JPH06136046A - Catalyst for polymerization of olefin and production of olefin polymer - Google Patents

Abstract

PURPOSE:To obtain a catalyst for polymerization of olefin having high activity, capable of providing a polymer having wide molecular weight distribution and good moldability by bringing a metallocene-based transition metal compound into contact with a transition metal compound other than metallocene, a clay (mineral), etc., and an organoaluminum compound. CONSTITUTION:An olefin (e.g. propylene) is subjected to homogeneous polymerization or copolymerization using a catalyst for polymerization of olefin obtained by bringing 4 components of (A) at least one kind of metallocene-based transition metal compound [e.g. biscyclopentadienylzirconium dichloride], (B) at least one kind of a transition metal compound other than metallocene (e.g. titanium tetrachloride), (C) clay, clay mineral or ion exchangeable layer compound (e.g. montmorillonite) and (D) an organoaluminum compound (e.g. trimethylaluminum) into contact with each other in the presence of (E) an organoaluminum (e.g. triethylaluminum) to provide the objective olefin polymer having wide molecular weight distribution and excellent in moldability.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for olefin polymerization and a method for polymerizing olefins using this catalyst, and more specifically, it has excellent polymerization activity and has a broad molecular weight distribution and / or multimodal molecular weight. The present invention relates to an olefin polymerization catalyst capable of giving an olefin (co) polymer having a distribution and a method for polymerizing olefins using this catalyst.

[0002]

2. Description of the Related Art A so-called Ziegler type catalyst composed of a titanium compound and an organoaluminum compound has been known as a catalyst for producing an olefin polymer such as an ethylene polymer or an ethylene / α-olefin copolymer. There is. However, the olefin polymer obtained with the catalyst generally has a wide molecular weight distribution and a composition distribution, and in particular, has a wide composition distribution, and thus has poor surface non-adhesiveness and transparency.

On the other hand, as a new olefin polymerization catalyst, a method using a metallocene compound and an aluminoxane is widely known (Japanese Patent Laid-Open No. 58-193).
09 publication). The olefin (co) polymer obtained using this new olefin polymerization catalyst is usually characterized by a narrow molecular weight distribution and composition distribution. However, an olefin polymer having a wide molecular weight distribution and excellent moldability has been desired depending on the use.

In order to solve these problems, several methods have been proposed in which two or more metallocene compounds having different growth reaction rate constants and termination reaction rate constants are used in the polymerization of olefins (JP-A-60-). 35006
No. 60-35008). Further, a method of combining a catalyst composed of this metallocene compound and aluminoxane with a Ziegler type catalyst has also been proposed (Japanese Patent Publication No. 63-501369, Japanese Patent Publication No. 1-503715).
JP-A-3-203903 and JP-A-3-203906). However, in these methods, the polymerization activity per transition metal or aluminum is not sufficient, and the step of removing the catalyst residue from the finally obtained polymer has not been made necessary.

[0005]

The present invention has been made in view of the above circumstances, and an object thereof is to obtain an olefin polymer having excellent polymerization activity and having a wide molecular weight distribution and excellent moldability. It is an object of the present invention to provide a catalyst for olefin polymerization capable of achieving the above and a method for polymerizing an olefin using this catalyst.

[0006]

The present inventors have arrived at the present invention as a result of extensive studies to solve the above problems. That is, the present invention includes [A] at least one metallocene-based transition metal compound, [B] at least one non-metallocene transition metal compound, [C] clay, clay mineral or ion-exchange layered compound, [D] organic compound. An olefin polymerization catalyst obtained by contacting four components of an aluminum compound, and an olefin polymer characterized by homopolymerizing or copolymerizing an olefin in the presence of the catalyst and [E] an organoaluminum compound, if necessary. Manufacturing method.

The present invention will be described in detail below. As the component [A] used in the present invention, that is, a metallocene-based transition metal compound, a compound containing a transition metal and a π-coordinating ligand can be used.

[0008]

[Chemical 1]

Compounds represented by are preferably used.
Here, R ¹ and R ² are optionally substituted hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing substituents, phosphorus-containing substituents,
It is a nitrogen-containing substituent and may be the same or different.

However, a, b, n, p, q, r and s are
It is an integer that satisfies the following formula. 0 ≦ a ≦ 5, 0 ≦ b ≦ 5, p ≧ 1, q ≧ 0, r ≧ 0 In the case of the formula [1], p + q + r = s, and in the case of the formula [2], p + q + r = s−n. .

Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-
Butyl group, pentyl group, isopentyl group, hexyl group,
Alkyl groups such as heptyl group, octyl group, nonyl group, decyl group, phenyl group, p-tolyl group, o-tolyl group, m
-Aryl group such as tolyl group, fluoromethyl group, fluoroethyl group, fluorophenyl group, chloromethyl group, chloroethyl group, chlorophenyl group, bromomethyl group, bromoethyl group, bromophenyl group, iodomethyl group, iodoethyl group, iodophenyl group, etc. And a silicon-containing substituent such as a halo-substituted hydrocarbon group, a trimethylsilyl group, a triethylsilyl group and a triphenylsilyl group.

