (i) used is the ratio of the number of silicon atoms to the total titanium atoms in the titanium compound (ii), usually Si / Ti = 1 to 500, preferably 1.5 to 300, particularly preferably. Is in the range of 3-100.
Furthermore, the amount of the organomagnesium compound (iii) used is usually (Ti + Si) /Mg=0.1 to 10, preferably 0.2 to, in terms of the ratio of the sum of titanium atoms and silicon atoms to the number of magnesium atoms. 5.0, particularly preferably in the range of 0.5 to 2.0.
Further, the value of the molar ratio of Mg / Ti in the solid catalyst component is usually 1 to 51, preferably 2 to 31 and particularly preferably 4 to 26, so that the titanium compound (ii) and organic The usage-amount of a silicon compound (i) and an organomagnesium compound (iii) is determined.
Moreover, the usage-amount of ester compound (iv) of arbitrary components is a molar ratio of the ester compound with respect to the titanium atom of a titanium compound (ii), and is ester compound / Ti = 0.05-100 normally, Preferably it is 0.00. It is 1-60, Most preferably, it is the range of 0.2-30.

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

(B) Halogenated compound The halogenated compound is preferably a compound that can replace the hydrocarbon oxy group in the solid component (a) with a halogen atom. More preferably, it is a halogen compound of Group 4 element, a halogen compound of Group 13 element or a halogen compound of Group 14 element, and more preferably a halogen compound (b1) of Group 4 element or Group 14 element. This is an elemental halogen compound (b2).

The halogen compound (b1) of the Group 4 element is preferably represented by the general formula M ¹ (OR ⁹ ) _b X ⁴ _4-b (wherein M ¹ represents a Group 4 atom and R ⁹ has 1 carbon atom) Represents a hydrocarbon group of ˜20, X ⁴ represents a halogen atom, and b represents a number satisfying 0 ≦ b <4. Examples of M ¹ include a titanium atom, a zirconium atom, and a hafnium atom. Among these, a titanium atom is preferable. As R ⁹ , for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, amyl group, isoamyl group, tert-amyl group, hexyl group, heptyl group, octyl group, Examples thereof include alkyl groups such as decyl group and dodecyl group, aryl groups such as phenyl group, cresyl group, xylyl group and naphthyl group, allyl groups such as propenyl group, and aralkyl groups such as benzyl group. Among these, an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms is preferable. Particularly preferred is a linear alkyl group having 2 to 18 carbon atoms. It is also possible to use halogen compounds of Group 4 elements having two or more different OR ⁹ groups.

Examples of the halogen atom represented by X ⁴ include a chlorine atom, a bromine atom, and an iodine atom. Among these, a chlorine atom is particularly preferable.

In the halogen compounds of Group 4 elements represented by the general formula M ¹ (OR ⁹ ) _b X ⁴ _4-b , b is a number that satisfies 0 ≦ b <4, and preferably satisfies 0 ≦ b ≦ 2. Particularly preferably, b = 0.

Examples of the halogen compound represented by the general formula M ¹ (OR ⁹ ) _b X ⁴ _4-b include titanium tetrachloride such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide, methoxy titanium trichloride, Trihalogenated alkoxy titanium such as ethoxy titanium trichloride, butoxy titanium trichloride, phenoxy titanium trichloride, ethoxy titanium tribromide, dimethoxy titanium dichloride, diethoxy titanium dichloride, dibutoxy titanium dichloride, diphenoxy titanium dichloride, diethoxy titanium dichloride Examples thereof include dihalogenated dialkoxytitanium such as bromide, and similarly include a zirconium compound and a hafnium compound corresponding to each. Most preferred is titanium tetrachloride.

The halogen compound of group 13 element or the halogen compound (b2) of group 14 element of the periodic table is preferably a general formula M ² R ¹ _mc X ⁸ _c (wherein M ² is an atom of group 13 or group 14). R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, X ⁸ represents a halogen atom, m represents a number corresponding to the valence of M ² , and c represents 0 <c ≦ m. Represents a satisfactory number.).
Examples of the Group 13 atom include a boron atom, an aluminum atom, a gallium atom, an indium atom, and a thallium atom, preferably a boron atom or an aluminum atom, and more preferably an aluminum atom. Examples of the Group 14 atom include a carbon atom, a silicon atom, a germanium atom, a tin atom, and a lead atom, preferably a silicon atom, a germanium atom, or a tin atom, and more preferably a silicon atom or a tin atom. Is an atom.

m is a number corresponding to the valence of M ^2, for example, M ² is an m = 4 when the silicon atoms.
c is a number satisfying 0 <c ≦ m. When M ² is a silicon atom, c is preferably 3 or 4.
Examples of the halogen atom represented by X ⁸ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.

Examples of R ¹ include alkyl such as methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, decyl, and dodecyl. Group, phenyl group, tolyl group, cresyl group, xylyl group, aryl group such as naphthyl group, cycloalkyl group such as cyclohexyl group and cyclopentyl group, alkenyl group such as propenyl group, and aralkyl group such as benzyl group. An alkyl group or an aryl group is preferable, and a methyl group, an ethyl group, a normal propyl group, a phenyl group, or a paratolyl group is particularly preferable.

  Examples of Group 13 element halogen compounds include trichloroborane, methyldichloroborane, ethyldichloroborane, phenyldichloroborane, cyclohexyldichloroborane, dimethylchloroborane, methylethylchloroborane, trichloroaluminum, methyldichloroaluminum, and ethyldichloroaluminum. , Phenyldichloroaluminum, cyclohexyldichloroaluminum, dimethylchloroaluminum, diethylchloroaluminum, methylethylchloroaluminum, ethylaluminum sesquichloride, gallium chloride, gallium dichloride, trichlorogallium, methyldichlorogallium, ethyldichlorogallium, phenyldichlorogallium, cyclohexyldichloro Gallium, dimethylchlorogalli , 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, etc. Also included are compounds in which “chloro” in the compound name is replaced with “fluoro”, “bromo” or “iodo”.

