JP3392352B2 - α-olefin polymerization catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] [0001] The present invention relates to an α-olefin polymer.
It relates to a combined catalyst. [0002] 2. Description of the Related Art Mg, Ti, halogen and electron donating properties
Catalyst component with compound as essential component and organoaluminumization
Compound, catalyst for α-olefin polymerization comprising silane compound
Is well known. At that time, change the silane compound.
And the steric rule of the resulting poly-α-olefin
(Japanese Patent Application Laid-Open No. 7-109309)
No.). However, generally changing silane compounds
To improve the stereoregularity of the poly-α-olefin.
Then, the melt flow rate (MFR) of the polymer is
It tends to decrease. Therefore, with high stereoregularity and high M
Poly-α-ole having FR, that is, having good fluidity
Development of polymerization catalyst capable of producing fins is desired
ing. [0003] SUMMARY OF THE INVENTION The present invention provides a high stereoscopic rule.
To produce poly-α-olefins
Polymerizable solid catalyst component, and α-o
An object of the present invention is to provide a catalyst for refin polymerization. [0004] Means for Solving the Problems The present inventors have proposed α-ole
As a result of repeated studies on fin polymerization catalysts,
After treatment with a specific compound containing Br and I
Prepolymerization in the presence of an aluminum compound
In the presence of a specific metal halide compound
Polymerization to high stereoregularity and high MFR
To be able to produce a poly-α-olefin having
Thus, the present invention has been completed. That is, the present invention relates to (A) and (a)
Requires calcium, titanium, halogen and electron donating compounds.
The solid component used as a sub component is Br_Two, I_Two, CBr_Four, CI_Four,
Alkyl bromide, alkyl iodide, or
General formula MetR_X(Where Met is Mg, B, Al, G
a, Ge, In, Sn, Sb or a transition metal element;
R represents Br, I or a hydrocarbon-containing group, and at least
One is Br or I, and x represents the valency of Met.
You. A) a solid catalyst component treated with the compound represented by
(B) Formula (R^k)_rAl (Y)_3-r(Where R^kHaso
Each independently represents an alkyl group and an aryl group,
Y is each independently H, an alkoxy group and aryl.
And r is a group selected from the group of 0 ≦ r ≦ 3.
Is any number of boxes. Organoalumination indicated by)
Compound, or two or more via oxygen or nitrogen atom
Organic aluminum compound with aluminum
The catalyst obtained by pre-polymerizing an α-olefin
Medium component, (B) a general formula (R^k)_rAl (Y)_3-r(here
And R^kAre each independently an alkyl group and an aryl
Y is each independently an alkoxy group and
And an aryloxy group, wherein r is 0 ≦ r
Any number in the range of ≦ 3. Organic aluminum indicated by)
Via a nitrogen compound or an oxygen or nitrogen atom
Organoalumination with two or more aluminum bonded
A compound, (C) an alkylalkoxysilane compound, and
(D) General formula MetR_X(Where Met is Mg, B, A
1, Ga, Ge, In, Sn, Sb or a transition metal element
R represents a halogen atom or a hydrocarbon-containing group;
At least one is a halogen atom, and x is an atom of Met
Indicate the value. Α-olefin comprising a compound represented by the formula:
It is a catalyst for polymerization. An embodiment of the present invention will be described below. (A) Component (A) wherein (a) is magnesium, titanium,
Halogen, metal oxide and electron donating compound
The above-mentioned catalyst using a solid component to be used as a catalyst. (B) (a) of (A) is magnesium, titanium, halo
Solid component that contains gen and electron donating compound as essential components
To Br_Two, I_Two, CBr_Four, CI_Four, Alkyl bromide,
Alkyl iodide or general formula MetR_X(formula
Where Met is Ti, Mg, B, Al, Co, Rh, N
i, Pd, Zn, and R represents Br, I, or hydrocarbon
Represents a group, at least one of which is Br or I, x
Represents the valence of Met. )
Α-olefin polymerization catalyst,
Medium. (C) (A) (a) is magnesium, titanium, halo
Solid component that contains gen and electron donating compound as essential components
To Br_Two, I_Two, CBr_Four, CI_Four, Alkyl bromide,
Alkyl iodide or general formula MetR_X(formula
Where Met is Ti, Mg, B, Al, Co, Rh, N
i, Pd, Zn, and R represents Br, I, or hydrocarbon
Represents a group having two or more Br or I, and x is Me
Indicates the valence of t. )
The α-olefin polymerization catalyst, which is a body catalyst component. (D) Component (A) (b) is (i) trimethylaluminum
Organoaluminum compound or group containing aluminum as an essential component
A product, or (ii) AlR_Three(R is independent water
A hydrogen atom or an alkyl group, at least one of
One is a hydrogen atom. ) And the essential component
Said organoaluminum compound or composition,
Medium. (E) The pre-polymerization temperature of the component (A) is 5 to 50 ° C.
The above-mentioned catalyst characterized by the above-mentioned. (F) Component (B) is a trialkylaluminum
The above-mentioned catalyst characterized by the above-mentioned. (G) Component (C) alkylalkoxysilane compound,
General formula: R¹Si (OR^Two) (OCH_Three)_Two (In the above formula, R¹Is branched or cyclic having 3 to 6 carbon atoms
Is an alkyl group of^TwoIs branched having 3 to 6 carbon atoms
Alkyl, alkenyl or alkynyl groups
You. ) Is an alkyl trialkoxysilane represented by
The above catalyst. (H) The component (D) has the general formula MetR_x(Where Met
Is Ti, Mg, B, Al, Co, Rh, Ni, Pd, Z
n represents a halogen atom or a hydrocarbon-containing group.
And at least one is a halogen atom, and x is Met
Is the valence of ) Is a compound represented by the above formula
Medium. (I) Component (D) is represented by the general formula MetR_x(Where Met
Is Ti, Mg, B, Al, Co, Rh, Ni, Pd, Z
n represents a halogen atom or a hydrocarbon-containing group.
And has at least two or more halogen atoms, and x is M
valence of et. ))
catalyst. (Nu) The component (D) has the general formula MetR_x(Where Met
Is Ti, Mg, B, Al, Co, Rh, Ni, Pd, Z
n represents a halogen atom or a hydrocarbon-containing group.
And has at least one Br or I, and x is an element of Met
It is a child price. The above catalyst, which is a compound represented by the formula: (R) The component (D) has the general formula MetR_x(Where Met
Is Ti, Mg, B, Al, Co, Rh, Ni, Pd, Z
n represents a halogen atom or a hydrocarbon-containing group.
And has at least two Br or I, and x is an element of Met
The catalyst is a compound represented by the following formula: (ヲ) (A) (a) Magnesium, titanium, halogen,
And a solid component containing an electron donating compound as an essential component
_Two, I_Two, CBr_Four, CI_Four, Alkyl bromide, alk
Ruiodide or general formula MetR_X(Where Me
t is Mg, B, Al, Ga, Ge, In, Sn, Sb or
Represents a transition metal element, and R represents Br, I or hydrocarbon-containing.
Represents a group, at least one of which is Br or I, x
Represents the valence of Met. )
(B) a solid catalyst component having the general formula (R)^k)_rAl (Y)
_3-r(Where R^kAre each independently an alkyl group and
And Y is each independently H,
A group selected from a oxy group and an aryloxy group.
R is an arbitrary number in the range of 0 ≦ r ≦ 3. )
Organic aluminum compounds, or oxygen atoms or nitrogen
Organic compound in which two or more aluminum atoms are bonded via an elementary atom
Aluminum compound as an essential component, α-olefin
The catalyst component obtained by pre-polymerization, (B) the general formula (R^k)_r
Al (Y)_3-r(Where R^kAre each independently
A kill group and an aryl group, and Y is each independently
Selected from an alkoxy group and an aryloxy group
And r is any number in the range of 0 ≦ r ≦ 3. )
An organic aluminum compound or an oxygen atom
Has two or more aluminum atoms bonded through a nitrogen atom
Select at least one from organoaluminum compounds
Organic aluminum compound, (C) alkyl alcohol
Xysilane compound, (D) general formula MetR_X(Where M
et is Mg, B, Al, Ga, Ge, In, Sn, Sb
Or a transition metal element, and R is a halogen atom or a hydrocarbon
Represents a halogen-containing group, at least one of which is a halogen atom.
And x represents the valence of Met. ),
(E) ZnR_Two(R represents an alkyl group.)
Zinc compound and (F) AlR_Three(Where R is
Independent hydrogen or alkyl groups, of which
One is hydrogen. Α) consisting of the compound represented by
-An olefin polymerization catalyst. [0007] BEST MODE FOR CARRYING OUT THE INVENTION Catalyst component (A) The catalyst component (A) of the present invention comprises magnesium, titanium,
A solid component containing a halogen and an electron donating compound as essential components.
