JPH06179717A - Production of catalyst component for polymerizing olefin - Google Patents

Abstract

PURPOSE:To provide a catalyst component for the polymerization of olefins, capable of producing high rigidity polyolefins in good yields. CONSTITUTION:(C) A cycloalkene is polymerized in the presence of (A) a solid catalyst component containing the metallocene compound of a metal oxide, magnesium and a transition metal as essential components and (B) an aluminoxane and subsequently brought into contact with (D) a titanium compound to produce the catalyst component for the polymerization of olefins. The cycloalkene includes cyclobutene and cyclopentene.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a catalyst component for olefin polymerization.

[0002]

2. Description of the Related Art Demand for highly crystalline polypropylene produced by using various types of highly stereoregular catalysts has been rapidly increasing in recent years because of its excellent rigidity and heat resistance. However, these properties are still insufficient depending on the purpose of use, and various methods for improving the rigidity have been proposed, but most of them are the methods of performing post-treatment such as adding a nucleating agent to polypropylene. is there. Therefore, the process cost is high, and the appearance of the molded product may be impaired depending on the additive. A method of improving rigidity by a polymerization method without treatment with an additive has been proposed, but the rigidity is insufficient in both cases.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a catalyst component for olefin polymerization capable of producing a highly rigid polyolefin, especially an α-olefin polymer such as polypropylene, in a high yield.

[0004]

As a result of intensive studies, the present inventors have found that a titanium-containing catalyst component containing a cycloalkene polymer obtained by polymerization with a specific catalyst system has the object of the present invention. The present invention has been completed by finding out what can be achieved.

SUMMARY OF THE INVENTION That is, the gist of the present invention is to polymerize cycloalkene in the presence of aluminoxane and a solid catalyst component containing a metal oxide, a metallocene compound of magnesium and a transition metal as essential components, and then contact with a titanium compound. And a method for producing a catalyst component for olefin polymerization.

Catalyst Component The catalyst component of the present invention (hereinafter referred to as component B) is prepared by the above-mentioned method, but a solid catalyst component (hereinafter referred to as a metal catalyst component containing metal oxide, magnesium and a metallocene compound of a transition metal as essential components) , Component A) is usually obtained by contacting a metal oxide, a magnesium compound and a metallocene compound of a transition metal.

(1) Metal Oxide The metal oxide used in the present invention is a group II element of the periodic table of elements.
~ Is an oxide of an element selected from the group of Group IV elements,
For example, B₂O₃, MgO, Al ₂O₃,
SiO₂, CaO, TiO₂, ZnO, ZrO₂, Sn
O₂, BaO, ThO₂Etc. Among these
Also B₂O₃, MgO, Al₂O₃, SiO₂, Ti
O₂, ZrO₂Is desirable, especially SiO₂Is desirable.
Furthermore, complex oxides containing these metal oxides, such as Si
O₂-MgO, SiO₂-Al₂O₃, SiO₂-Ti
O₂, SiO₂-V₂O_Five, SiO₂-Cr₂O₃, S
iO₂-TiO₂-MgO etc. can also be used. These metals
The oxide is usually in powder form. Powder
The shape and size of the resulting olefin polymer
Since it often affects the shape of the
And is desirable. Metal oxides are used to remove poisonous substances.
For the purpose of removal, etc., bake at the highest temperature possible, and
It is desirable to handle it so that it does not come into direct contact with the air.

(2) Magnesium Compound The magnesium compound is represented by the general formula MgR ¹ R ² . In the formula, R ¹ and R ² are the same or different hydrocarbon groups, OR groups (R is a hydrocarbon group), and halogen atoms.
More specifically, the hydrocarbon group of R ¹ and R ² is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and the OR group is R having 1 to 10 carbon atoms Twelve alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups have chlorine as a halogen atom,
Examples include bromine, iodine and fluorine.

Specific examples of these compounds are shown below. In the chemical formulas, Me: methyl, Et: ethyl, Pr: propyl, Bu: butyl, He: hexyl, Oct: octyl, Ph: phenyl, cyHe: cyclohexyl, respectively. Show. MgMe ₂ , MgEt ₂ , Mgi-P
r ₂ , MgBu ₂ , MgHe ₂ , MgOct ₂ , MgE
tBu, MgPh ₂ , MgcyHe ₂ , Mg (OMe)
₂ , Mg (OEt) ₂ , Mg (OBu) ₂ , Mg (OH
e) ₂ , Mg (OOct) ₂ , Mg (OPh) ₂ , Mg
(OcyHe) ₂ , EtMgCl, BuMgCl, He
MgCl, i-BuMgCl, t-BuMgCl, Ph
MgCl, PhCH ₂ MgCl, EtMgBr, BuM
gBr, PhMgBr, BuMgI, EtMgCl, B
uOMgCl, HeOMgCl, PhOMgCl, Et
OMgBr, BuOMgBr, EtOMgI, MgCl
₂ , MgBr ₂ , MgI ₂ .