  Examples of the group 14 element halogen compound (b2) 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, di Chlorosilane, methyldichlorosilane, ethyldichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, methylethyldichlorosilane, monochlorosilane, trime Ruchlorosilane, triphenylchlorosilane, tetrachlorogermane, trichlorogermane, methyltrichlorogermane, ethyltrichlorogermane, phenyltrichlorogermane, dichlorogermane, dimethyldichlorogermane, diethyldichlorogermane, diphenyldichlorogermane, monochlorogermane, trimethylchlorogermane, triethylchlorogermane Germane, tri-normal butyl chloro germane, tetrachloro tin, methyl trichloro tin, normal butyl trichloro tin, dimethyl dichloro tin, dinormal butyl dichloro tin, diisobutyl dichloro tin, diphenyl dichloro tin, divinyl dichloro tin, methyl trichloro tin, phenyl trichloro tin , Dichlorolead, methylchlorolead, phenylchlorolead, etc. The Rolo "," fluoro ", compounds obtained by replacing the" bromo "or" iodo "can also be mentioned.

Particularly preferable as the halogenated compound (b), from the viewpoint of polymerization activity, titanium tetrachloride, methyldichloroaluminum, ethyldichloroaluminum, tetrachlorosilane, phenyltrichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, normal propyltrichlorosilane or tetra Chlorotin.
The halogenated compound (b) may be used alone from among the above compounds, or a plurality of types may be used simultaneously or sequentially.

（ただし、Ｒ²⁴〜Ｒ²⁷はそれぞれ独立に水素原子または炭化水素基、Ｓ⁶およびＳ⁷はそれぞれ独立にハロゲン原子であるか、または、水素原子、炭素原子、酸素原子およびハロゲン原子のうちの複数を任意に組み合わせて形成される置換基である。）
Ｒ²⁴〜Ｒ²⁷として好ましくは、水素原子、または炭素原子数１〜１０の炭化水素基であり、Ｒ²⁴〜Ｒ²⁷の任意の組み合わせは互いに結合して環構造を形成していてもよい。Ｓ⁶およびＳ⁷として好ましくは、それぞれ独立に塩素原子、水酸基、または炭素原子数１〜２０のアルコキシ基である。 (C) Phthalic acid derivative Examples of the phthalic acid derivative (c) include compounds represented by the following general formula.

(Wherein R ^{24 to} R ²⁷ are each independently a hydrogen atom or a hydrocarbon group, S ⁶ and S ⁷ are each independently a halogen atom, or a hydrogen atom, a carbon atom, an oxygen atom and a halogen atom) It is a substituent formed by arbitrarily combining a plurality.)
R ^{24 to} R ²⁷ are preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and any combination of R ^{24 to} R ²⁷ may be bonded to each other to form a ring structure. S ⁶ and S ⁷ are preferably each independently a chlorine atom, a hydroxyl group, or an alkoxy group having 1 to 20 carbon atoms.

Specific examples of the phthalic acid derivative (c) include phthalic acid, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, di-normal phthalate, diisopropyl phthalate, di-normal butyl phthalate, phthalic acid Diisobutyl, dipentyl phthalate, di-hexyl phthalate, di-normal heptyl phthalate, di-isoheptyl phthalate, di-normal octyl phthalate, di (2-ethylhexyl) phthalate, di-nordecyl phthalate, diisodecyl phthalate, dicyclohexyl phthalate , Diphenyl phthalate, dichloride phthalate, diethyl 3-methylphthalate, diethyl 4-methylphthalate, diethyl 3,4-dimethylphthalate, dinormal butyl 3-methylphthalate, dinormal butyl 4-methylphthalate, 3 4-normal butyl 4-dimethylphthalate, diisobutyl 3-methylphthalate, diisobutyl 4-methylphthalate, diisobutyl 3,4-dimethylphthalate, di (2-ethylhexyl) 3-methylphthalate, di (2-ethylhexyl) 4-methylphthalate ), 3,4-dimethylphthalic acid di (2-ethylhexyl), 3-methylphthalic acid dichloride, 4-methylphthalic acid dichloride, 3,4-dimethylphthalic acid dichloride, 3-ethylphthalic acid di (2-ethylhexyl), 4- Examples thereof include di (2-ethylhexyl) ethylphthalate and di (2-ethylhexyl) 3,4-diethylphthalate. Among them, diethyl phthalate, dinormal butyl phthalate, diisobutyl phthalate, diisoheptyl phthalate, di (2) phthalate -Ethylhexyl), dii phthalate Decyl are preferred.
When the esters contained in the solid catalyst component of the present invention are dialkyl phthalates, they are derived from phthalic acid derivatives, and are compounds in which S ⁶ and S ⁷ are alkoxy groups in the above general formula. In the preparation of the solid catalyst component, S ⁶ and S ⁷ of the phthalic acid derivative (c) used can be exchanged as they are or with other substituents.

Preparation of solid catalyst component (A) The solid catalyst component (A) of the present invention comprises a titanium compound (ii) represented by the general formula [I] in the presence of an organosilicon compound (i) having a Si-O bond. Can be obtained by subjecting the solid component (a), the halogenated compound (b), and the phthalic acid derivative (c) obtained by reduction of the compound to the organic magnesium compound (iii) to contact with each other. All of these contact treatments are usually performed in an inert gas atmosphere such as nitrogen gas or argon gas.

