JPH1036427A - α-Olefin polymerization catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerization catalyst capable of producing poly (α-olefin) having high stereoregularity and good fluidity. SOLUTION: (A) A solid component containing Mg, Ti, a halogen, a metal oxide and an electron-donating compound as essential components, and (B-1) an electronegative poling of an atom bonded to one Al atom. (B-2) an aluminum compound having a sum of the electronegativity values of poling of atoms bonded to one Al atom of not less than 7.8, and (C-2) A) An α-olefin polymerization catalyst comprising an alkylalkoxysilane compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

An α-olefin polymerization catalyst comprising a catalyst component containing Mg, Ti, a halogen and an electron donating compound as essential components, an organoaluminum compound and a silane compound is well known. At that time, by changing the silane compound, the stereoregularity of the obtained poly (α-olefin) can be changed (JP-A-7-109309). However, generally, when the silane compound is changed to improve the stereoregularity of poly (α-olefin), the melt flow rate (MFR) of the polymer tends to decrease. Therefore, development of a polymerization catalyst that can produce poly (α-olefin) having high stereoregularity and high MFR, that is, good fluidity, has been desired.

An object of the present invention is to provide a polymerization catalyst capable of producing poly (α-olefin) having high stereoregularity and good fluidity.

[0004]

Means for Solving the Problems The inventors of the present invention have studied the polymerization catalyst of α-olefin, and as a result, when a specific aluminum compound is used in combination with a specific component, a high stereoregularity and a high tacticity are obtained. Poly (α-
Olefin), and completed the present invention.

That is, the present invention relates to (A) magnesium,
(B-1) The sum of the poling electronegativity values of the atoms bonded to one Al atom is as follows: titanium, halogen, metal oxide, and an electron-donating compound.
An organoaluminum compound less than 8, (B-2) one A
An α-olefin polymerization catalyst comprising an aluminum compound having a sum of poling electronegativity values of atoms bonded to an l atom of 7.8 or more and an alkylalkoxysilane compound (C).

Preferred embodiments of the present invention are described below. (A) The above catalyst wherein the component (B-1) is selected from trialkylaluminums. As the alkyl, alkyl having 1 to 18 carbon atoms is preferable. (B) The above catalyst, wherein the component (B-2) is selected from the group consisting of dialkylaluminum monochloride, alkylaluminum dichloride, alkylaluminum sesquichloride, dialkylaluminum monoalkoxide, alkylaluminum dialkoxide and alkylaluminoxane. (C) The catalyst according to (b) above, wherein alkyl is alkyl having 1 to 18 carbon atoms and alkoxy is alkoxy having 1 to 10 carbon atoms. (D) Component (C) an alkylalkoxysilane compound,
The following formula:

[0007]

Embedded image R ¹ Si (OR ² ) (OCH ₃ ) ₂ (In the above formula, R ¹ is a branched or cyclic alkyl group having 3 to 6 carbon atoms, and R ² is a 3 to 6 carbon atoms. Is a branched alkyl group, alkenyl group or alkynyl group)
The above catalyst, which is an alkyltrialkoxysilane represented by the formula: (E) Component (B-1) per mole of titanium in component (A)
Is 70 to 600 mol, 2 to 200 mol of the component (B-2) and 10 to 30 mol of the component (C). (F) The above-mentioned catalyst, wherein the α-olefin is a linear or branched α-olefin having 2 to 10 carbon atoms.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Component (A) in the catalyst of the present invention
Contains magnesium, titanium, halogen, metal oxide and electron donating compound as essential components. Component (A)
It is a component known per se. Such components are usually prepared by contacting a magnesium compound, a titanium compound, a metal oxide, and an electron-donating compound, and, in the case where each of the compounds has no halogen, a halogen-containing compound.

The magnesium compound has the general formula MgR ^a R
It is represented by ^b . Here, ^Ra and ^Rb represent the same or different hydrocarbon groups, OR groups (R is a hydrocarbon group), and halogen atoms. More specifically, as the hydrocarbon group of R ^a and R ^b , an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, and an aralkyl group, and as the OR group,
R represents an alkyl group, cycloalkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms, and examples of the halogen atom include chlorine, bromine, iodine, and fluorine. Specific examples of these compounds are shown below. In the following chemical formula,
Me: methyl, Et: ethyl, Pr: propyl, i-P
r: isopropyl, Bu: butyl, i-Bu: isobutyl, t-Bu: tertiary butyl, He: hexyl, O
ct: octyl, Ph: phenyl, cyHe: cyclohexyl.

