JP3172597B2 - α-olefin polymerization catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to an α-olefin polymerization catalyst. More specifically, α-olefins, in particular,
The present invention relates to a polymerization catalyst suitable for producing an isotactic polyolefin.

[0002]

2. Description of the Related Art Various transition metal compounds are known as catalysts used for producing isotactic polyolefins. For example, Japanese Patent Application Laid-Open Nos. 61-264010 and 64-64
51408, 64-66216, 63-25140
5, 63-295607, 64-74202 and JP-A-3-12406.

[0003]

However, these transition metal compounds must have a complicated structure in order to secure the stereoregularity of the polymer, and are not only expensive but also difficult to obtain. .

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and uses an easily available compound such as cyclopentadienyltitanium trichloride (CpTiCl ₃ ) to obtain an α-olefin polymer, To provide a catalyst capable of producing an isotactic α-olefin-based polymer, and to provide a polymerization catalyst having good properties such as bulk density and particle size distribution of the obtained polymer or copolymer. The purpose is to:

[0005]

In order to achieve the above object, the present invention comprises the following compounds (A) and (B) as main components, and at least the compound (A) is supported on a carrier (D). An α-olefin polymerization catalyst characterized by comprising: (A): a transition metal compound represented by the following general formula: CpMXn [where Cp is a cyclic unsaturated hydrocarbon group-containing group, a transition metal atom selected from the group MIVB, X is a ligand having a σ bond, Indicates a ligand or Lewis base. Xs may be the same or different. n is an integer of valence-1 of the transition metal M. (B) a compound which reacts with the transition metal compound (A) to form an ionic complex, and further comprises the catalyst and an organoaluminum (C) as main components.
-To provide a catalyst for olefin polymerization.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. 1. Transition metal compound (A) In the present invention, compound (A) is represented by I in the periodic table.
A transition metal selected from the group VB, ie, titanium (T
i), any compound containing zirconium (Zr), hafnium (Hf) and a cyclic unsaturated hydrocarbon group can be used. In particular, a monocyclopentadienyl compound represented by the following general formula (I) or a monocyclopentadienyl compound represented by the following general formula (I): Derivatives are preferred. CpMXn (I) wherein M is a transition metal selected from Group IVB of the periodic table,
That is, it represents a Ti, Zr or Hf atom, and Cp is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group. And the like. X represents a ligand such as a σ-binding ligand, a chelating ligand, a Lewis base, etc. Specific examples of the σ-binding ligand include a hydrogen atom, an oxygen atom, a halogen atom,
C1-C20 alkyl group, C1-C20 alkoxy group, C6-C20 aryl group, aryloxy group, alkylaryl group or arylalkyl group, C1-C20 acyloxy group, allyl group , A substituted allyl group, a substituent containing a silicon atom and the like, and examples of the chelating ligand include an acetylacetonate group and a substituted acetylacetonate group. Xs may be the same or different from each other, and two or more of them may be bonded to each other to form a ring. n is an integer of valence-1 of the transition metal M. Further, as the compound (A), the following general formula (II):

[0007]

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[Where Cp, M, and X are the same as described in the formula I above. Z is ^{_{SiR 1 2, CR 1 2,}} SiR 1 2 S
^{_{iR 1 2, CR 1 2 CR}} 1 2, CR 1 = CR 1, CR 1 2 SiR 1 2
Or a GeR ¹ _2, Y is the formula -N (R ²⁾ -, or -
P (R ² ) —, wherein R ¹ is hydrogen or a moiety having up to 20 non-hydrogen atoms selected from alkyl, aryl, silyl, halogenated alkyl, aryl halide groups and combinations thereof. And R ² is carbon 1
It may be an alkyl of up to 10 alkyl or aryl of 6 to 10 carbons or form a fused ring system of up to 30 non-hydrogen atoms with one or more R ¹ . n ′ is an integer of 1 or 2. ] The compound shown by these is also included.