As a specific method of the contact treatment for obtaining the solid catalyst component (A),
A method for charging (a) with (b) and (c) (arbitrary order) and performing contact processing. (B) for (a) and (c) (arbitrary order) with contact processing. Method (c): (a) and (b) (input order is arbitrary) and contact processing method (a) (b) is input, after contact processing, (c) is input After (c) is added to (a) and contact processing is performed, after (b) is input and after (c) is input to (a) and (c) is subjected to contact processing. , (B) and (c) (arrangement order is arbitrary) and contact treatment method (c) is introduced into (a) and after contact treatment, the mixture of (b) and (c) is introduced. , Contact processing method ・ (b) and (c) (arbitrary order) are input to (a), and after contact processing, (b) is input and contact processing is performed. The method · (a), (b) and the (c) (on sequence Optional) were charged, and after the contact treatment (b) was charged a mixture of (c), and a method of contacting treatment. Among them, (b) and (c) (arbitrary order) are charged into (a), contact processing is performed and then (b1) is charged and contact processing is performed. (A) includes (b2) and ( It is more preferable to add the mixture of (b1) and (c) after the c) (addition order is arbitrary) and the contact treatment, and the contact treatment. Further, the polymerization activity may be improved by repeating the contact treatment with (b1) a plurality of times thereafter.

The contact treatment can be performed by any known method capable of bringing each component into contact, such as a slurry method or a mechanical pulverizing means such as a ball mill. However, mechanical pulverization generates a large amount of fine powder in the solid catalyst component. In some cases, the particle size distribution may be widened, which is not preferable for stably performing continuous polymerization. Therefore, it is preferable to contact both in the presence of a solvent.
Further, after the contact treatment, the next operation can be performed as it is, but in order to remove surplus, it is preferable to perform a washing treatment with a solvent.

The solvent is preferably inert to the component to be treated. Specific examples include aliphatic hydrocarbons such as pentane, hexane, heptane, and octane, aromatic hydrocarbons such as benzene, toluene, and xylene, cyclohexane, cyclohexane, and the like. Alicyclic hydrocarbons such as pentane and halogenated hydrocarbons such as 1,2-dichloroethane and monochlorobenzene can be used.
The amount of the solvent used in the contact treatment is usually 0.1 ml to 1000 ml per 1 g of the solid component (a) per one stage of contact treatment. Preferably, the amount is 1 ml to 100 ml per 1 g. In addition, the amount of solvent used in one washing operation is similar. The number of washing operations in the washing treatment is usually 1 to 5 times per one-step contact treatment.

The contact treatment and / or cleaning treatment temperature is usually −50 to 150 ° C., preferably 0 to 140 ° C., 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. Although the washing operation time is not particularly limited, it is preferably 1 to 120 minutes, more preferably 2 to 60 minutes.

The amount of the phthalic acid derivative (c) used is usually 0.01 to 100 mmol, preferably 0.05 to 50 mmol, more preferably 0.1 to 20 mmol with respect to 1 g of the solid component (a). It is.
When the amount of the phthalic acid derivative (c) used is excessively large, the particle size distribution of the solid catalyst component (A) may be broadened due to particle collapse.

  In particular, the amount of the phthalic acid derivative (c) used can be arbitrarily adjusted so that the content of the phthalic acid ester in the solid catalyst component (A) is appropriate. It is 0.1-100 mmol normally with respect to 1g of solid components (a), Preferably it is 0.3-50 mmol, More preferably, it is 0.5-20 mmol. Moreover, the usage-amount of the phthalic acid derivative (c) per 1 mol of magnesium atoms in a solid component (a) is 0.01-1.0 mol normally, Preferably it is 0.03-0.5 mol. .

  The usage-amount of a halogenated compound (b) is 0.5-1000 mmol normally with respect to 1 g of solid components (a), Preferably it is 1-200 mmol, More preferably, it is 2-100 mmol.

  When the contact treatment is performed using each compound a plurality of times, the amount of each compound described above represents the amount of each compound used once and for each kind of compound.

  The obtained solid catalyst component (A) may be used in polymerization in a slurry form in combination with an inert solvent, or may be used in polymerization as a fluid powder obtained by drying. Examples of the drying method include a method of removing volatile components under reduced pressure conditions and a method of removing volatile components under a flow of an inert gas such as nitrogen gas or argon gas. Preferably it is 0-200 degreeC as temperature at the time of drying, More preferably, it is 50-100 degreeC. The drying time is preferably 0.01 to 20 hours, more preferably 0.5 to 10 hours.

  The weight average particle diameter of the obtained solid catalyst component (A) is preferably 1 to 100 μm from an industrial viewpoint.

  The catalyst for polymerization is obtained by bringing the solid catalyst component (A) of the present invention into contact with the organoaluminum compound (B). Further, if necessary, the electron donating compound (C) can be added and brought into contact.

(B) Organoaluminum compound The organoaluminum compound (B) used for forming the α-olefin polymerization catalyst of the present invention has at least one aluminum-carbon bond in the molecule. A typical organoaluminum compound is represented by the following general formula.
R ¹⁹ _w AlY _3-w
R ²⁰ R ²¹ Al—O—AlR ²² R ²³
(In the above general formula, R ^{19 to} R ²³ represent a hydrocarbon group having 1 to 20 carbon atoms, Y represents a halogen atom, a hydrogen atom or an alkoxy group, and w represents a number satisfying 2 ≦ w ≦ 3. To express.)
Examples of the organoaluminum compound (B) include trialkylaluminum such as triethylaluminum, triisobutylaluminum and trihexylaluminum, dialkylaluminum hydride such as diethylaluminum hydride and diisobutylaluminum hydride, dialkylaluminum halide such as diethylaluminum chloride, Examples include a mixture of a trialkylaluminum and a dialkylaluminum halide such as a mixture of triethylaluminum and diethylaluminum chloride, and an alkylalumoxane such as tetraethyldialumoxane and tetrabutyldialumoxane.

  Among these organoaluminum compounds, trialkylaluminum, a mixture of trialkylaluminum and dialkylaluminum halide, or alkylalumoxane is preferable, and triethylaluminum, triisobutylaluminum, triethylaluminum and diethylaluminum chloride are particularly preferable. And a mixture or tetraethyldialumoxane.