Minute to Br_Two, I_Two, CBr_Four, CI_Four, Alkyl bromide
, Alkyl iodide, or the general formula MetR_xso
Solid catalyst component obtained by treatment with the compound shown
(A) and presence of aluminum compound or composition (b)
Below, it is obtained by prepolymerizing an α-olefin,
Items will be described. (1) Solid component Solid components in the catalyst of the present invention are magnesium, titanium,
, Halogen and an electron donating compound as essential components,
A metal oxide can be included as needed. Solid components
Is a component known per se. Such components are not
Always, magnesium compound, titanium compound and electron donation
Compounds, and each of the above compounds has no halogen.
In the case of a compound, contact each of the halogen-containing compounds
Thus, it is prepared. The following describes each component.
You. (I) Magnesium The magnesium compound has the general formula MgR^aR^bIt is represented by
Where R^aAnd R^bAre the same or different hydrocarbon groups, OR groups
(R is a hydrocarbon group) and a halogen atom. In more detail
Is R^aAnd R^bAs the hydrocarbon group, carbon atoms of 1 to 20
Alkyl groups, cycloalkyl groups, aryl groups, al
When the alkyl group is an OR group, R has 1 to 12 carbon atoms.
Alkyl group, cycloalkyl group, aryl group, arua
When the alkyl group is chlorine, bromine or iodine as a halogen atom
And fluorine and the like. Specific examples of these compounds are shown below. following
In the chemical formula, Me: methyl, Et: ethyl, Pr:
Propyl, i-Pr: isopropyl, Bu: butyl, i
-Bu: isobutyl, t-Bu: tertiary butyl,
He: hexyl, Oct: octyl, Ph: phenyl,
cyHe: represents cyclohexyl. [0010] MgMe_Two, MgEt_Two, Mg (i-Pr)
_Two, MgBu_Two, MgHe_Two, MgOct2, MgEtB
u, MgPh_Two, MgcyHe_Two, Mg (OMe)_Two, M
g (OEt)_Two, Mg (OBu)_Two, Mg (OHe)_Two,
Mg (OOct)_Two, Mg (OPh)_Two, Mg (OcyH
e)_Two, EtMgCl, BuMgCl, HeMgCl,
i-BuMgCl, t-BuMgCl, PhMgCl,
PhCH_TwoMgCl, EtMgBr, BuMgBr, P
hMgBr, BuMgI, EtOMgCl, BuOMg
Cl, HeOMgCl, PhOMgCl, EtOMgB
r, BuOMgBr, EtOMgl, MgCl_Two, Mg
Br_Two, MgI_Two. The above-mentioned magnesium compound is used to prepare component A.
When using metallic magnesium or other magnesium
It can also be prepared from a compound. As an example
Metal magnesium, halogenated hydrocarbon and general formula
X_nM (OR)_mnAn alkoxy group-containing compound of the formula
Is a hydrogen atom, a halogen atom or a carbon having 1 to 20 carbon atoms
Hydride group, M is boron, carbon, aluminum, silicon
Or a phosphorus atom, R is a hydrocarbon group having 1 to 20 carbon atoms, m
Represents the valence of M and m> n ≧ 0. How to contact
Is mentioned. X and X in the general formula of the alkoxy group-containing compound
And hydrocarbon groups of R include methyl (Me), ethyl
(Et), propyl (Pr), i-propyl, (i-P
r), butyl (Bu), i-butyl (i-Bu), hex
Alkyl groups such as sil (He) and octyl (Oct);
Clohexyl (cyHe), methylcyclohexyl, etc.
Cycloalkyl group, allyl, propenyl, butenyl, etc.
Alkenyl group, phenyl (Ph), tolyl, xylyl, etc.
Aryl group, phenethyl, 3-phenylpropyl
Aralkyl groups. Among them, especially charcoal
An alkyl group having a prime number of 1 to 10 is desirable. Below, Arco
Specific examples of the xy group-containing compound will be given. Compound when M is carbon Formula C (OR)_Four(OMe) contained in_Four, C (OEt)
_Four, C (OPr)_Four, C (OBu)_Four, C (Oi-B
u)_Four, C (OHe)_Four, C (OOct)_Four: Formula XC (O
R)_Three(OMe) contained in_Three, HC (OEt)_Three,
HC (OPr)_Three, HC (OBu)_Three, HC (OH
e)_Three, HC (OPh)_Three; MeC (OMe)_Three, Mec
(OEt)_Three, EtC (OMe)_Three, EtC (OE
t)_Three, CyHeC (OEt)_Three, PhC (OMe)_Three,
PhC (OEt)_Three, CH_TwoClC (OEt)_Three, MeC
HBrC (OEt)_Three, MeCHClC (OEt)_ThreeC
IC (OMe)_Three, ClC (OEt)_Three, ClC (Oi-
Bu)_Three, BrC (OEt)_ThreeFormula X_TwoC (OR)_TwoIncluded in
MeCH (OMe)_Two, MeCH (OEt)_Two, CH
_Two(OMe)_Two, CH_Two(OEt)_Two, CH_TwoClCH (O
Et)_Two, CHCl_TwoCH (OEt)_Two, CCl_ThreeCH (O
Et)_Two, CH_TwoBrCH (OEt)_Two, PhCH (OE
t)_Two. Compound when M is silicon Formula Si (OR)_Four(0Me) contained in_Four, Si (O
Et)_Four, Si (OBu)_Four, Si (Oi-Bu)_Four, S
i (OHe)_Four, Si (OOct)_Four, Si (OP
h)_Four: Formula XSi (OR)_Three(OEt) contained in
_Three, HSi (OBu)_Three, HSi (OHe)_Three, HSi
(OPh)_Three; MeSi (OMe)_Three, MeSi (OE
t)_Three, MeSi (OBu)_Three, EtSi (OEt)_Three,
PhSi (OEt)_Three, EtSi (OPh)_Three; ClSi
(OMe)_Three, ClSi (OEt)_Three, ClSi (OB
u)_Three, ClSi (OPh)_Three, BrSi (OEt)_Three;
Formula X_TwoSi (OR)_TwoMe included in_TwoSi (OMe)_Two,
Me_TwoSi (OEt)_Two, Et_TwoSi (OEt)_Two; MeC
lSi (OEt)_Two; CHCl_TwoSiH (OEt)_TwoC
Cl_ThreeSiH (OEt)_Two; MeBuSi (OEt)_Two:
X_ThreeMe contained in SiOR_ThreeSiOMe, Me_ThreeSiO
Et, Me_ThreeSiOBu, Me_ThreeSiOPh, Et_ThreeSi
OEt, Ph_ThreeSiOEt. Compound when M is boron Formula B (OR)_ThreeB (OEt) contained in_Three, B (OBu)
_Three, B (OHe)_Three, B (OPh)_Three. Compound when M is aluminum Formula Al (OR)_Three(OMe) contained in_Three, Al (O
Et)_Three, Al (OPr)_Three, Al (Oi-Pr)_Three, A
l (OBu)_Three, Al (Ot-Bu)_Three, Al (OHe)
_Three, Al (OPh)_Three. Compound when M is phosphorus Formula P (OR)_Three(OMe) contained in_Three, P (OEt)
_Three, P (OBu)_Three, P (OHe)_Three, P (OPh)_Three. Further, the magnesium compound may be selected from the following:
An organic compound of a Group II or Group IIIa metal (M ')
Can also be used. The complex has the general formula MgR
^aR^b・_p(M'R^c _q) (R^aAnd R^bIs
Synonymous with). Examples of the metal (M ') include aluminum and aluminum.
Lead, calcium, etc.^CIs a group having 1 to 12 carbon atoms.
Alkyl, cycloalkyl, aryl, alkyl
Group. Also, q is the valence of the metal M 'and p is 0.
The number of 1-10 is shown. M'R^C _qSpecific examples of compounds represented by
As AlMe_Three, AlEt_Three, Al (i-B
u)_Three, AlPh_Three, ZnMe_Two, ZnEt_Two, ZnB
u_Two, ZnPh_Two, CaEt_Two, CaPh_TwoEtc.
You. (Ii) Titanium Titanium compounds are trivalent and tetravalent titanium compounds.
Titanium tetrachloride, titanium tetrabromide
, Trichloroethoxy titanium, trichlorobutoxy
Tan, dichlorodiethoxytitanium, dichlorodibutoxy
Titanium, dichlorodiphenoxy titanium, chlorotriet
Xtitanium, chlorotributoxytitanium, tetrabutoki
Examples thereof include titanium and titanium trichloride. this
Among them, titanium tetrachloride, trichloroethoxytita
, Dichlorodibutoxy titanium, dichlorodiphenoxy
A tetravalent titanium halide such as titanium is desirable, especially
Titanium tetrachloride is preferred. (Iii) Electron-donating compound Examples of the electron donating compound include carboxylic acids and carboxylic acids.
Anhydrides, carboxylic esters, carboxylic acid halogenation
Substances, alcohols, ethers, ketones, amines,
Amides, nitriles, aldehydes, alcoholates
, Phosphorus bonded to an organic group via carbon or oxygen,
Arsenic and antimony compounds, phosphoamides, thioe
-Tels, thioesters, carbon esters, etc.
