JPH06128317A - Catalyst component for alpha-olefin polymerization - Google Patents

Abstract

PURPOSE:To provide the title component with which the strength of catalyst particles can be heightened, a polymer having improved stereoregularity can be obtained, high catalytic activity can be maintained, and the deterioration of catalytic performance during storage can be prevented. CONSTITUTION:The component is obtained by prepolymerizing an olefin with a solid ingredient comprising as essential components magnesium, titanium, a halogen, and an electron-donating compound in the presence of an organoaluminum compound and a cycloalkene.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a catalyst component for .alpha.-olefin polymerization.

[0002]

2. Description of the Related Art Catalyst components for .alpha.-olefin polymerization containing magnesium, titanium, halogen and an electron donating compound are known. When the particle strength of the catalyst component is low, the polymer produced by the polymerization is destroyed and pulverized. As a typical method for preventing this, there is so-called prepolymerization in which a catalyst component is brought into contact with an olefin in advance and a polymer produced therein is incorporated into the catalyst component to enhance the strength of the catalyst component particles. Attempts have been made to improve the particle strength and also the stereoregularity of the final poly α-olefin by adding an electron donating compound such as a silicon compound during the prepolymerization.

However, the addition of an electron-donating compound during the prepolymerization usually brings about an effect such as a decrease in the catalytic activity or a deterioration in the performance of the catalyst during storage. Further, as a silicon compound used in the prepolymerization, from the viewpoint of its performance,
A compound having an aromatic group is generally used, but a silicon compound having an aromatic group may be harmful depending on the purpose of use of the polymer.

[0004]

The object of the present invention is to increase the strength of catalyst particles, improve the stereoregularity of the obtained polymer, maintain the high activity of the catalyst, and prevent the performance deterioration of the catalyst during storage. To do.

[0005]

Means for Solving the Problems As a result of intensive studies by the present inventors, by contacting a specific solid component with an olefin in the presence of cycloalkene during prepolymerization, high catalytic activity and stereoregularity can be obtained. The present invention has been completed by finding that a catalyst component capable of polymerizing a high poly α-olefin can be obtained and the object of the present invention can be achieved.

SUMMARY OF THE INVENTION That is, the gist of the present invention is that the presence of (A) a solid component containing magnesium, titanium, a halogen and an electron-donating compound as essential components, (B) an organoaluminum compound and (C) a cycloalkene. Below, it is a catalyst component for α-olefin polymerization which is brought into contact with (D) olefin.

Solid Component Solid component used in the present invention (hereinafter referred to as component A)
Contains magnesium, titanium, a halogen and an electron donating compound as essential components. Such components are usually a magnesium compound, a titanium compound and an electron donating compound, and in the case where each of the above compounds is a compound having no halogen,
It is prepared by contacting each of the halogen-containing compounds.

(1) Magnesium Compound The magnesium compound is represented by the general formula MgR ¹ R ² . In the formula, R ¹ and R ² represent 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 a carbon number. As the halogen atom, 1 to 12 alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups are chlorine, 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, EtOMgCl,
BuOMgCl, HeOMgCl, PhOMgCl, E
tOMgBr, BuOMgBr, EtOMgI, MgC
l _2, MgBr _2, MgI ₂ .

The above-mentioned magnesium compound can be prepared from metallic magnesium or other magnesium compounds when preparing the component A. As an example thereof, a compound containing metal magnesium, a halogenated hydrocarbon and an alkoxy group represented by the general formula X _n M (OR) _mn [wherein X is a hydrogen atom, a halogen atom or a carbon number of 1 to 20]
Hydrocarbon groups, 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. ] The method of making it contact is mentioned. The hydrocarbon groups represented by X and R in the general formula of the alkoxy group-containing compound include methyl (Me), ethyl (Et), propyl (Pr), i-propyl (iP
r), butyl (Bu), i-butyl (i-Bu), hexyl (He), octyl (Oct) and other alkyl groups, cyclohexyl (cyHr), methylcyclohexyl and other cycloalkyl groups, allyl, propenyl, butenyl, etc. Alkenyl group, phenyl (Ph), tolyl, aryl group of xylyl group, phenethyl, aralkyl such as 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.