(C) Electron-donating compound Examples of the electron-donating compound (C) used for forming the olefin polymerization catalyst include oxygen-containing compounds, nitrogen-containing compounds, phosphorus-containing compounds, and sulfur-containing compounds. Is an oxygen-containing compound or a nitrogen-containing compound.
Examples of the oxygen-containing compound include alkoxy silicons, ethers, esters, ketones, and the like, preferably alkoxy silicons or ethers.

The alkoxysilicons Motorui general formula _R ³ _r Si (OR ⁴⁾ in _4-r (wherein, R ³ represents a hydrocarbon group, a hydrogen atom or a hetero atom-containing substituent group having a carbon number 1 to 20, R ⁴ Represents a hydrocarbon group having 1 to 20 carbon atoms, and r represents a number satisfying 0 ≦ r <4. When a plurality of R ³ and R ⁴ are present, each R ³ and R ⁴ is the same. Or an alkoxysilicon compound represented by the following formula: When R ³ is a hydrocarbon group, examples of the hydrocarbon group include linear alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, an isopropyl group, a sec-butyl group, and a tert-butyl group. Group, branched alkyl group such as tert-amyl group, cycloalkyl group such as cyclopentyl group and cyclohexyl group, cycloalkenyl group such as cyclopentenyl group, aryl group such as phenyl group and tolyl group. Among these, it is preferable that the carbon atom directly bonded to the silicon atom of the alkoxysilicon compound has at least one R ³ which is a secondary or tertiary carbon. When R ³ is a heteroatom-containing substituent, examples of the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom. Specifically, dimethylamino group, methylethylamino group, diethylamino group, ethyl-n-propylamino group, di-n-propylamino group, pyrrolyl group, pyridyl group, pyrrolidinyl group, piperidyl group, perhydroindolyl group, Examples include perhydroisoindolyl, perhydroquinolyl, perhydroisoquinolyl, perhydrocarbazolyl, perhydroacridinyl, furyl, pyranyl, perhydrofuryl, and thienyl groups. Preferably, the hetero atom is a substituent that can be directly chemically bonded to the silicon atom of the alkoxysilicon compound.

  Examples of the alkoxysilicones include diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butyl-n-propyldimethoxysilane, tert- Butyl-n-butyldimethoxysilane, tert-amylmethyldimethoxysilane, tert-amylethyldimethoxysilane, tert-amyl-n-propyldimethoxysilane, tert-amyl-n-butyldimethoxysilane, isobutylisopropyldimethoxysilane, tert-butyl Isopropyldimethoxysilane, dicyclobutyldimethoxysilane, cyclobutylisopropyldimethoxysilane, cyclobutylisobutyl Methoxysilane, cyclobutyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentyl-tert-butyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyl Dimethoxysilane, cyclohexylisobutyldimethoxysilane, cyclohexyl-tert-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylisopropyldimethoxysilane, Phenyl isobutyldimethoxysilane, phenyl-tert-butyldimethoxysilane, phenylcyclopentyldimethoxysilane, diisopropyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldiethoxysilane, tert-butylmethyldiethoxysilane, tert-butylethyldi Ethoxysilane, tert-butyl-n-propyldiethoxysilane, tert-butyl-n-butyldiethoxysilane, tert-amylmethyldiethoxysilane, tert-amylethyldiethoxysilane, tert-amyl-n-propyldiethoxy Silane, tert-amyl-n-butyldiethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldiethoxysilane Orchid, cyclohexylethyldiethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, 2-norbornanemethyldimethoxysilane, bis (perhydroquinolino) dimethoxysilane, bis (perhydroisoquinolino) dimethoxysilane, (perhydroquinolino ) (Perhydroisoquinolino) dimethoxysilane, (perhydroquinolino) methyldimethoxysilane, (perhydroisoquinolino) methyldimethoxysilane, (perhydroquinolino) ethyldimethoxysilane, (perhydroisoquinolino) ethyldimethoxysilane , (Perhydroquinolino) (n-propyl) dimethoxysilane, (perhydroisoquinolino) (n-propyl) dimethoxysilane, (perhydroquinolino) (tert-butyl) dimethoxysila , And (perhydroisoquinolino) (tert-butyl) dimethoxysilane.

Examples of ethers include cyclic ether compounds.
The cyclic ether compound is a heterocyclic compound having at least one —C—O—C— bond in the ring structure.
Examples of the cyclic ether compound include ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, 2,5-dimethoxytetrahydrofuran, tetrahydropyran, hexamethylene oxide, 1,3-dioxepane, 1,3-dioxane, 1,4-dioxane. 1,3-dioxolane, 2-methyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane, 4-methyl-1,3-dioxolane, 2,4-dimethyl-1,3-dioxolane , Furan, 2,5-dimethylfuran, or s-trioxane. Preferred is a cyclic ether compound having at least one —C—O—C—O—C— bond in the ring structure.

  Examples of the esters include mono- or polyvalent carboxylic acid esters, and examples thereof include saturated aliphatic carboxylic acid esters, unsaturated aliphatic carboxylic acid esters, alicyclic carboxylic acid esters, and aromatic carboxylic acid esters. . Specific examples include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, methyl toluate, toluyl Ethyl acetate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl phthalate Ethyl, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dipentyl phthalate, di-n-hexyl phthalate, diheptyl phthalate, di-n-octyl phthalate, Diphthalic acid (2 Ethylhexyl), diisodecyl phthalate, dicyclohexyl phthalate, may be mentioned diphenyl phthalate.

  Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dihexyl ketone, acetophenone, diphenyl ketone, benzophenone, and cyclohexanone.