You. Of these, carboxylic acids, carboxylic anhydrides,
Rubonates, carboxylic acid halides, alcohols
Tools and ethers are preferably used. Carboxylic acids Specific examples of carboxylic acids include formic acid, acetic acid, propion
Acid, butyric acid, isobutyric acid, valeric acid, caproic acid, pivalin
Aliphatic such as acid, acrylic acid, methacrylic acid, crotonic acid
Monocarboxylic acid, malonic acid, succinic acid, glutaric acid,
Fats such as dipic acid, sebacic acid, maleic acid and fumaric acid
Aliphatic dicarboxylic acids, aliphatic oxycarboxylic acids such as tartaric acid,
Cyclohexane monocarboxylic acid, cyclohexene monoca
Rubonic acid, cis-1,2-cyclohexanedicarboxylic acid
Acid, cis-4-methylcyclohexene-1,2-dical
Alicyclic carboxylic acids such as boric acid, benzoic acid, toluic acid,
Anisic acid, p-tert-butyl benzoic acid, naphthoic acid,
Aromatic monocarboxylic acids such as cinnamate, phthalic acid, isophthalic acid
Lulic acid, terephthalic acid, naphthalic acid, trimellitic acid, hemi
Melitic acid, trimesic acid, pyromellitic acid, melitic acid, etc.
And aromatic polycarboxylic acids. Carboxylic anhydride As the carboxylic anhydride, the anhydride of the above carboxylic acids
Things can be used. Carboxylic acid ester Examples of the carboxylic acid esters include those of the above carboxylic acids.
No. or polyhydric ester can be used, and specific examples thereof
As butyl formate, ethyl acetate, butyl acetate, isobutyrate
Isobutyl, propyl pivalate, isobu pivalate
Chill, ethyl acrylate, methyl methacrylate, methac
Ethyl acrylate, isobutyl methacrylate, die malonate
Chill, diisobutyl malonate, diethyl succinate,
Dibutyl succinate, diisobutyl succinate, glutaric acid die
Chill, dibutyl glutarate, diisobutyl glutarate,
Diisobutyl adipate, dibutyl sebacate, sebashi
Diisobutylate, diethyl maleate, maleate di
Butyl, diisobutyl maleate, monomethyl fumarate
, Diethyl fumarate, diisobutyl fumarate, tartaric acid
Diethyl, dibutyl tartrate, diisobutyl tartrate, cycle
Ethyl rohexanecarboxylate, methyl benzoate, benzoate
Ethyl acid, p-methyl toluate, p-tertiary butyl,
Ethyl benzoate, ethyl p-anisate, α-naphthoic acid
Ethyl, isobutyl α-naphthoate, ethyl cinnamate,
Monomethyl phthalate, Monobutyl phthalate, Diphthalate
Butyl, diisobutyl phthalate, dihexyl phthalate,
Dioctyl phthalate, di-2-ethylhexyl phthalate
, Diallyl phthalate, diphenyl phthalate, isophthalate
Diethyl luate, diisobutyl isophthalate, terephthal
Diethyl phosphate, dibutyl terephthalate, diethyl naphthalate
Dibutyl naphthalate, triethyl trimellitate,
Tributyl rimellitate, tetramethyl pyromellitate,
Tetraethyl romellitate, tetrabutyl pyromellitate, etc.
Is mentioned. Carboxylic acid halide As the carboxylic acid halide, the above carboxylic acids
Acid halides can be used, specific examples of which
Acetic acid chloride, bromide acetate, iodide acetate
, Propionyl chloride, butyric chloride, butyric bromide
, Butyric iodide, pivalic acid chloride, pivalin
Acid bromide, acrylic acid chloride, acrylic acid bromide
, Acrylic acid iodide, methacrylic acid chloride,
Methacrylic acid bromide, methacrylic acid iodide,
Rotonic acid chloride, malonic acid chloride, malonic acid bromide
Succinic chloride, succinic bromide, glutaric acid
Chloride, glutaric bromide, adipic chloride,
Adipic bromide, sebacic chloride, sebacic acid
Bromide, maleic chloride, maleic bromide,
Fumaric acid chloride, fumaric acid bromide, tartaric acid chloride
, Tartaric bromide, cyclohexanecarboxylic acid chloride
, Cyclohexanecarboxylic acid bromide, 1-cyclohexane
Xencarboxylic acid chloride, cis-4-methylcyclohexane
Xencarboxylic acid chloride, cis-4-methylcyclohexane
Xencarboxylic acid bromide, benzoyl chloride, benbromide
Zoyl, p-toluic acid chloride, p-toluic acid bromide
Amide, p-anisic acid chloride, p-anisic bromide,
α-naphthoic acid chloride, cinnamic acid chloride, cinnamic acid
Bromide, phthalic dichloride, phthalic dibromide,
Isophthalic acid dichloride, isophthalic acid dibromide,
Examples include phthalic dichloride and naphthalic dichloride.
It is. Also, adipic acid monomethyl chloride, maleic
Acid monoethyl chloride, maleic acid monomethyl chloride
And dicarboxylic acids such as butyl phthalate chloride.
Noalkyl halides can also be used. Alcohols Alcohols have the general formula R^dExpressed as OH. Expression
R^dIs an alkyl, alkenyl, or C 1-12 carbon atom.
Chloroalkyl, aryl and aralkyl. The utensil
Examples include methanol, ethanol, propanol
, Isopropanol, butanol, isobutanol,
Pentanol, hexanol, octanol, 2-ethyl
Luhexanol, cyclohexanol, benzyl alcohol
, Allyl alcohol, phenol, cresol,
Silenol, ethyl phenol, isopropyl phenol
, P-tert-butylphenol, n-octy
And phenol. Ethers Ethers have the general formula R^eOR^fIt is represented by In the formula
R^e, R^fRepresents an alkyl or alkenyl having 1 to 12 carbons
, Cycloalkyl, aryl, aralkyl,
R^eAnd R^fMay be the same or different. Specific examples
Is, diethyl ether, diisopropyl ether,
Dibutyl ether, diisobutyl ether, diisoamido
Diether, di-2-ethylhexyl ether, diali
Ether, ethyl allyl ether, butyl allyl ether
Ter, diphenyl ether, anisole, ethylpheny
And the like. (Iv) halogen Halogen-containing compounds include halogenated hydrocarbons, ha
Logen-containing alcohol, halo having hydrogen-silicon bond
Silicon Genide Compounds, Groups IIIa and IVa of the Periodic Table,
Ha group halides (hereinafter referred to as metal halides)
U. ) And the like. Halogenated hydrocarbon As the halogenated hydrocarbon, a saturated hydrocarbon having 1 to 12 carbon atoms is used.
Or monounsaturated aliphatic, alicyclic and aromatic hydrocarbons
And polyhalogen substituents. Those compounds
Specific examples of aliphatic compounds include methyl chloride
, Methyl bromide, methyl iodide, methylene
Chloride, methylene bromide, methylene iodide
, Chloroform, bromoform, iodoform, tetrasalt
Carbon, carbon tetrabromide, carbon tetraiodide, ethyl chloride
, Ethyl bromide, ethyl iodide, 1,2-
Dichloroethane, 1,2-dibromoethane, 1,2-di
Iodoethane, methyl chloroform, methyl bromophor
, Methyl iodoform, 1,1,2-trichloroethyl
Len, 1,1,2-tribromoethylene, 1,1,2,
2-tetrachloroethylene, pentachloroethane, hex
Sachloroethane, hexabromoethane, n-propylc
Chloride, 1,2-dichloropropane, hexachloroprop
Ropylene, octachloropropane, decabromobutane,
Chlorinated paraffin and the like can be mentioned. For alicyclic compounds,
Lorocyclopropane, tetrachlorocyclopentane, f
Xachlorocyclopentadiene, hexachlorocyclo
And xane. Chlorobenzene in aromatic compounds
, Bromobenzene, o-dichlorobenzene, p-dic
Lorobenzene, hexachlorobenzene, hexabromobe
Benzene, benzotrichloride, p-chlorobenzotri
Chloride and the like. These compounds are a kind of
In addition, two or more kinds may be used. Halogen-containing alcohol As the halogen-containing alcohol, one in one molecule or
In mono- or polyhydric alcohols having two or more hydroxyl groups
Any one or two or more hydrogen atoms other than a hydroxyl group
Compounds substituted with halogen atoms can be used. Haloge
Examples of chlorine atoms include chlorine, bromine, iodine and fluorine atoms.