The above magnesium compound can also be prepared from metallic magnesium or other magnesium compounds. As an example thereof, metal magnesium, a halogenated hydrocarbon and an alkoxy group-containing compound represented by the general formula X _n M (OR) _mn [wherein X is a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, M Is a boron, carbon, aluminum, silicon or phosphorus atom, R is a hydrocarbon group having 1 to 20 carbon atoms, m is a valence of M, and m> n ≧ 0.
Indicates. ] The method of making it contact is mentioned. Examples of the hydrocarbon group represented by X and R in the general formula of the alkoxy group-containing compound include methyl (Me), ethyl (Et), propyl, (P
r), i-propyl (i-Pr), butyl (Bu), i
Alkyl groups such as -butyl (i-Bu), hexyl (He), octyl (Oct), cyclohexyl (cyH)
e), cycloalkyl groups such as methylcyclohexyl, alkenyl groups such as allyl, propenyl and butenyl, aryl groups such as phenyl (Ph), tolyl and xylyl groups, aralkyl such as phenethyl and 3-phenylpropyl, and the like. Among these, an alkyl group having 1 to 10 carbon atoms is particularly desirable. Specific examples of the alkoxy group-containing compound will be given below.

Compounds where M is carbon C (OR)_FourIncluded in C (OMe)_Four, C (OE
t)_Four, C (OPr) _Four, C (OBu)_Four, C (Oi-
Bu)_Four, C (OHe)_Four, C (OOct)_Four: Formula X
C (OR)₃HC (OMe) contained in₃, HC (OE
t)₃, HC (OPr)_3,HC (OBu)₃, HC
(OHe)₃, HC (OPh)₃MeC (OM
e)₃, MeC (OEt)₃, EtC (OMe)₃ , E
tC (OEt)₃, CyHeC (OEt)₃, PhC
(OMe)₃, PhC (OEt)₃, CH₂ClC (O
Et)₃, MeCHBrC (OEt)₃, MeCHCl
C (OEt) ₃; ClC (OMe)₃, ClC (OE
t)₃, ClC (Oi-Bu)₃, BrC (OE
t)₃Formula X₂C (OR)₂Included in MeCH (O
Me)₂, MeCH (OEt)₂, CH₂(OM
e)₂, CH₂(OEt)₂, CH₂ClCH (OE
t)₂, CHCl₂CH (OEt)₂, CCl₃CH
(OEt)₂, CH ₂BrCH (OEt)₂, PhCH
(OEt)₂.

Compound when M is silicon Si (OMe) ₄ , Si contained in the formula Si (OR) ₄
(OEt) ₄ , Si (OBu) ₄ , Si (Oi-Bu)
₄ , Si (OHe) ₄ , Si (OOct) ₄ , Si (O
Ph) ₄ : HSi (O contained in the formula XSi (OR) ₃
Et) ₃ , HSi (OBu) ₃ , HSi (OHe) ₃ ,
HSi (OPh) ₃ ; MeSi (OMe) ₃ , MeSi
(OEt) ₃ , MeSi (OBu) ₃ , EtSi (OE
t) ₃ , PhSi (OEt) ₃ , EtSi (OP
h) ₃ ; ClSi (OMe) ₃ , ClSi (OE
t) ₃ , ClSi (OBu) ₃ , ClSi (OP
h) ₃ , BrSi (OEt) ₃ ; Formula X ₂ Si (OR)
₂ contained in Me ₂ Si (OMe) ₂ and Me ₂ Si (O
Et) ₂ , Et ₂ Si (OEt) ₂ ; MeClSi (O
Et) ₂ ; CHCl ₂ SiH (OEt) ₂ ; CCl ₃ S
iH (OEt) ₂ ; MeBeSi (OEt) ₂ : X ₃ S
Me ₃ SiOMe, Me ₃ SiOE contained in iOR
t, Me ₃ SiOBu, Me ₃ SiOPh, Et ₃ Si
OEt, Ph ₃ SiOEt.

Compound in which M is boron B (OEt) ₃ , B (OB) included in the formula B (OR) ₃
u) ₃ , B (OHe) ₃ , B (OPh) ₃ .

Compound when M is Aluminum Al (OMe) ₃ , Al contained in the formula Al (OR) ₃
(OEt) ₃ , Al (OPr) ₃ , Al (Oi-Pr)
₃ , Al (OBu) ₃ , Al (Ot-Bu) ₃ , Al
(OHe) ₃ , Al (OPh) ₃ .

Compounds where M is phosphorus P (OR)₃Included in P (OMe)₃, P (OE
t)₃, P (OBu) ₃, P (OHe)₃, P (OP
h)₃.

Further, as the magnesium compound, a complex with an organic compound of Group II or Group IIIa metal (M) of the periodic table can be used. The complex has the general formula MgR ¹ R
It is represented by ² · n (MR ³ _m ). The metal is aluminum, zinc, calcium or the like, and R ³ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. Further, m represents the valence of the metal M, and n represents the number of 0.1 to 10. Specific examples of the compound represented by MR ³ _m include AlMe ₃ , AlEt ₃ ,
_{Ali-Bu 3, AlPh 3,} ZnMe 2, ZnE
t ₂ , ZnBu ₂ , ZnPh ₂ , CaEt ₂ , CaPh
₂ etc.

(3) Metallocene Compound of Transition Metal As the metallocene compound of transition metal, a compound of the following general formula can be given as an example. General formula (I):

[Chemical 1]In the above formula, M is titanium, zirconium or hafnium.
Mu atom. R¹Is a divalent hydrocarbon having 2 to 20 carbon atoms
A divalent substituent containing an elementary group or a silicon atom, R²And R³Is
Cycloalkagenenyl having 4 to 20 carbon atoms which are the same or different
Group, X¹And X ²Are the same or different carbon numbers 1-10
It is an alkyl group or a halogen atom.