[0010] MgMe ₂ , MgEt ₂ , Mg (i-Pr)
₂ , MgBu ₂ , MgHe ₂ , MgOct ₂ , MgEt
Bu, MgPh ₂ , MgcyHe ₂ , Mg (OM
e) ₂ , Mg (OEt) ₂ , Mg (OBu) ₂ , Mg
(OHe) ₂ , Mg (OOct) ₂ , Mg (OP
h) ₂ , Mg (OcyHe) ₂ , EtMgCl, BuM
gCl, HeMgCl, i-BuMgCl, t-BuMgC
1, PhMgCl, PhCH ₂ MgCl, EtMgB
r, BuMgBr, PhMgBr, BuMgI, EtO
MgCl, BuOMgCl, HeOMgCl, PhOM
gCl, EtOMgBr, BuOMgBr, EtOMg
I, MgCl ₂ , MgBr ₂ , MgI ₂ .

The above magnesium compound can be prepared from metallic magnesium or other magnesium compounds when preparing component A. Examples thereof include metallic magnesium, halogenated hydrocarbons and alkoxy group-containing compounds of 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 an atom of M Value, m> n ≧ 0. ) Is contacted.

The hydrocarbon groups of X and R in the general formula of the alkoxy group-containing compound include methyl (Me), ethyl (Et), propyl (Pr), i-propyl (i-P
r), alkyl groups such as butyl (Bu), i-butyl (i-Bu), hexyl (He), octyl (Oct), cycloalkyl groups such as cyclohexyl (cyHe) and methylcyclohexyl, allyl, propenyl, butenyl, etc. Alkenyl group, aryl group of phenyl (Ph), tolyl, xylyl group, and aralkyl group such as phenethyl and 3-phenylpropyl. Among these, an alkyl group having 1 to 10 carbon atoms is particularly desirable. Hereinafter, specific examples of the alkoxy group-containing compound will be described.

Compound when 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) contained 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
Me ₂ Si (OMe) ₂ , 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 ; MeBuSi (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 when M is Boron B (OEt) ₃ , B (OB) contained 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 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 when M is phosphorus P (OMe) ₃ , P (OE) contained in formula P (OR) ₃
t) ₃ , P (OBu) ₃ , P (OHe) ₃ , P (OP
h) ₃ .

Further, as the magnesium compound, a complex with an organic compound of a metal (M ') of Group II or IIIa of the periodic table can be used. The complex has the general formula MgR ^a R ^b
· P is represented by (M'R ^c _q) (R ^a and R ^b are as defined above). As the metal (M '), aluminum, zinc, and calcium, and the like, R ^c is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group. Also, q is the valence of the metal M 'and p is 0.
The number of 1-10 is shown. Specific examples of the compound represented by M′R ^c _q include AlMe ₃ , AlEt ₃ , Al (i-B
u) ₃ , AlPh ₃ , ZnMe ₂ , ZnEt ₂ , ZnB
_{u 2, ZnPh 2, CaEt 2} , CaPh 2 , and the like.

The titanium compound is a divalent, trivalent or tetravalent titanium compound, and examples thereof include titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, trichlorobutoxytitanium, dichlorodiethoxytitanium, and dichlorodiethoxytitanium. Butoxytitanium, dichlorodiphenoxytitanium,
Examples thereof include chlorotriethoxytitanium, chlorotributoxytitanium, tetrabutoxytitanium, and titanium trichloride. Among these, tetravalent titanium halides such as titanium tetrachloride, trichloroethoxytitanium, dichlorodibutoxytitanium and dichlorodiphenoxytitanium are desirable, and titanium tetrachloride is particularly desirable.

Metal oxides are listed in the Periodic Tables of Elements II-IV.
An oxide of an element selected from the group of families of elements, To illustrate _{them, B 2 O 3, MgO,} Al 2 O 3, SiO
_{2, CaO, TiO 2, ZnO} , ZrO 2, SnO 2,
BaO, ThO _{2 and the} like can be mentioned. Among them, B ₂
O ₃ , MgO, Al ₂ O ₃ , SiO ₂ , TiO ₂ , Zr
O ₂ is preferred, and SiO ₂ is particularly preferred. Further, composite oxides containing these metal oxides, for example, SiO ₂ -M
gO, SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , S
_{iO 2 -V 2 O 5, SiO} 2 -Cr 2 O 3, SiO 2 -
TiO ₂ -MgO or the like can also be used.

These metal oxides are usually used in powder form. Since the form such as the size and shape of the powder often affects the form of the obtained olefin polymer, it is desirable to appropriately adjust the form. It is desirable that the metal oxide be fired at as high a temperature as possible for the purpose of removing poisonous substances when used, and that the metal oxide be handled so as not to come into direct contact with the atmosphere.