The substituted cyclopentadienyl group in the above formula (I) includes, for example, methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl Group, tetramethylcyclopentadienyl group,
1,3-dimethylcyclopentadienyl group, 1,2,3
-Trimethylcyclopentadienyl group, 1,2,4-trimethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group and the like. Specific examples of X in the above formula (I) include, for example, fluorine, chlorine, bromine and iodine as halogen atoms; methyl, ethyl and n-propyl as alkyl groups having 1 to 20 carbon atoms. Group, iso-propyl group, n-butyl group, octyl group, 2-ethylhexyl group;
A methoxy group, an ethoxy group,
Propoxy group, butoxy group, phenoxy group;
A phenyl group, a tolyl group, a xylyl group, or a benzyl group as an aryl group, an aryloxy group, an alkylaryl group or an arylalkyl group having 20; a heptadecylcarbonyloxy group as an acyloxy group having 1 to 20 carbon atoms;
A trimethylsilyl group as a substituent containing a silicon atom,
(Trimethylsilyl) methyl group: Lewis bases include ethers such as dimethyl ether, diethyl ether and tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as acetonitrile and benzonitrile, trimethylamine, triethylamine, tributylamine, and the like. N, N-
Dimethylaniline, pyridine, 2,2′-bipyridine,
Amines such as phenanthroline; phosphines such as triethylphosphine and triphenylphosphine; linear unsaturated hydrocarbons such as ethylene, butadiene, 1-pentene, isoprene, pentadiene, 1-hexene and derivatives thereof; and cyclic unsaturated hydrocarbons Examples include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene, and derivatives thereof.

Examples of such compounds include the following compounds and compounds obtained by substituting zirconium of these compounds with titanium or hafnium. (Pentamethylcyclopentadienyl) zirconium trimethyl,
(Pentamethylcyclopentadienyl) zirconium triphenyl, (pentamethylcyclopentadienyl) zirconium tribenzyl, (pentamethylcyclopentadienyl) zirconium trichloride, (pentamethylcyclopentadienyl) zirconium trimethoxide,
(Cyclopentadienyl) zirconium trimethyl,
(Cyclopentadienyl) zirconium triphenyl,
(Cyclopentadienyl) zirconium tribenzyl,
(Cyclopentadienyl) zirconium trichloride,
(Cyclopentadienyl) zirconium trimethoxide, (cyclopentadienyl) zirconium dimethyl methoxide, (methylcyclopentadienyl) zirconium trimethyl, (methylcyclopentadienyl) zirconium triphenyl, (methylcyclopentadienyl)
Zirconium tribenzyl, (methylcyclopentadienyl) zirconium trichloride, (methylcyclopentadienyl) zirconium dimethylmethoxide, (dimethylcyclopentadienyl) zirconium trichloride, (trimethylcyclopentadienyl) zirconium trichloride, ( Trimethylsilylcyclopentadienyl) zirconium trimethyl, (tetramethylcyclopentadienyl) zirconium trichloride, indenyl zirconium trichloride, fluorenyl zirconium trichloride, (t-butylamide) (tetramethyl-η
⁵ -cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (methylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediylzirconium dichloride

2. Compound (B) which forms an ionic complex by reacting with a transition metal compound As the compound (B) used in the present invention, a compound containing an anionic species which stably forms a cationic species derived from the transition metal compound (A) Among them, the compound (B-1) which reacts with a transition metal compound to form an ionic complex can be used. As the compound (B-1), for example, a compound composed of a cation and an anion in which a plurality of groups are bonded to an element, particularly a coordination complex compound, can be preferably exemplified.