The divalent hydrocarbon group for R ¹ has the formula --C
an alkylene group represented by _n H _2n- (provided that n = 2 to 10), a formula

[Chemical 2] (However, R ⁴ and R ⁵ are the same or different and each represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group or an aryl group.). The divalent substituent containing a silicon atom is represented by the formula:

[Chemical 3] (However, R ⁶ and R ⁷ are the same or different and each represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group or an aryl group.).

As a concrete example of R ¹ ,

[Chemical 4] Etc.

Examples of the alkagenyl group for R ² and R ³ include cyclopentagenyl, methylcyclopentaenyl, dimethylcyclopentaenyl, trimethylcyclopentagenyl, tetramethylcyclopentagenyl,
Examples thereof include ethylcyclopentaenyl, indenyl, tetrahydroindenyl and fluorenyl groups.

Examples of the alkyl group of X ¹ and X ² include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl and the like. Examples of the halogen atom include chlorine, bromine, iodine and the like.

The following are examples of the metallocene compound of the transition metal. In the following, Cp represents a cyclopentaenyl group, Ind represents an indenyl group, and Me represents a methyl group. or,

[Chemical 5]Are shown respectively. Ethylene Ind₂ZrCl₂, SiM
e₂Ind₂ZrCl₂, Ethylene (tetrahydro In
d)₂ZrCl₂, CMe₂(Tetrahydro Ind)₂
ZrCl ₂, Ethylene (methyl Cp)₂ZrCl₂, S
iMe₂(Methyl Cp)₂ZrCl₂, Ethylene Ind
₂HfCl₂, Ethylene (tetrahydro Ind)₂Cl
₂, SiMe₂(Methyl Cp)₂HfCl₂, SiPh
₂(Methyl Cp)₂HfCl₂, Ethylene (tetrahydr
(Ind)₂TiCl₂.

(4) Aluminoxane Aluminoxane is represented by the following general formula (II):

[Chemical 6] And / or the following general formula (III),

[Chemical 7] (R represents a hydrocarbon group having 1 to 8 carbon atoms) and can be usually produced by reacting an organoaluminum compound of the general formula AlR ₃ with water.

Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, triphenylaluminum, etc. Among them, trimethylaluminum is particularly preferable. As the water to be reacted with the organoaluminum compound, in addition to ordinary water, water of crystallization such as iron sulfate and copper sulfate can be used.

(5) Titanium Compound The titanium compound is a compound of divalent, trivalent, and tetravalent titanium. Examples thereof include titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, trichlorobutoxytitanium, and dichlorotitanium. Examples thereof include rudiethoxy titanium, dichlorodibutoxy titanium, dichlorodiphenoxy titanium, chlorotriethoxy titanium, chlortributoxy titanium, tetrabutoxy titanium and titanium trichloride. Among these, tetravalent titanium halides such as titanium tetrachloride, trichloroethoxy titanium, dichlorodibutoxy titanium, and dichlorodiphenoxy titanium are preferable, and titanium tetrachloride is particularly preferable.

When the component A is prepared, the order of contacting the metal oxide (component 1), the magnesium compound (component 2) and the metallocene compound of the transition metal (component 3) is arbitrary, but is particularly desirable. This is a method of contacting in that order and in the presence of an inert medium.

As the inert medium, saturated aliphatic hydrocarbons such as hexane, heptane and octane, saturated alicyclic hydrocarbons such as cyclopentane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene can be used. .

The contact of component 1, component 2 and component 3 is carried out at -50 ° C to 200 ° C for 0.2 to 100 hours, preferably 0 ° C to 15 ° C for 0.5 to 20 hours, respectively. The contact ratio of the component 2 is 0.01 per mol of the component 2.
-10 mol, component 3 is 0.01 mol or more, preferably 0.1-40 mol, per 1 mol of the component. The component A can be washed with the above-mentioned inert medium, if necessary.

In the present invention, the cycloalkene is then polymerized (hereinafter referred to as prepolymerization) by combining the component A thus obtained with the aluminoxane (component 4). The cycloalkene that can be used has 4 to 20 carbon atoms, and specific examples thereof include cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, norbornene, bicyclooctene and the like. The prepolymerization is to polymerize the cycloalkene so that the resulting polymer occupies 10 to 90% by weight in the component B, which is usually in the presence of the above-mentioned inert medium.
It is carried out at 100 to + 150 ° C. for 0.1 to 100 hours.

The amounts of the component A and the component 4 used in the prepolymerization are 1 × 10 ^{−5 to} 0.01 mol, preferably 1 ×, of the component A in the component A as the component 3 in 1 mol of the cycloalkene.
10 ^{−4 to} 5 × 10 ⁻³ mol, Component 4 is 1 × 10 ^{−3 to} 0.1
The amount is preferably 5 × 10 ^{−3 to} 0.01 mol. In addition, the component 4 is 1 to 1 per 1 mol of the component 3 in the component A.
000 mol, preferably 5 to 200 mol is used. The solid component (solid component I) obtained by prepolymerizing the component A can be washed with an inert medium if necessary.

The present invention then comprises contacting solid component I with a titanium compound (component 5) to form component B. At this time, it is also possible to contact with the electron donating compound (Component 6) by the following method. Solid component I, component 5 and component 6 are contacted in that order. After contacting solid component I with component 6, component 5 is contacted. Solid component I, component 5 and component 6 are contacted simultaneously. Also, ingredient 4
It is also possible to contact with a halogen-containing compound before using, and the method is often effective.

