JP3308359B2 - Polymerization catalyst and method for producing polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel and useful polymerization catalyst and a method for producing a polymer using the same. More specifically, the present invention relates to a polymerization catalyst particularly useful as an olefin polymerization catalyst, and a method for producing a polyolefin-based polymer using the same.

[0002]

2. Description of the Related Art Heretofore, as a highly active soluble olefin polymerization catalyst, a catalyst comprising a combination of a transition metal compound and an aluminoxane has been known (JP-A-58-1930).
No. 9 and JP-A-60-217209). Also, it has been proposed that cationic species are useful as active species of soluble olefin polymerization catalysts [J. Am. Chem. Soc. 81, 81 (1
959), J. Am. Chem. Soc. 82, 1953 (1960), J. Am. Chem. Soc.
107, 7219 (1985)]. As an example of isolating this active species and adapting it to olefin polymerization, J. Am. Chem. Soc. 108, 7410 (1
986), JP-T 01-502636, JP-A 03-13-13
No. 9504, European Patent Application No. 468,651 and the like, and examples of the use of an organic aluminum compound in combination with this active species include JP-A-03-207704 and International Patent Publication No. 92-1723.

[0003]

However, the polymer formed by the complex having a cyclopentadienyl ligand used in these prior arts has a reaction temperature of 70 to 70, which is efficient in an industrial process. When the polymerization is carried out at 100 ° C. or higher, there is a problem that the molecular weight of the obtained polymer is small.

The present invention has been made in view of the above-mentioned problems, and has high activity as a polymerization catalyst. The obtained polymer or copolymer has a large molecular weight, a uniform composition, and a high molecular weight. An object of the present invention is to provide a polymerization catalyst capable of controlling a distribution range narrowly and a method for producing a polymer using the same.

[0005]

In order to achieve the above object, according to a first aspect of the present invention, the following compound (A-
1) and (B-1), or the following compound (A-1),
A polymerization catalyst comprising (B-1) and (C) is provided. (A-1) Transition metal compound represented by the following formula

Embedded image [Wherein, M represents Ti, Zr or Hf. R independently represents hydrogen or a lower alkyl group having 1 to 5 carbon atoms. Y each independently represents a σ-binding ligand, a chelating ligand or a Lewis base. b represents an integer of 1 to 4, and c represents an integer of (4-b). (B-1) an ionic compound that forms an ionic complex by reacting with the compound (A-1) or a derivative thereof, or an aluminoxane (C) an organoaluminum compound according to the second aspect of the present invention. And the following compounds (A-2) and (B-2), or the following compounds (A-2) and (B-
A polymerization catalyst for copolymerizing ethylene and octene, characterized by containing (2) and (C), is provided. (A-2) Transition metal compound represented by the following formula

Embedded image [Wherein, M represents Ti, Zr or Hf. R independently represents hydrogen or a lower alkyl group having 1 to 5 carbon atoms. Y each independently represents a σ-binding ligand, a chelating ligand or a Lewis base. b represents an integer of 1 to 4, and c represents an integer of (4-b). (B-2) Aluminoxane (C) Organoaluminum compound

According to a third aspect of the present invention, the following compounds (A-3) and (B-3) or the following compound (A-
3) A polymerization catalyst comprising (B-3) and (C). (A) a transition metal compound represented by the following formula

Embedded image [Wherein, X represents P or N. M represents Ti, Zr or Hf. R is each independently hydrogen or 1 to 1 carbon atoms;
5 represents a lower alkyl group. Y each independently represents a σ-binding ligand, a chelating ligand or a Lewis base. b represents an integer of 1 to 4, and c represents an integer of (4-b). (B-3) Silver trifluoromethanesulfonate (C) Organoaluminum compound According to the fourth aspect of the present invention, the following compounds (A-4) and (B-4) or the following compound (A-4) ), (B-
A polymerization catalyst comprising 4) and (C) is provided. (A-4) Transition metal compound represented by the following formula

Embedded image [Wherein, X represents P or N. M represents Ti, Zr or Hf. R is each independently hydrogen or 1 to 1 carbon atoms;
5 represents a lower alkyl group. ] (B-4) Compound (A-
4) an ionic compound that forms an ionic complex by reacting with or a derivative thereof, or an aluminoxane (C) an organoaluminum compound

Hereinafter, for convenience of explanation, compound (A-1),
(A-2), (A-3) and (A-4) are referred to as compound (A), and compounds (B-1), (B-2), (B-3) and (B
-4) is referred to as compound (B). According to a fifth aspect of the present invention, there is provided a polymerization catalyst comprising at least one of compounds (A), (B) and (C) supported on a carrier [compound (D)].