The compound (B-1) is represented by the following formula (II)
The compound represented by (I), (IV) or (V) can be suitably used. ([L ¹ -H] ^{g +} ) _h ([M ² X ¹ X ² ... X ⁿ ] ^(nm)- ) _i (III) ([L ² ] ^{g +} ) _h ([M ³ X ¹ X ^{2 ... X n] (nm) -} ) i ··· (IV) ( where, L ² is ^{M 4, R 2 R 3 M} 5 or _{^{R 4 3 C) ([L}} 1 -Z] g +) h ( ^{[M 2 X 1 X 2 ...} X n] (nm) -) i ··· (V) [(III), (IV) and (V) wherein, L ¹ is a Lewis base,
Z is a hydrocarbon group such as an alkyl group, an aryl group, an arylalkyl group, or an alkylaryl group; and M ² and M ³ are groups VB, VIB, VIIB, VIII, and IB of the periodic table, respectively.
M ⁴ is an element selected from the group consisting of group IIB, group IIIB, group IIIA, group IVA and group VA;
Group, a metal selected from Group VIII, M ⁵ is a metal selected from Group VIII of the Periodic Table, X ¹ to X ⁿ are each a hydrogen atom, a dialkylamino group, an alkoxy group, an aryl group, a substituted aryl group, an aryloxy group , An alkyl group, a substituted alkyl group, an organic metalloid group or a halogen atom, and R ² and R ³ are each a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group,
R ⁴ represents an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an arylalkyl group, a substituted arylalkyl group, an alkylaryl group or a substituted alkylaryl group, and each R ⁴ may be the same or different. m is a valence of M ² or M ³ and is an integer of 1 to 7, n is an integer of 2 to 8,
g is an ionic valence of L ¹ -H and L ² and is an integer of 1 to 7, h is an integer of 1 or more, and i = (h × g) / (nm). ]

Specific examples of the above Lewis base include ethers such as dimethyl ether, diethyl ether and tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as acetonitrile and benzonitrile, dimethylaniline and pyridine. , 2-cyanopyridine, 3-cyanopyridine, 4-cyanopyridine, triethylamine, 2,2-
Examples include amines such as bipyridine and phenanthroline, and phosphines such as triethylphosphine and triphenylphosphine. Specific examples of Z include a methyl group,
Examples include an ethyl group, a benzyl group, and a trityl group. M
Examples ² and ^{M 3, B, Al, Si} , P, A
s, Sb, etc. Specific examples of ^{M 4,} Ag, Cu or the like, M
Specific examples of ⁵ include Fe, Co, and Ni.
Specific examples of X ^{1 to} X ⁿ include, for example, a dimethylamino group, a diethylamino group as a dialkylamino group; a methoxy group, an ethoxy group, an n-butoxy group as an alkoxy group; a phenyl group, 4 as an aryl group and a substituted aryl group.
Those having 6 to 20 carbon atoms, such as -tolyl group, 3,5-xylyl group, benzyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group and 4-tert-butylphenyl group; Phenoxy group, 2,6-dimethylphenoxy group, naphthyloxy group as oxy group; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-octyl group, 2-ethylhexyl as alkyl group A group having 1 to 20 carbon atoms such as a group; a 5-methylantimony group as an organic metalloid group;
Trimethylsilyl group, trimethylstannyl group; examples of halogen include F, Cl, Br, I and the like. Specific examples of the substituted cyclopentadienyl group for R ² and R ³ include:
Methylcyclopentadienyl group, butylcyclopentadienyl group, pentamethylcyclopentadienyl group, trifluoromethyltetramethylcyclopentadienyl group,
A nitrocyclopentadienyl group, an ethoxycarbonylcyclopentadienyl group, and a cyanocyclopentadienyl group. Specific examples of R ⁴ include methyl group, an ethyl group, a phenyl group, p- tolyl group, p- methoxyphenyl group, p- dimethylaminophenyl group and the like.