Further, R ¹ and R ² may form a cross-linking group which is bonded to each other. Specifically, methylene group, alkylene group such as ethylene group, ethylidene group, propylidene group, isopropylidene group, phenylmethylidene group, diphenylmethylidene group, and other alkylidene group, dimethylsilylene group, diethylsilylene group, dipropyl group. Silylene group,
Silicon-containing bridging groups such as diisopropylsilylene group, diphenylsilylene group, methylethylsilylene group, methylphenylsilylene group, methylisopropylsilylene group, methyl-t-butylsilylene group, dimethylgermylene group,
Germanium such as diethylgermylene group, dipropylgermylene group, diisopropylgermylene group, diphenylgermylene group, methylethylgermylene group, methylphenylgermylene group, methylisopropylgermylene group, methyl-t-butylgermylene group Examples thereof include a crosslinking group, amine and phosphine.

Further, R ^{1 s} or R ^{2 s} may be bonded to each other to form a ring. Specifically, indenyl group, tetrahydroindenyl group, fluorenyl group,
Examples include octahydrofluorenyl group. R ³ is
An optionally substituted hydrocarbon group having 1 to 20 carbon atoms, hydrogen, halogen, a silicon-containing substituent, an alkoxy group, an aryloxy group, an amide group, or a thioalkoxy group, specifically, a methyl group, Alkyl groups such as ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, phenyl group, p- Aryl groups such as tolyl group, o-tolyl group, m-tolyl group, fluoromethyl group, fluoroethyl group, fluorophenyl group, chloromethyl group, chloroethyl group, chlorophenyl group, bromomethyl group, bromoethyl group, bromophenyl group, Halo-substituted hydrocarbon groups such as iodomethyl group, iodoethyl group and iodophenyl group, fluorine, chlorine, odor , Halogen such as iodine, silicon-containing substituents such as trimethylsilyl group, triethylsilyl group, triphenylsilyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, t-butoxy group, etc. Alkoxy group, phenoxy group, p-tolyloxy group, m-tolyloxy group,
an aryloxy group such as an o-tolyloxy group, an amide group,
Dimethylamide group, diethylamide group, dipropylamide group, diisopropylamide group, amide group such as bis (trimethylsilyl) amide group, methylthioalkoxy group,
Ethylthioalkoxy group, propylthioalkoxy group,
Examples thereof include thioalkoxy groups such as a butylthioalkoxy group, a t-butylthioalkoxy group and a phenylthioalkoxy group.

Further, R ³ may be bonded to R ¹ or R ^2, and specific examples of such a ligand include C ₅
H ₄ (CH ₂ ) _i O ⁻ (1 ≦ i ≦ 5), C ₅ (CH ₃ ).
₄ (CH ₂ ) _i O ⁻ (1 ≦ i ≦ 5), C ₅ H ₄ [Si
(CH _{3) 2] (t-C 4 H 9)} N -, C 5 (CH 3)
₄ [Si (CH _{3) 2] (t-C 4 H 9)} N - , and the like.

Further, R³Are bound to each other to form a bidentate ligand
May be formed. R like this³As a specific example of
^-OCH₂O^-,^-OCH₂CH₂O^-,^-O (o-C
₆H _Four) O^-Etc. M is the third, fourth periodic table
A group 5 or 6 atom, specifically, scandium or
Thorium, lanthanum, cerium, praseodymium, ne
Ozimium, samarium, europium, gadolinium, te
Rubium, dysprosium, holmium, erbium,
Thulium, ytterbium, lutetium, actinium
Mu, thorium, protactinium, uranium, titaniu
Aluminum, zirconium, hafnium, vanadium, niobium,
Tantalum, chromium, molybdenum, tungsten
Be done. Of these, group 4 titanium and zirconium
Mu and hafnium are preferably used. Also, these are
You may mix and use it.

L represents an electrically neutral ligand, and specifically, ethers such as diethyl ether, tetrahydrofuran, dioxane, nitriles such as acetonitrile, amides such as dimethylformamide, and trimethyl. Examples thereof include phosphines such as phosphine and amines such as trimethylamine. [R ⁴ ]
^n- is an n-valent anion, specifically, tetraphenyl borate, tetra (p-tolyl) borate, carbadodecaborate, tetrakis (pentafluorophenyl)
Examples thereof include borate, tetrafluoroborate, hexafluorophosphate and the like.