According to a sixth aspect of the present invention, the first and second embodiments
In the presence of the polymerization catalyst according to any one of the embodiments 3, 4, and 5, an olefin is homopolymerized, or an olefin is copolymerized with another olefin or another monomer. A manufacturing method is provided. Seventh of the present invention
According to the aspect, there is provided a method for producing a polymer, characterized in that ethylene and octene are copolymerized in the presence of the polymerization catalyst according to the second or fifth aspect.

Hereinafter, the present invention will be described in detail. 1. Transition metal compound (A) Specific examples of the compound include the following, and compounds obtained by substituting zirconium with hafnium or titanium.

Bis (1-phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride, bis (1-phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride Bromide,
Bis (1-phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium dimethyl, bis (1
-Phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium dibenzyl, bis (1-phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium chloride hydride, bis (1 -Phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium dihydride, bis (1-phospha-
2,3,4,5-tetramethylcyclopentadienyl)
Bis (dimethylamino) zirconium, bis (1-phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium dimethoxide, bis (1-phospha-2,3,4,5-tetramethylcyclopenta Dienyl) zirconium diphenoxide, bis (1-phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium, bis (1-phospha-3,4-dimethylcyclopentadienyl) zirconium dichloride,
Bis (1-phospha-2,5-dimethylcyclopentadienyl) zirconium dichloride, bis (1-phospha-cyclopentadienyl) zirconium dichloride,
(1-phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium trichloride, (1-phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium trimethyl, (1- Phosphor
2,3,4,5-tetramethylcyclopentadienyl)
Zirconium tribenzyl, (1-phospha-2,3,3)
4,5-tetramethylcyclopentadienyl) zirconium methyl dichloride, (1-phospha-2,3,4,
5-tetramethylcyclopentadienyl) zirconium trihydride, (1-phospha-3,4-dimethylcyclopentadienyl) zirconium trichloride, bis (pyrrolyl) zirconium dichloride, bis (2,5-
Dimethylpyrrolyl) zirconium dichloride, bis (pyrrolyl) zirconium dimethyl, bis (pyrrolyl) zirconium dibenzyl, bis (pyrrolyl) zirconium chloride hydride, bis (pyrrolyl) zirconium dihydride,

2. Activation Cocatalyst (B) The activation cocatalyst (B) used in the present invention is a compound capable of forming a cationic species from the transition metal compound (A) or a derivative of (A). Examples of the compound include compounds that react with the transition metal compound (A) to form an ionic complex, aluminoxane, and the like.