And a chlorine atom is preferred. Examples of these compounds include 2-chloroe
Tanol, 1-chloro-2-propanol, 3-chloro
-1-propanol, 1-chloro-2-methyl-2-p
Lopanol, 4-chloro-1-butanol, 5-chloro
-1-pentanol, 6-chloro-1-hexanol,
3-chloro-1,2-propanediol, 2-chlorosi
Clohexanol, 4-chlorobenzhydrol,
(M, o, p) -chlorobenzyl alcohol, 4-chloro
Locatechol, 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-crezo
, 1-bromo-2-naphthol, 6-bromo-2-
Naphthol, (m, o, p) -bromophenol, 4-
Bromoresorcinol, (m, o, p) -fluoropheno
, P-iodophenol: 2,2-dichloroethanol
2,3-dichloro-1-propanol, 1,3-di
Chloro-2-propanol, 3-chloro-1- (α-c
(Rolomethyl) -1-propanol, 2,3-dibromo-
1-propanol, 1,3-dibromo-2-propano
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-trichlorophen
Nol, 2,4,6-trichlorophenol, 2,4
6-tribromophenol, 2,3,5-tribromo-
2-hydroxytoluene, 2,3,5-tribromo-4
-Hydroxytoluene, 2,2,2-trifluoroeta
Knol, α, α, α-trifluoro-m-cresol,
2,4,6-triiodophenol: 2,2,4,6-
Tetrachlorophenol, tetrachlorohydroquino
, Tetrachlorobisphenol A, tetrabromobis
Phenol A, 2,2,3,3-tetrafluoro-1-
Propanol, 2,3,5,6-tetrafluoropheno
And tetrafluororesorcinol. Halogenated ke having a hydrogen-silicon bond
Iodine compounds As a silicon halide compound having a hydrogen-silicon bond
HSiCl_Three, H_TwoSiCl_Two, H_ThreeSiCl, H
(CH_Three) SiCl_Two, H (C_TwoH_Five) SiCl_Two, H (t
-C_FourH₉) SiCl_Two, H (C₆H_Five) SiCl_Two, H (C
H_Three)_TwoSiCl, H (i-C_ThreeH₇)_TwoSiCl, H_Two(C
_TwoH_Five) SiCl, H_Two(N-C_FourH₉ ) SiCl, H
_Two(C₆H_FourCH_Three) SiCl, HSiCl (C₆H_Five)_Twoetc
Is mentioned. Metal halide As metal halides, B, Al, Ga, In, Tl,
Chloride of Si, Ge, Sn, Pb, As, Sb, Bi,
Fluoride, bromide and iodide, especially BC
l_Three, BBr_Three, BI_Three, AlCl_Three, AlBr_Three, GaC
l_Three, GaBr_Three, InCl_Three, TlCl_Three, SiCl_Four, S
nCl_Four, SbCl_Five, SbF_FiveEtc. are preferred. (V) Metal oxide For solid components, metal oxides can be used as carriers.
Wear. Metal oxides are listed in Groups II to IV of the Periodic Table of the Elements.
Oxides of elements selected from the group of
Then, B_TwoO_Three, MgO, Al_TwoO_Three, SiO_Two, CaO,
TiO_Two, ZnO, ZrO_Two, SnO_Two, BaO, ThO_Two
And the like. Among these, B_TwoO_Three, MgO, Al
_TwoO_Three, SiO_Two, TiO_Two, ZrO_TwoIs preferable, and especially S
iO_TwoIs preferred. Furthermore, the complex containing these metal oxides
Oxides such as SiO_Two-MgO, SiO_Two-Al
_TwoO_Three, SiO_Two-TiO_Two, SiO_Two-V_TwoO_Five, SiO_Two−
Cr_TwoO_Three, SiO_Two-TiO_Two-Use MgO etc.
Can also. These metal oxides are usually in the form of powder.
used. The form, such as the size and shape of the powder,
Often affects the morphology of the olefin polymer
Therefore, it is desirable to adjust appropriately. Metal oxides
In order to remove poisonous substances,
Fire at as high a temperature as possible, and avoid direct contact with the atmosphere
It is desirable to handle. (Vi) Preparation of solid component Magnesium compound (component 1), titanium compound (component
2), an electron donating compound (component 3), and if necessary
Contactable metal oxides and halogen-containing
Contact with the compound may be in the presence or absence of an inert medium
Mixing under stirring or mechanically co-milling
Is done. The contact can be performed under heating at 40 to 150 ° C.
Wear. Inert media include hexane, heptane, octane
Saturated aliphatic hydrocarbons such as tan, cyclopentane, cyclo
Saturated alicyclic hydrocarbons such as hexane, benzene, toluene
And aromatic hydrocarbons such as xylene. Desirable method for adjusting solid components in the present invention
As magnesium, titanium, halogen and electron
In the case of a solid component containing a donor compound as an essential component,
No. 63-264607, No. 58-198503,
No. 62-146904 and the like.
No. More specifically, (A) Metal magnesium, (B) Halogenated hydrocarbon
Element, (c) general formula X_nM (OR)_mnOf the compound (above
(Same as the compound containing a alkoxy group)
The resulting magnesium-containing solid is (d) halogen-containing
And (e) an electron donating compound and
(F) contacting with a titanium compound
No. 264607), (A) Magnesium dialkoxide and (b) hydrogen-ke
Contacted with a silicon halide compound having an iodine bond
Thereafter, (c) contacting the titanium halide compound, and then
(D) Contact with an electron donating compound (if necessary,
Contacting with a titanium-logenated titanium compound)
-146904), (A) Magnesium dialkoxide and (b) hydrogen-ke
Contacted with a silicon halide compound having an iodine bond
Thereafter, (c) contact with an electron donating compound, and then (d)
A method of contacting a titanium compound (JP-A-58-1985)
03 publication). Of these, the method is desirable
No. The solid component is prepared as described above.
However, if necessary, the solid component may be washed with the above inert medium.
And may be further dried. Some solid components are preferred
Or 5 to 40% by weight of Mg and 1 to 2.5% by weight of Ti
%, 30 to 70% by weight of halogen, and electron-donating compound
0-20% by weight. Further, magnesium, titanium, halogen,
Solid containing metal oxide and electron donating compound as essential components
A desirable method for adjusting body components is described in JP-A-58-162.
Nos. 607 and 55-94909 and 55-1
Nos. 15405, 57-108107, 6
Nos. 1-21109, 61-174204,
Nos. 61-174205 and 61-174206
And Japanese Patent Application Laid-Open No. 62-7706.
Is mentioned. More specifically, Reaction between metal oxide and magnesium dialkoxide
The product is treated with an electron-donating compound and tetravalent halogenated titanium.
(Japanese Unexamined Patent Publication No. 58-162607)
Information), Inorganic oxides and magnesium hydrocarbyl halides
The reaction product with the compound is converted to a Lewis base compound and tetrachloride.
Method of contacting with titanium (JP-A-55-94909)
Information), Porous carriers such as silica and alkyl magnesium compounds
Before contacting the reaction product with the titanium compound
Contact with a donor compound and a silicon halide compound
(Japanese Unexamined Patent Publication Nos. 55-115405 and 57-1)
08107), Metal oxides, alkoxy group-containing magnesium compounds,
Aromatic polycarboxylic acid having carboxyl group at ortho position
Or those that contact its derivative and titanium compound
Method (Japanese Patent Application Laid-Open No. 61-174204), Metal oxides, alkoxy group-containing magnesium compounds,
Silicon compound having hydrogen-silicon bond, electron donating
Of contacting the compound with a titanium compound
-174205), Metal oxides, alkoxy group-containing magnesium compounds,
Halogen element or halogen-containing compound, electron donating
Contacting a compound with a titanium compound
1-1174206), Metal oxides, dihydrocarbyl magnesium and
Obtained by contacting an alcohol containing
Reaction product, an electron donating compound and a titanium compound
(JP-A-61-21109), Metal oxides, hydrocarbyl magnesium and hydride
Locarbyloxy group-containing compound (containing the alkoxy group
Solid obtained by contacting the compound)
With a halogen-containing alcohol and further donate electrons
Contacting with a reactive compound and a titanium compound (JP-A
62-7706). Among these ~
The above method is particularly preferable. Among the solid components containing metal oxides, preferred are
Preferably, Mg is 2 to 12%, Ti is 1 to 5%, halogen
Is 10 to 35% by weight, the metal oxide is 30 to 70% by weight,
The electron-donating compound is contained in an amount of 0 to 20% by weight. 2. Solid catalyst components from solid component processing
Production of (a) The solid catalyst component (a) of the present invention is characterized in that the solid component is B
r_Two, I_Two, CBr_Four, CI_Four, Alkyl bromide, al
Kill iodide or general formula MetR_xIndicated by
It is produced by treating with a compound. General used in the present invention
Formula MetR_xIn the compound shown by Met, Met
g, B, Al, Ga, Ge, In, Sn, Sb or transition
Transfer metal elements, preferably Ti, Mg, B, Al, Co,
Rh, Ni, Pd, and Zn. R is Br, I or
Represents a hydrocarbon-containing group, at least one of which is Br or I
And preferably contains two or more Br or I. Charcoal
Hydrogen-containing groups include methyl, ethyl, propyl,
Alkyl groups such as tyl, hexyl and octyl;
And phosphine groups such as luphosphine. on the other hand
Unsuitable as R is Cl or OR '(R' is
Alkyl group and aryl group)
MFR direction of the produced polypropylene even when using no compound
No effect. x is the valence of Met described above. Specific compounds include boron bromide, iodine
Boron chloride, ethyl dibromo boron, ethyl aluminum
Sesquibromide, ethyl aluminum sesquiioda
, Ethyl aluminum dibromide, aluminum bromide
, Palladium bromide, bis (triphenylphosphine)
N) Palladium dibromide, nickel bromide, sub-bromide
Lead, magnesium bromide, titanium bromide and the like. Ma
Of alkyl bromide and alkyl iodide
Alkyl groups include methyl, ethyl, propyl, butyi
Hexyl, octyl and the like. The method for treating the solid component is Br_Two, I_Two, CB
r_Four, CI_Four, Alkyl bromide, alkyl iodide
Or the general formula MetR_xInactive compounds represented by
Mix and stir with solid components in the presence or absence of a medium
Or by mechanically co-milling. Processing is 4
This is performed under heating at 0 to 150 ° C. As an inert medium,
Saturated aliphatic hydrocarbons such as xane, heptane and octane;
Saturated alicyclic hydrocarbons such as cyclopentane and cyclohexane
Aromatic hydrocarbons such as nitrogen, benzene, toluene and xylene
Can be used. (2) Aluminum compound or composition
(B) The catalyst component of the present invention comprises the above solid catalyst component (a) and a general formula
(R^k)_rAl (Y)_3-r(Where R^kAre independent
And Y is an alkyl group or an aryl group,
Independently of H, alkoxy and aryloxy groups
R is an arbitrary number in the range of 0 ≦ r ≦ 3
It is. ) Organoaluminum compounds or acids
Two or more aluminum atoms through an elementary or nitrogen atom
Organoaluminum compound to which the system is bound
Aluminum compound or composition (b) that satisfies
It is obtained by prepolymerizing an α-olefin as a sub ingredient.