Examples of the electron-donating compound include carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid halides, alcohols, ethers, ketones, amines, amides, nitriles, aldehydes,
Examples thereof include alcoholates, phosphorus, arsenic and antimony compounds bonded to an organic group through carbon or oxygen, phosphoamides, thioethers, thioesters, carbonic acid esters and the like. Of these, carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid halides, alcohols and ethers are preferably used.

Specific examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid, methacrylic acid, crotonic acid, and other aliphatic monocarboxylic acids, and malonic acid. , Succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid and other aliphatic dicarboxylic acids, tartaric acid and other aliphatic oxycarboxylic acids, cyclohexanemonocarboxylic acid, cyclohexenemonocarboxylic acid, cis-1,2- Cyclohexanedicarboxylic acid, cis-4-methylcyclohexene-1,
Alicyclic carboxylic acids such as 2-dicarboxylic acid, benzoic acid, toluic acid, anisic acid, aromatic monocarboxylic acids such as p-tertiary butyl benzoic acid, naphthoic acid and cinnamic acid, phthalic acid, isophthalic acid, Terephthalic acid, naphthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, pyromellitic acid,
Examples thereof include aromatic polycarboxylic acids such as mellitic acid. As the carboxylic acid anhydride, acid anhydrides of the above carboxylic acids can be used.

As the carboxylic acid ester, mono- or polyvalent esters of the above-mentioned carboxylic acids can be used, and specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, propyl pivalate, pivalic acid. Isobutyl, ethyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, diisobutyl malonate, diethyl succinate, dibutyl succinate, diisobutyl succinate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate, Diisobutyl adipate, dibutyl sebacate, diisobutyl sebacate, diethyl maleate, dibutyl maleate, diisobutyl maleate,
Monomethyl fumarate, diethyl fumarate, diisobutyl fumarate, diethyl tartrate, dibutyl tartrate, diisobutyl tartrate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, methyl p-toluate, p
-Ethyl tertiary butyl benzoate, ethyl p-anisate,
Ethyl α-naphthoate, isobutyl α-naphthoate, ethyl cinnamate, monomethyl phthalate, monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di2-ethylhexyl phthalate, phthalic acid Diallyl, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate, tetramethyl pyromelliticate, tetraethyl pyromelliticate, tetrabutyl pyromelliticate. Etc.

As the carboxylic acid halide, acid halides of the above carboxylic acids can be used.
Specific examples thereof include acetic acid chloride, acetic acid bromide, acetic acid iodide, propionic acid chloride, butyric acid chloride,
Butyric acid bromide, butyric acid iodide, pivalic acid chloride, pivalic acid bromide, acrylic acid chloride, acrylic acid bromide, acrylic acid iodide, methacrylic acid chloride, methacrylic acid bromide, methacrylic acid iodide, crotonic acid chloride, malonic acid chloride, malonic acid bromide, Succinic acid chloride, succinic acid bromide,
Glutaric acid chloride, glutaric acid bromide, adipic acid chloride, adipic acid bromide, sebacic acid chloride,
Sebacic acid bromide, maleic acid chloride, maleic acid bromide, fumaric acid chloride, fumaric acid bromide, tartaric acid chloride, tartaric acid bromide, cyclohexanecarboxylic acid chloride, cyclohexanecarboxylic acid bromide, 1-
Cyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid bromide, benzoyl chloride,
Benzoyl bromide, p-toluic acid chloride, p-toluic acid bromide, p-anisic acid chloride, p-anisic acid bromide, α-naphthoic acid chloride, cinnamic acid chloride,
Examples thereof include cinnamic acid bromide, phthalic acid dichloride, phthalic acid dibromide, isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, and naphthalic acid dichloride. Also, a monoalkyl halide of a dicarboxylic acid such as adipic acid monomethyl chloride, maleic acid monoethyl chloride, maleic acid monomethyl chloride, phthalic acid butyl chloride may be used.

Alcohols are represented by the general formula ROH. In the formula, R is alkyl having 1 to 12 carbons, alkenyl, cycloalkyl, aryl or aralkyl. Specific examples thereof include methanol, ethanol,
Propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, octanol, 2-ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, cresol, xylenol, ethylphenol, isopropylphenol, p-tertiarybutylphenol,
Examples include n-octylphenol. Ethers are represented by the general formula ROR ¹ . In the formula, R and R ¹ are alkyl having 1 to 12 carbons, alkenyl, cycloalkyl,
It is aryl or aralkyl, and R and R ¹ may be the same or different. Specific examples thereof include diethyl ether,
Diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether,
Examples include anisole and ethyl phenyl ether.

As the halogen-containing compound, halogenated hydrocarbons, halogen-containing alcohols, silicon halide compounds having a hydrogen-silicon bond, Group IIa, IVa of the periodic table.
Examples thereof include halides of Group III and Group Va elements (hereinafter referred to as metal halides).

The halogenated hydrocarbon has 1 to 10 carbon atoms.
Twelve saturated or unsaturated aliphatic, cycloaliphatic and aromatic hydrocarbon mono- and polyhalogen substitutes. Specific examples of those compounds include, in aliphatic compounds, methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, and tetrachloride. Carbon iodide, ethyl chloride, ethyl bromide, ethyl iodide, 1,2-
Dichloroethane, 1,2-dibromoethane, 1,2-diiodoethane, methylchloroform, methylbromoform, methyliodoform, 1,1,2-trichloroethylene, 1,1,2-tribromoethylene, 1,1,2,
2-tetrachloroethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1,2-dichloropropane, hexachloropropylene, octachloropropane, decabromobutane,
Chlorinated paraffins are chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentadiene and hexachlorocyclohexane for alicyclic compounds, and chlorobenzene, bromobenzene, o- for aromatic compounds.
Examples thereof include dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, hexabromobenzene, benzotrichloride and p-chlorobenzotrichloride. These compounds may be used alone or in combination of two or more.