The ionic compound which reacts with the transition metal compound (A) to form an ionic complex includes the ionic compound which reacts with the transition metal compound (A) to form an ionic complex. Any of these can be used, but those of the following general formulas (II) and (III) can be suitably used. ([L ¹ −R ¹ ] ^{k +} ) _p ([Z] ⁻ ) _q (II) ([L ² ] ^{k +} ) _p ([Z] ⁻ ) _q (III) (where L ² is M ^{2 , R 2 R 3 M 3,} R 4 3 C or R ⁵ M ³
It is. ) [(II), (III ) wherein, [Z] - is a non-coordinating anion [Z ^{1] -} or [Z ^{2] -} indicates, [Z ^{1] -} is coupled to a plurality of groups element Anion, ie, [M ¹ A ¹ A ²
... A ⁿ ] ^- (where M ¹ represents a Group 5 to 15 element, preferably a Group 13 to 15 element. A ^{1 to An} are a hydrogen atom, a dialkylamino group, and contain oxygen having 1 to 20 carbon atoms. Group, a hydrocarbon group having 1 to 20 carbon atoms, an organic metalloid group, a halogen atom, or a halogen-substituted hydrocarbon group, and two or more may form a ring, and n is [(atom of central metal M ¹ Value) +
1], at least one of which is an anion in which a plurality of groups are bonded to an element selected from Groups 13 to 15 of the periodic table.
[Z ² ] − represents a conjugate base of a Bronsted acid having an acid dissociation constant (pKa) of −10 or less alone or a combination of a Bronsted acid and a Lewis acid, or a conjugate base of a substance generally defined as a superstrong acid. . A Lewis base may be coordinated. Specific examples of an anion [Z ¹ ] ⁻ in which a plurality of groups are bonded to an element, that is, [M ¹ A ¹ A ² ... ^An ] include, as M ¹ , B, Al, Si, P, As, Sb, Preferably B,
Al and A ^{1 to An} are dialkylamino groups: dimethylamino group, diethylamino group, oxygen-containing groups having 1 to 20 carbon atoms: methoxy group, ethoxy group, n-butoxy group, phenoxy group, 2,6-di- t-butyl-4-methylphenoxy group, a hydrocarbon group having 1 to 20 carbon atoms: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-octyl group, n-eicosyl Group, phenyl group, p-tolyl group, benzyl group, 4-t-
Butylphenyl group, 3,5-dimethylphenyl group, halogen atom: fluorine, chlorine, bromine, iodine, carbon number 1-2
0 halogen-substituted hydrocarbon group: p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-di (trifluoro Methyl) phenyl group, organic metalloid group: pentamethylantimony group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group, diphenylboron group. Non-coordinating anion, that is, an acid dissociation constant (pKa) of -10
Specific examples of the following conjugated base of a Brönsted acid alone or a combination of a Brönsted acid and a Lewis acid, or a conjugated base [Z ² ] ⁻ of those generally defined as a super strong acid include a trifluoromethanesulfonic acid anion (CF ₃ S
O ₃ ) ^- , bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl)
Amide, perchlorate anion (ClO ₄₎ ^-, trifluoroacetic acid anion (CF ₃ CO ₂₎ ^-, hexafluoroantimony anion (SbF ₆₎ ^-, fluorosulfonic acid anion (FSO ₃₎ ^- chlorosulfonic acid anion (cls
O ₃₎ ^-, fluorosulfonic acid anion / antimony pentafluoride (FSO ₃ -SbF ₅₎ ^-, fluorosulfonic acid anion / 5- fluoride arsenic (FSO ₃ -AsF ₅₎ ^-, trifluoromethyl meth acid / 5 -Antimony fluoride (CF
₃ -SO ₃ / SbF ₅ ) ^- . L ¹ is a Lewis base; R ¹ is a hydrogen atom; a hydrocarbon group having 1 to 20 carbon atoms; R ² and R ³ are each a cyclopentadienyl group or a substituted cyclopentadienyl group (each Cp is Two or more Cp
May have a crosslinked structure. ). R ⁴ represents a hydrocarbon group having 1 to 20 carbon atoms or an oxygen-containing group having 1 to 20 carbon atoms. k is an ionic valence of [L ¹ -R ¹ ] and [L ² ], and is an integer of 1 to 3, p is an integer of 1 or more, and q = p ×
k. M ² is one comprising at 1～3,11～13,17 group elements, M ³ represents a 7-12 group elements. R
⁵ represents porphines, phthalocyanines, allyl group derivatives and the like. ]

Here, specific examples of the Lewis base (L ¹ ) include amines: ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline,
Trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N
-Dimethylaniline, phosphines: triethylphosphine, triphenylphosphine, diphenylphosphine, thioethers: tetrahydrothiophene, esters: ethyl benzoate, nitriles: acetonitrile,
Benzonitrile can be mentioned. Specific examples of R ¹ include hydrogen, methyl, ethyl, benzyl, and trityl. Specific examples of R ² and R ³ include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Specific examples of R ⁴ include phenyl, p-tolyl, p-methoxyphenyl and the like. Specific examples of R ⁵ may be mentioned tetraphenylporphyrin, phthalocyanine, allyl, methallyl. Specific examples of M ² can be mentioned Li, Na, K, Ag, Cu, Br, I, and I _3. Specific examples of M ³ include Mn, F
e, Co, Ni, Zn and the like.