Compound wherein M is carbon C (OMe) ₄ , C (OE contained in the formula C (OR) ₄
t) ₄ , C (OPr) ₄ , C (OBu) ₄ , C (Oi-
Bu) ₄ , C (OHe) ₄ , C (OOct) ₄ : Formula XC
HC (OMe) ₃ , HC (OE contained in (OR) ₃
t) ₃ , HC (OPr) ₃ , HC (OBu) ₃ , HC
(OHe) ₃ , HC (OPh) ₃ ; MeC (OM
e) ₃ , MeC (OEt) ₃ , EtC (OMe) ₃ , E
tC (OEt) ₃ , cyHeC (OEt) ₃ , PhC
(OMe) ₃ , PhC (OEt) ₃ , CH ₂ ClC (O
Et) ₃ , MeCHBrC (OEt) ₃ ; MeCHCl
C (OEt) ₃ ; ClC (OMe) ₃ , ClC (OE
t) ₃ , ClC (Oi-Bu) ₃ , BrC (OE
t) ₃ ; MeCH (OM included in the formula X ₂ C (OR) ₂
e) ₂ , MeCH (OEt) ₂ , CH ₂ (OMe) ₂ ,
CH ₂ (OEt) ₂ , CH ₂ ClCH (OEt) ₂ , C
HCl ₂ CH (OEt) ₂ , CCl ₃ CH (OE
t) ₂ , CH ₂ BrCH (OEt) ₂ , PhCH (OE
t) 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 (OE contained in the formula XSi (OR) ₃
t) ₃ , HSi (OBu) ₃ , HSi (OHe) ₃ , H
Si (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
Included in Me ₂ Si (OMe) ₂ and Me ₂ Si (OE
t) ₂ , Et ₂ Si (OEt) ₂ ; MeClSi (OE
t) ₂ ; CHCl ₂ SiH (OEt) ₂ ; CCl ₃ Si
H (OEt) ₂ ; MeBrSi (OEt) ₂ : X ₃ Si
Me ₃ SiOMe, Me ₃ SiOEt contained in OR,
Me ₃ SiOBu, Me ₃ SiOPh, Et ₃ SiOE
t, Ph ₃ SiOEt.

Compound in which M is Boron B (OEt) ₃ and B (OB contained in Formula B (OR) ₃
u) ₃ , B (OHe) ₃ , B (OPh) ₃ .

Compound in which 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 .

Compound in which M is Phosphorus P (OMe) ₃ , P (OE) included in Formula P (OR) ₃
t) ₃ , P (OBu) ₃ , P (OHe) ₃ , P (OP
h) ₃ .

Further, the magnesium compound is a periodic table.
Complexes with organic compounds of Group II or Group IIIa metals (M)
Can also be used. The complex has the general formula MgR¹R²
・ N (MR³ _m). As the metal,
Minium, zinc, calcium, etc., R³Has 1 carbon
~ 12 alkyl groups, cycloalkyl groups, aryl
And an aralkyl group. In addition, m is the valence of the metal M
And n represents a number of 0.1 to 10. MR³ _mRepresented by
Specific examples of the compound include AlMe₃, AlEt ₃,
Ali-Bu₃, AlPh₃, ZnMe₂,, ZnEt
₂, ZnBu₂, ZnPh₂, CaEt₂, CaPh₂
Etc.

(2) 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.

(3) Electron-donating compound As the electron-donating compound, carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid halides, alcohols, ethers, ketones, amines,
Examples thereof include amides, nitriles, aldehydes, 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 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 R ⁴ OH. In the formula, R ⁴ is alkyl having 1 to 12 carbons,
Alkenyl, cycloalkyl, aryl and aralkyl. Specific examples thereof include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, octanol, 2-ethylhexanol, cyclohexanol,
Benzyl alcohol, allyl alcohol, phenol,
Examples include cresol, xylenol, ethylphenol, isopropylphenol, p-tertiarybutylphenol, n-octylphenol and the like.