As the halogen-containing alcohol, any one or two or more hydrogen atoms other than hydroxyl groups in a mono- or polyhydric alcohol having one or two or more hydroxyl groups in one molecule are substituted with halogen atoms. Means a compound. Examples of the halogen atom include chlorine, bromine, iodine and fluorine atoms, and chlorine atom is preferable.

Examples of these compounds are 2-chloroethanol, 1-chloro-2-propanol, 3-chloro-1-propanol, 1-chloro-2-methyl-2-propanol, 4-chloro-1-butanol, 5-chloro-1-pentanol, 6-chloro-1-hexanol,
3-chloro-1,2-propanediol, 2-chlorocyclohexanol, 4-chlorobenzhydrol,
(M, o, p) -chlorobenzyl alcohol, 4-chlorocatechol, 4-chloro- (m, o) -cresol,
6-chloro- (m, o) -cresol, 4-chloro-
3,5-dimethylphenol, chlorohydroquinone,
2-benzyl-4-chlorophenol, 4-chloro-1
-Naphthol, (m, o, p) -chlorophenol, p
-Chlor-α-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6-chlorothymol, 4-
Chlorresorcin, 2-bromoethanol, 3-bromo-1-propanol, 1-bromo-2-propanol,
1-bromo-2-butanol, 2-bromo-p-cresol, 1-bromo-2-naphthol, 6-bromo-2-
Naphthol, (m, o, p) -bromophenol, 4-
Bromresorcin, (m, o, p) -fluorophenol, p-iodophenol: 2,2-dichloroethanol, 2,3-dichloro-1-propanol, 1,3-dichloro-2-propanol, 3- Chlor-1- (α-chloromethyl) -1-propanol, 2,3-dibromo-
1-propanol, 1,3-dibromo-2-propanol, 2,4-dibromophenol, 2,4-dibromo-
1-naphthol: 2,2,2-trichloroethanol,
1,1,1-trichloro-2-propanol, β, β,
β-trichloro-tert-butanol, 2,3,4-
Trichlorophenol, 2,4,5-trichlorophenol, 2,4,6-trichlorophenol, 2,4,6
-Tribromophenol, 2,3,5-tribromo-2
-Hydroxytoluene, 2,3,5-tribrom-4-
Hydroxytoluene, 2,2,2-trifluoroethanol, α, α, α-trifluoro-m-cresol,
2,4,6-Triiodophenol: 2,3,4,6-
Tetrachlorophenol, tetrachlorohydroquinone, tetrachlorobisphenol A, tetrabromobisphenol A, 2,2,3,3-tetrafluoro-1-
Propanol, 2,3,5,6-tetrafluorophenol, tetrafluororesorcin and the like can be mentioned.

As the silicon halide compound having a hydrogen-silicon bond, HSiCl ₃ , H ₂ SiCl ₂ , H ₃ S may be used.
iCl, HCH ₃ SiCl ₂ , HC ₂ H ₅ SiCl ₂ ,
_{H (t-C 4 H 9} ) SiCl 2, HC 6 H 5 SiCl
_{2, H (CH 3) 2} SiCl, H (i-C 3 H 7) 2 S
_{iCl, H 2 C 2 H 5} SiCl, H 2 (n-C 4 H 9)
SiCl, H ₂ (C ₆ H ₄ CH ₃ ) SiCl, HSiC
1 (C ₆ H ₅ ) _{2 and the} like.

As the metal halide, B, Al, Ga,
In, Tl, Si, Ge, Sn, Pb, As, Sb, B
Examples thereof include chlorides, fluorides, bromides, and iodides of i, particularly BCl ₃ , BBr ₃ , BI ₃ , AlCl ₃ , and AlBr.
₃ , GaCl ₃ , GaBr ₃ , InCl ₃ , TlC
l ₃ , SiCl ₄ , SnCl ₄ , SbCl ₅ , SbF ₅
Etc. are suitable.

The solid component I and the component 5, and optionally the component 6 and the halogen-containing compound which can be brought into contact with each other are mixed and stirred in the presence or absence of an inert medium or mechanically. It is made by co-milling.
Desirably, a method of mixing and stirring in the presence of the above-mentioned inert medium. The contact can be performed under heating at 40 to 150 ° C.

The contact ratio of each component is such that the component 5 is 0.1 g mol or more, preferably 1 to 50 g mol or more, and the component 6 is 0.
It is 005-10 grammol. The component B prepared as described above may be washed with the above-mentioned inert medium, if necessary, and further dried.

Although the component B is obtained as described above, the component B
Usually contains a polymer of cycloalkene, contains a metal oxide, magnesium, titanium and halogen as essential components and an electron-donating compound as an optional component. 90% by weight, metal oxide 0.3 to 80% by weight, magnesium 0.1 to 2
0 wt%, titanium 0.05-9 wt%, halogen 0.0
It is 4 to 60% by weight, and the electron donating compound is 0.1 to 5% by weight.

Component B, which is the catalyst component obtained by the method of the present invention, is an organometallic compound, and if necessary, in combination with an electron donating compound, homopolymerization of an olefin having 2 to 10 carbon atoms or another monoolefin. Olefin or C3 ~ 1
It is useful as a catalyst for copolymerization with 0 diolefins, but is particularly an α-olefin having 3 to 8 carbon atoms, such as propylene, 1-butene, 4-methyl-1-pentene,
It exhibits extremely excellent performance as a catalyst for homopolymerization of 1-hexene or the like or for random and block copolymerization with the above α-olefins and / or ethylene.