The general formula (R^k)_rAl (Y)_3-rAs a compound represented by
Is preferably an aluminum compound or composition shown below
Things. (I) Organic compounds containing trimethylaluminum as an essential component
Trimethylaluminium with a luminium compound or composition
Triethyl aluminum, triethyl aluminum
It can be used in combination with isobutyl aluminum, etc.
You. (Ii) AlR_Three(R is each independently hydrogen or
Alkyl groups, at least one of which is hydrogen
You. ), A compound represented by AlR_ThreeA
As the luminium hydride compound, specifically,
Aluminum hydride, dimethyl aluminum hydride
, Diethyl aluminum hydride, dipropyl alcohol
Luminium hydride, diisobutyl aluminum
Idride and the like. These may be used alone
, Triethyl aluminum, triisobutyl aluminum
It is also possible to use it in combination with an aluminum alloy. (3) Component (c) The prepolymerization in the preparation of the catalyst component (A) of the present invention comprises
(A) component and (b) component, if necessary, (c) component
Of the component to which the alkylalkoxysilane compound is added as
Can be done in the presence. Alkylalkoxysilane
The compound represented by the general formula R¹Si (OR^Two) (OCH_Three)_Two
(In the above formula, R¹Is branched or cyclic having 3 to 6 carbon atoms
Is an alkyl group of^TwoRepresents a branched alkyl group having 3 to 6 carbon atoms.
It is an alkyl group, an alkenyl group or an alkynyl group. )
And a silane compound represented by the following formula (C).
The same silane compound as the component can be used. (4) Pre-polymerization conditions In the present invention, the pre-polymerization comprises the component (a) and the component (b)
Components and, if necessary, olefins in the presence of component (c).
This is done by contact. Ole used for prepolymerization
As the fin, ethylene, propylene, 1-butene,
Α-ole such as 1-hexene and 4-methyl-1-pentene
Fins. Prepolymerization is normal butane, iso
Butane, normal pentane, isopentane, hexane,
Heptane, octane, cyclohexane, benzene, tol
It is preferably carried out in an inert hydrogen such as ene or xylene.
The pre-polymerization temperature is 0 to 50 ° C, preferably 0 to 30 ° C,
More preferably, it can be carried out at a temperature of 5 to 25 ° C.
The polymerization method may be a batch type or a continuous type, and may be two or more stages.
The above may be performed in multiple stages. Component (b) has a concentration of 10 to 10 in the prepolymerized system.
500 mmol / l, preferably 30-200
It is used to make up to mol / l, and the ingredients
1 to 50,000 moles per mole of titanium in (a),
It is preferably used in an amount of 2 to 1,000 mol.
You. Olefin polymer is added to component (a) by pre-polymerization.
The amount of the polymer is 1 g of the component (a).
0.1 to 200 g, especially 0.5 to 50 g
Is preferred. The solid catalyst component thus prepared
Can be diluted or washed with the above-mentioned inert medium.
However, from the viewpoint of preventing catalyst deterioration,
Is preferred. After washing, it may be dried if necessary. Touch
When storing media, it is best to store them at as low a temperature as possible.
Preferably, -50 ° C to + 30 ° C, especially -20 ° C to + 5 ° C
Temperature ranges are recommended. 2. Component (B) Formula (R^k)_rAl
(Y)_3-r(Where R^kAre each independently an alkyl
And Y are each independently
A group selected from a alkoxy group and an aryloxy group.
R is an arbitrary number in the range of 0 ≦ r ≦ 3. )
Organic aluminum compounds or oxygen atoms or nitrogen
Organic compounds with two or more aluminum atoms bonded through atoms
Luminium compound component (B) Organoaluminum compound
Is represented by the general formula: (R^k)_rAl (Y)_3-r(Where R^kHaso
Each independently selected from an alkyl group and an aryl group
Y is each independently chlorine, alkoxy,
A group selected from the group consisting of
Is an arbitrary number in the range of 0 ≦ r ≦ 3. )
It is a compound. Preferably, one of the following compounds is used alone
Or you can select and use a combination of two or more
You. (I) Dialkyl aluminum monoalcohol
Oxides such as dimethylaluminum methoxide, die
Chill aluminum ethoxide, dipropyl aluminum
Ethoxide, diisopropylaluminum ethoxide,
Diisobutylaluminum ethoxide, di (n-butyl
L) aluminum ethoxide, di (n-hexyl) al
Minium ethoxide, di (n-octyl) aluminum
Ethoxide and the like can be mentioned. (Ii) Alkyl aluminum dialkoxy
Sid, such as methylaluminum diethoxide, ethyl
Aluminum diethoxide, propyl aluminum die
Toxide, n-butylaluminum diethoxide, iso
Butyl aluminum diethoxide, n-hexyl aluminum
Num ethoxide, n-octyl aluminum dieth
Oxide and the like. (Iii) trialkoxy aluminum
For example, trimethoxyaluminum, triethoxyaluminum
And the like. (Iv) alkylaluminoxane, for example,
Methyl aluminoxane, ethyl aluminoxane and the like
Can be (V) Dialkylaluminum monopheno
Oxides such as diethylaluminum phenoxide, di
Isobutylaluminum phenoxide and the like. (Vi) Trialkyl aluminum, for example
Trimethyl aluminum, triethyl aluminum,
Tripropyl aluminum, triisopropyl aluminum
Aluminum, tributyl aluminum, triisobutyl aluminum
And trihexyl aluminum. The alkyl group preferably has 1 carbon atom.
To 18 alkyl groups, and the alkoxy group is preferably
It is an alkoxy group having 1 to 10 carbon atoms. An aryl group is
For example, a phenyl group and the like, and an aryloxy group is, for example,
For example, a phenoxy group. Of these, trialkyl aluminum is preferred.
Preferably, especially trimethyl aluminum, triethyl aluminum
Minium and triisobutylaluminum are preferred
From the viewpoint of improving MFR, trimethyl aluminum
Is most preferred. Also, trialkyl aluminum is
Can be used in combination with other organic aluminum compounds
You. Alternatively, an organoaluminum other than those described above
Two or more compounds via an oxygen atom or a nitrogen atom
Use of organoaluminum compound with luminium
Wear. Such compounds include, for example, (C_TwoH_Five)_Two
AlOAl (C_TwoH_Five)_Two, (C_FourH₉)_TwoAlOAl (C_Four
H₉)_Two, (C_TwoH_Five)_TwoAlN (C_TwoH_Five) Al (C_TwoH_Five)_Two
And the like. 3. Component (C) Alkylalkoxysilane
Compound Examples of the alkylalkoxysilane compound include, for example, general
formula: R¹Si (OR^Two) (OCH_Three)_Two (In the above formula, R¹Is branched or cyclic having 3 to 6 carbon atoms
Is an alkyl group of^TwoRepresents a branched alkyl group having 3 to 6 carbon atoms.
It is an alkyl group, an alkenyl group or an alkynyl group. )
Alkyl trialkoxysilane represented by
You. R¹For example, isopropyl group, t-butyl
Group, s-butyl group, t-amyl group, cyclopentyl group,
And cyclohexyl group. R^TwoFor example,
Isopropyl, t-butyl, s-butyl, t-butyl
Mill group, 2-methyl-3-butenyl group, 3-methyl-2
-Butenyl group, 2-methyl-3-butynyl group and the like.