The ethers are represented by the general formula R ⁵ OR ⁶ . In the formula, R ⁵ and R ⁶ are alkyl, alkenyl, cycloalkyl, aryl and aralkyl having 1 to 12 carbon atoms, and R ⁵ and R ⁶ may be the same or different. Specific examples thereof include diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether,
Examples include diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole, ethyl phenyl ether.

The component A is prepared by contacting a magnesium compound (component 1), a titanium compound (component 2) and an electron donating compound (component 3) in that order. After contacting component 1 and component 3, component 2 is contacted. A method such as contacting the components 1, 2 and 3 at the same time can be adopted. It is also possible to contact with the halogen-containing compound before contacting with component 2.

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

The halogenated hydrocarbon has 1 to 1 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 include 2-chloroethanol, 1-chloro-2-propanol, 3-chloro-1-propanol, 1-chloro-2-methyl-2-propanol, 4-chloro-1-butanol, and 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-tribromo-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 etc. are 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 SiC
l ₂ , H (CH ₃ ) ₂ SiCl, H (i-C ₃ H ₇ ) 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 , TlCl ₃ ,
SiCl ₄ , SnCl ₄ , SbCl ₅ , SbF _{5 and the} like are preferable.

The contact with Component 1, Component 2 and Component 3, and optionally with a halogen-containing compound which can be optionally contacted is carried out by mixing and stirring in the presence or absence of an inert medium, but mechanically. It is made by co-milling. The contact can be performed under heating at 40 to 150 ° C.

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. .

A desirable method for preparing the component A in the present invention is described in JP-A-63-264607 and JP-A-58-19850.
No. 3, No. 62-146904 and the like. More specifically, it can be obtained by bringing (a) metallic magnesium, (b) a halogenated hydrocarbon, and (c) a compound of the general formula X _n M (OR) _mn (the same as the aforementioned alkoxy group-containing compound) into contact with each other. A method of bringing a magnesium-containing solid into contact with a (d) halogen-containing alcohol, and then contacting with (e) an electron-donating compound and (f) a titanium compound (JP-A-63-63).
-264607), (a) magnesium dialkoxide and (b) hydrogen-
After contacting a silicon halide compound having a silicon bond, (c) a titanium halide compound is contacted, and then (d) an electron-donating compound (if necessary, further contacted with a titanium halide compound). (JP-A-62-146904), (a) magnesium dialkoxide and (b) hydrogen-
After contacting a silicon halide compound having a silicon bond, (c) contacting with an electron donating compound, and then (d)
Method of contacting with titanium compound (JP-A-58-1985)
No. 03). Of these, the method (1) is most preferable.

Component A is prepared as described above,
Component A may be washed with the above-mentioned inert medium, if necessary, and further dried.

Organoaluminum Compound Specific examples of the organoaluminum compound (hereinafter referred to as component B) include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum and the like. To be

Cycloalkene Cycloalkene (hereinafter referred to as component C) is a cyclic olefin having 4 to 20 carbon atoms. Specific examples thereof include cyclobutene, cyclopentene, cyclohexene,
Examples thereof include cycloheptene, cyclooctene, norbornene and bicyclooctene.

The prepolymerization of prepolymerized solid component (component A), an organoaluminum compound the presence of (component B) and cycloalkene (component C), is done by contacting the olefin (component D).

If necessary, an electron donating compound (hereinafter referred to as component E) may be added together with the components B and C during the prepolymerization of the component A. As the electron donating compound, an electron donating compound composed of an organic silicon compound or an electron donating compound containing a hetero atom such as nitrogen, sulfur, oxygen or phosphorus can be used.

Specific examples of the organic silicon compound include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, tetraphenoxysilane, tetra (p-methylphenoxy) silane, tetrabenzyloxysilane and methyltrimethoxy. Silane, methyltriethoxysilane, methyltributoxysilane, methyltriphenoxysilane, ethyltriethoxysilane, ethyltriisobutoxysilane, ethyltriphenoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane, butyltri Phenoxysilane, isobutyltriisobutoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, Methyl dihexyl silane,
Dimethyldiphenoxysilane, diethyldiethoxysilane, diethyldiisobutoxysilane, diethyldiphenoxysilane, dibutyldiisopropoxysilane, dibutyldibutoxysilane, dibutyldiphenoxysilane, diisobutyldiethoxysilane, diisobutyldiisobutoxysilane, diphenyldimethoxysilane, Examples thereof include diphenyldiethoxysilane, diphenyldibutoxysilane, dibenzyldiethoxysilane, divinyldiphenoxysilane, diallyldipropoxysilane, diphenyldiallyloxysilane, methylphenyldimethoxysilane and chlorophenyldiethoxysilane.