The organometallic compound used in combination with Component B (hereinafter referred to as Component C) is an organic compound of Group I to Group III metal of the periodic table. As component C, organic compounds of lithium, magnesium, calcium, zinc and aluminum can be used. Among these,
Organoaluminum compounds are preferred. Organoaluminum compounds that can be used include those represented by the general formula R _n AlX
_3-n (wherein R is an alkyl group or an aryl group, X is a halogen atom, an alkoxy group or a hydrogen atom, and n is 1 ≦
It is an arbitrary number in the range of n ≦ 3. ), For example, a trialkylaluminum, a dialkylaluminum monohalide, a monoalkylaluminum dihalide, an alkylaluminum sesquihalide, a dialkylaluminum monoalkoxide, a dialkylaluminum monohydride and the like having 1 to 18 carbon atoms.
Particularly preferred are alkylaluminum compounds, preferably C2 to C6 or mixtures or complex compounds thereof. Specifically, trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trialkyl aluminum such as trihexyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide,
Dialkyl aluminum monohalide such as diisobutyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, ethyl aluminum dibromide, ethyl aluminum diiodide, monoalkyl aluminum dihalide such as isobutyl aluminum dichloride, ethyl aluminum sesquichloride, etc. Alkyl aluminum sesquihalide, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, diisobutyl aluminum phenoxide and other dialkyl aluminum monoalkoxides, dimethyl aluminum hydride, diethyl ether Aluminum hydride, dipropyl aluminum hydride, dialkyl aluminum hydride such as diisobutyl aluminum hydride. Among these, trialkylaluminums, particularly triethylaluminum and triisobutylaluminum are preferable. Further, these trialkylaluminums are other organoaluminum compounds, for example, industrially readily available diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride or a mixture or complex compound thereof. Etc. can be used together.
Further, an organoaluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom can also be used. Examples of such compounds include

[Chemical 8] Etc. can be illustrated.

Examples of organic compounds of metals other than aluminum metal include diethylmagnesium, ethylmagnesium chloride, diethylzinc and the like, and LiAl (C
Examples thereof include compounds such as ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

The electron-donating compound which may be used in combination with Component B and Component C as required (hereinafter referred to as Component D) is a compound which may be used when Component B is prepared (Component 5). Other than the above, an organic silicon compound or an electron-donating compound containing an electron containing a hetero atom such as nitrogen, sulfur, oxygen, phosphoric acid or phosphorus can be used.

The organosilicon compound may be an organosilicon compound having a Si--O--C bond or a Si--N--C bond, preferably a compound having a Si--O--C bond. Such compounds include those represented by the general formula R _n Si
(OR ¹ ) _4-n [wherein R represents a hydrocarbon group or a halogen atom, R ¹ represents a hydrocarbon group, and 0 ≦ n ≦ 3 is shown. ] The compound represented by these is mentioned. Examples of the hydrocarbon group represented by R in the above general formula include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkadienyl group, a cycloalkenyl group and a cycloalkazinyl group. Examples of the halogen atom of R include chlorine, bromine, iodine and the like. Examples of the hydrocarbon group for R ¹ include an alkyl group, a cycloalkyl group, an aryl group and an alkenyl group. Furthermore, n hydrocarbons of R and (4-
n) The hydrocarbon groups of R ¹ of OR ¹ may be the same or different.

Specific examples thereof include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, tetraphenoxysilane, tetra (p-methylphenoxy) silane, tetrabenzyloxysilane, methyltrimethoxysilane and methyl. Triethoxysilane, methyltributoxysilane, methyltriphenoxysilane, ethyltriethoxysilane, ethyltriisobutoxysilane, ethyltriphenoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane, butyltriphenoxysilane, Isobutyltriisobutoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, phenyltriethoxysilane, dimethyldiisopropoxysilane, dimethyldi Toxysilane, dimethyldihexyloxysilane, dimethyldiphenoxysilane, diethyldiethoxysilane, diethyldiisobutoxysilane, diethyldiphenoxysilane, dibutyldiisopropoxysilane, dibutyldibutoxysilane, dibutyldiphenoxysilane, diisobutyldiethoxysilane, diisobutyldiisobu Toxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, dibenzyldiethoxysilane, divinyldiphenoxysilane, diallyldipropoxysilane, diphenyldiallyloxysilane, methylphenyldimethoxysilane, chlorophenyldiethoxysilane and the like. To be