It is. Specific compounds include, for example, t-butoxyc
Lopentyldimethoxysilane, isopropoxycyclope
Dimethyl dimethoxysilane, s-butoxycyclopentyl
Dimethoxysilane, t-amyloxycyclopentyldi
Methoxysilane, (2-methyl-3-butene-2-oxo
B) cyclopentyldimethoxysilane, (3-methyl-
2-butene-1-oxy) cyclopentyldimethoxy
Orchid, (2-methyl-3-butene-2-oxy) cyclo
Pentyl dimethoxysilane, t-butoxycyclohexyl
Rudimethoxysilane, isopropoxycyclohexyldi
Methoxysilane, s-butoxycyclohexyldimethoxy
Sisilane, t-amyloxycyclohexyldimethoxy
Silane, (2-methyl-3-butene-2-oxy) cyclo
Rohexyl dimethoxysilane, (3-methyl-2-bute
1-oxy) cyclohexyldimethoxysilane,
(2-methyl-3-butene-2-oxy) cyclohexyl
Rudimethoxysilane and the like. As the alkylalkoxysilane compound,
In addition to the above, lactone and carboxyl group-containing
Alkylalkoxysilane, silicon atom as a ring constituent atom
And alkyl having a heterocyclic substituent having a nitrogen atom
Alkoxysilanes and the like can also be preferably used.
You. 4. Component (D) The compound of the component (D) has the general formula MetR_xRepresented by
It is a compound. Where Met is Mg, Al, B, Ga, G
e, In, Sn, Sb or a transition metal element. concrete
Include B, Mg, Al, Sc, Ti, V, Cr, Mn,
Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, M
o, Tc, Ru, Rh, Pd, Ag, Cd, La, H
f, Ta, W, Re, Os, Ir, Pt, Au, Hg,
Ga, In, Ge, Sn, and Sb, among which
But Ti, Mg, B, Al, Co, Rh, Ni, P
Metal elements selected from d and Zn are preferred, and more preferred.
And B and Al. R represents a halogen atom or a hydrocarbon
It is a group, and at least one is a halogen atom. R
May be the same or different combinations. x is the source of Met
Indicates the child price. As the halogen atom for R, bromine, iodine
Element and chlorine. In addition, as a hydrocarbon-containing group of R
Alkyl, alkoxy, aryl, aryl
A luoxy group and a phosphine group. Alkyl
Groups include methyl, ethyl, propyl, butyl, hex
Methoxy, ethoxy, etc.
Xy, propoxy, isopropoxy, butoxy, t-bu
Aryl groups such as phenyl;
Phenoxy, etc. and phosphine
May include triphenylphosphine and the like.
R is preferably two or more halogen atoms.
More preferably contains at least one bromine or iodine.
And more preferably two bromine or iodine
It is a compound containing the above. Specific compounds include bromide
Boron, boron iodide, ethyldibromoboron, ethyla
Luminium sesquibromide, ethyl aluminum ces
Chiaodide, aluminum bromide, palladium bromide,
Bis (triphenylphosphine) palladium diblomer
, Zinc bromide, magnesium bromide, nickel bromide, etc.
No. 5. Component (E) As the polymerization catalyst of the present invention, if necessary, ZnR_Two
Can be used by adding a zinc compound (E) represented by
Wear. ZnR_TwoThe zinc compound represented by is an alkyl zinc
Wherein the alkyl group is an alkyl group having 1 to 4 carbon atoms.
Groups. Specifically, dimethyl zinc, diethyl
Zinc and the like. 6. Component (F) Further, in the present invention, if necessary, component (F)
And use by adding aluminum hydride compound
be able to. By using component (F), stereoregularity can be improved.
The MFR can be increased while maintaining the
The combined use of (E) and (F) further increases the MFR
Can be higher. Aluminum hydride
The compound is AlR_Three(R is each independently hydrogen
Or an alkyl group, at least one of which is water
Is prime. ) And the organic compound of component (B)
It is a compound that does not correspond to a luminium compound. Specifically
Is aluminum hydride, dimethyl aluminum hydride
Ride, diethyl aluminum hydride, dipropy
Aluminum hydride, diisobutylaluminum
Mu hydride and the like. 7. (A), (B), (C), (D),
(E), ratio of (F) component The catalyst of the present invention comprises the above-mentioned components, but is preferably
Is the amount of component per mole of titanium in component (A)
70 to 600 mol of (B) and 10 to 30 mol of component (C)
2-200 moles of component (D) and 9 of component (E)
６００600 moles are blended. More preferably in component (A)
90 to 400 mol of the component (B) per 1 mol of titanium,
15 to 25 mol of the component (C) and 9-1 to the component (D)
Mix 50 moles. When using components (E) and (F)
In the case, the component (E) per mole of titanium in the component (A) is
30 to 500 mol, and 20 to 300 mol for the component (F).
It is preferable to combine them. 8. Polymerization of α-olefin Component (A) preliminarily polymerized as described above, component
(B), component (C), component (D), if necessary, component
(E), α-olefin in the presence of a catalyst comprising component (F)
Polymerization of the resin. As the α-olefin, carbon
Linear or branched α-olefins having a number of 2 to 10 are preferred.
Preferably, for example, ethylene, propylene, butylene, pen
Ten, hexene, heptene, octene and the like.
The catalyst of the present invention is not limited to homopolymerization of α-olefin.
Can be used for copolymerization of two or more α-olefins
You. The catalyst of the present invention is particularly preferably
Polymerization and their copolymerization (random copolymerization or
Or any one of copolymerization). Reaction conditions for polymerization of α-olefin
Can be used under conventional conditions. For example, -20 to +15
At 0 ° C., preferably 0-100 ° C. and 1-60 atm.
Performed for 5-7 hours. The polymerization reaction can be carried out in the gas phase or in the liquid phase.
May be performed. When the reaction is performed in the liquid phase, the above-mentioned inert medium is used.
It can be performed in the body or in a liquid monomer. Also,
The polymerization may be carried out either batchwise or continuously. Heavy
The combined reaction may be performed in one step, and the polymerization conditions were changed.
And the type of monomer used is changed,
You may. To control the molecular weight of the resulting polymer
A known molecular weight controlling agent such as hydrogen is present in the polymerization reaction system.
Can be made. [0065] The present invention will be described in more detail with reference to the following examples.
I will tell. The percentages are by weight unless otherwise specified. Example 1 (1) Preparation of solid component (a1) In a 1 liter reaction vessel equipped with a reflux condenser, add nitrogen gas
Under an atmosphere, chip-shaped metallic magnesium (purity 99.
5%, average particle size 1.6 mm) 8.3 g and n-hexa
After stirring at 68 ° C for 1 hour,
A method of removing nesium and drying it at 65 ° C under reduced pressure
To obtain preactivated magnesium metal. Next, n-butyric acid was added to the metallic magnesium.
Luether 140 ml and n-butylmagnesium chloride
Chloride in n-butyl ether (1.75 mol / l
Torr) 0.5 ml of the added suspension was kept at 55 ° C.
n-butyl chloride 3 in 50 ml of n-butyl ether
A solution in which 8.5 ml was dissolved was added dropwise over 50 minutes. Stirring
After conducting the reaction at 70 ° C for 4 hours, the reaction solution was kept at 25 ° C.
I carried it. Next, HC (OC) was added to the reaction solution._TwoH_Five)_Three5
5.7 ml was added dropwise over 1 hour. After dropping, 60
At 15 ° C. for 15 minutes.
Wash with 300ml each 6 times and dry under reduced pressure at room temperature for 1 hour.
Containing 19.0% of Mg and 28.9% of chlorine
31.6 g of a solid containing cesium was recovered. Remove the reflux condenser, stirrer and dropping funnel.
In a 300 ml reaction vessel attached under nitrogen gas atmosphere,
6.3 g of magnesium-containing solid and 50 n-heptane
into a suspension and stirred at room temperature while stirring.
20 ml of 2-trichloroethanol (0.02 mM
And a mixed solution of 11 ml of n-heptane and a dropping funnel
From 30 minutes, and further stirred at 80 ° C. for 1 hour.
Was. The obtained solid was filtered, and n-hexane at room temperature for 10
Wash 4 times with 0 ml, then add 2 ml with 100 ml each of toluene.
Washed twice to obtain a solid component. [0068] 40 ml of toluene was added to the above solid components.
Furthermore, the volume ratio of titanium tetrachloride / toluene is reduced to 3/2.
Then, titanium tetrachloride was added thereto, and the temperature was raised to 90 ° C. Stirring
Under stirring, mix 2 ml of dibutyl phthalate and 5 ml of toluene
The solution was added dropwise over 5 minutes and stirred at 120 ° C for 2 hours
did. In addition, a new volume of titanium tetrachloride / toluene
Add titanium tetrachloride so that the ratio becomes 3/2, and add 120
Stirred at C for 2 hours. The obtained solid substance was filtered at 110 ° C.