The compounds of formulas (III), (IV) and (V)
Among them, specifically, the following can be particularly preferably used.
You.Compound of formula (III)  Trimethylammonium tetraphenylborate, tetraf
Triethylammonium phenylborate, tetraphenylboron
(N-butyl) ammonium acid, tetrakis (pen
Tafluorophenyl) dimethylanilinium borate, tet
Lakis (pentafluorophenyl) borate triethylan
Monium, tetrakis (pentafluorophenyl) borate
Tri (n-butyl) ammonium, hexafluoroarsenic
Triethylammonium acid,

[0015]Compound of formula (IV)  Ferrocenium tetraphenylborate, tetraphenylboron
Trityl acid, tetrakis (pentafluorophenyl) boron
Ferrocenium acid, tetrakis (pentafluorophenyl)
M) methylferrocenium borate, tetrakis (pentaf
(Fluorophenyl) decamethylferrocenium borate, tet
Lakis (pentafluorophenyl) borate, tetrakis
(Pentafluorophenyl) trityl borate, tetraflu
Silver boroborate, silver hexafluorophosphate, hexafluoro
Silver arsenate, silver perchlorate, hexafluoroantimonic acid
Silver, silver trifluoroacetate, trifluoromethanesulfone
Silver acid,

[0016]Compound of formula (V)  Tetrakis (pentafluorophenyl) borate (N-ben
Zyl-2-cyanopyridinium), tetrakis (penta
Fluorophenyl) boric acid (N-benzyl-3-cyanopi)
Lydinium), tetrakis (pentafluorophenyl)
Boric acid (N-benzyl-4-cyanopyridinium), tet
Lakis (pentafluorophenyl) borate (N-methyl-
2-cyanopyridinium), tetrakis (pentafluoro)
(Rophenyl) boric acid (N-methyl-3-cyanopyridinium)
), Tetrakis (pentafluorophenyl) borate (N
-Methyl-4-cyanopyridinium), tetrakis (pe
(Tantafluorophenyl) trimethylanilinium borate,
Trimethyl tetrakis (pentafluorophenyl) borate
(M-trifluoromethylphenyl) ammonium,
Benzylpyrky (pentafluorophenyl) borate
Dinium,

Further, as compound (B), compound (B-
Aluminoxane (compound (B-2)) can also be used in place of 1). The following can be mentioned as aluminoxanes.

[0018]

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(R ¹² has 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms.
And 12 hydrocarbon groups such as an alkyl group, an alkenyl group, an aryl group, and an arylalkyl group. s indicates the degree of polymerization, and is usually 3 to 50, preferably 7 to 40. Aluminoxane represented by the formula:

[0020]

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[0021] (R ¹² having 1 to 20 carbon atoms, preferably 1 to
And 12 hydrocarbon groups such as an alkyl group, an alkenyl group, an aryl group, and an arylalkyl group. S indicates the degree of polymerization, and the number of repeating units is preferably 3 to 50, and more preferably 7 to 40. A) a cyclic alkylaluminoxane having a repeating unit represented by the formula: Preferred among the compounds VI to VII are aluminoxanes having a degree of polymerization of 7 or more. When an aluminoxane having a degree of polymerization of 7 or more or a mixture thereof is used, high activity can be obtained.
Further, modified aluminoxanes insoluble in ordinary solvents obtained by modifying the aluminoxane represented by the formulas VI to VII with a compound having active hydrogen such as water can also be suitably used.

Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water. The method is not particularly limited, and the reaction may be carried out according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, a method in which an organoaluminum compound is added at the beginning of polymerization and water is added later, a crystal water contained in a metal salt or the like, A method of reacting water adsorbed on an inorganic or organic substance with an organoaluminum compound, a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and further reacting water to obtain a solvent-insoluble aluminoxane. The catalyst according to the present invention comprises the component (A)
And (B) as main components. In this case, the use conditions of these components are not limited, but the use ratio of component (A): component (B) is 1: 0.1 to 1: 100, particularly 1: 0.5 to 1:10, and especially 1 : 0.8 to 1: 5.