  Examples of the nitrogen-containing compound include 2,6-substituted piperidines such as 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, 2,5-substituted piperidines, N, N, N ′. , N′-tetramethylmethylenediamine, substituted methylenediamines such as N, N, N ′, N′-tetraethylmethylenediamine, and substituted imidazolidines such as 1,3-dibenzylimidazolidine. Preferred are 2,6-substituted piperidines.

  Particularly preferred as the electron donating compound (C) is cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, diisopropyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butyl-n-propyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxy. Silane, dicyclobutyldimethoxysilane, dicyclopentyldimethoxysilane, 1,3-dioxolane, 1,3-dioxane, 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine.

The catalyst using the solid catalyst component obtained by the present invention is a polymerization obtained by bringing the solid catalyst component (A) and the organoaluminum compound (B) into contact with the electron donating compound (C) as necessary. Catalyst. The term “contact” as used herein refers to any means as long as the catalyst components (A) and (B) (if necessary (C)) are brought into contact with each other to form a catalyst. A method of mixing and contacting each of them without dilution, a method of separately supplying them to the polymerization tank and bringing them into contact with each other in the polymerization tank can be employed.
As a method of supplying each catalyst component to the polymerization tank, it is preferable to supply the catalyst components in an inert gas such as nitrogen or argon in the absence of moisture. Each catalyst component may be supplied in contact with any two components in advance.

  Although it is possible to polymerize olefins in the presence of the catalyst, prepolymerization described below may be performed before such polymerization (main polymerization).

  The prepolymerization is usually carried out by supplying a small amount of olefin in the presence of the solid catalyst component (A) and the organoaluminum compound (B), and is preferably carried out in a slurry state. Examples of the solvent used for the slurry include inert hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, and toluene. Further, when slurrying, a liquid olefin can be used instead of a part or all of the inert hydrocarbon solvent.

  The amount of the organoaluminum compound used in the prepolymerization can be selected in a wide range such as 0.5 to 700 mol per mol of titanium atom in the solid catalyst component, but preferably 0.8 to 500 mol. Particularly preferred is 1 to 200 mol.

  The amount of olefin to be prepolymerized is usually 0.01 to 1000 g, preferably 0.05 to 500 g, particularly preferably 0.1 to 200 g, per 1 g of the solid catalyst component.

  The slurry concentration at the time of prepolymerization is preferably 1 to 500 g-solid catalyst component / L-solvent, particularly preferably 3 to 300 g-solid catalyst component / L-solvent. The prepolymerization temperature is preferably -20 to 100 ° C, particularly preferably 0 to 80 ° C. Further, the partial pressure of the olefin in the gas phase during the prepolymerization is preferably 1 kPa to 2 MPa, and particularly preferably 10 kPa to 1 MPa, but for the olefin that is liquid at the prepolymerization pressure and temperature, This is not the case. Further, the prepolymerization time is not particularly limited, but is usually 2 minutes to 15 hours.

  As a method of supplying the solid catalyst component (A), the organoaluminum compound (B), and the olefin when carrying out the prepolymerization, the olefin after the solid catalyst component (A) and the organoaluminum compound (B) are brought into contact with each other is used. Any method may be used, such as a method of supplying the organic aluminum compound (B) after the solid catalyst component (A) and the olefin are brought into contact with each other. In addition, as a method for supplying olefin, either a method of sequentially supplying olefin while maintaining the inside of the polymerization tank at a predetermined pressure, or a method of supplying all of the predetermined amount of olefin first is used. Good. It is also possible to add a chain transfer agent such as hydrogen in order to adjust the molecular weight of the resulting polymer.

  Further, when the solid catalyst component (A) is prepolymerized with a small amount of olefin in the presence of the organoaluminum compound (B), an electron donating compound (C) may coexist if necessary. The electron donating compound used is a part or all of the electron donating compound (C). The amount used is usually 0.01 to 400 mol, preferably 0.02 to 200 mol, particularly preferably 0.03 to 100 mol, per 1 mol of titanium atoms contained in the solid catalyst component (A). Yes, with respect to the organoaluminum compound (B), it is usually 0.003 to 5 mol, preferably 0.005 to 3 mol, and particularly preferably 0.01 to 2 mol.

  The method for supplying the electron donating compound (C) in the prepolymerization is not particularly limited, and may be supplied separately from the organoaluminum compound (A) or may be supplied in contact with the organic aluminum compound (A). Further, the olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization.

  After the prepolymerization as described above, or without performing the prepolymerization, in the presence of the polymerization catalyst comprising the above-mentioned solid catalyst component (A) and organoaluminum compound (B), ethylene-α-olefin Copolymerization can be performed.

  The amount of the organoaluminum compound used in the main polymerization can usually be selected in a wide range such as 1 to 1000 mol per 1 mol of the titanium atom in the solid catalyst component (A), particularly preferably in the range of 5 to 600 mol. It is.

  Moreover, when using an electron-donating compound (C) at the time of this superposition | polymerization, it is 0.1-2000 mol normally with respect to 1 mol of titanium atoms contained in a solid catalyst component (A), Preferably 0.3- 1000 mol, particularly preferably 0.5 to 800 mol, and usually 0.001 to 5 mol, preferably 0.005 to 3 mol, particularly preferably 0.01 to mol of the organoaluminum compound. ~ 1 mole.

  Although this superposition | polymerization can be implemented over -30-300 degreeC normally, Preferably it is 20-180 degreeC, More preferably, it is 40-100 degreeC. Although it does not specifically limit regarding a polymerization pressure, From a viewpoint of being industrial and economical, generally it is a normal pressure-10MPa, Preferably the pressure of about 200kPa-5MPa is employ | adopted. As the polymerization method, either batch type or continuous type is possible. Various distributions (molecular weight distribution, comonomer composition distribution, etc.) can be imparted by continuously passing through a plurality of polymerization stages or reactors having different polymerization conditions. In addition, slurry polymerization or solution polymerization using an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, and octane, bulk polymerization using a liquid olefin as a medium at the polymerization temperature, or gas phase polymerization is also possible.