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.

Two or more kinds of these electron donating compounds may be used. Further, these electron donating compounds may be used when an organometallic compound is used in combination with a catalyst component, or may be used after being brought into contact with the organometallic compound in advance.

As olefins, in addition to ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-
Alpha-olefins such as pentene may be used. The prepolymerization is preferably carried out in the presence of the above-mentioned inert medium. The prepolymerization is usually performed at a temperature of 100 ° C or lower, preferably -30.
C. to + 30.degree. C., more preferably -20.degree. C. to + 15.degree. The polymerization method may be a batch method or a continuous method, or may be a multi-step polymerization of two or more steps.
When carrying out in multiple stages, it goes without saying that the polymerization conditions can be changed.

Component B has a concentration of 50 to 5 in the prepolymerization system.
It is used in an amount of 00 mmol / liter, preferably 80 to 200 mmol / liter, and is 4 to 50,000 mol, preferably 6 to 1,000 mol, per gram atom of titanium in the component A. Used.

Component C has a concentration of 10 to 2 in the prepolymerization system.
000 mmol / l, preferably 100-100
It is used so as to be 0 mmol / liter.

The olefin polymer is incorporated in the component A by the prepolymerization, and the amount of the polymer is preferably 0.1 to 200 g, particularly 0.5 to 50 g per 1 g of the component A.

The catalyst component of the present invention prepared as described above can be diluted or washed with the above-mentioned inert medium, but from the viewpoint of preventing storage deterioration of the catalyst component,
It is particularly desirable to wash. After washing, it may be dried if necessary. When the catalyst component is stored, it is desirable to store it at a low temperature as much as possible, and a temperature range of -50 ° C to + 30 ° C, particularly -20 ° C to + 5 ° C is recommended.

Polymerization of α-Olefin The catalyst component of the present invention obtained as described above is used in combination with an organometallic compound and, if necessary, an electron donating compound to form an α-olefin having 3 to 10 carbon atoms. Are useful as catalysts for the homopolymerization of 1 or of other mono-olefins or copolymers with other mono-olefins or di-olefins having 3 to 10 carbon atoms, in particular α-olefins having 3 to 6 carbon atoms such as propylene, 1-butene, -Methyl-1-pentene, homopolymerization of 1-hexene or the like or the above α-olefins and / or
Alternatively, it exhibits extremely excellent performance as a catalyst for random and block copolymerization with ethylene.

Organometallic compounds that can be used are organic compounds of metals of Groups I to III of the periodic table. As the compound, organic compounds of lithium, magnesium, calcium, zinc and aluminum can be used. Among these, organoaluminum compounds are particularly preferable. Organoaluminum compounds that can be used include those represented by the general formula R ⁷ _n Al
X'3 _-n (wherein R is an alkyl group or an aryl group, X '
Represents a halogen atom, an alkoxy group or a hydrogen atom, and n
Is an arbitrary number in the range of 1 ≦ n ≦ 3. ), For example, trialkyl aluminum, dialkyl aluminum monohalide, monoalkyl aluminum dihalide, alkyl aluminum sesquihalide,
Particularly preferred are alkylaluminum compounds having 1 to 18 carbon atoms, preferably 2 to 6 carbon atoms, such as dialkylaluminum monoalkoxides and dialkylaluminum monohydrides, or mixtures or complex compounds thereof. Specifically, such as 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, diisobutyl aluminum chloride, etc. Alkyl aluminum sesquihalides such as dialkyl aluminum monohalide, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, ethyl aluminum dibromide, ethyl aluminum diiodide, isobutyl aluminum dichloride, ethyl aluminum sesquichloride, etc. 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 aluminum hydride, dipropyl aluminum hydride, diisobutyl Examples include dialkyl aluminum hydrides such as 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.