3. Organoaluminum Compound (C) As the organoaluminum compound (C) used in the present invention, those represented by the following general formula (VIII) can be mentioned. R ¹⁴ _r AlQ _3-r (VIII) (R ¹⁴ is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms such as an alkyl group, an alkenyl group, an aryl group and an arylalkyl group; Q is a hydrogen atom; And represents an alkoxy group having 1 to 20 carbon atoms or a halogen atom. R is in the range of 1 ≦ r ≦ 3.) As the compound of the formula (VIII), specifically, trimethylaluminum, triethylaluminum, triisopropyl Aluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like can be mentioned. Among the compounds of the formula (VIII), an alkyl group-containing aluminum compound having at least one alkyl group having 3 or more carbon atoms, particularly an alkyl group having at least one branched alkyl group, is preferred. Particularly preferred is triisobutylaluminum. When this triisobutylaluminum is used, high activity can be obtained. When the component (C) is used, the amount of the compound (B)
When (B-1) is used, the amount is usually 1 to 2,000 mol, preferably 5 to 1,000 mol, particularly preferably 10 to 500 mol, per 1 mol of the component (A). When the component (C) is used, the polymerization activity can be improved. However, when the amount is too large, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable. (C)
The components may be used in contact with the catalyst of the present invention. The contact may be made in advance, or may be brought into contact in the polymerization system.

4. Carrier (D) In the present invention, the type of the carrier (D) is not limited, and any of an inorganic carrier, an inorganic oxide carrier, an inorganic metal chloride carrier and an organic carrier can be used. Inorganic metal chloride carriers are preferred. In particular,
As the inorganic oxide carrier, SiO ₂ , Al ₂ O ₃ , Mg
O, ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , B ₂ O ₃ , CaO, Z
Examples thereof include nO, BaO, ThO _2, and mixtures thereof, for example, silica alumina, zeolite, ferrite, and glass fiber. Among them, SiO ₂ , A
l ₂ O ₃ is particularly preferred. Incidentally, the inorganic oxide carrier,
It may contain a small amount of carbonate, nitrate, sulfate and the like. Examples of the inorganic chloride carrier include MgCl ₂ and its complex salts. Organic carriers include polystyrene, polyethylene, linear low-density polyethylene,
Examples thereof include polymers such as polypropylene, substituted polystyrene, and polyarylate, starch, and carbon.

The properties of the carrier (D) used in the present invention vary depending on its kind and production method, but the average particle size is usually 1 to 30.
0 μm, preferably 10 to 200 μm, more preferably 20 to 100 μm. If the particle size is small, fine powder in the polymer increases, and if the particle size is large, coarse particles in the polymer increase, causing a decrease in bulk density and clogging of a hopper. The specific surface area of the carrier (D) is usually 1 to 1,000 m ^2.
/ G, preferably 50-500 m ² / g, the pore volume is
Usually 0.1 to ⁵ cm ³ / g, preferably 0.3 to ³ cm ³
/ G. If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and pore volume can be determined, for example, from the volume of nitrogen gas adsorbed according to the BET method [Journal of American Chemical Society (J. Am. Chem. Soc.)] Volume 60, page 309 (1
983). Further, the carrier (D) usually contains 15
It is desirable to use by firing at 0 to 1000 ° C, preferably 200 to 800 ° C.

The α-olefin polymerization catalyst of the present invention comprises the compounds (A) and (B) as main components, and at least the compound (A), preferably the compounds (A) and (B).
Are carried on the carrier (D). Carrier (D)
The method for supporting the compound (A) is not particularly limited, and examples thereof include the following methods. A method of mixing the compound (A) with the carrier (D). A method in which the carrier (D) is treated with an organoaluminum compound or a halogen-containing silicon compound, and then mixed with the compound (A) in an inert solvent. A method of reacting the carrier (D) with the compound (A) with an organoaluminum compound or a halogen-containing silicon compound. A method in which compound (A) is supported on carrier (D) and then mixed with compound (B). A method in which the contact reaction product of compound (A) and compound (B) is mixed with carrier (D). A method in which the carrier (D) coexists during the contact reaction between the compound (A) and the compound (B). In the above reactions, an organoaluminum compound (C) may be added. In the present invention, a stereoregular α-olefin-based polymer can be obtained by supporting at least the compound (A) on the carrier (D).