Specific examples of the electron-donating compound containing a hetero atom include compounds containing a nitrogen atom:
6,6-Tetramethylpiperidine, 2,6-Dimethylpiperidine, 2,6-Diethylpiperidine, 2,6-Diisopropylpiperidine, 2,6-Diisobutyl-4-methylpiperidine, 1,2,2,6,6- Pentamethylpiperidine, 2,2,5,5-tetramethylpyrrolidine,
2,5-dimethylpyrrolidine, 2,5-diethylpyrrolidine, 2,5-diisopropylpyrrolidine, 1,2,
2,5,5-pentamethylpyrrolidine, 2,2,5-trimethylpyrrolidine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,6-diisopropylpyridine, 2,6-diisobutylpyridine, 1, Two
4-trimethylpiperidine, 2,5-dimethylpiperidine, methyl nicotinate, ethyl nicotinate, nicotinic acid amide, benzoic acid amide, 2-methylpyrrole, 2,5
-Dimethylpyrrole, imidazole, toluic acid amide, benzonitrile, acetonitrile, aniline, paratoluidine, orthotoluidine, metatoluidine, triethylamine, diethylamine, dibutylamine, tetramethylenediamine, tributylamine, etc., as a compound containing a sulfur atom, thiol Phenol, thiophene,
Ethyl 2-thiophenecarboxylate, Ethyl 3-thiophenecarboxylate, 2-Methylthiophene, Methylmercaptan, Ethylmercaptan, Isopropylmercaptan, Butylmercaptan, Diethylthioether, Diphenylthioether, Methylbenzenesulfonate, Methylsulfite, Ethylsulfite Etc., as a compound containing an oxygen atom, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran,
2-methyltetrahydrofuran, 2,2,5,5-tetraethyltetrahydrofuran, 2,2,5,5-tetramethyltetrahydrofuran, 2,2,6,6-tetraethyltetrahydropyran, 2,2,6,6-tetrahydropyran , Dioxane, dimethyl ether, diethyl ether, dibutyl ether, diisoamyl ether, diphenyl ether, anisole, acetophenone, acetone, methyl ethyl ketone, acetylacetone, o-tolyl-t-butyl ketone, methyl-2,6-di-t-butylphenyl ketone, 2- Ethyl fullerate, isoamyl 2-furate, methyl 2-furate, propyl 2-furate and the like are compounds containing a phosphorus atom, such as triphenylphosphine, tributylphosphine, triphenylphosphite and triben. Ruhosufaito, diethyl phosphate, and diphenyl phosphate and the like.

The polymerization reaction of the α-olefin with the polymerization catalyst in which the component B and the component C and optionally the component D are combined may be in the gas phase or the liquid phase. When the polymerization is carried out in the liquid phase, It can be carried out in an inert hydrocarbon such as normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene and in a liquid monomer. The polymerization temperature is usually -80 ° C to + 150 ° C, preferably 40 to 120 ° C. The polymerization pressure may be, for example, 1 to 60 atmospheres. Further, the molecular weight of the obtained polymer is controlled by the presence of hydrogen or other known molecular weight regulator. Also, in copolymerization α-
The amount of other olefin copolymerized with the olefin is α-
Usually up to 30% by weight, especially 0.3 to 1 relative to olefin
It is selected in the range of 5% by weight. The polymerization reaction is carried out by a continuous or batch reaction, and the conditions therefor may be those usually used. Further, the copolymerization reaction may be carried out in one step or in two or more steps.

The proportion of component B, component C and component D used is such that component C is 1 to 1 gram atom of titanium in component B.
2,000 g mol, preferably 20 to 500 g mol, and component D is 0.001 to 10 mol, preferably 0.01 to 1 mol, per mol of component C.

The polymerization reaction of the olefin may be in a gas phase or a liquid phase. When the polymerization is carried out in a liquid phase, normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, It can be carried out in an inert hydrocarbon such as xylene and in a liquid monomer. The polymerization temperature is usually -80 ° C to + 150 ° C, preferably 40 to 120 ° C. The polymerization pressure may be, for example, 1 to 60 atmospheres. Further, the molecular weight of the obtained polymer is controlled by the presence of hydrogen or other known molecular weight regulator. Further, the amount of the other olefin to be copolymerized with the α-olefin in the copolymerization is usually selected in the range of up to 30% by weight, particularly 0.3 to 15% by weight based on the α-olefin. The polymerization reaction by the catalyst system according to the present invention is carried out as a continuous or batch reaction, and the conditions may be those usually used. Further, the copolymerization reaction may be carried out in one step or in two or more steps.

[0056]

EXAMPLES The present invention will be specifically described with reference to examples and application examples. The percentages (%) in the examples are by weight unless otherwise specified. Polymer physical properties were measured by adding BHT (2,6-ditertiarybutyl-4) to the polymer powder.
-Methylphenol) 0.18% by weight, DSTDP
(Distearyl thiodipropionate) 0.08% by weight, IRGANOX 1010 [tetrakis- {methylene- (3,5-ditertiarybutyl-4-hydroxyhydro-cinnamate) methane}] 0.04% by weight, calcium stearate After adding 0.06% by weight of each of them to form pellets by melt-kneading, a test piece was prepared by injection molding. Flexural modulus: JIS K
According to 7203-1982.

Example 1 Preparation of Component A A 200 ml flask equipped with a dropping funnel and a stirrer was replaced with nitrogen gas. In this flask, silicon oxide (D
2.5 g and 20 ml of n-heptane were put into a product of AVISON, trade name G-952) baked in a nitrogen stream at 200 ° C. for 2 hours and further at 700 ° C. for 5 hours. Further, 10 ml of a 20% n-heptane solution of n-butylethylmagnesium (hereinafter referred to as BEM) (trade name: MAGALA BEM, manufactured by Texas Alkyls Co.) was added,
The mixture was stirred at 90 ° C for 1 hour. After the above suspension was cooled to 0 ° C., 5.6 g of tetraethoxysilane was added thereto in an amount of 10 ml of n.
-The solution dissolved in heptane was added dropwise from the dropping funnel over 30 minutes. After the dropping was completed, the temperature was raised to 50 ° C. over 2 hours, and stirring was continued at 50 ° C. for 1 hour. After the reaction was completed, the supernatant was removed by decantation, and the resulting solid was washed with 30
The mixture was washed with ml of n-heptane at room temperature, and the supernatant was removed by decantation. This washing treatment with n-heptane was further performed 4 times. To the above solid, 25 ml of n-heptane was added to make a suspension, and 2,2,2-
A solution prepared by dissolving 4.0 g of trichloroethanol in 5 ml of n-heptane was added dropwise from the dropping funnel over 15 minutes at 25 ° C. After completion of dropping, stirring was continued at 25 ° C. for 30 minutes. After completion of the reaction, the mixture was washed twice with 30 ml of n-heptane and three times with 30 ml of toluene at room temperature. When the obtained solid component was analyzed, it was found that SiO
₂ , containing magnesium and chlorine.