Specific examples of the compound of the formula [I]
Is bis (cyclopentadienyl) zirconium dichloride
Ride, bis (cyclopentadienyl) zirconium di
Methyl, bis (cyclopentadienyl) zirconium di
Phenyl, (methylcyclopentadienyl) (Cyclope
N-dienyl) zirconium dichloride, (methyl
Clopentadienyl) (cyclopentadienyl) zirco
Dimethyl, bis (pentamethylcyclopentadiene)
Nyl) zirconium dichloride, bis (pentamethyl)
Cyclopentadienyl) zirconium dimethyl, (tri
Methylsilylcyclopentadienyl) (Cyclopentadiene
(Enyl) zirconium dichloride, (trimethylsilyl
Cyclopentadienyl) (cyclopentadienyl) di
Ruconium dimethyl, bis (cyclopentadienyl) di
Ruconium dihydride, bis (cyclopentadiene
Z) Zirconium difluoride, bis (cyclopenta
Dienyl) zirconium bis (trimethylsilyl), bi
Sus (cyclopentadienyl) zirconium dimethoxy
De, bis (cyclopentadienyl) zirconium diphe
Nocside, bis (cyclopentadienyl) zirconium
Mubis (dimethylamide), bis (cyclopentadiene)
Z) Zirconium bis (methylthiolate)
Clopentadienyl) zirconium bis (phenylthio
Lat), [(η^Five: Η¹-3- (2,3,4,5-TE
Tramethylpentadienyl) propoxy] zirconium
Dichloride, (biscyclopentadienyl) zirconi
Umm (η ²-1,2-benzenedioxide), methyl
Bis (cyclopentadienyl) zirconium dichlora
Id, ethylene bis (cyclopentadienyl) zirconi
Umdi chloride, isopropylidene bis (cyclopen
Tadienyl) zirconium dichloride, diphenylmeth
Tylidene bis (cyclopentadienyl) zirconium di
Chloride, ethylene bis (indenyl) zirconium
Dichloride, ethylene bis (tetrahydroindeni
Z) Zirconium dichloride, dimethyl silylene bis
(Cyclopentadienyl) zirconium dichloride,
Dimethylsilylene bis (trimethylcyclopentadiene
Z) Zirconium dichloride, dimethylgermylene bis
(Cyclopentadienyl) zirconium dichloride,
Isopropylidene (cyclopentadienyl) (1-full
(Olenyl) zirconium dichloride, isopropylide
(Cyclopentadienyl) (1-fluorenyl) dil
Conium dimethyl, dimethyl silylene (cyclopentadiene
(Enyl) (1-fluorenyl) zirconium dichlorate
De, cyclopentadienyl zirconium trichloride
Etc.

Specific examples of the compound represented by the formula [2] include bis (cyclopentadienyl) zirconium methyl tetraphenyl borate, bis (cyclopentadienyl) zirconium phenyl tetraphenyl borate and bis (cyclo Pentadienyl) zirconium methyl tetrakis (pentafluorophenyl) borate, bis (cyclopentadienyl) zirconium phenyl tetrakis (pentafluorophenyl) borate, (methylcyclopentadienyl) (cyclopentadienyl) zirconium methyl tetraphenyl borate, Bis (pentamethylcyclopentadienyl) zirconium methyltetraphenylborate, bis (pentamethylcyclopentadienyl) zirconiummethyltetrakis (pentafluorophenyl) borate, ( Trimethylsilylcyclopentadienyl) (cyclopentadienyl) zirconium methyl tetraphenylborate, 3- (2,3,4,5-
Tetramethylcyclopentadienyl) propoxy zirconium methyl tetraphenylborate, methylenebis (cyclopentadienyl) zirconium methyltetraphenylborate, ethylenebis (cyclopentadienyl) zirconium methyltetraphenylborate, ethylenebis (cyclopentadienyl) zirconium Methyl tetrakis (pentafluorophenyl) borate, isopropylidene bis (cyclopentadienyl) zirconium methyl tetraphenyl borate, diphenyl methylidene bis (cyclopentadienyl) zirconium methyl tetraphenyl borate, ethylene bis (indenyl) zirconium methyl tetraphenyl borate , Ethylene bis (indenyl) zirconium methyl tetrakis (pentafluorophenyl) volley , Ethylenebis (tetrahydroindenyl) zirconium methyl tetraphenylborate, ethylenebis (tetrahydroindenyl) zirconium tetrakis (pentafluorophenyl) borate, dimethylsilylene bis (cyclopentadienyl) zirconium methyl tetraphenylborate,
Dimethyl silylene bis (trimethylcyclopentadienyl) zirconium methyl tetraphenyl borate, dimethyl silylene bis (trimethyl cyclopentadienyl)
Zirconium methyl tetrakis (pentafluorophenyl) borate, isopropylidene (cyclopentadienyl) (1-fluorenyl) zirconium methyl tetraphenyl borate, isopropylidene (cyclopentadienyl) (1-fluorenyl) zirconium methyl tetrakis (pentafluorophenyl) Borate, dimethylsilylene (cyclopentadienyl) (1-fluorenyl)
Examples thereof include zirconium methyltetraphenylcyclopentadienyltetraphenylborate, and tetrahydrofuran complexes of these compounds.