The catalyst thus obtained may be subjected to solvent distillation once, taken out as a solid, and then used for polymerization, or may be used for polymerization as it is. In the present invention, a catalyst can also be produced by carrying out the operation of loading the compound (A) on the carrier (D) in a polymerization system. As such a method, for example, an inert solvent is placed in an autoclave, a compound (A) and a carrier (D), and if necessary, a compound (C) are added. Then, an α-olefin is added at normal pressure to 20 kg / cm ² , There is a method of performing prepolymerization at -20 to 100 ° C. for 1 minute to 2 hours to generate catalyst particles. In the present invention, the mixing ratio (weight ratio) of the compound (B) and the carrier (D) is preferably 1: 5 to 1: 10000, particularly preferably 1:10 to 1: 500. The mixing ratio (weight ratio) of the compound (A) and the carrier (D) is as follows:
The ratio is preferably from 1: 5 to 1: 10000, particularly preferably from 1:10 to 1: 500. When the mixing ratio of the compound (B) and the carrier (D) or the mixing ratio of the compound (A) and the carrier (D) is out of the above range, the activity may decrease.

The α-form of the present invention prepared as described above
The average particle size of the olefin polymerization catalyst is usually 2 to 200 μm.
m, preferably 10 to 150 μm, particularly preferably 20 μm.
１００100 μm, and the specific surface area is usually 20-1000
m ² / g, preferably from 50 to 500 m ² / g. If the average particle size is less than 2 μm, fine powder in the polymer may increase, and if it exceeds 200 μm, coarse particles in the polymer may increase. If the specific surface area is less than 20 m ² / g, the activity may decrease, and if it exceeds 1000 m ² / g, the bulk density of the polymer may decrease. Further, in the catalyst of the present invention, the amount of transition metal in 100 g of the support is:
Usually, it is preferably 0.05 to 10 g, particularly preferably 0.1 to 2 g. If the amount of the transition metal is out of the range, the activity may decrease.

5. Polymerization Method The polymerization method of the α-olefin is the homopolymerization of the α-olefin or the α-olefin and ethylene using the above-mentioned α-olefin polymerization catalyst of the present invention, and other α-olefins.
It is characterized by copolymerization of olefins or other unsaturated compounds. In this case, the type of the α-olefin is not particularly limited, but an α-olefin having 3 to 20 carbon atoms is preferable. Specifically, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-
Dodecene, 1-tetradecene, 1-hexadecene, 1-
Octadecene, 1-eicosene and the like can be preferably used. When copolymerizing two or more α-olefins, the above monomers can be arbitrarily combined. For example, propylene and ethylene or carbon number 4-1
When the α-olefin of 0 is copolymerized, the copolymerization ratio of propylene with ethylene or an α-olefin having 4 to 10 carbon atoms is usually 99.9: 0.1 to 60.
0: 40.0, preferably 99.5: 0.5 to 75.0:
25.0.

In addition to the above olefins, other unsaturated compounds,
For example, vinyl aromatic compounds such as styrene, p-methylstyrene, isopropylstyrene, and t-butylstyrene; chain diolefins such as butadiene, isoprene, and 1,5-hexadiene; norbornene;
8-Dimethano-1,2,3,4,4a, 5,8,8a-
Copolymerization can be performed using cyclic olefins such as octahydronaphthalene and cyclic diolefins such as norbornadiene and ethylidene norbornene. Usually, the content of the other unsaturated compound is not more than 20 mol% based on the α-olefin. In this case, one or more α-olefins can be preferably used. The polymerization method is not particularly limited, a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method,
Any method such as a suspension polymerization method may be used, but a slurry polymerization method and a gas phase polymerization method are particularly preferable. Regarding the polymerization conditions, the polymerization temperature is usually −100 to 250 ° C., preferably −
It is 50-200 ° C, more preferably 0-130 ° C.
Further, the ratio of the catalyst to the reaction raw material used is expressed as raw material monomer / component (A) (molar ratio) or raw material monomer /
The component (B) (molar ratio) is 1 to 10 ⁸ , especially 100 to 100
It is preferred that the 10 ^5. Further, the polymerization time is usually from 5 minutes to 10 hours, and the reaction pressure is from normal pressure to 100 kg / cm ^2.
G, preferably normal pressure to 30 kg / cm ² G.