Specific examples of such an ionic compound which reacts with the transition metal compound (A) to form an ionic complex include triethylammonium tetraphenylborate,
Tri (n-butyl) ammonium tetraphenylborate,
Trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, ammonium (tri-n-butyl) ammonium tetraphenylborate, ammonium benzyl (tri-n-butyl) tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, triphenyltetraphenylborate (Methyl) ammonium, trimethylanilinium tetraphenylborate,
Methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyl (2-cyanopyridinium) tetraphenylborate, triethylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tetrakis ( Triphenylammonium pentafluorophenyl) borate, tetra-n-butylammonium tetrakis (pentafluorophenyl) borate, tetraethylammonium tetrakis (pentafluorophenyl) borate, benzyl (tri-n-butyl) ammonium tetrakis (pentafluorophenyl) borate Diphenyl ammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate Phenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate-methyl anilinium, tetrakis (pentafluorophenyl)
Dimethylanilinium borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, methylpyridinium tetrakis (pentafluorophenyl) borate,
Benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), methyl tetrakis (pentafluorophenyl) borate (4 -Cyanopyridinium), triphenylphosphonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate, ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, Manganese tetraphenylporphyrin tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Acid (1,1′-dimethylferrocenium), decamethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Lithium borate, sodium tetrakis (pentafluorophenyl) borate, tetraphenylporphyrin manganese tetrakis (pentafluorophenyl) borate,
Examples thereof include silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate, silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate.

The following can be mentioned as aluminoxanes.

Embedded image

(R ⁶ 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, and halogen atoms, which may be the same or different. Also, s
Represents the degree of polymerization, the preferred number of repeating units is 3 to 50,
More preferably, it is 7 to 40. Aluminoxane represented by the formula:

[0017]

Embedded image

(R ⁶ is the same as in formula (IV). S is the degree of polymerization, and the preferred number of repeating units is 3 to
50, more preferably 7 to 40. A) a cyclic alkylaluminoxane having a repeating unit represented by the formula: Examples of the method for producing the aluminoxane include a method in which an alkylaluminum (one or two or more) is brought into contact with a condensing agent such as water, but the method is not particularly limited, and the reaction is carried out according to a known method. I just need. 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 inorganic or organic substances with an organoaluminum compound, a method of reacting a trialkylaluminum with a tetraalkyldialuminoxane, and further reacting water. In addition,
The aluminoxane may be toluene-insoluble.

[0019]

Here, the mixing ratio (molar ratio) of the compound (A) and the compound (B) is from 10: 1 to 1: 100 when an ionic compound is used as the compound (B), preferably 2: 1 to 1:10, and 1 when aluminoxane is used.
1-1: 100,000, preferably 1: 10-1: 1
It is 0000. Further, as the compound (B), an ionic compound, an aluminoxane or the like can be used alone, but two or more of these can be used in combination.

[0021]

3. Organoaluminum Compound (C) As described above, the polymerization catalyst of the present invention contains, as a main component, an organoaluminum compound (C) in addition to the compounds (A) and (B). You may. The polymerization activity can be improved by performing polymerization or copolymerization using this catalyst.

Here, examples of the organoaluminum compound (C) include those represented by the following general formula (VI). R ⁷ _r AlQ _3-r (VI) (R ⁷ is a hydrocarbon group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms, Q is a hydrogen atom, a halogen atom, Alkoxy group or carbon number 6-20
Represents an aryl group. r is an integer of 0 to 3. As the compound of the formula (VI), specifically, trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride,
Examples thereof include methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, and ethylaluminum sesquichloride. Among the compounds of the formula (VI), preferred are alkyl groups having 3 or more carbon atoms, especially alkyl group-containing aluminum compounds having at least one or more branched alkyl groups. Particularly preferred is triisobutylaluminum. When this triisobutylaluminum or a mixture thereof is used, high activity can be obtained.

The mixing ratio (molar ratio) of compound (A) to compound (C) is 1: 1 to 1: 2,000, preferably 1: 1.
5 to 1: 1,000, particularly preferably 1:10 to 1: 5
00. By using the compound (C), the polymerization activity per transition metal can be improved. However, if the amount is too large, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable.