  During the main polymerization, a chain transfer agent such as hydrogen can be added to adjust the molecular weight (intrinsic viscosity) of the polymer.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not specifically limited by the following examples. In the examples, polymerization catalysts and methods for evaluating various physical properties of the polymer are as follows.

(1) Composition analysis of solid sample such as solid catalyst component Titanium atom content is about 3 mg% hydrogen peroxide solution which decomposes about 20 milligrams of solid sample with 47 ml of 0.5 mol / L sulfuric acid and becomes excessive. 3 ml was added, and the characteristic absorption at 410 nm of the obtained liquid sample was measured using a Hitachi double beam spectrophotometer model U-2001, and was determined by a separately prepared calibration curve. The alkoxy group content is obtained by decomposing about 2 grams of a solid sample with 100 ml of water, and then determining the amount of alcohol corresponding to the alkoxy group in the obtained liquid sample using a gas chromatography internal standard method. Converted. The phthalate compound content was determined by dissolving about 30 milligrams of a solid sample in 100 ml of N, N-dimethylacetamide, and then determining the amount of the phthalate compound in the solution by gas chromatography internal standard method.
(2) BET specific surface area The specific surface area of the solid catalyst component was determined by the BET method based on the nitrogen adsorption / desorption amount using Flowsorb II 2300 manufactured by Micromeritics.
(3) Intrinsic viscosity (hereinafter abbreviated as [η])
The polymer was dissolved in a tetralin solvent and measured at 135 ° C. using an Ubbelohde viscometer.
(4) DSC melting point Using a differential scanning calorimeter (Diamond DSC manufactured by PerkinElmer), the test piece in the measurement pan was held at 150 ° C for 5 minutes, cooled from 150 ° C to 20 ° C at 5 ° C / minute, and 20 ° C. The temperature was raised from 20 ° C. to 150 ° C. at 5 ° C./min, and the peak of the melting curve obtained at this time was taken as the DSC melting point.
(5) Cold xylene soluble part (CXS)
5 g of the polymer was dissolved in 1000 ml of boiling xylene, air-cooled, and left in a thermostatic bath at 25 ° C. for 20 hours. And filtered. The xylene in the filtrate was distilled off under reduced pressure, and the weight percentage of the remaining polymer was determined to obtain CXS (unit = wt%).
(6) Content of α-olefin Using an infrared spectrophotometer (1600 series manufactured by PerkinElmer Co., Ltd.), the number of short-chain branches per 1000 carbon atoms is determined using a calibration curve from the characteristic absorption of ethylene and α-olefin. Expressed as (SCB).
(7) Preparation of press sheet The obtained polymer powder is sandwiched between Lumirror film T60 (manufactured by Toray) and further a steel flat plate and preheated for 5 minutes by a heat press at 190 ° C. to fuse polymer particles. It was pressed for 5 minutes at a sufficient pressure, and then cooled with a cooling press at 25 ° C. The obtained press sheet was divided into four equal parts and further subjected to hot pressing in the same manner, and used for measurement. Under the present circumstances, it adjusted to the press sheet of desired thickness by using steel spacers.
(8) Transparency Haze (cloudiness value) and light transmittance were measured by a method based on JIS K7105-1981. A press sheet having a thickness of 1.5 ± 0.15 mm was prepared and measured using a direct reading haze meter (manufactured by Toyo Seiki Seisakusho).
(9) Mechanical Strength Tensile impact strength (tensile impact) was measured by a method based on ASTM D1822-89. A type S test piece was prepared from a press sheet having a thickness of 0.5 ± 0.1 mm, and measured using a universal impact tester (manufactured by Toyo Seiki Seisakusho).
Moreover, the tensile fracture strength and the tensile fracture elongation were measured by a method based on JIS K7113-1995. A No. 2 type test piece was prepared from a press sheet having a thickness of 2 ± 0.4 mm and measured at a tensile speed of 200 mm / min using a fully automatic tensile tester ATM-C (manufactured by Orientec).
(10) Bulk density It was measured according to JIS K-6721 (1966).

[Example 1]
(1) Synthesis of Solid Catalyst Component Precursor 80 L of hexane, 20.6 kg of tetraethoxysilane and 2.2 kg of tetrabutoxytitanium were charged into a 200 L reactor equipped with a nitrogen-substituted stirrer and baffle plate and stirred. Next, 50 L of a dibutyl ether solution of butyl magnesium chloride (concentration: 2.1 mol / L) was added dropwise to the stirred mixture over 4 hours while maintaining the temperature of the reactor at 5 ° C. After completion of the dropwise addition, the mixture was stirred at 5 ° C. for 1 hour and further at 20 ° C. for 1 hour and filtered. The obtained solid was washed with 70 L of toluene three times, and 63 L of toluene was added to form a slurry. A part of the slurry was collected, the solvent was removed, and drying was performed to obtain a solid catalyst component precursor.
The solid catalyst component precursor contained 1.86% by weight of Ti, 36.1% by weight of OEt (ethoxy group), and 3.0% by weight of OBu (butoxy group).

(2) Solid catalyst component synthesis After replacing the reactor of 210 L with an internal volume equipped with a stirrer with nitrogen, the solid catalyst component precursor slurry synthesized in (1) above was charged into the reactor, and tetrachlorosilane 14. 4 kg and 9.5 kg of di (2-ethylhexyl) phthalate were added and stirred at 105 ° C. for 2 hours. Next, solid-liquid separation was performed, and the obtained solid was repeatedly washed with 90 L of toluene at 95 ° C. three times, and then 63 L of toluene was added. After raising the temperature to 70 ° C., 13.0 kg of TiCl ₄ was added and stirred at 105 ° C. for 2 hours. Next, solid-liquid separation was performed, and the obtained solid was repeatedly washed with 90 L of toluene at 95 ° C. six times, and further washed with 90 L of hexane twice at room temperature, and the washed solid was dried. As a result, 15.2 kg of a solid catalyst component was obtained.
The solid catalyst component contained 0.93% by weight of Ti and 26.8% by weight of di (2-ethylhexyl) phthalate. The specific surface area by the BET method was 8.5 m ² / g.