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

Specific examples of carboxylic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid, methacrylic acid, crotonic acid, and malonic acid. Aliphatic carboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid and fumaric acid, aliphatic oxycarboxylic acids such as tartaric acid, cyclohexanemonocarboxylic acid, cyclohexenemonocarboxylic acid, cis-1,2- Cyclohexanedicarboxylic acid, cis-4-methylcyclohexene-1,2-
Alicyclic carboxylic acids such as dicarboxylic acids, benzoic acid, toluic acid, anisic acid, aromatic monocarboxylic acids such as p-tert-butylbenzoic acid, naphthoic acid, and cinnamic acid, phthalic acid, isophthalic acid, terephthalic acid And aromatic polycarboxylic acids such as naphthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, pyromellitic acid and melitic acid.

As the carboxylic anhydride, anhydrides of the above-mentioned carboxylic acids can be used.

As the carboxylic acid ester, mono- or polyvalent esters of the above-mentioned carboxylic acids can be used. Specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, propyl pivalate, and 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
-Tertiary butyl ethyl benzoate, ethyl p-anisate,
Ethyl α-naphthoate, isobutyl α-naphthoate, ethyl cinnamate, monomethyl phthalate, monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, phthalate Diallyl acid, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate, tetramethyl pyromellitate, tetraethyl pyromellitate, pyromellitic acid Tetrabutyl and the like.

As the carboxylic acid halide, acid halides of the above carboxylic acids can be used.
Specific examples thereof include acetate chloride, acetate bromide, acetate iodide, propionate chloride, butyrate 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 chloride, succinic 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 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, Examples include cinnamic acid chloride, cinnamic acid bromide, phthalic acid dichloride, phthalic acid dibromide, isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, and naphthalic acid dichloride. Further, monoalkyl halides of dicarboxylic acids such as adipic acid monomethyl chloride, maleic acid monoethyl chloride, maleic acid monomethyl chloride, and butyl phthalate chloride can also be used.

Alcohols are represented by the general formula R ^d OH. In the formula, R ^d is alkyl, alkenyl, cycloalkyl, aryl, aralkyl having 1 to 12 carbon atoms. Specific examples include methanol, ethanol,
Propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, octanol, 2-ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, cresol, xylenol, ethylphenol, isopropylphenol, p-tert-butylphenol, n -
Octylphenol and the like.

The ether is represented by the general formula R ^e OR ^f. In the formula, R ^e and R ^f are alkyl, alkenyl, cycloalkyl, aryl and aralkyl having 1 to 12 carbon atoms, and R ^e and R ^f 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, anisole, ethylphenyl ether and the like.

The component (A) can be prepared by contacting a metal oxide (component 1), a magnesium compound (component 2), a titanium compound (component 3) and an electron donating compound (component 4) in that order. After contacting Component 1 and Component 2, contact Component 4 and Component 3 in that order. After contacting Component 1 and Component 2, contact Component 3 and Component 4 simultaneously. Component 2 and Component 3 After the contact, the components 4 and 1 are brought into contact in that order. After the components 2 and 4 are brought into contact, the components 3 and 1 are brought into contact in that order. The components 2, 3 and 4 are simultaneously brought into contact. After contact
A method such as contacting the component 1 can be employed. Also, the contact with the halogen-containing compound can be carried out before the contact of the component 3.

Examples of the halogen-containing compound include halogenated hydrocarbons, halogen-containing alcohols, silicon halide compounds having a hydrogen-silicon bond, group IIIa of the periodic table,
Examples include halides of Group IVa and Group Va elements (hereinafter, referred to as metal halides). As the halogenated hydrocarbon, mono- and polyhalogen-substituted saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms are used. Specific examples of such compounds include, for aliphatic compounds, methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, 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 paraffin, and the like. Examples of the alicyclic compound include chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentadiene, and hexachlorocyclohexane. Examples of the aromatic compound include chlorobenzene, bromobenzene, o-dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, hexabromobenzene, benzotrichloride, p-chlorobenzotrichloride and the like. These compounds may be used alone or in combination of two or more.

As the halogen-containing alcohol, one or two or more hydrogen atoms other than a hydroxyl group in a mono- or polyhydric alcohol having one or more hydroxyl groups in one molecule are substituted with a halogen atom. Compounds can be used. Examples of the halogen atom include chlorine, bromine, iodine, and fluorine atoms, and a 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, 5-chloro-1-pentanol, 6-chloro-1-hexanol, 3-chloro-1,2-propanediol, 2-chlorocyclohexanol, 4-chlorobenzhydrol, (m, o, p) -chloro Benzyl 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-chloro-α-methylbenzyl alcohol, 2-
Chloro-4-phenylphenol, 6-chlorothymol, 4-
Chlororesorcin, 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-bromoresorcinol, (m, o, p) -fluorophenol, p-iodophenol: 2,2-dichloroethanol, 2,3-dichloro-1-propanol, 1,3-dichloro-2-
Propanol, 3-chloro-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-trichloro Phenol, 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,
Examples thereof include tetrachlorohydroquinone, tetrachlorobisphenol A, tetrabromobisphenol A, 2,2,3,3-tetrafluoro-1-propanol, 2,3,5,6-tetrafluorophenol, and tetrafluororesorcin.