Further, regarding other Group 3, 4, 5 and 6 metal compounds such as titanium compounds and haunium compounds,
The compound similar to the above is mentioned. Further, a mixture of these compounds may be used. On the other hand, as the transition metal compound component which is not [B] metallocene, a conventionally known transition metal compound of a Ziegler-Natta type catalyst can be used. Examples of the transition metal compound component [B] include the following general formula

[0020]

[Chemical 2]

The compounds represented by can be used. here
M'is a transition metal atom of group 4, group 5 or group 6,
Titanium, zirconium, hafnium, vanadium
Aluminum, niobium, tantalum, chromium, molybdenum, tongs
Ten and so on. X¹Represents a halogen atom, R^Five
Is a hydrogen atom, a hydrocarbon group, an alkoxy group, an aryl group
Si group and cycloalkyloxy group are shown. R⁶Is a hydrocarbon
Indicates a group. Also, f and g are when the valence of M'is h
Is a non-negative number that satisfies f + g = h. These ingredients
As a physical example, TiCl₃, TiCl_Four, TiB
r_Four, TiI_Four, Ti (OC₂H_Five)₃Cl, Ti (O
C₂H_Five)₂Cl₂, Ti (OC₂H_Five) Cl₃, Ti
(OC₃H₇)₃Cl, Ti (OC_FourH₉)₃Cl, T
i (OC ₆H₁₃)₃Cl, Ti (OC₈H₁₇)₃Cl,
Ti (OC₂H_Five)_Four, ZrCl _Four, Zr (OC
₂H_Five) Cl₃, Zr (OC₂H_Five)₂Cl₂, Zr
(OC₂H _Five)₃Cl, Zr (OC₂H_Five)_Four, Zr
(OC_FourH₉) Cl₃, Zr (OC₆H₁₃) Cl₃, H
fCl_Four, Hf (OC₂H_Five) Cl₃, Hf (OC₂H
_Five)₂Cl₂, Hf (OC₂H_Five)₃Cl, Hf (OC
₂H_Five)_Four, Hf (OC_FourH₉) Cl₃, Hf (OC₆
H₁₃) Cl₃, NbF_Five, NbCl_Five, NbBr_Five, N
bI_Five, TaF_Five, TaCl_Five, TaBr_Five, Ta
I_Five, MoCl_Five, MoBr _Five, WCl₆, WBr₆,
CrCl₃Etc.

On the other hand, as an example of the vanadium compound, V
Cl ₃ , VCl ₄ , VOCl ₃ , VO (OC ₂ H ₅ )
₃ , and VO (OC ₄ H ₉ ) _{3 and the} like. Furthermore, if necessary, a plurality of these transition metal compounds can be mixed and used. As the transition metal compound component [B], a conventionally known transition metal compound supported on a magnesium compound can be preferably used.
Particularly preferably, titanium, magnesium and halogen are used as essential components, and if necessary, an electron donating compound is used. This is prepared by contacting (a) a magnesium compound, (b) a titanium compound, and optionally (c) an electron donating compound.

The magnesium compound (a) used herein has a general formula

[0024]

[Chemical 3]

Is a hydrocarbon group, an alkoxy group, an aryl group
An oxy group, an aroxy group or a hydrogen atom, R⁷, R
⁸May be the same or different. Also, X²
Represents a halogen atom, so that j + k + l = 2
j, k, l are chosen. ) Is used
Be done. Specifically, Mg (CH₃)₂, Mg (C₂H_Five)
₂, Mg (C₃H₇)₂, Mg (C_FourH₉)₂, Mg
(C₆H₁₃)₂, Mg (C₆H_Five)₂, Mg (C₂H_Five)
 (C₆H_Five), Mg (C₆H_FourCH₃)₂, Mg (O
CH₃)₂, Mg (OC₂H_Five)₂, Mg (OC
₃H₇)₂, Mg (OC_FourH ₉)₂, Mg (OC
₆H₁₃)₂, Mg (OC₆H_Five)₂, Mg (OC₆H_Four
CH ₃)₂, Mg (C_FourH₉) (OC₂H_Five), Mg
(C_FourH₉) (OC₆H_Five), MgH (C_FourH₉), M
g (C₂H_Five) Cl, Mg (C₃H₇) Cl, Mg (C
_FourH₉) Cl, Mg (C₆H_Five) Cl, Mg (OC
H₃) Cl, Mg (OC₂H _Five) Cl, Mg (OC₆H
_Five) Cl, MgCl₂, MgBr₂, MgI₂, MgF
₂Etc. can be mentioned. These are also for mixing
You can also As the titanium compound (b),
formula

[0026]

[Chemical 4]

(R⁹Represents a hydrocarbon group, X³Is a halogen
And a compound represented by 0 ≦ t ≦ 4) is used.
Be done. Specifically, TiCl_Four, TiBr_Four, TiI_Four,
Ti (OCH₃) Cl₃, Ti (OC₂H_Five) Cl₃,
Ti (OC_FourH₉) Cl₃, Ti (OC₆H₁₁) C
l₃, Ti (OC₂H_Five) Br₃, Ti (OCH₃)₂
Cl ₂, Ti (OC₂H_Five)₂Cl₂, Ti (OC_FourH
₉)₂Cl₂, Ti (OC₆H₁₁)₂Cl₂, Ti (O
C₂H_Five)₂Br₂, Ti (OCH₃)₃Cl, Ti
(OC₂H_Five)₃Cl, Ti (OC_FourH₉)₃Cl, T
i (OC₆H₁₁)₃Cl, Ti (OC₂H_Five)₃Br,
Ti (OCH₃)_Four, Ti (OC₂H_Five)_Four, Ti (O
C_FourH₉)_Four, Ti (OC₆H₁₁)_FourEtc.
Alcohols, amines as the electron donating compound (c)
, Amides, ethers, ketones, esters,
Examples include lucoxysilanes. Magnesium compound
(A), titanium compound (b), and optionally a child
There is no limitation on the method of contacting the addictive compound (c),
A known method is adopted. For example (1) MgCl₂Magnesium halides such as TiC
l_FourTitanium halide such as, and ester if necessary
For obtaining solid products by reacting electron-donating compounds such as
Law. (2) Mg (OC₂H_Five)₂Magnesium compounds, such as
TiCl_FourTitanium halide, such as
Solid formation by reacting electron donating compounds such as stells
How to get things. Etc. The amount of each ingredient used is usually
0.01 mol of titanium compound per mol of gnesium compound
To 100 mol, preferably 0.1 to 50 mol, and
0 to 10 moles of the child-giving compound, preferably 0.05 to 1
Used in molar amounts. And responsible for magnesium compounds
The amount of titanium retained is usually 0.05 to 30% by weight, preferably
It is preferably 0.1 to 20% by weight.

The ratio of the metallocene-based transition metal compound [A] to the non-metallocene transition metal compound [B] used can be arbitrarily selected. In the present invention, as the component [C], clay, clay minerals or ion-exchange layered compounds are used. Clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with each other with weak bonding forces, and the ions contained therein are exchangeable. Most clay minerals are ion-exchangeable layered compounds. Also, these clays, clay minerals,
Examples of ion-exchange layered compounds are not limited to naturally occurring compounds,
An artificial synthetic product can also be preferably used. Specific examples of the clay or clay mineral of the component [C] include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hissingelite, pyrophyllite, talc, hummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite. , Kaolinite, nacrite, dickite, halloysite and the like. Specific examples of the ion-exchange layered compound include α-Zr (HAsO ₄ ) ₂ · H
₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (HPO ₄ ).
_{2 · 3H 2 O, α-} Ti (HPO 4) 2, α-Ti (H
_{AsO 4) 2 · H 2 O} , α-Sn (HPO 4) 2 · H 2
O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ).
₂ , crystalline acid salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ · H ₂ O.

The component [C] preferably has a pore volume of 20 cc or more and a volume of 0.1 cc / g or more, particularly 0.3 to 5 cc / g, as measured by the mercury penetration method. here,
The pore volume is measured by a mercury porosimetry method using a mercury porosimeter in the range of 20 to 30000Å as the pore radius. In this example, “Au” manufactured by Shimadzu Corporation is used.
to Pore 9200 ”.

It is also preferable that the component [C] is chemically treated. Here, as the chemical treatment, both surface treatment for removing impurities adhering to the surface and treatment for affecting the crystal structure of clay can be used. In particular,
Acid treatment, alkali treatment, salt treatment, organic matter treatment and the like can be mentioned. The acid treatment removes impurities on the surface and increases the surface area by eluting cations such as Al, Fe and Mg in the crystal structure. Alkali treatment destroys the crystal structure of clay, resulting in a change in clay structure.
Further, in the salt treatment and the organic substance treatment, an ionic complex, a molecular complex, an organic derivative and the like can be formed to change the surface area and the interlayer distance.

Utilizing the ion-exchange property, the exchangeable ion between layers is exchanged.
Layer by replacing the ion with another large, bulky ion.
It is also possible to obtain a layered material in a state where the space is enlarged. sand
That is, bulky ions play the role of pillars that support the layered structure.
It is carried and is called a pillar. Also, between layered materials
Introducing another substance into the material is called intercalation.
U As the guest compound to be intercalated,
TiCl_Four, ZrCl _FourInorganic compounds such as T, T
i (OR^Ten)_Four, Zr (OR^Ten)_Four, PO (OR^Ten)
 ₃, B (OR^Ten)₃[R^TenIs a hydrocarbon group]
Lucolato, [Al ₁₃O_Four(OH)_{twenty four}]⁷⁺ , [Zr_Four
(OH)₁₄]²⁺, [Fe₃O (OCOCH₃)₆]⁺etc
The metal hydroxide ion and the like can be mentioned. These compounds
Can be used alone or in combination of two or more.
Good. It also intercalates these compounds
When using Si (OR)_Four, Al (OR)_Four, Ge (O
R)_FourPolymerization obtained by hydrolyzing metal alcoholates, etc.
Thing, SiO₂Coexist with colloidal inorganic compounds such as
You can also In addition, examples of the pillar include the above hydroxide
Heat dehydration after intercalation of ions between layers
Oxides and the like generated by doing so are listed.

The component [C] may be used as it is, or may be used after treatment such as ball milling and sieving. Further, it may be used after newly adsorbing and adsorbing water, or after heat dehydration treatment. Furthermore, they may be used alone or in combination of two or more of the above solids. As the component [C], preferred is clay or clay mineral, and most preferred is montmorillonite.

Examples of the organoaluminum compound used as the component [D] in the present invention include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, diethylaluminum monochloride, diethylaluminum methoxide. And the like, halogen- or alkoxy-containing alkylaluminum, aluminoxane such as methylaluminoxane, and the like, among which trialkylaluminum is particularly preferable.

Regarding the contact method for obtaining the polymerization catalyst from the component [A], the component [B], the component [C], and the component [D], when the component [C] is clay or clay mineral,
The molar ratio of the sum of the transition metals in each of the components [A] and [B] to the hydroxyl group in the clay or clay mineral and the amount of aluminum in the organoaluminum compound as the component [D] is 1: 0.1.
100,000: 0.1-10,000,000, especially 1: 0.5-10000: 0.5-10000
It is preferable that the reaction is carried out at 00.

Contact is made with pentane in an inert gas such as nitrogen,
It may be carried out in an inert hydrocarbon solvent such as hexane, heptane, toluene or xylene. The contact temperature is -20 ℃ ~
It is preferably carried out between the boiling points of the solvent, particularly preferably between room temperature and the boiling point of the solvent. Furthermore, in the present invention, as the organoaluminum compound [E] used as necessary,
The same compounds as the component [D] can be mentioned. The amount of the organoaluminum compound used in this case is [A], [B]
The molar ratio of the sum of the transition metals in each component to the aluminum in the component [E] is selected to be 1: 0 to 10,000.

The contact order of the catalyst components is not particularly limited. During or after the contact of each component of the catalyst, a polymer such as polyethylene or polypropylene, or a solid of an inorganic oxide such as silica or alumina may coexist or contact. The olefin may be prepolymerized in the presence of the above components [A], [B], [C] and [D] and, if necessary, [E]. The prepolymerization temperature is −50 to 100 ° C., and the prepolymerization time is 0.1 to 100 hours, preferably 0.1.
It is about 1 to 50 hours.

As the organoaluminum compound optionally used in the prepolymerization, the same compounds as the component [D] can be mentioned. The amount of the organoaluminum compound used at this time is such that the molar ratio of the sum of the transition metals in the catalyst components [A] and [B] to the aluminum in the [E] component is 1: 0.
Selected to be 10,000. The olefin used in the prepolymerization is preferably the olefin used in the polymerization, but other olefins may be used. Also, olefins can be mixed and used.

The polymerized weight produced by the prepolymerization is
It is in the range of 0.001 to 1000 g, preferably 0.1 to 300 g per 1 g of the component [C]. Solvents used during prepolymerization include butane, pentane, hexane, heptane,
It is octane, cyclohexane, toluene, xylene, etc., or a mixture thereof.

The prepolymerization catalyst thus obtained may be used without washing or may be used after washing. Examples of the organoaluminum compound that is optionally used when the olefin polymerization is performed using the olefin polymerization catalyst in which the above olefin is prepolymerized include the same compounds as the component [D]. The amount of the organoaluminum compound used in this case is selected so that the molar ratio of the sum of the transition metals in the components [A] and [B] to the aluminum in the organoaluminum compound is 1: 0 to 10000.

The olefins which can be polymerized by the above olefin polymerization catalysts include ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene and 4-methyl-. Examples thereof include 1-pentene, vinylcycloalkane, styrene or derivatives thereof, internal olefins such as 2-butene and 2-pentene or derivatives thereof, and cyclic olefins such as cyclohexene or derivatives thereof. Further, a polyene such as a diene or a functional group-containing olefin such as methyl methacrylate may coexist during the polymerization reaction. Polymerization can be suitably applied to not only homopolymerization but also generally known random copolymerization and block copolymerization.

Known processes can be used for the polymerization. That is, slurry polymerization using an inert hydrocarbon such as n-hexane as a solvent, bulk polymerization using a monomer itself such as liquid propylene as a solvent, and liquid phase such as inert hydrocarbon or liquid propylene are substantially A gas phase polymerization that does not exist is used. Further, these processes can be used in combination. The reaction system may be either a batch system or a continuous system.

The reaction is usually carried out under a pressure of 1 to 2000 atm.
It is carried out in the range of −50 to 250 ° C., and a known molecular weight regulator such as hydrogen can be appropriately used. Also, the polymerization temperature,
Polymerization may be carried out in multiple stages by changing the concentration of the molecular weight modifier. The components [A], [C] and [D] of the present invention
A double bond is present at the terminal of the polymer obtained from the catalyst containing, and terminal modification or graft polymerization can be performed by utilizing the double bond.

[0043]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited by these examples without departing from the gist thereof. Also,
FIG. 1 is a flow chart for facilitating the understanding of the technical contents included in the present invention, and the present invention is not restricted by the flow chart unless it deviates from the gist thereof.

In the examples, the melt flow index (shown as MFI) is ASTM-D-1238.
Based on -57T, it measured at 190 degreeC with a 2.16 kg load. The molecular weight distribution (Mw / Mn) of the polymer was measured by GPC (gel permeation chromatography). The solvent was o-dichlorobenzene and the operating temperature was 135 ° C.

(Example 1) (1) Preparation of catalyst A montmorillonite (manufactured by Aldrich Co., Montm, having a pore volume of 1.044 cc / g with a radius of 20 Å or more measured in a 300 ml round bottom flask by a commercially available mercury porosimetry method.
(orilonite K10; the same applies hereinafter) 51 g was collected, the inside of the flask was replaced with nitrogen, and then toluene 50 ml
Was added to form a slurry. Separately, 7.21 g of trimethylaluminum was dissolved in 50 ml of toluene. While stirring the montmorillonite slurry vigorously, a trimethylaluminum solution was slowly added dropwise thereto at room temperature. It generated heat with the generation of gas. The stirring was continued for 2 hours while appropriately cooling with ice water to obtain a gray-green slurry. A toluene solution containing 50 mg of commercially available biscyclopentadienylzirconium dichloride was placed in another 500 ml round bottom flask, and contacted with 96 ml of a toluene solution of trimethylaluminum (0.0179 M) for 30 minutes while stirring at room temperature. Next, 94 ml of a grayish green slurry which had been prepared in advance in the above-mentioned separate container was added and contacted for 20 minutes. Then, a solution of titanium tetrachloride in toluene (0.05
M) 50 ml slowly added dropwise at room temperature with stirring,
After contacting for a time, it was dried to obtain a catalyst.

(2) Polymerization of Ethylene A 2-liter induction stirring autoclave sufficiently substituted with purified N ₂ was charged with 0.3 mmol of triethylaluminum and 1 liter of purified hexane at room temperature under a N ₂ seal. After heating to 90 ° C., hydrogen was introduced at 0.9 kg / cm ² , and the catalyst obtained in (1) above (3.0 μmol in terms of zirconium atom) was introduced together with ethylene to bring the total pressure to 10
It was set to kg / cm ² . Although absorption of ethylene was observed as ethylene was introduced, ethylene was additionally introduced so as to keep the total pressure at 10 kg / cm ² , and 1 hour later, polymerization was stopped by ethanol injection. As a result, MFI was 0.39g / 10
320 g of polyethylene having a bar Mw / bar Mn of 11.2 was obtained. The amount of polyethylene obtained per 1 g of the transition metal was 1.4 × 10 ⁵ g.

Comparative Example 1 (1) Preparation of Catalyst A catalyst was obtained in the same manner as in (1) of Example 1 except that the toluene solution of titanium tetrachloride was not added in (1) of Example 1. It was

(2) Polymerization of ethylene The catalyst produced in the above (1) is converted into zirconium atom by 4
Polymerization of ethylene was carried out in the same manner as in (2) of Example 1 except that μmol was used. As a result, the MFI was 30.
4, 292 g of polyethylene with Mw / Mn of 2.4
Was obtained.

(Comparative Example 2) (1) Preparation of catalyst A commercially available biscyclopentadienyl zirconium dichloride (0.1 ml) was added to a 100 ml round bottom flask which had been sufficiently replaced with N ₂ .
A 97 mg toluene solution and a titanium tetrachloride 7.76 mg toluene solution were collected and stirred at room temperature to prepare a methylaluminoxane (molecular weight 1,232; manufactured by Tosoh Akzo) toluene solution in an amount of 6.0 m in terms of aluminum atom.
mol was added. After the addition was completed, the catalyst was obtained by stirring at room temperature for 1 hour.

(2) Polymerization of ethylene Polymerization of ethylene was carried out in the same manner as in (2) of Example 1 except that the catalyst prepared in (1) above was used in an amount of 3.0 μmol in terms of zirconium atom. As a result, 140 g of polyethylene was obtained. The amount of polyethylene obtained per 1 g of the transition metal was 7.5 × 10 ⁴ g.

Example 2 (1) Production of Component [B] Purified N ₂ was added to a 500 ml flask equipped with a stirrer and a thermometer.
Under the seal, collect 5 g of commercially available Mg (OC ₂ H ₅ ) ₂ and
7.4 g of i (OC ₄ H ₉ ) ₄ and 4.6 g of tetraethoxysilane were mixed, and the temperature was raised with stirring. After heating to 130 ° C., a toluene solution of 8.2 g of phenol was added. Then, the mixture was reacted at 130 ° C. for 1 hour to obtain a yellow slurry-like reaction product. After adding 63 ml of purified toluene to this product, it was cooled to -20 ° C and TiCl 2 was added at -20 ° C.
The ₄ 25g was added. After the addition, the inside of the system became uniform. When the temperature of this homogeneous solution was gradually raised to 50 ° C., solid formation was observed during the temperature rise. Then, the temperature was further raised, and when the temperature reached 110 ° C., 1.0 g of diethyl phthalate was added and the temperature was maintained for 1 hour. Then, after washing with purified toluene at room temperature, 42 g of TiCl ₄ was added, and the mixture was treated again at 110 ° C. for 1 hour. Then, toluene washing was performed at room temperature to obtain a component [B]. The Ti content of this product was 3.0% by weight.

(2) Preparation of catalyst A commercially available montmorillonite (manufactured by Aldrich, Montmorillonit was placed in a 300 ml round bottom flask.
e K10; the same applies hereinafter), 51 g was collected, the inside of the flask was replaced with nitrogen, and 150 ml of toluene was added to form a slurry. Separately, 21.63 g of trimethylaluminum
Was dissolved in 150 ml of toluene. While stirring the montmorillonite slurry vigorously, a trimethylaluminum solution was slowly added dropwise thereto at room temperature. It generated heat with the generation of gas. If necessary, stir 2 while cooling with ice water.
Continued for hours to obtain a gray-green slurry.

Commercially available biscyclopentadienyl zirconium dichloride in another 500 ml round bottom flask 12.
5 mg of toluene solution was collected and stirred at room temperature while stirring with a toluene solution of trimethylaluminum (0.0179).
M) Contacted with 240 ml for 30 minutes. Then, the gray-green slurry 235m which was previously prepared in the above separate container
1 was added and contact was performed for 20 minutes. Then, it dried and obtained the solid. On the other hand, separately from this, in a 200 ml round-bottomed flask sufficiently replaced, the component [B] prepared in (1) was converted into titanium atom of 0.5 mmol, and the solid prepared above was converted into zirconium atom of 0.18 mmol. , And 100 ml of purified hexane were added, and the mixture was stirred at room temperature for 30 minutes to obtain a catalyst slurry.

(3) Prepolymerization In a hexane slurry of the catalyst obtained in (2) above, a hexane solution of triethylaluminum (0.5M) 5.0 m
1 was added, and the mixture was stirred at room temperature for 30 minutes. Then, ethylene gas was introduced into the system, and prepolymerization was performed at room temperature for 30 minutes. After that, the supernatant was removed and washed with hexane.
By this reaction, 1 g of zirconium atom to 1 g of catalyst
A prepolymerization catalyst containing 0.2 μmol, titanium atom 28.2 μmol, and polyethylene 3.2 g was obtained.

(4) Polymerization of Ethylene A 2-liter induction stirring autoclave sufficiently substituted with purified N ₂ was charged with 0.3 mmol of triethylaluminum and 1 liter of purified hexane at room temperature under a N ₂ seal. After the temperature was raised to 90 ° C, 0.9 kg / cm ^{2 of} hydrogen was introduced, and the prepolymerization catalyst (3.13 µmol in terms of titanium atom) obtained in (3) above was introduced together with ethylene to give a total pressure of 10 kg / cm 2. ^{I chose 2} . Although absorption of ethylene was observed as ethylene was introduced, ethylene was additionally introduced so as to keep the total pressure at 10 kg / cm ² , and 1 hour later, polymerization was stopped by ethanol injection. As a result, MFI was 0.96 g /
10 minutes, polyethylene with Mw / Mn of 10.2 is 3
09 g was obtained. The amount of polyethylene obtained per 1 g of the transition metal was 1.2 × 10 ⁶ g.

[0056]

According to the present invention described above, there is provided a method for producing an olefin polymer having excellent polymerization activity as shown in Examples, a broad molecular weight distribution, and excellent moldability. Therefore, the industrial value of the present invention is remarkable.

[Brief description of drawings]

FIG. 1 is a flowchart showing one embodiment of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toru Suzuki Tohoku, Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryoh Kasei Co., Ltd. Ryokasei Co., Ltd.

Claims (4)

[Claims] 1. [A] at least one metallocene-based transition metal compound, [B] at least one non-metallocene transition metal compound, [C] clay, clay mineral or ion-exchange layered compound, [D] organoaluminum An olefin polymerization catalyst obtained by contacting four components of a compound. 2. A method for producing an olefin polymer, which comprises homopolymerizing or copolymerizing an olefin in the presence of the catalyst according to claim 1, and optionally [E] an organoaluminum compound. 3. An olefin polymerization catalyst, which is formed by prepolymerizing an olefin by combining the catalyst according to claim 1 and an [A] organoaluminum compound as the case requires. 4. Production of an olefin polymer, characterized in that an olefin is homopolymerized or copolymerized in the presence of the olefin polymerization catalyst according to claim 3 and optionally [E] an organoaluminum compound. Method.