Separately, wash 7 times with 100 ml of n-hexane at room temperature
did. Thus, 5.5 g of a solid component (a1) was obtained. (2) Adjustment of solid catalyst component 300 ml reaction with reflux condenser and stirrer
Under a nitrogen gas atmosphere, put 4 g of the above-mentioned solid component in a vessel.
120 ml of butane were added. 1 mol / l of boron bromide
Add 23 ml of n-heptane solution and stir at 65 ° C for 1 hour.
Stirred. The obtained treated solid was added to n-hexane at room temperature for 10 times each.
After washing 7 times with 0 ml, drying under reduced pressure and solid touch of red-orange powder
A medium component was obtained. (3) Preliminary polymerization In a 200 ml reactor equipped with a stirrer, add a nitrogen gas atmosphere.
Under ambient atmosphere, 2.1 g of the solid catalyst component obtained in (2) above
And 100 ml of n-heptane.
Cool. Next, trimethyl aluminum (TMAL)
The concentration in the reaction system will be 60 mmol / l
And stirred for 5 minutes. Next, the pressure in the system was reduced.
Thereafter, propylene gas is continuously supplied, and propylene is supplied for 6 hours.
Polymerized for 0 minutes. After polymerization is completed, propylene in the gas phase is
Purge with raw gas and 3 times with 100 ml of n-hexane each
The solid phase was washed at room temperature. In addition, let the solid phase
The mixture was dried under reduced pressure to prepare a catalyst component. Included in catalyst components
As a result of measuring the amount of magnesium
The amount was 1.9 g per 1 g of the catalyst component. (4) Polymerization of propylene 1.5 liter stainless steel oven with stirrer
The catalyst obtained in the above (3) was placed in a nitrogen atmosphere under a nitrogen atmosphere.
Ingredient 4.4mg, triethylaluminum (TEAL)
1.6 mmol, t-amyloxycyclopentyl dimethoate
0.08 mmol of xysilane and 7 ml of n-heptane
Were mixed and the one kept for 5 minutes was added. Then bromination
0.016 mmol of boron is added as a molecular weight controlling agent
6000 ml (normal temperature, normal pressure) and liquid prop
After injecting 1 liter of ren, the reaction system was heated to 70 ° C.
Then, propylene was polymerized for 1 hour. After polymerization is completed,
Purging propylene and hydrogen from the reaction and taking out the polymer
And dried. The total amount of the obtained polymer was 196 g,
Its melt flow rate (MFR) is 165.6 g / 1
0 minutes, the content of hot heptane insolubles (HI) was 95.7%.
Was. The MFR is in accordance with ASTM D1238.
At 230 ° C. under a load of 2160 g,
In a modified Soxhlet extractor with boiling n-heptane
This is the remaining amount when extracted for 6 hours. These measurement methods
Is the same in the following. Embodiment 2 In the prepolymerization of Example 1 (3),
And the time was as shown in Table 1.
Preparation of the catalyst component and polymerization of propylene
Was. Table 1 shows the results. Embodiments 3 and 4 In the preparation of the solid catalyst component of Example 1 (2),
Example except that the treating agents shown in Table 1 were used instead of urine
Preparation was performed in the same manner as in Example 1. (3) Prepolymerization smell
Except that the prepolymerization temperature and time were as shown in Table 1.
Preparation of the catalyst component and propylene
Was polymerized. Table 1 shows the results. Examples 5 to 6 In the prepolymerization of Example 1 (3), trimethyl aluminum
Use triethylaluminum instead of
Except that the polymerization temperature and time were as shown in Table 1,
Preparation of catalyst component and propylene weight in the same manner as in Example 1.
Was performed. Table 1 shows the results. Embodiment 7 In the prepolymerization of Example 1 (3), trimethyl aluminum
Use the aluminum composition shown in Table 1 instead of Ni
And the prepolymerization temperature and time were as shown in Table 1.
Was performed in the same manner as in Example 1. (4) Propylene
In the polymerization of t-amyloxycyclopentyldimethyl
Sec-butoxycyclopentene in place of toxic silane
Same as Example 1 except that rudimethoxysilane was used.
To polymerize propylene. Table 1 shows the results. Embodiment 8 In the prepolymerization of Example 1 (3), trimethyl aluminum
Use the aluminum compounds shown in Table 1 in place of Ni
And the prepolymerization temperature and time were as shown in Table 1.
Was performed in the same manner as in Example 1. (4) Propylene
In the polymerization of aluminum bromide instead of boron bromide
Propylene in the same manner as in Example 1 except that
Was polymerized. Table 1 shows the results. Embodiment 9 (1) Preparation of solid component (a2) 200 ml flask equipped with dropping funnel and stirrer
The gas was replaced with nitrogen gas. The flask is flushed with nitrogen
2 hours at 200 ° C and 5 hours at 700 ° C
Sintered silicon oxide (manufactured by DAVISON, trade
Product name G-952) 5 g and n-heptane 40 ml
Was. Further, n-butylethylmagnesium (hereinafter, referred to as n-butylethylmagnesium)
BEM) in a 20% -n-heptane solution (Texa
MAGALA BEM (trade name, manufactured by Salkyls) 20
Then, the mixture was stirred at 90 ° C. for 1 hour. The obtained suspension was cooled to 0 ° C.
Then, 11.2 g of tetraethoxysilane was added to 20 ml of n-
Take the solution dissolved in heptane from the dropping funnel for 30 minutes
And dropped. After dropping, heat up to 50 ° C over 2 hours
Then, stirring was continued at 50 ° C. for 1 hour. After completion of stirring, decane
The supernatant is removed by filtration, and the resulting solid is
Wash with n-heptane at room temperature and add decane
The supernatant was removed by filtration. This n-hepta
Washing treatment was further performed four times. To the above solid, 50 ml of n-heptane was added.
Into a suspension and add 2,2,2-trichloroethane
Of ethanol in 10 ml of n-heptane.
The solution was dropped from the dropping funnel at 25 ° C. over 15 minutes.
Was. After completion of the dropwise addition, stirring was continued at 25 ° C. for 30 minutes. Stirring
At the end, at room temperature, add 2 ml with 60 ml of n-heptane.
Wash three times with 60 ml toluene each time
Was. The resulting solid (solid component I) was analyzed.
Roller, SiO_Two: 36.6%, Mg: 5.1%, Cl:
It contained 38.5%. The solid component I obtained above was added to n-hepta
10 ml of titanium tetrachloride and 40 ml of titanium tetrachloride.
The temperature was raised to 5 ml, and phthalic acid
0.6 g of n-butyl was added over 5 minutes. afterwards,
The temperature was raised to 115 ° C., and the reaction was performed for 2 hours. Cool down to 90 ° C
After removing the supernatant by decantation, the n-hepta
Washing was performed twice with 70 ml. Further n-heptane 1
Add 5 ml and titanium tetrachloride 40 ml, and at 115 ° C for 2 hours
Reaction. After the reaction is completed, the obtained solid substance is
Washing was performed 8 times at room temperature with 1 n-hexane. Next
And dried at room temperature under reduced pressure for 1 hour to obtain 8.3 g of solid
The component (a2) was obtained. As a result of analysis, this component contained Ti
3.1% by weight, and Si, Mg, C
l and di-n-butyl phthalate
I accepted. (2) Preparation of solid catalyst component 300 ml reaction with reflux condenser and stirrer
Under a nitrogen gas atmosphere, put 4 g of the above-mentioned solid component in a vessel.
120 ml of butane were added. 1 mol / l of boron bromide
Add 23 ml of n-heptane solution and stir at 65 ° C for 1 hour.
Stirred. The obtained treated solid was added to n-hexane at room temperature for 10 times each.
After washing 7 times with 0 ml, drying under reduced pressure and solid touch of red-orange powder
A medium component was obtained. (3) Preliminary polymerization In a 200 ml reactor equipped with a stirrer, add a nitrogen gas atmosphere.
Under ambient atmosphere, 2.0 g of the solid catalyst component obtained above and n-
Add 100 ml of heptane and cool to 10 ° C with stirring
did. Next, trimethylaluminum is concentrated in the reaction system.
Add the solution to a concentration of 60 mmol / l and add 5 minutes
While stirring. Then, after the pressure in the system was reduced,
And continuously polymerize propylene for 40 minutes.
Was. After polymerization, purge gas phase propylene with nitrogen gas
And three times with 100 ml of n-hexane at room temperature three times.
Was washed. Further, the solid phase is dried under reduced pressure for 1 hour at room temperature.
Thus, a catalyst component was prepared. Magnesium contained in catalyst components
As a result of the measurement of the amount of
Weight was 1.9 g. (4) Polymerization of propylene 1.5 liter stainless steel oven with stirrer
The catalyst obtained in the above (3) was placed in a nitrogen atmosphere under a nitrogen atmosphere.