Examples of the silicon halide compound having a hydrogen-silicon bond include HSiCl ₃ , H ₂ SiCl ₂ , H
₃ SiCl, H (CH ₃ ) SiCl ₂ , H (C ₂ H ₅ )
SiCl ₂ , H (t-C ₄ H ₉ ) SiCl ₂ , H (C ₆ H
₅ ) SiCl ₂ , H (CH ₃ ) ₂ SiCl, H (i-C _{3
H 7) 2 SiCl, H 2} (C 2 H 5) SiCl, H 2 (n
-C ₄ H ₉ ) SiCl, H ₂ (C ₆ H ₄ CH ₃ ) SiC
1, HSiCl (C ₆ H ₅ ) _{2 and the} like.

As the metal halide, B, Al, Ga,
In, Tl, Si, Ge, Sn, Pb, As, Sb, B
i chlorides, fluorides, bromides, iodides,
In particular, BCl ₃ , BBr ₃ , BI ₃ , AlCl ₃ , AlB
r 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, component 3 and component 4, and optionally a halogen-containing compound, can be carried out in the presence or absence of an inert medium.
This can be done by mixing and stirring or by mechanically 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. .

Preferred methods for preparing the component (A) in the present invention are described in JP-A-58-162607, JP-A-55-94909, JP-A-55-115405, JP-A-57-108107 and JP-A-61-108107. Two
Methods disclosed in 1109, 61-174204, 61-174205, 61-174206, 62-7706 and the like can be mentioned. More specifically, a method in which a reaction product of a metal oxide and a magnesium dialkoxide is brought into contact with an electron-donating compound and a tetravalent titanium halide (JP-A-58-162607); A method in which a reaction product of a hydrocarbyl halide compound is contacted with a Lewis base compound and titanium tetrachloride (JP-A-55-94909). A reaction product of a porous carrier such as silica and an alkylmagnesium compound is treated with titanium. A method of contacting with an electron-donating compound and a silicon halide compound before contacting with a compound (JP-A-55-115405 and JP-A-57-108107), metal oxides, alkoxy-containing magnesium compounds,
A method of contacting an aromatic polycarboxylic acid having a carboxyl group at the ortho position or a derivative thereof and a titanium compound (JP-A-61-174204), a metal oxide, an alkoxy group-containing magnesium compound,
A method of contacting a silicon compound having a hydrogen-silicon bond, an electron donating compound and a titanium compound (JP-A-61-1)
No. 74205) Metal oxide, alkoxy-containing magnesium compound,
A method in which a halogen element or a halogen-containing compound, an electron-donating compound and a titanium compound are brought into contact (Japanese Patent Application Laid-Open No.
-174206), a method of contacting a reaction product obtained by contacting a metal oxide, dihydrocarbylmagnesium and a halogen-containing alcohol with an electron-donating compound and a titanium compound (JP-A-61-21109), A method in which a solid obtained by contacting a metal oxide, hydrocarbyl magnesium and a hydrocarbyloxy group-containing compound (corresponding to the alkoxy group-containing compound) is contacted with a halogen-containing alcohol, and further contacted with an electron-donating compound and a titanium compound ( JP
62-7706). Of these, methods (1) and (2) are particularly desirable.

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

In component (A), Mg is preferably 2 to 2.
12% by weight, 1 to 5% by weight of Ti, 10 to 35% by weight of halogen, 30 to 70% by weight of metal oxide, 0% of electron donating compound
-20% by weight.

Next, the organometallic component will be described.

Component (B-1) is an organoaluminum compound in which the sum of the Pauling electronegativity values of the atoms bonded to one Al atom is less than 7.8. In a compound having two or more Al atoms, the sum of the electronegativities of the atoms bonded to each Al atom is obtained, and the determination is made based on the average value of all the atoms. Poling's electronegativity is widely known and, to name a few, H: 2.1, C: 2.5, O:
3.5, Cl: 3.0. Examples of the organoaluminum compound in which the sum of the values of the electronegativity of the poling of the atom bonded to one Al atom is less than 7.8 include the following compounds. One of these alone or 2
It can be used in combination of more than one species. Trialkyl aluminum, for example, trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tributyl aluminum, triisobutyl aluminum, trihexyl aluminum and the like can be mentioned.

The component (B-2) is an aluminum compound in which the sum of the poling electronegativity values of the atoms bonded to one Al atom is 7.8 or more. In a compound having two or more Al atoms, the sum of the electronegativities of the atoms bonded to each Al atom is obtained, and the determination is made based on the average value of all the atoms. Examples of the aluminum compound in which the sum of the poling electronegativity values of the atoms bonded to one Al atom is 7.8 or more include the following compound group. One of these can be used alone or in combination of two or more. (i) dialkylaluminum monohalides such as dimethylaluminum chloride, dimethylaluminum bromide, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum fluoride, dipropylaluminum chloride, di (n-butyl)
Aluminum chloride, diisobutylaluminum chloride, di (n-hexyl) aluminum chloride, di (n-
Octyl) aluminum chloride and the like. (ii) alkylaluminum dihalides, such as methylaluminum dichloride, ethylaluminum dichloride, ethylaluminum difluoride, methylaluminum dibromide, ethylaluminum dibromide, propylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride, n-hexyl Aluminum dichloride, n-octyl aluminum dichloride and the like can be mentioned. (iii) alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum sesquibromide, propylaluminum sesquichloride, n-butylaluminum sesquichloride, isobutylaluminum sesquichloride, n-hexylaluminum sesquichloride, n- Octyl aluminum sesquichloride, ethyl aluminum sesquifluoride and the like can be mentioned. (iv) dialkylaluminum monoalkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dipropylaluminum ethoxide, diisopropylaluminum ethoxide, diisobutylaluminum ethoxide, di (n-butyl) aluminum ethoxide, di (n-hexyl) ) Aluminum ethoxide,
Di (n-octyl) aluminum ethoxide and the like. (v) alkylaluminum dialkoxides, for example methylaluminum diethoxide, ethylaluminum diethoxide, propylaluminum diethoxide, n-butylaluminum diethoxide, isobutylaluminum diethoxide, n-hexylaluminum diethoxide,
n-octyl aluminum diethoxide and the like. (vi) trialkoxyaluminum, for example, trimethoxyaluminum, triethoxyaluminum and the like. (vii) Alkyl aluminoxanes such as methylaluminoxane and ethylaluminoxane. (viii) alkylaluminum alkoxy halides such as methylaluminum methoxychloride, ethylaluminum methoxychloride, ethylaluminum ethoxychloride, ethylaluminum ethoxybromide, isobutylaluminum methoxychloride, isobutylaluminum ethoxychloride, isobutylaluminum ethoxybromide, isobutylaluminum isopropoxychloride, Isobutyl aluminum isopropoxy bromide and the like. (ix) Dialkylaluminum monophenoxide, for example, diethylaluminum phenoxide, diisobutylaluminum phenoxide and the like. (x) Aluminum trihalides, such as aluminum trichloride and aluminum tribromide.

In each of the above groups, preferably, alkyl is alkyl having 1 to 18 carbons, alkoxy is alkoxy having 1 to 10 carbons, and halides are chloride and bromide.

Particularly preferably, component (B-2) comprises dialkylaluminum monochloride, dialkylaluminum monobromide, alkylaluminum dichloride, alkylaluminum dibromide, alkylaluminum sesquichloride, alkylaluminum sesquibromide, dialkylaluminum alkoxide, alkylaluminum It is selected from the group consisting of dialkoxides and alkylaluminoxanes.

Next, the component (C) alkylalkoxysilane compound will be described. Preferred alkylalkoxysilane compounds include, for example, those represented by the general formula

[0046]

Embedded image R ¹ Si (OR ² ) (OCH ₃ ) ₂ (In the above formula, R ¹ is a branched or cyclic alkyl group having 3 to 6 carbon atoms, and R ² is a 3 to 6 carbon atoms. Is a branched alkyl group, alkenyl group or alkynyl group)
The alkyl trialkoxy silane shown by these is mentioned. Examples of R ¹ include an isopropyl group, a t-butyl group, a s-butyl group, a t-amyl group, a cyclopentyl group, a cyclohexyl group and the like. As R ² , for example, isopropyl group, t-butyl group, s-butyl group, t-amyl group,
2-methyl-3-butenyl group, 3-methyl-2-butenyl group, 2-
And a methyl-3-butynyl group. Specific compounds include, for example, t-butoxycyclopentyldimethoxysilane, isopropoxycyclopentyldimethoxysilane, s-butoxycyclopentyldimethoxysilane, t-amyloxycyclopentyldimethoxysilane, (2-methyl-3-buten-2-oxy) cyclopentyldimethoxy Silane, (3-methyl-2-butene-1-oxy) cyclopentyldimethoxysilane, (2-methyl-3-butyn-2-oxy) cyclopentyldimethoxysilane, t-butoxycyclohexyldimethoxysilane, isopropoxycyclohexyldimethoxysilane, s -Butoxycyclohexyldimethoxysilane, t-amyloxycyclohexyldimethoxysilane, (2-methyl-3-butene-2-oxy) cyclohexyldimethoxysilane, (3-methyl-2-butene-1-
Oxy) cyclohexyldimethoxysilane, (2-methyl
-3-butyne-2-oxy) cyclohexyldimethoxysilane.

As the alkylalkoxysilane compound,
In addition to the above, an alkylalkoxysilane containing a lactone group or a carboxyl group, an alkylalkoxysilane having a heterocyclic substituent having a silicon atom or a nitrogen atom as a ring-constituting atom, and the like can also be preferably used.

The catalyst of the present invention comprises the above-mentioned components. Preferably, 70 to 600 mol of the component (B-1) and 70 to 600 mol of the component (B-2) per 1 mol of titanium in the component (A). From 2 to 20
0 mol and 10 to 30 mol of the component (C) are blended. More preferably, the component (B-
1) 90 to 400 moles, 9 to 45 moles of component (B-2) and 15 to 25 moles of component (C).

In the present invention, the component (A) may or may not be subjected to prepolymerization. When the prepolymerization is performed, the olefin is added in the presence of an organoaluminum (component D) and an organosilicon compound (component E). This is done by contacting with. The organic aluminum (component D) is the component (B-1) described above,
One or more compounds can be selected from the compounds described in Component (B-2)) and used. Of these, trialkylaluminums, particularly triethylaluminum and triisobutylaluminum, are preferred. As the organosilicon compound (component E), any of the compounds described in the above-mentioned component (C) can be used, but any other compounds having a total of four alkyl groups and alkoxy groups bonded to a silicon atom can be used. It is possible. For example, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane methyltributoxysilane, methyltriphenoxysilane, ethyltriethoxysilane ethyltriisobutoxy Silane, propyltriethoxysilane, butyltrimethoxysilane,
Butyltriethoxysilane, butyltributoxysilane, isobutyltriisobutoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, dimethyldiphenoxysilane, diethyldiethoxysilane, diethyldiisobutoxy Examples thereof include silane, diphenyldimethoxysilane, diphenyldiethoxysilane, dibenzyldiethoxysilane, divinyldiphenoxysilane, diallyldipropoxysilane, diphenyldiallyloxysilane, methylphenyldimethoxysilane, and chlorophenyldiethoxysilane. Preferred organosilicon compounds (component E) are t-butoxycyclopentyldimethoxysilane, isopropoxycyclopentyldimethoxysilane or s-butoxycyclopentyldimethoxysilane.

Examples of the olefin used for the prepolymerization include, in addition to ethylene, α-olefins such as propylene, 1-butene, 1-hexene and 4-methyl-1-pentene. Prepolymerization is normal butane, isobutane,
Normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene,
It is preferably carried out in an inert hydrocarbon such as xylene. Preliminary polymerization is usually performed at a temperature of 100 ° C or lower, preferably -30 ° C.
To + 30 ° C, more preferably at a temperature of -20 ° C to + 20 ° C. The polymerization system may be either a batch system or a continuous system, and may be performed in two or more stages.

Component D has a concentration of 10 to 50 in the prepolymerized system.
0 mol / l, preferably 30 to 200 mmol / l, and 1 to 50,000 mol, preferably 2 to 1,000 mol, per 1 mol of titanium in the component (A). Used. The component (E) is used so that the concentration in the prepolymerization system becomes 1 to 1,000 mmol / L, preferably 5 to 200 mmol / L. By the pre-polymerization, the component (A)
The olefin polymer is incorporated therein, and the amount of the polymer is preferably 0.1 to 200 g, particularly preferably 0.5 to 50 g per 1 g of the component (A). The catalyst component thus prepared can be diluted or washed with the above-mentioned inert medium, but it is particularly preferable to wash it from the viewpoint of preventing catalyst deterioration. After washing, it may be dried if necessary. When storing the catalyst, it is preferable to store it at a temperature as low as possible.
A temperature range of 20 ° C. to + 5 ° C. is recommended.

Polymerization of α-olefin in the presence of a catalyst consisting of component (A), component (B-1), component (B-2) and component (C) pre-polymerized or not pre-polymerized as described above Is made. As the α-olefin, a linear or branched α-olefin having 2 to 10 carbon atoms is preferable, and examples thereof include ethylene, propylene, butylene, pentene, hexene, heptene, and octene. The catalyst of the present invention can be used not only for homopolymerization of α-olefins but also for copolymerization of two or more α-olefins. The catalyst of the present invention is particularly preferably used for propylene homopolymerization and copolymerization thereof (which may be either random copolymerization or block copolymerization).

As the reaction conditions in the polymerization of α-olefin, conventional conditions can be used. For example, -20 ~ + 150 ℃,
Preferably, the reaction is carried out at 0 to 100 ° C. and 1 to 60 atm for 0.5 to 7 hours. The polymerization reaction may be performed in a gas phase or a liquid phase. When the reaction is carried out in a liquid phase, the reaction can be carried out in the above-mentioned inert medium or in a liquid monomer. Further, the polymerization may be performed in either a batch system or a continuous system. The polymerization reaction may be performed in one stage, or may be performed in two or more stages by changing the polymerization conditions or changing the type of monomer used.

In order to control the molecular weight of the produced polymer, a known molecular weight controlling agent such as hydrogen can be present in the polymerization reaction system.

[0055]

The present invention will be described in more detail with reference to the following examples. The percentages are by weight unless otherwise specified.

Example 1 (1) Preparation of Component (A) A 200 ml flask equipped with a dropping funnel and a stirrer was replaced with nitrogen gas. This flask was baked in a nitrogen stream at 200 ° C. for 2 hours and further at 700 ° C. for 5 hours. Silicon oxide (Davison, trade name G)
952) 5 g and 40 ml of n-heptane were charged. Further, 20 ml of a 20% -n-heptane solution of n-butylethylmagnesium (hereinafter, referred to as BEM) (manufactured by Texas Alkyls, trade name: MAGALA BEM) was added, and 90 ° C.
For 1 hour.

After the obtained suspension was cooled to 0 ° C., a solution of 11.2 g of tetraethoxysilane dissolved in 20 ml of n-heptane was dropped from the dropping funnel over 30 minutes. After dropping, the temperature was raised to 50 ° C over 2 hours,
Stirring was continued for hours. After completion of the stirring, the supernatant was removed by decantation, and the resulting solid was washed with 60 ml of n-heptane at room temperature, and the supernatant was removed by decantation. This washing treatment with n-heptane was further performed four times.

To the above solid, 50 ml of n-heptane was added to form a suspension, and 2,2,2-trichloroethanol 8.0 was added thereto.
g in 10 ml of n-heptane was dropped from the dropping funnel at 25 ° C. over 15 minutes. After dropping, 25 ° C
For 30 minutes. After completion of stirring, at room temperature, 60
Washing was performed twice with ml of n-heptane and three times with 60 ml of toluene. When the obtained solid (referred to as solid component I) was analyzed, SiO ₂ : 36.6%, Mg: 5.
It contained 1% and Cl: 38.5%.

The solid component I obtained above was added to n-heptane
10 ml and 40 ml of titanium tetrachloride were added, the temperature was raised to 90 ° C., and di-n-butyl phthalate was dissolved in 5 ml of n-heptane.
6 g was added over 5 minutes. Thereafter, the temperature was raised to 115 ° C., and the reaction was carried out for 2 hours. After the temperature was lowered to 90 ° C., the supernatant was removed by decantation, and the mixture was washed twice with 70 ml of n-heptane. In addition, 15 ml of n-heptane and titanium tetrachloride
40 ml was added and reacted at 115 ° C. for 2 hours. After completion of the reaction, the obtained solid substance was washed eight times with 60 ml of n-hexane at room temperature. Next, drying was performed at room temperature under reduced pressure for 1 hour to obtain 8.3 g of a solid component (component A). As a result of analysis, this component A contained 3.1% by weight of Ti,
In addition, it was confirmed that Si, Mg, Cl and di-n-butyl phthalate were contained.

(2) Preparation of Catalyst and Polymerization of Propylene Component A1 obtained in the above (1) was placed in a 1.5-liter stainless steel autoclave equipped with a stirrer under a nitrogen atmosphere.
7.1 mg, 0.4 mmol of triethylaluminum, 0.08 mmol of diethylaluminum ethoxide, 0.08 mmol of isopropoxycyclopentyldimethoxysilane and 7 ml of n-heptane were mixed, and the mixture kept for 5 minutes was added. Next, 2500 ml of hydrogen (normal temperature, normal pressure) as a molecular weight controlling agent and 1 liter of liquid propylene were injected, and then the temperature of the reaction system was increased to 70 ° C., and propylene was polymerized for 1 hour. After completion of the polymerization, unreacted propylene and hydrogen were purged, and the polymer was taken out and dried.

The total amount of the obtained polymer was 222 g, its melt flow rate (MFR) was 27.5 g / 10 min, and heptane insoluble matter (HI) was 96.4%. In addition, MFR
According to ASTM D1238 at 230 ° C., 2160 ° C.
HI is the remaining amount when extracted with boiling n-heptane for 6 hours using a modified Soxhlet extractor. These measuring methods are the same in the following.