In addition to the above solid components, ethylene bisindenyl zirconium dichloride (ethylene Ind ₂ ZrC
100 ml of a 1.0 mol / liter toluene solution of 1 ₂ )
The mixture was added and stirred at 50 ° C. for 2 hours to obtain the obtained solid (component A).
Was washed twice with 100 ml each of n-hexane.

Preparation of component B To the above washed component A, 10 ml of n-hexane was added,
Cooled to 0 ° C. 1.0 mol of methylaluminoxane /
10 g of n-hexane solution of liter was added, 35 g of cyclopentene was liquefied and dissolved, and cyclopentene was polymerized at 0 ° C. for 5 hours. The obtained solid is n-hexane 1
It was washed 4 times with 00 ml each.

To the solid obtained above, 5 ml of n-heptane
And 20 ml of titanium tetrachloride are added, the temperature is raised to 90 ° C, and n-
Di-n-butyl phthalate dissolved in 2.5 ml heptane.
3g was added over 5 minutes. Then, the temperature was raised to 115 ° C. and the reaction was performed for 2 hours. After the temperature was lowered to 90 ° C, the supernatant was removed by decantation, and the mixture was washed with 2 ml of n-heptane (35 ml).
Washed twice. Further, 8 ml of n-heptane and 20 ml of titanium tetrachloride were added and reacted at 115 ° C for 2 hours. After completion of the reaction, the obtained solid substance was washed with 30 ml of n-hexane 8 times at room temperature. Then, it was dried under reduced pressure at room temperature for 1 hour to obtain 10.4 g of a catalyst component (component B).
As a result of analyzing the obtained component B, the polymer of cyclopentene contained 60.6%, SiO ₂ contained 20.9%, magnesium contained 2.9%, titanium contained 1.2%, and chlorine contained 8.9%. Was.

[0061] EXAMPLE 2 Ethylene instead of ethylene Ind ₂ ZrCl ₂ (tetrahydro Ind) ₂ ZrCl _2, using each of the norbornene instead of cyclopentene, preliminary polymerization temperature 20 ° C.
13.1 g of component B containing 68.7% of a norbornene polymer was prepared in the same manner as in the example except that the above was added.

[0062] Example 3 Ethylene Ind ₂ ethylene instead of ZrCl ₂ Ind ₂
HfCl ₂ was used instead of cyclopentene, and the prepolymerization temperature was −40 ° C.
In the same manner as in Example 1, the polymer of cyclobutene was 64.0.
% Component B1, 11.4 g was prepared.

Comparative Example 1 A catalyst component was obtained in the same manner as in Example 1 except that the contact with ethylene Ind ₂ ZrCl ₂ was not carried out and the step of preliminarily polymerizing cyclopentene using methylaluminoxane was omitted.

Application Example 1 In a 1.5-liter stainless steel autoclave equipped with a propylene polymerization stirrer, 4 ml of an n-heptane solution of triethylaluminum (0.1 mol / liter) and n of diphenyldimethoxysilane were placed in a nitrogen gas atmosphere. -Heptane solution (0.
2 mol (04 mol / l) and mixed for 5 minutes were added. Then, 1 liter of hydrogen gas as a molecular weight control agent and 1 liter of liquid propylene were injected under pressure, and then the reaction system was heated to 70 ° C. After charging 40 mg of the catalyst component obtained in Example 1 to the reaction system, propylene was polymerized for 1 hour. After completion of the polymerization, unreacted propylene was purged to obtain white polypropylene powder. The amount of polypropylene produced (CE) per 1 g of the component B was 9.6 kg. The flexural modulus of the obtained polymer is 16,400 kgf /
It was cm ² .

Application Examples 2 to 4 Propylene was applied in the same manner as in Application Example 1 except that the catalyst components obtained in Examples 2 and 3 and Comparative Example 1 were used in place of the catalyst components obtained in Example 1. Was polymerized. The results are shown in Table 1.

[0066]

[Table 1]

[0067]

INDUSTRIAL APPLICABILITY The catalyst component of the present invention can produce a highly rigid polyolefin, particularly poly α-olefin with a high yield.

[Brief description of drawings]

FIG. 1 is a flowchart showing the steps for preparing a catalyst component of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Hiroyuki Furuhashi 1-3-3 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture Tonen Co., Ltd. Research Institute (72) Tadanao Ohara Nishitsuruokaoka, Nishii-gun, Saitama Prefecture 3-3-1 Tonen Co., Ltd. Research Institute

Claims (1)

[Claims] 1. A catalyst component for olefin polymerization, which comprises polymerizing a cycloalkene in the presence of a solid catalyst component containing a metal oxide compound of a metal oxide, magnesium and a transition metal as essential components and an aluminoxane, and then contacting the cycloalkene with a titanium compound. Manufacturing method.