4. Support [Compound (D)] The polymerization catalyst of the present invention may contain a support as a catalyst component. The type of the carrier [compound (D)] is not limited, and any of an inorganic carrier, an inorganic oxide carrier and an organic carrier can be used, but an inorganic carrier or an inorganic oxide carrier is particularly preferable. Specifically, MgCl ₂ , MgCl (OEt), Mg (OE
t) Magnesium compound such as ₂ or its complex salt, or Mg
An organic magnesium compound represented by R ⁸ _X X ¹ _Y can be exemplified. Here, R ⁸ is an alkyl group having 1 to 20 carbon atoms,
X ¹ represents a halogen atom or an alkyl group having 1 to 20 carbon atoms, wherein x is 0 to 2 and y is 0 to 2;

As the inorganic oxide carrier, SiO ₂ , Al
₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , B
Examples include ₂ O ₃ , CaO, ZnO, BaO, ThO _2, and mixtures thereof, for example, silica alumina, zeolite, ferrite, and glass fiber.
Of these, SiO ₂ and Al ₂ O ₃ are particularly preferred. The inorganic oxide carrier may contain a small amount of a carbonate, a nitrate, a sulfate, or the like. Examples of the organic carrier include polymers such as polystyrene, styrene-divinylbenzene copolymer, polyethylene, linear low-density polyethylene, polypropylene, poly-4-methyl-1-pentene, substituted polystyrene, and polyarylate, and starch. , Carbon, and the like.

Carrier [Compound (D)] used in the present invention
The properties vary depending on the type and manufacturing method, but the average particle size is usually 1 to 300 μm, preferably 10 to 200 μm,
More preferably, it is 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 [compound (D)] is usually 1 to 1,000 m ² / g, preferably 50 to ⁵ m ² / g.
00 m ² / g, pore volume is usually 0.1-5 cm ³ / g,
Preferably it is 0.3-3 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 the 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.)] 6
0, page 309 (1983)]. Furthermore, the above-mentioned carrier [compound (D)] is usually used at 150 to 1,000 ° C.
Preferably, it is desirable to use by firing at 200 to 800 ° C.

The polymerization catalyst of the present invention comprises the above compounds (A) and (B) as main components, and at least one of the compounds (A) and (B), preferably the compound (A) or (B). Both can be supported on the carrier [compound (D)]. Compound (A) as carrier [Compound (D)]
The method for supporting at least one of (B) and (B) is not particularly limited, and examples thereof include the following methods (1) to (5). A method of mixing at least one of compounds (A) and (B) with a carrier [compound (D)]. A method in which a carrier [compound (D)] is treated with an organoaluminum compound or a halogen-containing silicon compound, and then mixed with at least one of the compounds (A) and (B) in an inert solvent. A method of reacting a carrier [compound (D)] with a compound (A) and / or (B) with an organoaluminum compound or a halogen-containing silicon compound. A method in which compound (A) or (B) is supported on a carrier [compound (D)], and then mixed with compound (B) or (A). A method in which a contact reaction product of compound (A) and compound (B) is mixed with a carrier [compound (D)]. A method in which a carrier [compound (D)] coexists during the contact reaction between compound (A) and compound (B). In the above reactions (1) and (2), the organoaluminum compound (C) may be added. 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 at least one of the compounds (A) and (B) on the carrier (E) in a polymerization system. At least one of compounds (A) and (B) and a carrier [compound (D)], and if necessary, an organoaluminum compound (C) are added, and an olefin such as ethylene is added at normal pressure to 20 kg / cm ² . 1 at -20 to 100 ° C
There is a method in which prepolymerization is performed for minutes to 2 hours to generate catalyst particles.

In the present invention, the mixing ratio (weight ratio) of the ionic compound of compound (B) and the carrier [compound (D)]
Is 1: 5 to 1: 10,000, especially 1:10 to 1: 5
00 is preferable. Mixing ratio (weight ratio) of aluminoxane of compound (B) and carrier [compound (D)]
Is 1: 0.5 to 1: 1,000, especially 1: 1 to 1: 5
It is preferably set to 0. The mixing ratio (weight ratio) of the compound (A) and the carrier [compound (D)] is 1: 5 to 5:
The ratio is preferably 1: 10,000, especially 1:10 to 1: 500. When the mixing ratio of the compound (B) and the carrier [Compound (D)] or the mixing ratio of the compound (A) and the carrier [Compound (D)] is out of the above range, the activity may be reduced. The average particle size of the polymerization catalyst of the present invention prepared as described above is usually 2 to 200 μm, preferably 10 to 200 μm.
To 150 μm, particularly preferably 20 to 100 μm, and the specific surface area is usually 20 to 1,000 m ² / g, preferably 50 to 500 m ² / g. Average particle size is 2μm
If it is less than 1, the fine powder in the polymer may increase,
If it exceeds 00 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 1,000 m ² / g, the bulk density of the polymer may decrease.

In the catalyst of the present invention, the carrier 100
The amount of the transition metal in g is usually 0.05 to 10 g, particularly 0.1 g.
It is preferable that the weight is 1 to 2 g. If the amount of the transition metal is out of the range, the activity may decrease. As described above, a polymer having an industrially advantageous high bulk density and an excellent particle size distribution can be obtained by supporting on the carrier [compound (D)].

6. According to the method for producing a polymer of the present invention, using the polymerization catalyst of the present invention described above, for example, homopolymerization of olefins, or olefin and ethylene, other olefins or other unsaturated compounds Can be suitably copolymerized. In this case, the type of the olefin is not particularly limited, but an α-olefin having 2 to 20 carbon atoms is preferable. Specifically, ethylene, 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-
Styrenes such as octadecene and 1-eicosene, and styrenes such as styrene, p-methylstyrene, p-chlorostyrene, pt-butylstyrene, p-phenylstyrene, p-methylsilylstyrene and p-trimethylsilylmethylstyrene are preferably used. Can be used.

In the present invention, when copolymerizing two or more olefins, the above monomers can be arbitrarily combined. For example, when copolymerizing propylene and ethylene or ethylene and an α-olefin having 3 to 10 carbon atoms, the copolymerization ratio of propylene and ethylene or ethylene and an α-olefin having 3 to 10 carbon atoms is as follows:
Usually, the molar ratio is 99.9: 0.1 to 60.0: 40.0.
Preferably, it is 99.5: 0.5 to 75.0: 25.0.

The process for producing a polymer of the present invention is particularly suitable for the polymerization of olefins, but other unsaturated compounds, for example, chain diolefins such as butadiene, isoprene and 1,5-hexadiene. , Norbornene,
1,4,5,8-dimethano-1,2,3,4,4a,
Cyclic olefins such as 5,8,8a-octahydronaphthalene, cyclic diolefins such as norbornadiene and ethylidene norbornene, unsaturated esters such as ethyl acrylate and methyl methacrylate, β-propiolactone, β-butyrolactone, It can also be used for the polymerization of lactones such as γ-butyrolactone or the copolymerization of these unsaturated compounds with olefins.

In the method for producing a polymer of the present invention, the polymerization method is not particularly limited, and a slurry polymerization method, a gas phase polymerization method,
Any method such as a bulk polymerization method, a solution polymerization method, and 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 -50 to 200 ° C, more preferably 0 to 130 ° C. Further, the usage ratio of the catalyst to the reaction raw material is such that the raw material monomer / the component (A) (molar ratio) or the raw material monomer / the component (B) (molar ratio) is 1 to 10 ⁸ , particularly 100 to 10 ^5. Is preferred.
Further, the polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is normal pressure to 100 kg / cm ² G, preferably normal pressure to 30 kg.
/ Cm ² G. Methods for adjusting 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 a 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 method for producing a polymer of the present invention, preliminary polymerization can be carried out using the polymerization catalyst of the present invention. The prepolymerization can be performed by contacting the solid catalyst component with, for example, a small amount of an olefin.
The method is not particularly limited, and a known method can be used. There is no limitation on the olefin used for the prepolymerization, the same as those described above, such as ethylene, alpha-olefin C ₃ -C _20, or may be a mixture thereof or the like, the same olefin as the olefin used in the main polymerization Preferably, it is used. The pre-polymerization temperature is usually-
It is 20-100 degreeC, Preferably it is -10-70 degreeC, More preferably, it is 0-50 degreeC. 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 is 0.2 dl / g or more, particularly 0.5 dl / g or more,
The amount of the prepolymerized product per 1 mmol of the transition metal component in the catalyst is from 1 to 10,000 g, especially from 10 to 1,000 g.
It is preferable to adjust the conditions so as to be 0 g.

[0037]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention in any way. Example 1 (1) Catalyst component (A): Synthesis of tetrakis (2,5-dimethylpyrrolyl) zirconium Reference: Can. J. Ch
em. 64, p1306 (1986).

(2) Preparation of Catalyst Tetrakis (2,5-dimethylpyrrolyl) [(2,5-Me
₂ C ₄ H ₂ N) takes the ₄ Zr] 0.087 mmol, purified toluene 8.7ml _{addition, [(2,5-Me 2 C} 4
H ₂ N) ₄ Zr] was prepared as a 0.01 M toluene solution. Catalyst component (B): N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate ([PhNMe) is added to Schlenk sufficiently purged with nitrogen under a nitrogen atmosphere.
_{2 H] [B (C 6} F 5) 4]) 0.0876g (0.109
mmol), 10.9 ml of purified toluene was added thereto, and 0.01 parts of [PhNMe ₂ H] [B (C ₆ F ₅ ) ₄ ] was added.
A toluene solution of M was prepared.

(3) Polymerization Under a nitrogen atmosphere, 400 ml of purified toluene was introduced into a 1-liter autoclave with stirring blades sufficiently purged with nitrogen, and triisobutylaluminum (TIBA) was introduced under a nitrogen atmosphere.
Of a 1.0 M toluene solution of 0.6 ml (0.06 mmol
l) Added and kept at 20 ° C. One hour later, 0.3 ml (3.0 μmol) of (2,5-Me ₂ C ₄ H ₂ N) ₄ Zr prepared in (2) was added under a nitrogen atmosphere, and then under (2) under a nitrogen atmosphere. The prepared [PhNMe ₂ H] [B (C ₆ F
₅ ) ₄ ] was added in an amount of 0.3 ml (3.0 μmol). Ethylene was introduced thereinto with stirring, and polymerization was carried out for 1 hour while ethylene was continuously introduced so as to be constant at 3 atm.

As a result, as shown in Table 2, 0.03 g
Of polyethylene was obtained.

Examples 2 and 3 and Comparative Example 1 The procedure was carried out in the same manner as in Example 1 except that the conditions were as shown in Table 1. Table 2 shows the results. The molecular weight, molecular weight distribution, viscosity and melting point (Tm) were measured by the following methods. (1) Molecular weight, molecular weight distribution: measured by GPC. GP
The measurement conditions for C were as follows. Apparatus: Waters ALC / GPS 150C Column: Tosoh Corp. TSK HM + GMH6 × 2 Solvent: 1,2,4-trichlorobenzene Temperature: 135 ° C. (2) Melting point (Tm): Measurement conditions were as described below. Apparatus: 7 series DSC manufactured by Perkin Elmer Inc. Temperature rising rate: 10 ° C./min Temperature range: −50 ° C. to 150 ° C. (3) [η] (intrinsic viscosity): 135 ° C., measured in decalin.

[0042]

[Table 1]

[0043]

[Table 2]

Example 4 (1) Catalyst component (A) + catalyst component (B): Preparation of bis (1-phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium ditriflate −
Phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride [(Me ₄ C ₄ P) ₂
ZrCl ₂ ] (0.088 g, 0.20 mmol) was dissolved in dry nitrogen-substituted toluene (10 ml).
020 mol of solution A was prepared. Next, 0.103 g (0.40 mmol) of silver trifluoromethanesulfonate was dissolved in 10 ml of toluene purged with dry nitrogen,
A 0.040 mol solution B was prepared. The solution B was dropped into the solution A while stirring the solution A at room temperature. The formed precipitate of silver chloride was separated by filtration and bis (1-phospha-2,3,3) was removed.
4,5-tetramethylcyclopentadienyl) zirconium ditriflate [(Me ₄ C ₄ P) ₂ Zr] [OT
f] ₂ was prepared as a 0.010 molar solution. (2) Polymerization It carried out according to Example 1 except having implemented on the conditions shown in Table 3. Table 4 shows the results.

Examples 5 to 7 The same procedures as in Example 1 were carried out except that the conditions shown in Table 3 were used. Table 4 shows the results.

[0046]

[0047]

[0048]

[Table 3]

[0049]

[Table 4]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

As described above, the polymerization catalyst of the present invention has high activity, and the polymer or copolymer obtained by using this catalyst for the production of polyolefin or the like has a large molecular weight. And its composition is uniform, and its molecular weight and molecular weight distribution can be controlled. Without using a large amount of organometallic compounds,
A polymer or copolymer having excellent properties can be produced efficiently.

────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-6-49120 (JP, A) JP-A-6-49123 (JP, A) JP-A-6-49121 (JP, A) JP-A-3-49 207704 (JP, A) JP-A-1-501950 (JP, A) Nief Francois, Mathey Francois, Ricard Louis, Reactivity of a diphosphazir conocene dichloride. Organomet. Chem. , 384/3, 271-278 Meunier P .; Gauthe ron B .; , Synthesis of phospha-and diph osphazirconocene dic, J. et al. Organomet. Chem. , 193/1. C13-C16 (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 4/64-4/658 CA (STN)

Claims (10)

(57) [Claims] 1. The following compounds (A-1) and (B-1):
Or the following compounds (A-1), (B-1) and (C)
A polymerization catalyst comprising: (A-1) a transition metal compound represented by the following formula: [Wherein, M represents Ti, Zr or Hf. R independently represents hydrogen or a lower alkyl group having 1 to 5 carbon atoms. Y each independently represents a σ-binding ligand, a chelating ligand or a Lewis base. b represents an integer of 1 to 4, and c represents an integer of (4-b). (B-1) an ionic compound that forms an ionic complex by reacting with the compound (A-1) or a derivative thereof, or an aluminoxane (C) an organoaluminum compound 2. The following compounds (A-2) and (B-2):
Or the following compounds (A-2), (B-2) and (C)
A polymerization catalyst for copolymerizing ethylene and octene, comprising: (A-2) a transition metal compound represented by the following formula: [Wherein, M represents Ti, Zr or Hf. R independently represents hydrogen or a lower alkyl group having 1 to 5 carbon atoms. Y each independently represents a σ-binding ligand, a chelating ligand or a Lewis base. b represents an integer of 1 to 4, and c represents an integer of (4-b). (B-2) Aluminoxane (C) Organoaluminum compound 3. The following compounds (A-3) and (B-3):
Or the following compounds (A-3), (B-3) and (C)
A polymerization catalyst comprising: (A) a transition metal compound represented by the following formula: [Wherein, X represents P or N. M represents Ti, Zr or Hf. R is each independently hydrogen or 1 to 1 carbon atoms;
5 represents a lower alkyl group. Y each independently represents a σ-binding ligand, a chelating ligand or a Lewis base. b represents an integer of 1 to 4, and c represents an integer of (4-b). (B-3) Silver trifluoromethanesulfonate (C) Organoaluminum compound 4. The following compounds (A-4) and (B-4):
Or the following compounds (A-4), (B-4) and (C)
A polymerization catalyst comprising: (A-4) a transition metal compound represented by the following formula: [Wherein, X represents P or N. M represents Ti, Zr or Hf. R is each independently hydrogen or 1 to 1 carbon atoms;
5 represents a lower alkyl group. (B-4) an ionic compound which forms an ionic complex by reacting with the compound (A-4) or a derivative thereof, or an aluminoxane (C) an organoaluminum compound 5. The polymerization catalyst according to claim 1, wherein at least one of the compounds (A-1), (B-1) and (C) is supported on a carrier [compound (D)]. 6. The polymerization catalyst according to claim 2, wherein at least one of the compounds (A-2), (B-2) and (C) is supported on a carrier [compound (D)]. 7. The polymerization catalyst according to claim 3, wherein at least one of the compounds (A-3), (B-3) and (C) is supported on a carrier [compound (D)]. 8. The polymerization catalyst according to claim 4, wherein at least one of the compounds (A-4), (B-4) and (C) is supported on a carrier [compound (D)]. 9. An olefin is homopolymerized in the presence of the polymerization catalyst according to claim 1, 3, 4, 5, 7, or 8, or an olefin and another olefin or another monomer. And a method for producing a polymer. 10. A method for producing a polymer, comprising copolymerizing ethylene and octene in the presence of the polymerization catalyst according to claim 2 or 6.