Methods for controlling the molecular weight of the polymer include selection of the type and amount of each catalyst component used, the polymerization temperature, and polymerization in the presence of hydrogen. When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, and aliphatic hydrocarbons such as pentane, hexane, heptane and octane And halogenated hydrocarbons such as chloroform and dichloromethane. These solvents may be used alone or in combination of two or more. Further, a monomer such as an α-olefin may be used as the solvent. The polymerization may be performed without a solvent.

In the polymerization method, preliminary polymerization can be carried out using the catalyst of the present invention. The prepolymerization can be carried out by bringing a small amount of olefin into contact with the solid catalyst component, but the method is not particularly limited, and a known method can be used. The olefin used for the prepolymerization is not limited, and may be the same as described above, for example, ethylene, C
Examples thereof include α-olefins having ₃ to ₂₀ carbon atoms, and mixtures thereof, and it is preferable to use the same α-olefin as the α-olefin used in the main polymerization.
The pre-polymerization temperature is usually -20 to 100C, preferably -10 to 70C, more preferably 0 to 50C.

In the prepolymerization, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, a monomer or the like can be used as a solvent. Particularly preferred among these are aliphatic hydrocarbons. Further, the prepolymerization may be performed without a solvent. In the prepolymerization, the intrinsic viscosity [η] (measured in decalin at 135 ° C.) of the prepolymerized product was 0.2.
The conditions are adjusted so that the amount of the prepolymerized product is at least dl / g, especially at least 0.5 dl / g, and per 1 mmol of the transition metal component in the catalyst, from 1 to 10,000 g, especially from 10 to 1,000 g. Is preferred.

By the above-mentioned polymerization method, excellent steric regularity (isotactic) having excellent properties, which is granular, has a high bulk density, and has a good particle size distribution, without using an expensive transition metal having a complicated structure. The high molecular weight α-olefin homopolymer or copolymer can be efficiently produced.

[0035]

The present invention will be described below in further detail with reference to examples. [Example 1] ₂ g of MgCl2, 50 ml of a toluene solution of mono (pentamethylcyclopentadienyl) titanium trichloride (0.002 mol / l), 3 mmol of triisobutylaluminum, 3 mmol of tetrakis (pentafluoro) Phenyl) dimethylanilinium borate 0.1mmo
and co-ground for 24 hours at room temperature. Thereafter, washing was performed with toluene under an inert gas. T in the catalyst
The i content was 3.3 mg. Then, the solid catalyst obtained above was placed in an autoclave together with 400 ml of toluene and 0.6 mmol of TIBA in an amount of 0.01% in terms of titanium.
5 mmol was added, the temperature was raised to 50 ° C., and the propylene pressure was 7 kg /
The mixture was continuously supplied to the autoclave at cm ² G and polymerization was carried out for 3 hours. As a result, 40 g of isotactic polypropylene was obtained. Its molecular weight Mw is 114,00
0, melting point: 156 ° C. Note that Mw and Mn are G
It is a value measured under the following conditions by PC. GPC: Waters ALC / GPC 150C Column: TSK HM + GMH6 × 2 manufactured by Tosoh Solvent: 1,2,4-trichlorobenzene Temperature: 135 ° C. Flow rate: 1.0 ml / min