It is also possible to use an organoaluminum compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom. Examples of such compounds include

[Chemical 1] Etc. can be illustrated.

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

The amount of the organometallic compound used with respect to the catalyst component of the present invention is, based on 1 gram atom of titanium in the catalyst component,
Usually 1 to 2,000 gram moles, especially 20 to 500 gram moles are desirable.

When an electron-donating compound is used, the ratio of the organometallic compound to the electron-donating compound is 0.1 to 40, preferably 1 to 40, preferably 1 to 10 mol of the electron-donating compound. Selected in the range of 25 gram atoms.

The polymerization reaction of the α-olefin may be either a gas phase or a liquid phase. When the polymerization is carried out in the liquid phase, normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane,
It can be carried out in an inert hydrocarbon such as 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. The amount of the other olefin to be copolymerized with the α-olefin in the copolymerization is usually 3 with respect to the α-olefin.
It is selected up to 0% by weight, especially in the range 0.3 to 15% 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.

[0054]

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. The heptane-insoluble matter (hereinafter abbreviated as HI) showing the ratio of the crystalline polymer in the polymer is
6 with boiling n-heptane in a modified Soxhlet extractor
It is the remaining amount when time is extracted.

Example 1 Preparation of Component A In a 1 liter reaction vessel equipped with a reflux condenser, under a nitrogen gas atmosphere, chip-shaped metal magnesium (purity 99.5) was prepared.
%, Average particle size 1.6 mm) 8.3 g and n-hexane 25
After adding 0 ml and stirring at 68 ° C for 1 hour, metallic magnesium was taken out and dried under reduced pressure at 65 ° C to obtain preactivated metallic magnesium. Next, 140 ml of n-butyl ether and a solution of n-butyl magnesium chloride in n-butyl ether (1.
(75 mol / l) 0.5 ml of a suspension added at 55 ° C.
A solution of 38.5 ml of n-butyl chloride dissolved in 50 ml of n-butyl ether was added dropwise over 50 minutes. After reacting at 70 ° C. for 4 hours with stirring, the reaction solution was mixed with 2
Hold at 5 ° C. Then, HC (OC ₂ H
₅ ) 35.7 ml of _{3 was} added dropwise over 1 hour. 6 after the dropping
The reaction was carried out at 0 ° C. for 15 minutes, and the reaction product solid was washed 6 times with 300 ml of n-hexane each time and dried under reduced pressure at room temperature for 1 hour to obtain a magnesium-containing solid containing 19.0% magnesium and 28.9% chlorine. 31.6 g was recovered. In a 300 ml reaction vessel equipped with a reflux condenser, a stirrer and a dropping funnel, magnesium-containing solid 6.3 in a nitrogen gas atmosphere.
g and n-heptane (50 ml) were added to form a suspension, and 2,2,2-trichloroethanol (20 ml) was stirred at room temperature.
A mixed solution of (0.02 mmol) and 11 ml of n-heptane was added dropwise from the dropping funnel over 30 minutes, and the mixture was further stirred at 80 ° C. for 1 hour. The obtained solid was filtered off, washed with 100 ml of n-hexane at room temperature 4 times each, and further washed with 100 ml of toluene twice each to obtain a solid component. To the above solid component, 40 ml of toluene was added, titanium tetrachloride was further added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and the temperature was raised to 90 ° C. With stirring, 2 ml of di-n-butyl phthalate and 5 toluene
The mixed solution (ml) was added dropwise over 5 minutes and then stirred at 120 ° C for 2 hours. The solid substance obtained was filtered off at 90 ° C. and washed twice with 100 ml of toluene each time at 90 ° C. Further, new titanium tetrachloride was added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and the mixture was stirred at 120 ° C for 2 hours and washed with 100 ml of n-hexane at room temperature seven times. Ingredient A5.
5 g was obtained.

In a 500 ml reactor equipped with a prepolymerization stirrer, under a nitrogen gas atmosphere, 2.8 g of the component A obtained above and n-heptane 2 were added.
80 ml was added and cooled to -5 ° C with stirring. Next, a solution of triethylaluminum (hereinafter abbreviated as TEAL) in n-heptane (2.0 mol / liter) and cyclopentene were added so that the concentrations of TEAL and cyclopentene in the reaction system were 100 mmol / liter and 50, respectively.
It was added so that the concentration would be 0 mmol / liter, and the mixture was stirred for 5 minutes. Then, after depressurizing the system, propylene gas was continuously supplied to polymerize propylene for 15 minutes. After completion of the polymerization, purge propylene in the gas phase with nitrogen gas, and
The solid phase portion was washed with 00 ml of n-hexane three times at room temperature. Further, the solid phase portion was dried under reduced pressure at room temperature for 1 hour to prepare a catalyst component. As a result of measuring the amount of magnesium contained in the catalyst component, the amount of preliminary polymerization was 1.7 g per 1 g of component A.

Examples 2 to 4 In the prepolymerization of Example 1, instead of cyclopentene, cycloalkenes shown in Table 1 and TEAL or triisobutylaluminum (hereinafter abbreviated as TiBAL) in concentrations shown in Table 1 were used. Example 1 except that the electron donating compounds shown in Table 1 were used at the concentrations shown in Table 1 and the prepolymerization conditions were as shown in Table 1.
Preliminary polymerization of component A was carried out in the same manner as above to prepare a catalyst component.

Comparative Example 1 In Example 1, except that prepolymerization was not carried out.
A catalyst component was prepared in the same manner as in Example 1.

Comparative Example 2 The prepolymerization of Example 1 was repeated except that cyclopentene was not used and the prepolymerization conditions were as shown in Table 1.
Preliminary polymerization of component A was carried out in the same manner as in Example 1 to prepare a catalyst component.

Comparative Example 3 In the prepolymerization of Example 4, norbornene was not used,
Preliminary polymerization of Component A was carried out in the same manner as in Example 4 except that TiBAL and phenyltriethoxysilane were used at the concentrations shown in Table 1 and the prepolymerization conditions were as shown in Table 1, to prepare the catalyst component. .

[0061]

[Table 1]

Application Example 1 In a 1.5-liter stainless steel autoclave equipped with a propylene polymerization stirrer, 2 ml of a TEAL n-heptane solution (0.1 mol / liter) and n-diphenyldimethoxysilane were placed in a nitrogen gas atmosphere. 2 ml of a heptane solution (0.01 mol / liter) was mixed and held for 5 minutes. 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 29 mg of the catalyst component obtained in Example 1 was charged into the reaction system, propylene was polymerized for 1 hour. After the polymerization was completed, unreacted propylene was purged, and the flexural modulus was 1
A white polypropylene powder of 3,600 kg / cm ² was obtained. The polypropylene production amount (CE) per 1 g of the component A was 45.8 kg.

Application Examples 2, 3 and 5 The procedure of Application Example 1 was repeated except that the catalyst components obtained in Examples 2 and 3 and Comparative Example 1 were used instead of the catalyst components obtained in Example 1. Polymerization of propylene was carried out, and the results are shown in Table 2.

Application Examples 4, 6, 7 The catalyst components obtained in Example 4 and Comparative Examples 2 and 3 were used in place of the catalyst components obtained in Example 1, and phenyltrimethoxy was used instead of diphenyldimethoxysilane. Polymerization of propylene was carried out in the same manner as in Application Example 1 except that ethoxysilane was used, and the results are shown in Table 2.

[0065]

[Table 2]

[0066]

According to the present invention, by adopting the above constitution, the strength of the catalyst component can be improved, and the catalyst component can maintain high activity in the (co) polymerization of α-olefin, A catalyst component that exhibits high stereoregularity and that is particularly washed exhibits an excellent effect of suppressing deterioration of performance during storage of the catalyst.

[Brief description of drawings]

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

Claims (1)

[Claims] 1. A solid component comprising (A) magnesium, titanium, a halogen and an electron donating compound as essential components,
A catalyst component for α-olefin polymerization, which is brought into contact with (D) olefin in the presence of (B) organoaluminum compound and (C) cycloalkene.