Examples 2 to 4 Propylene was polymerized in the same manner as in Example 1 except that the aluminum compounds shown in Table 1 were used instead of diethylaluminum ethoxide in (2) of Example 1. . Table 1 shows the results.

Comparative Example 1 Propylene was polymerized in the same manner as in Example 1 except that only triethylaluminum was used as the aluminum compound and no diethylaluminum ethoxide was used in (2) of Example 1. . Table 1 shows the results.

Comparative Example 2 Propylene was polymerized in the same manner as in Example 1 except that triisobutylaluminum was used instead of diethylaluminum ethoxide in (2) of Example 1. Table 1 shows the results.

[0065]

[Table 1] Example 5 (1) Prepolymerization of Component (A) In a 200 ml reactor which was sufficiently dried by replacing with nitrogen,
Under a nitrogen gas atmosphere, 2.5 g of the solid component A obtained in (1) of Example 1 and 100 ml of n-hexane were added, and the mixture was cooled to 0 ° C. with stirring. Then, with stirring, 5 mmol of triethylaluminum and 1 mmol of sec-butoxycyclopentyldimethoxysilane were added. After stirring was continued at the same temperature for 10 minutes, propylene gas was continuously supplied. When the consumption of propylene reached 7.5 g, the supply of propylene was stopped. Then, after stirring was continued for 10 minutes, the stirring was stopped, and washing by decantation was performed 5 times with 80 ml of hexane to obtain a slurry of a solid catalyst component (component A ′). (2) Polymerization of propylene In a 1.5-liter stainless steel autoclave equipped with a stirrer, the above catalyst component (component A ') 6 was placed under a nitrogen atmosphere.
9.0 mg, 0.4 mmol triethylaluminum,
Isopropoxycyclopentyldimethoxysilane 0.0
8 mmol, ethyl aluminum sesquichloride 0.
08 mmol and 7 ml of n-heptane were mixed and kept for 5 minutes. Then, after 3000 ml of hydrogen (normal temperature, normal pressure) as a molecular weight controlling agent and 1 liter of liquid propylene were injected, the temperature of the reaction system was raised to 70 ° C., and propylene was polymerized for 1 hour. After completion of the polymerization, unreacted propylene and hydrogen were purged, the polymer was taken out, and dried.

The total amount of the polymer was 235 g and the MFR was 30.
HI was 96.5% at 2 g / 10 min. The activity is 13.
It was 6 kg / g-component A.

Comparative Example 3 In a 1.5-liter stainless steel autoclave equipped with a stirrer, 71.1 mg of the catalyst component (component A ') produced in (1) of Example 5 and 0.1 ml of triethylaluminum were prepared in a nitrogen atmosphere. 4 mmol, 0.08 mmol of isopropoxycyclopentyldimethoxysilane and 7 m of n-heptane
were mixed and kept for 5 minutes. Then, after 3000 ml of hydrogen (normal temperature, normal pressure) as a molecular weight controlling agent and 1 liter of liquid propylene were injected, the reaction system was heated to 70 ° C.
And the polymerization of propylene was carried out for 1 hour. After completion of the polymerization, unreacted propylene and hydrogen were purged, the polymer was taken out, and dried.

The total amount of the polymer was 243 g, and the MFR was 16.
9 g / 10 min, HI was 96.6%. The activity is 13.
It was 7 kg / g-component A.

[0069]

[Table 2]

[0070]

According to the present invention, when a polymerization reaction of an α-olefin is carried out using the catalyst of the present invention, poly (α-olefin) having high stereoregularity, good fluidity and high rigidity can be obtained.

[Brief description of the drawings]

FIG. 1 is a flowchart schematically showing a process for preparing an α-olefin polymerization catalyst of the present invention.

Continuation of the front page (72) Inventor Issei Aichi 1-3-1, Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama Inside the Tonen Co., Ltd. Chome 3-1, Tonen Co., Ltd. (72) Inventor Hiroyuki Ozaki 1-3-1, Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama Prefecture Tonen Co., Ltd. (72) Inventor Satoshi Shimizu, Iruma-gun, Saitama 1-3-1 Nishi-Tsurugaoka, Oimachi Inside the Tonen Research Laboratory

Claims (1)

[Claims] 1. A solid component containing magnesium, titanium, halogen, a metal oxide and an electron-donating compound as essential components, and (B-1) a poling electricity of an atom bonded to one Al atom. An organoaluminum compound having a sum of negative values of less than 7.8, (B-2) an aluminum compound having a sum of poling electronegativity values of atoms bonded to one Al atom of 7.8 or more, and (C) An α-olefin polymerization catalyst comprising an alkylalkoxysilane compound.