(3) Ethylene-1-butene slurry polymerization An autoclave with a stirrer with an internal volume of 3 L was sufficiently dried and then evacuated, charged with 500 g of butane and 250 g of 1-butene, and heated to 70 ° C. Next, ethylene was added so that the partial pressure was 1.0 MPa. Polymerization was initiated by injecting 5.7 mmol of triethylaluminum and 10.7 mg of the solid catalyst component obtained in (2) above with argon. Thereafter, polymerization was carried out at 70 ° C. for 180 minutes while keeping the total pressure constant while continuously supplying ethylene.
After the completion of the polymerization reaction, the unreacted monomer was purged to obtain 204 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 amount of catalyst (polymerization activity) was 19100 g polymer / g solid catalyst component, and the bulk density of the polymer powder was 0.38 g / ml. Table 1 shows various physical property values of the obtained polymer.

[Example 2]
(1) Ethylene-1-butene slurry polymerization Polymerization was conducted in the same manner as in Example 1 (3) except that 19.3 mg of the solid catalyst component obtained in Example 1 (2) was used and the polymerization temperature was set to 60 ° C. As a result, 121 g of a polymer having good powder properties was obtained.
The amount of polymer produced per unit amount of catalyst (polymerization activity) was 6270 g polymer / g solid catalyst component, and the bulk density of the polymer powder was 0.39 g / ml. Table 1 shows various physical property values of the obtained polymer.

[Example 3]
(1) Ethylene-1-butene slurry polymerization This was carried out except that 27.5 mg of the solid catalyst component obtained in Example 1 (2) was used and 0.57 mmol of 1,3-dioxolane was added before the solid catalyst component was charged. Polymerization was carried out in the same manner as in Example 1 (3) to obtain 275 g of a polymer having good powder properties.
The amount of polymer produced per unit amount of catalyst (polymerization activity) was 10,000 g polymer / g solid catalyst component, and the bulk density of the polymer powder was 0.42 g / ml. Table 1 shows various physical property values of the obtained polymer.

[Comparative Example 1]
(1) Ethylene-1-butene slurry polymerization In place of 500 g of butane and 250 g of 1-butene, 600 g of butane and 150 g of 1-butene were charged, heated to 70 ° C., and hydrogen was added at a partial pressure of 0.2 MPa. Polymerization was carried out in the same manner as in Example 1 (3) except that 15.2 mg of the solid catalyst component obtained in Example 1 (2) was added to obtain 160 g of a polymer.
The amount of polymer produced per unit amount of catalyst (polymerization activity) was 10500 g polymer / g solid catalyst component, and the bulk density of the polymer powder was 0.37 g / ml. Table 1 shows various physical property values of the obtained polymer. It was inferior in haze and tensile impact strength as compared with a high intrinsic viscosity [η].

[Comparative Example 2]
(1) Synthesis of solid catalyst component A solid catalyst component was obtained according to the catalyst synthesis method of Example 1 of JP-B-5-86803 except that the synthesis scale was 1/960 and the final component was dried under reduced pressure.
The solid catalyst component contained 1.88% by weight of titanium atoms and 14.4% by weight of phthalates. The specific surface area according to the BET method was 330 m ² / g.
(2) Ethylene-1-butene slurry polymerization Using 4.1 mg of the solid catalyst component obtained in (1) above, 0.57 mmol of diphenyldimethoxysilane was charged before charging the solid catalyst component, and the polymerization time was 90 minutes. Polymerization was carried out in the same manner as in Example 1 (3) except that 184 g of a polymer was obtained.
The amount of polymer produced per unit amount of catalyst (polymerization activity) was 45000 g polymer / g solid catalyst component, and the bulk density of the polymer powder was 0.43 g / ml. Table 1 shows various physical property values of the obtained polymer. Compared with the case where a solid catalyst component having a low BET specific surface area was used, the haze and tensile fracture strength were inferior.

[Comparative Example 3]
(1) Synthesis of solid product (a) After replacing a 500 ml separable flask equipped with a stirrer and baffle with nitrogen, 270 ml of hexane, 8.10 ml of tetrabutoxytitanium, and 79.9 ml of tetraethoxysilane were added. To obtain a homogeneous solution. Next, 181.3 ml of a dibutyl ether solution (concentration 2.1 mmol / ml) of n-butylmagnesium chloride was added dropwise over about 2.5 hours while maintaining the temperature in the flask at 20 ° C. After completion of dropping, the mixture was further stirred at 20 ° C. for 1 hour. The obtained slurry was separated into solid and liquid, and washed with 220 ml of toluene three times, and then 220 ml of toluene was added.
A part of the solid product slurry was sampled and subjected to composition analysis. As a result, the solid product was 2.2% by weight of titanium atoms, 37.8% by weight of ethoxy groups, and 4.1% by weight of butoxy groups. Contained.