Ingredient 8.9 mg, triethylaluminum 1.6 mmol
, T-amyloxycyclopentyldimethoxysilane
Mixing 0.08 mmol and 7 ml of n-heptane,
The one held for 5 minutes was placed. Then, boron bromide 0.
016 mmol, and hydrogen as a molecular weight controlling agent was added to 6
000 ml (normal temperature, normal pressure) and 1 liter of liquid propylene
After the pressure was increased, the temperature of the reaction system was raised to 70 ° C. and
Propylene was polymerized. After the polymerization,
Purge pyrene and hydrogen, remove polymer and dry
Was. The total amount of the obtained polymer was 195 g,
Flow rate (MFR) is 201.0 g / 10 min, heat
The heptane insoluble content (HI) was 94.8%. Embodiment 10 In the preparation of the solid catalyst component of Example 9 (2),
Example 8 with the exception that boron iodide was used instead of iodine.
Preparation of the catalyst component and polymerization of propylene were performed in the same manner.
Was. Table 1 shows the results. Examples 11 to 12 In the preparation of the solid catalyst component of Example 9 (2),
Use aluminum bromide in place of iodine.
Trimethyl aluminum instead of trimethyl aluminum
Use ethyl aluminum and adjust the pre-polymerization temperature and time.
The contact was carried out in the same manner as in Example 8 except that it was as shown in Table 1.
Preparation of a medium component and polymerization of propylene were performed. Table of results
It is shown in FIG. Embodiment 13 In a 200 ml reactor equipped with a stirrer, add a nitrogen gas atmosphere.
2.1 g of the solid catalyst component obtained in (2) of Example 1 under ambient atmosphere
And 100 ml of n-heptane, and with stirring, 20
° C. Next, trimethylaluminum, t-amiloki
Cycyclopentyldimethoxysilane is concentrated in the reaction system.
The degree is 60 mmol / l and 10 mmol / l respectively.
Liter and stirred for 5 minutes. Next
After the pressure in the system is reduced, propylene gas is continuously supplied.
Then, propylene was polymerized for 30 minutes. After the polymerization,
The phase propylene is purged with nitrogen gas and 100 ml of each
The solid phase was washed three times with n-hexane at room temperature. Furthermore,
The solid phase was dried under reduced pressure at room temperature for 1 hour to prepare a catalyst component.
Was. The results of measuring the amount of magnesium contained in the catalyst component
As a result, the prepolymerization amount was 2.0 g per 1 g of the solid catalyst component.
Was. Using the obtained solid components, the same procedures as in Example 1 were carried out.
To polymerize propylene. Table 1 shows the results. Embodiment 14 In the prepolymerization of Example 1 (3), the prepolymerization temperature and
As in Example 1, except that the time was as shown in Table 1.
I went. In the polymerization of propylene of (4),
Trimethylaluminum instead of triethylaluminum
System instead of boron bromide
Except that iodide was used, the same as in Example 1
Propylene was polymerized. Table 1 shows the results. Embodiment 15 In the prepolymerization of Example 13, the prepolymerization temperature and time
Was performed in the same manner as in Example 13 except that
I went. In the propylene polymerization of Example 1,
Using the obtained catalyst component, triethylaluminum
Instead, trimethylaluminum is replaced with t-amyloxycycline.
Sec-butoxy instead of lopentyldimethoxysilane
Except for using cyclopentyldimethoxysilane,
Polymerization of propylene was carried out in the same manner as in Example 1. result
Are shown in Table 1. Embodiment 16 1.5 liter stainless steel oven with stirrer
The catalyst obtained in Example 13 in a nitrogen atmosphere under a nitrogen atmosphere.
5.1 mg of component, 1.6 mmol of trimethylaluminum
, T-amyloxycyclopentyldimethoxysilane
Mixing 0.08 mmol and 7 ml of n-heptane,
The one held for 5 minutes was placed. Then, boron bromide 0.
016 mmol, 1.6 mmol diethyl zinc, diethyl
0.4 mmol of aluminum hydride and add
6000 ml of hydrogen as a molecular weight control agent (normal temperature, normal pressure)
And 1 liter of liquid propylene
Was heated to 70 ° C., and propylene was polymerized for 1 hour.
Was. After polymerization, purge unreacted propylene and hydrogen
Then, the polymer was taken out and dried. Table 1 shows the results. Comparative Example 1 In the prepolymerization of Example 1 (3), trimethyl aluminum
Use triethylaluminum instead of
Example 1 was repeated except that the polymerization time was as shown in Table 2.
A catalyst component was prepared in the same manner. (4) propyle
Except that boron bromide was not used in the polymerization of
In the same manner as in Example 1, propylene was polymerized.
Table 2 shows the results. Comparative Example 2 In the preparation of the solid catalyst component of Example 1 (2),
Preliminary polymerization in the preliminary polymerization of (3) without using urine
Example 1 except that the temperature and time were as shown in Table 2.
Preparation of a catalyst component was carried out in the same manner as described above. (4) Propi
The reason for not using boron bromide in the polymerization of
Outside, polymerization of propylene was carried out in the same manner as in Example 1.
Was. Table 2 shows the results. Comparative Example 3 In the prepolymerization of Example 1 (3), the prepolymerization temperature and
As in Example 1, except that the time was as shown in Table 2.
Thus, a catalyst component was prepared. (4) Weight of propylene
In practice, except that boron bromide was not used,
Propylene was polymerized in the same manner as in Example 1. The result
It is shown in Table 2. Comparative Example 4 In Example 1, the solid catalyst component (2) was prepared.
Preparation of the catalyst component in the same manner as in Example 1 except that there was no
And propylene. Table 2 shows the results. Comparative Example 5 In Example 1, the solid catalyst component (2) was prepared.
Table 2 shows the prepolymerization temperature and time in the prepolymerization of (3).
Except as shown, a catalyst composition was prepared in the same manner as in Example 1.
Was prepared and propylene was polymerized. Table 2 shows the results
Show. Comparative Example 6 In Example 15, the solid catalyst component (2) was prepared.
Except for that, the catalyst component was
Preparation and polymerization of propylene were performed. The results are shown in Table 2.
You. Comparative Example 7 In the polymerization of propylene in Example 9 (4),
Except that no element was used.
Pyrene was polymerized. Table 2 shows the results. Comparative Example 8 In Example 9, the solid catalyst component (2) was prepared.
In the prepolymerization of (3), the prepolymerization temperature and time
In the same manner as in Example 9 except that the interval was as shown in Table 2,
To polymerize propylene. Table 2 shows the results. Comparative Example 9 In Example 9, the solid catalyst component (2) was prepared.
In the prepolymerization of (3), trimethylaluminum
Use triethyl aluminum instead of aluminum
Except that the polymerization temperature and time were as shown in Table 2,
Preparation of catalyst components and polymerization of propylene as in Example 9.
Was done. Table 2 shows the results. [0099] [Table 1] [0100] [Table 2][0101] According to the present invention, α-olefins can be
When the polymerization reaction is performed, it has high stereoregularity and high MFR
To obtain a poly-α-olefin suitable as a molding material
be able to.

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.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Issei Akira 1-3-1, Nishi-Tsurugaoka, Oi-machi, Iruma-gun, Saitama (56) References JP-A-11-349621 (JP, A) JP-A-11-302316 (JP, A) JP-A-11-140116 (JP, A) JP-A-2-229805 (JP, A) JP-A-9-52910 (JP, A) JP-A-2 -160806 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (1)

(57) [Claims 1] (A) (a) Solid components containing magnesium, titanium, halogen and an electron donating compound as essential components are Br ₂ , I ₂ , CBr ₄ , CI ₄ , Alkyl bromide, alkyl iodide, or general formula MetR
_X (where Met is Mg, B, Al, Ga, Ge, I
n, Sn, Sb or a transition metal element, and R is Br, I
Or a hydrocarbon-containing group, at least one of which is Br or I, and x represents the valency of Met. A) a solid catalyst component treated with the compound represented by the formula (b): (b) a general formula (R ^k ) _r Al (Y) _3-r (where R ^k is each independently an alkyl group or an aryl group; , Y are each independently a group selected from H, an alkoxy group and an aryloxy group, and r is an arbitrary number in the range of 0 ≦ r ≦ 3), or an oxygen atom Or an organic aluminum compound in which two or more aluminums are bonded via a nitrogen atom as an essential component,
a catalyst component obtained by prepolymerizing an α-olefin,
(B) a general formula (R ^k ) _r Al (Y) _3-r (where R ^k is each independently an alkyl group or an aryl group;
Y is each independently a group selected from an alkoxy group and an aryloxy group, and r is an arbitrary number in the range of 0 ≦ r ≦ 3. An organoaluminum compound represented by the formula: or an organoaluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom,
(C) an alkylalkoxysilane compound, and (D) a general formula MetR _X (where Met is Mg, B, Al, G
a, Ge, In, Sn, Sb or a transition metal element;
R represents a halogen atom or a hydrocarbon-containing group, at least one of which is a halogen atom, and x represents the valency of Met. ) A catalyst for polymerization of α-olefins comprising the compound represented by the formula: