JP3264338B2 - Polymerization catalyst containing specific aluminum compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION This invention is, certain of aluminized
The present invention relates to a polymerization catalyst comprising a compound as one component and a method for producing a polyolefin using the catalyst. For more information,
The present invention relates to a highly active catalyst particularly useful for olefin polymerization using an aluminum compound of the formula (1) , and a method for producing a polyolefin capable of increasing the molecular weight and controlling the molecular weight using the catalyst.

[0002]

2. Description of the Related Art A catalyst system comprising a transition metal compound such as a metallocene compound and an organoaluminum is already known, but it has problems in that it has low activity and does not exhibit stereoregular polymerization. It cannot be used industrially. On the other hand, it is known that a catalyst system comprising a transition metal compound such as a metallocene compound and methylaluminoxane as an aluminum oxy compound as a co-catalyst can be already used as a catalyst for producing isotactic or syndiotactic polypropylene. . However, a catalyst system containing a transition metal compound such as a metallocene compound and a conventional aluminum oxy compound has an excellent surface in terms of high stereoregularity and activity, but has a molecular weight at an industrially usable polymerization temperature. Is difficult to obtain. In addition, there are disadvantages such as the necessity of using a relatively large amount of expensive aluminoxane and the requirement of a relatively high degree of polymerization of the aluminoxane, which limits the range. As described above, when used for industrial production, there was no product having excellent productivity (activity), molecular weight of the obtained polymer, etc., and thus a transition metal compound such as a metallocene compound and an organoaluminum compound or There has been a demand for an improved catalyst system that can be used industrially while taking advantage of the catalyst system containing an aluminum oxy compound.

[0003]

Accordingly, the present invention is directed to a catalyst system containing a transition metal compound such as a metallocene compound and a novel aluminum compound as a co-catalyst. An object of the present invention is to obtain a catalyst system capable of producing a polymer capable of producing a polymer having a molecular weight or the like, particularly a polyolefin.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have succeeded in obtaining an aluminum compound into which a special group has been introduced. By using together with a metal compound or further containing an organoaluminum compound as a catalyst system for olefin polymerization, the present invention has succeeded in dramatically increasing the polymerization activity and increasing the polymer molecular weight. Was completed. That is, the gist of the present invention is as follows: [1] (A) (II)-(V)
Transfer metal compound and (B) aluminum alloy described in general formula (1)
Or copolymerization of olefins composed of sulfur compounds
Catalyst, AlR ¹ R ² R ³ (1) [where R ¹ is —X ¹ R ⁴ (X ¹ is a group 15 or 16 element)
R ⁴ is a pentahaloaryl group bonded to X ¹
It is. ) And R ² and R ³ are each independently hydrogen
Atom, halogen atom, R ¹ , hydrocarbon having 1 to 20 carbon atoms
Group consisting of a group and an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms
Is a group selected from ] _{^{CpM 1 R 5 a R 6 b}} R 7 c (II) CpM 1 R 5 a R 6 b (III) (Cp-A e -Cp) M 1 R 5 a R 6 b (IV) M 1 R 5 a R ⁶ _b R ⁷ _c R ⁸ _d (V) [Cp is a cyclopentadienyl group, substituted cyclopentadiene
Enyl group, indenyl group, substituted indenyl group, tetrahi
A droindenyl group, a substituted tetrahydroindenyl group,
Indicates Ruoreniru group or a substituted fluorenyl group, M ¹ is Chi
Indicates tan, zirconium or hafnium. R ⁵ ,
R ⁶ , R ⁷ and R ⁸ are each independently a ligand, and A is shared
Shows crosslinking by bonding. a, b, c and d are each German
The letter e is an integer of 0-6, and e is an integer of 0-6. ] [2] described in 1 (A) component and the (B) component and
(C) an organoaluminum compound represented by the general formula (VIII)
A catalyst for homopolymerization or copolymerization of olefins comprising: R ¹³ AlQ _3-r (VIII) (R ¹³ is an alkyl group having 1 to 10 carbon atoms, Q is a hydrogen atom,
C1-C20 alkoxy group, C6-C20 ant
And r represents an integer of 1 to 3.
You. ) [3] the presence of the catalyst according to the above 1 or 2, an olefin
Characterized by homopolymerization or copolymerization of phenols
Fin manufacturing method . Hereinafter, the contents of the present invention will be described in detail.

[0005] According to the present invention, an A represented by the general formula (1)
R of the ruminium compound¹Is -X¹R ^FourAnd X¹Is 1
At least one element selected from Group 5 or 16 elements
In Group 15, nitrogen and phosphorus are particularly preferred. Also one
In Group VI, oxygen and sulfur are particularly preferred. R^FourIs X¹Joined to
Electron-withdrawing group or a group containing an electron-withdrawing group
It is necessary that Hammett's substituent constant σ be positive.
And specifically include an electron-withdrawing group or an electron-withdrawing group.
At least one selected from the group Electron suction here
Functional groups include halogen atoms, nitro groups, sulfone groups,
Examples thereof include an ano group, a carbonyl group, and an aldehyde group.
Further, as the group containing an electron-withdrawing group, trihaloal
Kill group, pentahaloaryl group, pentakis (triha
B) aryl group, trihaloaryl group, dihaloaryl
Group, monohaloaryl group, ester group, etc.
You. -X¹R^FourIs specifically pentafluorophenoxy
Group, pentachlorophenoxy group, pentabromophenoxy
Si group, 2,3-difluorophenoxy group, 3,4-diph
Fluorophenoxy groups are exemplified, and particularly as a co-catalyst
When used for olefin polymerization, the catalyst activity
Pentafluorophenoxy group is preferred
You.

R ² and R ³ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, R ¹ , a hydrocarbon group having 1 to 20 carbon atoms and an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, an aryl group, an alkylaryl group, and an arylalkyl group. Specifically, as the alkyl group, a methyl group, an ethyl group, a propyl group,
There are an isopropyl group, a butyl group, an isobutyl group, an octyl group, and a 2-ethylhexyl group. Examples of the aryl group, the alkylaryl group, and the arylalkyl group include a phenyl group, a naphthyl group, a tolyl group, a xylyl group, and a benzyl group. .

[0007] Examples of the oxygen-containing hydrocarbon group having 1 to 20 carbon atoms include an alkoxy group and aryloxy. Specifically, the alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group and the like, and the aryloxy group includes a phenoxy group, a 2,6-dimethylphenoxy group, a naphthyloxy group and the like. .

In any case, the aluminum compound represented by the general formula (1) may be a compound having at least one R ¹ , and R ² and R ³ are usually an alkyl group or a halogen atom, Groups, ethyl groups, isobutyl groups and chloro groups are preferred. The content of -XR ⁴ aluminum compound of component (B), unconditionally good even although 100% can not be said.

As described above, R ¹ , R ² and R ^{3 in the} general formula (1)
Has been specifically described. Specific examples of the aluminum compound represented by the general formula (1) include pentafluorophenoxyaluminum dimethyl, pentafluorophenoxyaluminum diethyl, pentafluorophenoxyaluminum ethyl chloride, and pentafluorophenoxyaluminum methyl. Chloride, pentafluorophenoxyaluminum dichloride, bis-pentafluorophenoxyaluminum ethyl, bis-pentafluorophenoxyaluminum chloride, bis-pentafluorophenoxyaluminum isobutyl and the like.

The method for producing the aluminum compound represented by the above general formula (1) depends on the type of R ¹ , R ² and R ³ , but examples thereof include trialkylaluminum, dialkylaluminum monochloride, monoalkylaluminum dichloride and the like. Of the above aluminum compound with a halogenated phenol. As a specific treatment method, these aluminum compounds are dissolved in a solvent such as toluene, and then cooled to −50 ° C. or lower, and a halogenated phenol dissolved in the solvent is added dropwise thereto. A method of holding for about 1 to 50 hours can be employed. Arbitrary R ¹ can be introduced by changing the drop amount of the halogenated phenol used for the aluminum compound. In this case, an unreacted raw aluminum compound may remain. As the halogenated phenol as a treating agent used here,
Pentachlorophenol, pentafluorophenol,
3,5-difluorophenol and the like are exemplified.

The first polymerization catalyst proposed in the present invention comprises a transition metal compound and the above-mentioned novel aluminum compound. The transition metal compound is not particularly limited, but a compound containing an element belonging to Groups 4 to 10 of the periodic rule and a lanthanoid element is particularly preferable. In addition, metallocene containing these elements can be effectively used. As the transition metal compound, various compounds can be mentioned, and the general formula CpM ¹ R ⁵ _a R ⁶ _b R ⁷ _c (II) Cp ₂ M ¹ R ⁵ _a R ⁶ _b (III) (III) ^{_{cp-A e -Cp) M 1}} R 5 a R 6 b ··· (IV) or a compound represented by the general formula _{^{M 1 R 5 a R 6 b}} R 7 c R 8 d ··· (V) or its Derivatives are preferred. In the general formulas (II) to (V), M ¹ represents a transition metal such as titanium, zirconium, hafnium, vanadium, niobium, chromium, etc., and Cp represents 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. R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently σ
Ligands such as a binding ligand, a chelating ligand, and a Lewis base are shown. Specific examples of the σ-binding ligand include a hydrogen atom, an oxygen atom, a halogen atom, and a carbon atom having 1 carbon atom. ~ 20
An alkyl group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, an acyloxy group having 1 to 20 carbon atoms,
Examples of chelating ligands such as an allyl group, a substituted allyl group, and a substituent containing a silicon atom include acetylacetonate groups and substituted acetylacetonate groups, and examples of Lewis bases include ethers and nitriles. it can.
A represents a covalent crosslink. a, b, c and d each independently represent an integer of 0 to 4; e represents an integer of 0 to 6;
Two or more of R ⁵ , R ⁶ , R ⁷ and R ⁸ may combine with each other to form a ring. When the Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms. In the formulas (III) and (IV), two Cp's may be the same or different from each other.

The substituted cyclopentadienyl group in the above formulas (II) to (IV) includes, for example, methylcyclopentadienyl group; ethylcyclopentadienyl group; isopropylcyclopentadienyl group; Pentadienyl group; tetramethylcyclopentadienyl group; 1,3-dimethylcyclopentadienyl group;
2,3-trimethylcyclopentadienyl group;
4-trimethylcyclopentadienyl group; pentamethylcyclopentadienyl group; trimethylsilylcyclopentadienyl group and the like. The above (II) ~
Specific examples of R ^{5 to} R ^{8 in} the formula (V) include, besides the above hydrogen atom and oxygen atom, halogen atoms such as fluorine, chlorine, bromine and iodine;
As an alkyl group of 0, methyl, ethyl, n-propyl, isopropyl, n-butyl, octyl, 2
-Ethylhexyl group; methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group as C1-C20 alkoxy group; phenyl group, tolyl group as C6-C20 aryl group, alkylaryl group or arylalkyl group , Xylyl group, benzyl group; carbon number 1
A heptadecylcarbonyloxy group as an acyloxy group of -20 to 20; a trimethylsilyl group, a (trimethylsilyl) methyl group as a substituent containing a silicon atom; ethers such as dimethyl ether, diethyl ether, and tetrahydrofuran as Lewis bases; thioethers such as tetrahydrothiophene; Esters such as benzoate, nitriles such as acetonitrile, benzonitrile, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 2,
Amines such as 2'-bipyridine and phenanthroline,
And phosphines such as triethylphosphine and triphenylphosphine. Still further, ethylene; butadiene; 1-pentene; isoprene; pentadiene; linear unsaturated hydrocarbons such as 1-hexene and derivatives thereof, benzene; toluene; xylene; cycloheptatriene; cyclooctadiene; And cyclic unsaturated hydrocarbons such as cyclooctatetraene and derivatives thereof. Examples of the cross-link by a covalent bond of A in the above formula (IV) include a methylene cross-link, a dimethyl methylene cross-link, an ethylene cross-link,
1′-cyclohexylene bridge, dimethylsilylene bridge,
Examples include dimethylgermylene crosslink and dimethylstannylene crosslink.

The compound represented by the general formula (II) includes, for example, (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl) Tribenzyl zirconium, (pentamethylcyclopentadienyl) trichloro zirconium, (pentamethyl cyclopentadienyl) trimethoxy zirconium, (cyclopentadienyl) trimethyl zirconium, (cyclopentadienyl) triphenyl zirconium, (cyclopentadi (Enyl) tribenzylzirconium, (cyclopentadienyl) trichlorozirconium, (cyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) dimethyl (methoxy) zirconium , (Methylcyclopentadienyl) trimethylzirconium, (methylcyclopentadienyl) triphenylzirconium, (methylcyclopentadienyl) tribenzylzirconium, (methylcyclopentadienyl) trichlorozirconium, (methylcyclopentadienyl) ) Dimethyl (methoxy) zirconium, (dimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium, and the like, and the like. In these, a compound in which zirconium is replaced with titanium or hafnium is mentioned.

Examples of the compound represented by the general formula (III) include bis (cyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) diethyl zirconium, and bis (cyclopentadienyl) diethyl zirconium. Cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium, bis (cyclopentadienyl) dihydridozirconium, bis (cyclopentadienyl) monochloromonohydride Zirconium, bis (methylcyclopentadienyl) dimethyl zirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclopentadienyl) dibenzylzirconium, bis (pentamethy Lecyclopentadienyl) dimethyl zirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, bis (pentamethylcyclopentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) chloromethylzirconium, bis (penta Methylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl)
Examples thereof include (pentamethylcyclopentadienyl) dichlorozirconium, and further, a compound in which zirconium is replaced by titanium or hafnium.

Examples of the compound represented by the general formula (IV) include ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) dichloro zirconium, ethylene bis (tetrahydroindenyl) dimethyl zirconium, and ethylene bis (tetrahydro (Indenyl) dichlorozirconium, dimethylsilylenebis (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, isopropylidene (cyclo Pentadienyl) (9-fluorenyl) dichlorozirconium, [phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium M, diphenylmethylene (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, ethylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclohexalidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, Cyclopentylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclobutylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, Dimethylsilylene bis (2,3,5
-Trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dimethylzirconium, dimethylsilylenebis (indenyl) dichlorozirconium, and the like. Alternatively, a compound can be given by substituting hafnium.

Further, as the compound represented by the general formula (V), for example, tetramethyl zirconium, tetrabenzyl zirconium, tetramethoxy zirconium, tetraethoxy zirconium, tetrabutoxy zirconium, tetrachloro zirconium, tetrabromo zirconium, butoxy trichloro Zirconium, dibutoxydichlorozirconium, bis (2,5-di-t-butylphenoxy) dimethylzirconium, bis (2,5-di-
t-butylphenoxy) dichlorozirconium, zirconiumbis (acetylacetonate) and the like,
In these, the compound which substituted titanium or hafnium for zirconium is mentioned.

Specific examples of the vanadium compound include vanadium trichloride, vanadyl trichloride,
Vanadium triacetylacetonate, vanadium tetrachloride, vanadium tributoxide, vanadyl dichloride, vanadyl bisacetylacetonate, vanadyl triacetylacetonate, dibenzene vanadium, dicyclopentadienyl vanadium, dicyclopentadienyl vanadium dichloride, cyclopentane Dienyl vanadium dichloride, dicyclopentadienyl methyl vanadium and the like can be mentioned.

Next, specific examples of the chromium compound include tetramethylchromium, tetra (t-butoxy) chromium, bis (cyclopentadienyl) chromium, hydridetricarbonyl (cyclopentadienyl) chromium, and hexacarbonyl (cyclohexane). Examples thereof include (pentadienyl) chromium, bis (benzene) chromium, tricarbonyltris (triphenylphosphonate) chromium, tris (allyl) chromium, triphenyltris (tetrahydrofuran) chromium, and chromium tris (acetylacetonate).

Furthermore, in the above general formula (IV), two substituted or unsubstituted conjugated cyclopentadienyl groups (at least one of which is a substituted cyclopentadienyl group) are represented by A Group 4 transition metal compound having a ligand as a multiple coordinating compound bonded to each other via an element selected from Group 14 can be suitably used. Such compounds include, for example, those represented by the general formula (VI)

[0020]

Embedded image

The compounds represented by the following or derivatives thereof
be able to. Y in the general formula (VI)¹Is carbon, kei
Element, germanium or tin atom, R⁹ _t-C_FiveH_4-tPassing
And R⁹ _u-C_FiveH_4-uAre each substituted cyclopentadie.
The nyl group, t and u represent an integer of 1 to 4. Where R⁹
Represents a hydrogen atom, a silyl group or a hydrocarbon group,
They may be one or different. Also at least one piece
One of the cyclopentadienyl groups has Y¹Bound to
R on at least one carbon next to the carbon⁹Exists.
R^TenIs a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or carbon
An aryl group, an alkylaryl group, or
It represents an arylalkyl group. M^TwoIs titanium, zirconium
Or hafnium atom, X^TwoIs hydrogen atom, halogen
Atom, alkyl group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
An aryl group, an alkylaryl group or an aryl group
It represents an alkyl group or an alkoxy group having 1 to 20 carbon atoms. X
^TwoMay be the same or different from each other, and R^TenAlso
They may be the same or different.

The substituted cyclopentadienyl group in the above general formula (VI) includes, for example, methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl Group, 1,3-dimethylcyclopentadienyl group, 1,2,3-trimethylcyclopentadienyl group,
1,2,4-trimethylcyclopentadienyl group and the like. Specific examples of X ² include a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom as a halogen atom; a methyl group, an ethyl group, an n-propyl group, and an isopropyl group as an alkyl group having 1 to 20 carbon atoms. , N-
Butyl, octyl, 2-ethylhexyl; C1-C20 alkoxy as methoxy, ethoxy, propoxy, butoxy, phenoxy; C6-C20 aryl, alkylaryl or arylalkyl Examples of the group include a phenyl group, a tolyl group, a xylyl group, and a benzyl group. Specific examples of R ¹⁰ include a methyl group, an ethyl group, a phenyl group, a tolyl group, a xylyl group, and a benzyl group.

Specific examples of the compound represented by the above general formula (VI) include dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride and dimethylsilylenebis (2,3,5-trimethyl Cyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) hafnium dichloride and the like. Furthermore, the general formula (VII)

[0024]

Embedded image

The compounds represented by the following formulas are also included. The general formula
In the compound of the formula (VII), Cp is cyclopentadienyl
Group, substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, tetrahydroindenyl group, substituted tetra
Hydroindenyl, fluorenyl or substituted fluor
Cyclic unsaturated hydrocarbon group such as an n-yl group or chain unsaturated carbon
Shows a hydrogen group. M^ThreeIs titanium, zirconium or hafni
X^ThreeIs hydrogen atom, halogen atom, carbon
An alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms
Group, alkylaryl group or arylalkyl group or
Represents an alkoxy group having 1 to 20 carbon atoms. Z is SiR¹¹
_Two , CR¹¹ _Two , SiR¹¹ _Two SiR¹¹ _Two , CR¹¹ _Two CR¹¹
_Two , CR¹¹ _Two CR¹¹ _Two CR¹¹ _Two , CR¹¹= CR¹¹, CR
¹¹ _Two SiR¹¹ _TwoOr GeR¹¹ _Two And Y^TwoIs -N (R
¹²)-, -O-, -S- or -P (R¹²)-. Up
Note R¹¹Is an atom with hydrogen atoms or up to 20 non-hydrogen atoms
Alkyl, aryl, silyl, alkyl halide, halo
A group selected from gallified aryl groups and their combinations
Yes, R¹²Is an alkyl group having 1 to 10 carbon atoms or carbon
6 to 10 aryl groups or one or more
More R¹¹Forms a fused ring system of up to 30 non-hydrogen atoms
May be implemented. w represents 1 or 2.

Specific examples of the compound represented by the general formula (VII) include (tertiary butylamide) (tetramethyl-
[eta] ⁵ -cyclopentadienyl) -1,2-ethanediylzirconium dichloride; (tert-butylamide) (tetramethyl- [eta] ⁵ -cyclopentadienyl) -1,2-
Ethanediyl titanium dichloride; (methylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-
Ethanediylzirconium dichloride; (methylamide) (tetramethyl-η ⁵ -cyclopentadienyl)-
1,2-ethanediyltitanium dichloride; (ethylamide) (tetramethyl-η ⁵ -cyclopentadienyl)-
Methylene titanium dichloride; (tert-butylamido) dimethyl (tetramethyl-eta ⁵ - cyclopentadienyl)
Silane titanium dichloride; (tert-butylamido) dimethyl (tetramethyl-eta ⁵ - cyclopentadienyl) silane zirconium dibenzyl; (benzylamide) dimethyl - (tetramethyl-eta ⁵ - cyclopentadienyl)
Silane titanium dichloride; (phenyl phosphide) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane zirconium dibenzyl and the like.

The second polymerization catalyst proposed in the present invention comprises a transition metal compound (component A), the novel aluminum compound (component B), and an organoaluminum compound (component C). Examples of the organoaluminum compound include a compound represented by the following general formula (VIII): R ¹³ _r AlQ _3-r (VIII) (where R ¹³ is an alkyl group having 1 to 10 carbon atoms, Q is a hydrogen atom, and an alkoxy group having 1 to 20 carbon atoms) , C6-20
Wherein r is an integer of 1 to 3).

Specific examples of the compound represented by the general formula (VIII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride,
Examples thereof include diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, and ethylaluminum sesquichloride. These organoaluminum compounds may be used alone or in combination of two or more.

Next, the use ratio of each catalyst component in the present invention will be described. When (A) a transition metal compound and (B) an aluminum compound are used as the catalyst components,
(A): (B) is preferably 1: 1 to 1: 5,000,
The ratio is more preferably from 1: 1 to 1: 1,000, but particularly preferably from 1: 1 to 1: 600 from the viewpoints of activity, economy and post-treatment. (A) and (B) and (C) as the catalyst component
When an organoaluminum compound is used, (A):
(B) is preferably in the above range, but (A) :( C) is preferably 1: 1 to 1: 10,000, and 1: 5 to 1:
2,000 is more preferred, but in particular 1:10 to 1:10
00 is preferred.

In the present invention, at least the catalyst component
One can be used by supporting it on a suitable carrier. The charge
There is no particular limitation on the type of body, inorganic oxide carrier,
Use any other inorganic or organic carrier
Can be formed, but in particular, inorganic oxide carrier or other
Organic carriers are preferred. As the inorganic oxide carrier, specifically,
Is SiO_Two, Al_TwoO_Three, MgO, ZrO_Two, TiO
_Two, Fe_TwoO_Three, B_TwoO_Three, CaO, ZnO, BaO,
ThO_TwoAnd mixtures thereof, such as silica alumina and zeolite.
Olite, ferrite, glass fiber, smectite
And the like. Among them, especially SiO 2_Two,
Al _TwoO_ThreeIs preferred. Incidentally, the inorganic oxide carrier,
It may contain a small amount of carbonate, nitrate, sulfate and the like.
On the other hand, as a carrier other than the above, MgCl_Two, Mg (OC
_TwoH_Five)_TwoSuch as magnesium compounds
General formula MgR¹⁴ _XX^Four _yA magnesium compound represented by
Examples thereof include complex salts. Where R¹⁴Is charcoal
Alkyl group having 1 to 20 carbon atoms and alkoxy having 1 to 20 carbon atoms
A cyclo group or an aryl group having 6 to 20 carbon atoms, X^FourIs halogen
X represents an atom or an alkyl group having 1 to 20 carbon atoms;
An integer of 2 and y is an integer of 0 to 2 and x + y = 2
You. Each R¹⁴And each X^FourMay be the same or different
It may be. In addition, as an organic carrier, police
Tylene, polyethylene, polypropylene, substituted polystyrene
Polymers such as ren and polyarylate, starch and carbohydrate
And the like.

When a carrier is used in the present invention, preferred carriers are MgCl ₂ , MgCl (OC
₂ H _5), and the like _{Mg (OC 2 H 5) 2} , SiO 2, Al 2 O 3. The properties of the carrier vary depending on the type and manufacturing method, but the average particle size is usually 1 to 300 μm, preferably 1
It is 0 to 200 μm, more preferably 20 to 100 μm. If the particle size is too small, the fine powder of the polymer will increase. Conversely, if the particle size is too large, the coarse particles of the polymer will increase, causing a decrease in bulk density and clogging of the hopper. The specific surface area of the carrier is usually 1 to 1000 m ² / g, preferably 50 to 1000 m ² / g.
500 m ² / g, pore volume is usually 0.1-5 cm ³ / g,
Preferably it is 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 are
For example, it can be determined from the volume of nitrogen gas adsorbed according to the BET method (see Journal of the American Chemical Society, Vol. 60, p. 309 (1983)). Further, the carrier is usually 1
It is desirable to use by baking at 50 to 1000 ° C, preferably 200 to 800 ° C.

When the catalyst component is supported on the carrier,
When (A) is composed of a transition metal compound and (B) an aluminum compound, at least one, preferably both, of (A) and (B) are used, and both (A), (B) and (C) When it is made of an aluminum compound, it is desirable to support at least one of them, preferably all the components. The method of supporting at least one of the component (A), the component (B) and the component (C) on the carrier is not particularly limited.
A method of mixing at least one of the components (B) and (C) with a carrier, treating the carrier with the component (C) (or treating with a halogen-containing silicon compound when the component (C) is not used), A method of mixing with at least one of the component (A) and the component (B) in an active solvent, a carrier and the component (A) and / or the component (B) and the component (C) (or silicon when the component (C) is not used) Compound) with
After supporting the component (A) or the component (B) on a carrier,
A method of mixing the component (B) or the component (A), a method of mixing the contact reactant of the component (A) and the component (B) with a carrier,
At the time of the contact reaction between the component (A) and the component (B), a method in which a carrier coexists may be used. In addition, in the above or the above-mentioned reaction or mixing, the component (C) may be added.

The thus-obtained supported or unsupported catalyst may be subjected to polymerization by removing the solvent used for the preparation once and removing it as a solid, and then subjecting it to polymerization. It may be used for polymerization as it is without performing. Further, in the present invention, a catalyst can be generated by performing an operation of loading at least one of the component (A) and the component (B) on a carrier in a polymerization system.
For example, at least one of the components (A) and (B), a carrier and, if necessary, the component (C) are added, and an olefin such as ethylene is added at normal pressure to 20 kg / cm ² ,
A method in which prepolymerization is performed at 20 to 200 ° C. for about 1 minute to 2 hours to generate catalyst particles can be used.

Next, the preferred use ratio of each catalyst component and carrier will be described. When the catalyst according to the present invention is used with the component (A), (B) or (C) supported on a carrier, the use ratio (weight ratio) between each component and the carrier is preferably 1: 1, respectively. The ratio is from 5 to 1: 10000, more preferably from 1:10 to 1: 500. (A), (B)
Alternatively, when the use ratio of the component (C) and the carrier is outside the above range, the activity may be reduced. The average particle size of the polymerization catalyst of the present invention thus prepared, supported on a carrier, is usually 2 to 200 μm, preferably 10 to 150 μm.
m, particularly preferably 20 to 100 μm, and the specific surface area is usually 20 to 1000 m ² / g, preferably 50 to ⁵ m ² / g.
00 m ² / g. If the average particle size is less than 2 μm, the fine powder of the polymer may increase, and if it exceeds 200 μm, the coarse particles of the polymer may increase. If the specific surface area is less than 20 m ² / g, the activity may decrease,
If it exceeds 1000 m ² / g, the bulk density of the polymer may decrease. By supporting on a carrier in this way, a polymer having an industrially advantageous range of bulk density and excellent particle size distribution can be obtained.

According to the process for producing a polymer of the present invention, homopolymerization of olefins or copolymerization of olefins with other olefins and / or other monomers using the polymerization catalyst described above ( That is, copolymerization with different olefins, copolymerization of olefins with other monomers, or copolymerization of different olefins with other monomers can be suitably performed. The olefin is not particularly limited, but is preferably an α-olefin having 2 to 20 carbon atoms. Examples of the α-olefin include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, -Dodecene, 1
-Tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. Also,
The other olefins described above may be appropriately selected from the above olefins.

In the present invention, the above olefins may be used alone or in combination of two or more. When copolymerizing two or more olefins, the above olefins can be arbitrarily combined. In this case, for example, when propylene and ethylene, or ethylene and an α-olefin having 3 to 10 carbon atoms are copolymerized, the copolymerization ratio of propylene and ethylene or ethylene and an α-olefin having 3 to 10 carbon atoms may be used. Polymerization ratio (molar ratio)
Is usually 99.9: 0.1 to 0.1: 99.9, preferably 99.9.
5: 0.5 to 75.0: 25.0. In the present invention, the above-mentioned olefins and other monomers may be copolymerized. Examples of other monomers used in this case include styrene, p-methylstyrene, isopropylstyrene, and t-styrene. Vinyl aromatic compounds such as butylstyrene, chain diolefins such as butadiene, isoprene and 1,5-hexadiene, norbornene,
5,8-Dimethano-1,2,3,4,4a, 5,8,8
Cyclic olefins such as a-octahydronaphthalene and 2-norbornene, cyclic diolefins such as norbornadiene, 5-ethylidene norbornene, 5-vinylnorbornene and dicyclopentadiene, and unsaturated esters such as ethyl acrylate and methyl methacrylate , Β-
Lactones such as propiolactone, β-butyrolactone, γ-butyrolactone, ε-caprolactam, lactams such as δ-valerolactam, epoxypropane,
Epoxides such as 1,2-epoxybutane can be exemplified. In addition, the polymerization catalyst of the present invention can be used not only for the polymerization of the olefins but also for the polymerization of other olefins.

In the present invention, the polymerization method is not particularly limited.
Slurry polymerization, gas phase polymerization, bulk polymerization, solution weight
Any method such as a legal method or a suspension polymerization method may be used.
However, a slurry polymerization method and a gas phase polymerization method are particularly preferred. polymerization
Regarding the conditions, the polymerization temperature is usually −100 to 250 ° C.,
Preferably -50 to 230C, more preferably 0 to 20
0 ° C. Also, the ratio of the catalyst used to the reactants
Is preferably the raw material monomer / component (A) (molar ratio)
1 to 10 ⁸, Especially 100 to 10^FivePreferably
New Further, the polymerization time is usually 5 minutes to 10 hours,
The force is preferably normal pressure to 200 kg / cm^TwoG, especially preferred
Or normal pressure ~ 100kg / cm^TwoG. Minute of polymer
As for the method of adjusting the amount of catalyst, the type of each catalyst component, the amount used,
Selection of the polymerization temperature, and polymerization in the presence of hydrogen, etc.
You. When using a polymerization solvent, for example, benzene, toluene
Aromatic hydrocarbons such as xylene, xylene and ethylbenzene,
Cyclopentane, cyclohexane, methylcyclohexa
Alicyclic hydrocarbons such as pentane, hexane, hepta
, Octane and other aliphatic hydrocarbons, chloroform, di
Use halogenated hydrocarbons such as chloromethane.
Can be. These solvents may be used alone.
Alternatively, two or more kinds may be combined. Also, α-
A monomer such as an olefin may be used as the solvent.
In addition, depending on the polymerization method, it can be carried out without a solvent.
The molecular weight of the polymer thus obtained is particularly limited.
Although it is not a thing, intrinsic viscosity [η] (135 ° C decalin
Is 0.1 deciliter / g or more, preferably 0.1 deciliter / g or more.
2 to 20 deciliters / g, especially 0.3 to 15 deciliters
Torr / g is preferred.

In the present invention, prepolymerization can be carried out using the polymerization catalyst. 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,
A known method can be used. The olefin used in the prepolymerization is not particularly limited, and may be the same as those exemplified above, for example, ethylene, α having 3 to 20 carbon atoms.
Olefins, or mixtures thereof, and the like, but it is advantageous to use the same olefins as those used in the polymerization. The prepolymerization temperature is usually -20 to 200C, preferably -10 to 1C.
The temperature is 30 ° C, more preferably 0 to 80 ° C. 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 of the prepolymerized product [η] (135
C. (measured in decalin) at 0.2 deciliters / g or more, especially 0.5 deciliters / g or more.
The amount of the prepolymerized product per 1 mmol is 1 to 10
It is desirable to adjust the conditions so as to be 000 g, especially 10 to 1000 g.

Hereinafter, description will be made using an embodiment.

【Example】

Example 1 [Aluminum compound (I)] trimethylaluminum 2.
0 g (27.2 mmol in terms of aluminum atoms) was dissolved in 100 ml of toluene, cooled to -78 ° C,
A solution of 5.0 g (27.2 mmol) of pentafluorophenol dissolved in 80 ml of toluene was added dropwise thereto, and the mixture was reacted at room temperature for 24 hours. After the completion of the reaction, the resultant was washed with toluene and dried to obtain 6.2 g of a white aluminum compound (I) solid component.

[Polymerization] In a 1-liter stainless steel autoclave, 400 ml of dehydrated toluene, 5.0 mmol of aluminum compound (I) (in terms of aluminum atom), biscyclopentadienyl titanium dichloride
0.05 mmol is placed in this order, ethylene pressure 7.0 kg
The polymerization was carried out for 1 hour at a polymerization temperature of 50 ° C./cm ² and then deashed and washed with a hydrochloric acid / methanol solution, followed by drying under reduced pressure at 70 ° C. for 2 hours. As a result, polyethylene 15.
0 g was obtained, but its catalytic activity was 6.3 kg PE / gT
i · hr, and [η] was 3.1 deciliter / g.

Comparative Example 1 [Polymerization] 400 ml of dehydrated toluene, 5.0 mmol of trimethylaluminum (in terms of aluminum atom), and 0.05 mmol of biscyclopentadienyltitanium dichloride were placed in this order in a 1 liter stainless steel autoclave. Polymerization was carried out at an ethylene pressure of 7.0 kg / cm ² and a polymerization temperature of 50 ° C. for 1 hour, followed by deashing and washing with a hydrochloric acid / methanol solution, and drying under reduced pressure at 70 ° C. for 2 hours. As a result, polyethylene was hardly obtained.

Example 2 [Aluminum compound (II)] triethylaluminum 2.
6 g (23 mmol in terms of aluminum atoms) was dissolved in 100 ml of toluene, cooled to -78 ° C, and 8.5 g (46 mmol) of pentafluorophenol was added thereto.
Was dissolved in 80 ml of toluene, and then reacted at room temperature for 24 hours. After the completion of the reaction, the resultant was washed with toluene and dried to obtain 2.7 g of a white aluminum compound (II) solid component.

[Polymerization] In a 1-liter stainless steel autoclave, 400 ml of dehydrated toluene, 0.2 mmol of trimethylaluminum, and an aluminum compound (I
I) 1.0 mmol (in terms of aluminum atoms) and 0.01 mmol of biscyclopentadienyltitanium dichloride were added in this order, and polymerization was carried out at an ethylene pressure of 5.0 kg / cm ² and a polymerization temperature of 50 ° C. for 15 minutes. And then hydrochloric acid /
Deashing and washing were performed with a methanol solution, and drying was performed under reduced pressure at 70 ° C. for 2 hours. As a result, 15.7 g of polyethylene was obtained. Its catalytic activity was 131 kgPE / gTi · hr, and [η] was 10.3 deciliter / g.

Example 3 [Aluminum compound (III)] 2.4 g of diethylaluminum monochloride (20 mmol in terms of aluminum atom) was dissolved in 100 ml of toluene, and -78 was obtained.
Cooled to ° C. 3.7 g of pentafluorophenol
(20 mmol) dissolved in 80 ml of toluene was added dropwise, followed by reaction at room temperature for 24 hours. After completion of the reaction, the resultant was washed with toluene and dried to obtain 5.0 g of a white aluminum compound (III) solid component.
The chemical shift δ of ²⁷ Al-NMR (FIG. 1) is 95 and 75 ppm, and the half width of each is 260 Hz and 950H.
z. The chemical shift δ of diethyl aluminum monochloride before the treatment was 167 ppm, and the half width was 3300 Hz. From this result, it was found that diethylaluminum monochloride was pentafluorophenoxyaluminum ethyl monochloride. [Polymerization] A polyethylene was produced in the same manner as in Example 2 except for the conditions described in Table 1. The results are shown in Table 1.

Example 4 [Aluminum Compound (IV)] 2.6 g of dimethylaluminum monochloride (37 mmol in terms of aluminum atom)
Was dissolved in 100 ml of toluene and cooled to -78 ° C. 6.7 g of pentafluorophenol (3
(7 mmol) dissolved in 80 ml of toluene was added dropwise, and then reacted at room temperature for 24 hours.
After the completion of the reaction, the resultant was washed with toluene and dried to obtain 9.0 g of a white aluminum compound (IV) solid component. [Polymerization] A polyethylene was produced in the same manner as in Example 2 except for the conditions described in Table 1. The results are shown in Table 1.

Example 5 [Aluminum compound (V)] Dimethylaluminum monochloride (1.7 g, 14 mmol in terms of aluminum atom) was dissolved in toluene (100 ml), and -78 was obtained.
Cooled to ° C. 5.1 g of pentafluorophenol
(28 mmol) in 80 ml of toluene was added dropwise, and then reacted at room temperature for 24 hours. After the completion of the reaction, the resultant was washed with toluene and dried to obtain 0.7 g of a white aluminum compound (V) solid component. [Polymerization] A polyethylene was produced in the same manner as in Example 2 except for the conditions described in Table 1. The results are shown in Table 1.

Example 6 [Aluminum compound (VI)] The same procedure as in Example 2 was carried out except that 4.9 g of triisobutylaluminum (23 mmol in terms of aluminum atom) was used. [Polymerization] A polyethylene was produced in the same manner as in Example 2 except for the conditions described in Table 1. The results are shown in Table 1.

Example 7 [Polymerization] A polyethylene was produced in the same manner as in Example 2 except for the conditions described in Table 1. The results are shown in Table 1.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

As is clear from the above results and explanation,
The novel aluminum compound according to the present invention is excellent as a component for polymerization, especially for olefin polymerization, when used in combination with a transition metal compound and also in combination with the transition metal compound and organoaluminum. It can be seen that the effect is large in increasing the molecular weight and controlling the molecular weight.

[Brief description of the drawings]

FIG. 1 shows an aluminum compound obtained in Example 3.
It is a ²⁷ Al-NMR chart of (III).

Continuation of the front page (56) References JP-A-4-323204 (JP, A) JP-T4-506381 (JP, A) Kazuki Ishihara, Reductive Creative of China's physical statistics, New Year's newsletter, 1993 No. 2, pp. 127-129 (58) Fields investigated (Int. Cl. ⁷ , DB name) CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. Homopolymerization or copolymerization of (A) an olefin comprising a transition metal compound represented by any one of formulas (II) to (V) and (B) an aluminum compound represented by formula (1). Catalyst for polymerization. AlR ¹ R ² R ³ (1) [where R ¹ is —X ¹ R ⁴ (X ¹ is a group 15 or 16 element)
R ⁴ is a pentahaloaryl group bonded to X ¹
It is. ) And R ² and R ³ are each independently hydrogen
Atom, halogen atom, R ¹ , hydrocarbon having 1 to 20 carbon atoms
Group consisting of a group and an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms
Is a group selected from ] _{^{CpM 1 R 5 a R 6 b}} R 7 c (II) CpM 1 R 5 a R 6 b (III) (Cp-A e -Cp) M 1 R 5 a R 6 b (IV) M 1 R 5 a R ⁶ _b R ⁷ _c R ⁸ _d (V) [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 It represents a fluorenyl group, and M ¹ represents titanium, zirconium or hafnium. R ⁵ ,
R ⁶ , R ⁷ and R ⁸ each independently represent a ligand, and A represents a crosslink by a covalent bond. a, b, c and d each independently represent an integer of 0 to 4; e represents an integer of 0 to 6; ] 2. A catalyst for homopolymerization or copolymerization of olefins comprising the components (A) and (B) according to claim 1 and (C) an organoaluminum compound represented by the general formula (VIII). R ¹³ AlQ _3-r (VIII) (R ¹³ is an alkyl group having 1 to 10 carbon atoms, Q is a hydrogen atom,
It represents an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a halogen atom, and r is an integer of 1 to 3. ) 3. A method for producing a polyolefin, comprising homopolymerizing or copolymerizing an olefin in the presence of the catalyst according to claim 1 or 2 .