(2) Synthesis of solid catalyst component After a 100 ml flask equipped with a stirrer, a dropping funnel and a thermometer was replaced with nitrogen, 49.8 ml of the solid product slurry obtained in (1) above was charged and the supernatant liquid was added. 23.3 ml was extracted to make the slurry volume 26.5 ml. The slurry was kept at about 40 ° C., and a mixture of titanium tetrachloride 16.0 ml and dibutyl ether 0.8 ml was added thereto, and a mixture of phthalic acid chloride 1.6 ml and toluene 1.6 ml was added dropwise over 5 minutes. After completion of the dropwise addition, the reaction mixture was stirred at 115 ° C. for 3 hours. Thereafter, solid-liquid separation was performed at the same temperature, and washing was performed 3 times at 115 ° C. with 40 ml of toluene.
After washing, toluene was added to 105 ° C. so that the volume of the slurry was 26.5 ml. Thereto was added a mixture of 0.8 ml of dibutyl ether, 0.45 ml of diisobutyl phthalate and 16 ml of titanium tetrachloride, and the mixture was stirred at 105 ° C. for 1 hour. Thereafter, solid-liquid separation was performed at the same temperature, and washing was performed twice at 105 ° C. with 40 ml of toluene.
Next, toluene was added so that the volume of the slurry was 26.5 ml, and the temperature was adjusted to 105 ° C. Thereto was added a mixture of 0.8 ml of dibutyl ether and 16 ml of titanium tetrachloride, and the mixture was stirred at 105 ° C. for 1 hour. Thereafter, solid-liquid separation was performed at the same temperature, and washing was performed twice at 105 ° C. with 40 ml of toluene.
Furthermore, toluene was added so that the volume of the slurry was 26.5 ml, and the temperature was adjusted to 105 ° C. Thereto was added a mixture of 0.8 ml of dibutyl ether and 16 ml of titanium tetrachloride, and the mixture was stirred at 105 ° C. for 1 hour. Thereafter, solid-liquid separation was performed at the same temperature, and washing was performed three times with 40 ml of toluene at 105 ° C. and three times with 40 ml of hexane at room temperature. This was dried under reduced pressure to obtain 7.05 g of a solid catalyst component.
The solid catalyst component contained 2.25 wt% titanium atom, 10.2 wt% phthalate ester, 0.06 wt% ethoxy group, and 0.14 wt% butoxy group. The specific surface area according to the BET method was 414 m ² / g.

(3) Ethylene-1-butene slurry polymerization Polymerization was carried out in the same manner as in Example 1 (3) except that 4.3 mg of the solid catalyst component obtained in (2) was used and the polymerization time was 60 minutes. 208 g of polymer was obtained.
The amount of polymer produced per unit amount of catalyst (polymerization activity) was 48700 g polymer / g solid catalyst component, and the bulk density of the polymer powder was 0.42 g / ml. Table 1 shows various physical property values of the obtained polymer. Compared with the case of using a solid catalyst component having a low BET specific surface area, the haze, tensile impact strength, and tensile fracture strength were inferior.

[Comparative Example 4]
(1) Ethylene-1-butene slurry polymerization The autoclave was evacuated and charged with hydrogen at a partial pressure of 0.01 MPa, butane 500 g and 1-butene 250 g, and 5.2 mg of the solid catalyst component obtained in Comparative Example 3 (2) The polymerization was carried out in the same manner as in Example 1 (3) except that the polymerization time was 150 minutes, to obtain 281 g of a polymer.
The amount of polymer produced per unit amount of catalyst (polymerization activity) was 54500 g polymer / g solid catalyst component, and the bulk density of the polymer powder was 0.41 g / ml. Table 1 shows various physical property values of the obtained polymer. Compared with the case where a solid catalyst component having a low BET specific surface area was used, the haze and tensile fracture strength were inferior.

Claims (7)

An ultrahigh molecular weight ethylene-α-olefin copolymer obtained by copolymerizing ethylene and α-olefin in the presence of a polymerization catalyst obtained by contacting the following component (A) and component (B): A method for producing an ultrahigh molecular weight ethylene-α-olefin copolymer, wherein the copolymer satisfies the following requirements (a) and (a).
(A) A solid catalyst component containing a titanium atom, a magnesium atom, a halogen atom and an ester compound and having a specific surface area of 80 m ² / g or less by BET method (B) Organoaluminum compound (A) Intrinsic viscosity [η] is 5 ~ 30dl / g
(B) Melting point of 110 to 130 ° C. by differential scanning calorimetry   The ultrahigh molecular weight ethylene according to claim 1, wherein the content of the cold xylene-soluble part (CXS) in the copolymer is 4% by weight or less (provided that the entire copolymer is 100% by weight). -Manufacturing method of alpha-olefin copolymer.   The super catalyst according to claim 1 or 2, wherein the solid catalyst component (A) having an ester compound content of 15 to 50 wt% is used when the total amount of the dried solid catalyst component (A) is 100 wt%. A method for producing a high molecular weight ethylene-α-olefin copolymer.   The method for producing an ultrahigh molecular weight ethylene-α-olefin copolymer according to any one of claims 1 to 3, wherein the ester compound is dialkyl phthalate.   The ultrahigh molecular weight ethylene-α-olefin copolymer according to claim 4, wherein the dialkyl phthalate is a dialkyl phthalate having a total of 9 or more carbon atoms in two alkyl groups bonded to each ester bond. Production method.   6. The solid catalyst component (A) having a titanium atom content of 0.6 to 1.6% by weight when the total amount of the dried solid catalyst component (A) is 100% by weight. The manufacturing method of the ultra high molecular weight ethylene-alpha-olefin copolymer in any one of these. In the presence of the organosilicon compound (i) having the Si—O bond, the solid catalyst component (A) is converted from the titanium compound (ii) represented by the following general formula [I] to the organomagnesium compound (iii). The ultrahigh molecular weight ethylene-α-olefin copolymer according to any one of claims 1 to 6, which is a contact product of a solid component (a), a halogenated compound (b) and a phthalic acid derivative (c) obtained by reduction. A method for producing a polymer.

(In the above general formula [I], a represents a number of 1 to 20, R ² represents a hydrocarbon group having 1 to 20 carbon atoms. X ² is a halogen atom or a carbon atom having 1 to 20 carbon atoms, respectively. Represents a hydrocarbon oxy group, and all X ² may be the same or different.)