Example 2 ₂ g of MgCl ₂ , 50 ml of a mono (pentamethylcyclopentadienyl) titanium trichloride toluene solution (0.002 mol / l), 3 mmol of triisobutylaluminum, 3 mmol of tetrakis Dimethylanilinium (pentafluorophenyl) borate
1 mmol was charged and co-ground for 24 hours at room temperature. Thereafter, washing was performed with toluene under an inert gas. The Ti content in the catalyst was 9.1 mg. Then, 400 ml of toluene and 0.6 mm of TIBA were placed in an autoclave.
The solid catalyst obtained above was added together with 0.015 mmol in terms of titanium in an amount of 0.015 mmol, heated to 50 ° C., and continuously supplied to the autoclave at a propylene pressure of 7 kg / cm ² G.
After polymerization for 3 hours, 35 g of isotactic polypropylene was obtained. Its molecular weight Mw is 5
The melting point was 5,000.

Example 3 2 g of silica and 30 mg of monoindenyl titanium trichloride were placed in a stainless steel ball mill having a capacity of 100 ml and ground at room temperature for 24 hours. Thereafter, the resultant was washed with toluene under an inert gas. The Ti content in the catalyst was 2.8 mg. Next, 400 ml of toluene and 0.3 mm of TIBA were placed in an autoclave.
ol, 0.015 mmol of the above catalyst, dimethylanilinium tetrakis (pentafluorophenyl) borate 0.0
Add 15 mmol and raise the temperature to 50 ° C.
The autoclave was continuously fed at g / cm ² G and polymerized for 3 hours to obtain 30 g of isotactic polypropylene. Its molecular weight Mw is 65,000,
Melting point was 155 ° C.

Comparative Example 1 (When Compound (A) is not Supported) 400 ml of toluene was placed in an autoclave, and
0.3 mmol, 0.03 mmol of monoindenyltitanium trichloride and 0.03 mmol of dimethylanilinium tetrakis (pentafluorophenyl) borate are added, and the temperature is raised to 50 ° C. and continuously supplied to the autoclave at a propylene pressure of 7 kg / cm ² G. Then, after polymerization for 3 hours, only a small amount of atactic polypropylene was obtained.

[Reference Example] MgCl ₂ was added to a stainless steel ball mill having an inner volume of 100 ml.
Was added and 30 mg of mono (pentamethylcyclopentadienyl) titanium trichloride was added, and the mixture was co-ground for 24 hours at room temperature. Then, the soluble matter was washed with toluene under an inert gas atmosphere to obtain a supported solid catalyst. Then 1
400 ml of toluene, 15 mmol of methylaluminoxane and 0.015 mmol of a solid catalyst in terms of Ti atoms were put in a liter autoclave, heated to 50 ° C., continuously supplied to the autoclave at a propylene pressure of 7 kg / cm ² G, and polymerized for 3 hours. As a result, 20 g of isotactic polypropylene was obtained. Its molecular weight Mw is
38,000, melting point 157 ° C.

[0040]

As described above, according to the present invention, α-olefins having high activity and good properties such as bulk density and particle size distribution of the resulting polymer can be obtained from raw materials which are inexpensive and easily available. A polymerization catalyst can be provided.

────────────────────────────────────────────────── ─── Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (2)

(57) [Claims] 1. A composition comprising the following compounds (A) and (B) as main components and at least the compound (A) as a carrier (D)
An α-olefin polymerization catalyst characterized by being supported on. (A): a transition metal compound represented by the following general formula: CpMXn wherein Cp is a cyclic unsaturated hydrocarbon group-containing group, M is a transition metal atom selected from the group IVB, X is a σ-binding ligand, chelate Sexual ligand or Lewis base. Xs may be the same or different. n is an integer of valence-1 of the transition metal M. (B) a compound which reacts with the transition metal compound (A) to form an ionic complex 2. An α-olefin polymerization catalyst comprising the catalyst according to claim 1 and an organoaluminum compound (C) as main components.