CA2114317A1 - Process for producing polyolefin - Google Patents
Process for producing polyolefinInfo
- Publication number
- CA2114317A1 CA2114317A1 CA002114317A CA2114317A CA2114317A1 CA 2114317 A1 CA2114317 A1 CA 2114317A1 CA 002114317 A CA002114317 A CA 002114317A CA 2114317 A CA2114317 A CA 2114317A CA 2114317 A1 CA2114317 A1 CA 2114317A1
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- polyolefin
- atom
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/03—Narrow molecular weight distribution, i.e. Mw/Mn < 3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/15—Isotactic
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- Polymers & Plastics (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
There is disclosed a process for producing a polyolefin which comprises polymerizing an olefin by the use of a catalyst comprising a specific transition metal compound, an aluminoxane and a specific magnesium compound or a catalyst comprising a specific transition metal compound, an aluminoxane, a specific magnesium compound and an organoaluminum compound. The use of the above process in polymerizing the olefin enables efficient stable production of a high molecular weight polyolefin improved in the powder morphology of the produced polymer, facilitated in the regulation of the molecular weight distribution and gifted with excellent particle shape.
There is disclosed a process for producing a polyolefin which comprises polymerizing an olefin by the use of a catalyst comprising a specific transition metal compound, an aluminoxane and a specific magnesium compound or a catalyst comprising a specific transition metal compound, an aluminoxane, a specific magnesium compound and an organoaluminum compound. The use of the above process in polymerizing the olefin enables efficient stable production of a high molecular weight polyolefin improved in the powder morphology of the produced polymer, facilitated in the regulation of the molecular weight distribution and gifted with excellent particle shape.
Description
~;lff, PIN iN THIS ~B
-- 1:~ TRANSLATION 2114 317 PROCESS FOR PRODUCING POLYOLEFIN
TECHNICAL FIELD
" :
The present invention relates to a process for producing -a polyolefin. More particularly, it pertains to a process for producing a polyolefin capable of enhancin~ the powder morphology of the resultant polymer and facilitating the regulation of the molecular weight distribution of the polymer, a process for efficiently producing in a stable manner a high-molecular weight polyolefin having excellent particle shapes, and a process for efficiently producing a polyolefin characterized by any of the aforestated process by the use of a catalyst enhanced in polymerization activity.
BACKGROVND ART
There has heretofore been known a process for producing a polyolefin by the use of a solid titanium-based catalyst and an organoaluminum compound. However, the polyolefin produced by the above-mentioned process generally has involved the problem that its transparency is poor when formed into films because of its being broad in the molecular weight distribution and compositional distribution.
orl the other hand, there has recently been proposed a homogeneous catalyst having high activity and capable of producing a polymer witll narrow molecular-weight ~ ;~
distribution, which catalyst is exemplified by a catalyst composed of a metallocene compound of a transition metal and an aluminoxane. (Refer to Japanese Patent Application Laid-Open No. 19303/1983.) Nevertheless, the aforesaid process for producing a polyolefin by the use of the above-mentioned -- 21~4317 : ~
homogeneous catalyst involves the problems that ~1) the resultant polymer dissolves in a solvent or becomes gel, thereby making it difficult to separate the polymer from the solvent, (2~ The polymer is likely to adhere to a reaction vessel and (3) a high-molecular weight polymer is difficult to produce.
There is proposed, as a process for producing a high-molecular weight polymer, a method in which a homogeneous catalyst composed of an oxygen-containing titanium compound and an aluminoxane is employed. (~efer to Japanese Patent Application Laid-Open No.3008/1988). However, the above-mentioned process suffers the disadvantage that the formed polymer adheres to a polymerization reactor, thus making it dlfficult to proceed with the reaction in a stable manner.
As a means for regulating the molecular weight distribution in the case of a homogeneous catalyst being used, there are proposed (1) a method in which at least two kinds of metallocene compounds are employed (Japanese Patent Application Laid-Open Nos. 35006/1985 and 35008/1985) and (2) a method in which polymerization is carried out at a specific temperature by the use of a hafnocene compound (Japane8e Patent Application Laid-Open No. 75605/1990). However, any of the aforesaid methods suffers the disadvantage that the operat:Lon is troublesome or only a specific condition is utilizable for the method.
On the other hand, there is proposed a technique by using a solid substance which is obtained by allowing a homogeneous catalyst to be supported on an inorganic oxide --" 21143~7 carrier (Japanese Patent Application Laid-Open No.
108610/1985). Nevertheless, the above-proposed technique involv,es the problems of low activity of the catalyst per unit a~ount of the carrier and frequent occurrence of film gelling due to the carrier remainlng in the polymer. There is also disclosed a catalyst composed of a non-metallocene transition metal compound and an aluminoxane that are supported on silica (Japanese Patent Application Laid-Open No. 503715/1989 through PCT). However, the above-mentioned catalyst involves the problem of low polymerization-activity in spite of a high-molecular weight of the polymer to be obtained.
DISCLOSURE OF THE INVENTION
Under such circumstances, intensive research and investigation were made by the present inventors in order to develop a process for producing a polyolefin capable of ~
enhancing the powder morphology of the resultant polymer and ~;
facilitating the regulation of the molecular weight distribution of the polymer, a process for efficiently producing in a stable manner a high-molecular weight polyolefin having excellent particle shapes, and process for efflciently producing a polyolefin characterized by any of the above-mentioned process by the use of a catalyst enhanced in polymerization activity. `~
As a result, it has been found by the present inventors that the foregoing ob;ects are attained by the use of the catalyst comprising a specific transition-metal compound, an ~;
aluminoxane and a specific magnesium compound or the catalyst further comprising an organoaluminum compound in addition thereto. The present invention has been accomplished on the basis of the above-mentioned finding and information.
Specifically, the first aspect of the present invention provides a process for producing a polyolefin which comprises polymerizing an olefin by the use of a catalyst comprising (A) a transition metal compound having a group with conjugated ~ electron as a ligand, (B) an aluminoxane and (C) a magnesium compound represented by the general formula g( )n 2-n (I) wherein R is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group; X1 is a halogen atom; and n is a number from 1 to 2, the second aspect thereof provides a process for producing a polyolefin which comprises polymerizing an olefin by the use of a catalyst comprising the above-mentioned components (A), (B), (C) and (D) an organoaluminum compound, the third aspect thereof provides a process for producing a polyolefin which comprises polymerizing an olefin by the use of a catalyst comprising (E) a transition metal compound represented by the general formula MlRlaR2bR3CR4d (II) wherein M1 is a transition metal belonging to the group IVB
in the Periodic table; Rl, R2, R3 and R4 are each a a-bonding ligand, a chelating ligand or a Lewis base and may be the same o:r different from each other; and a, b, c and d are each an integer from 1 to 4, and the aforesaid components (B) and (C), and the fourth aspects thereof provides a process for -~~~` 21~1317 produci~g as polyolefin which comprises polymerizing an olefin by the use of a castalyst comprising the aforesaid components (E), (B), (C) and (D).
THE MOST PREFERRED EM~ODIMENT TO CARRY OUT THE INVENTION
In the first aspect of the present invention, there is used as the catalyst the composition comprising the above-mentioned components (A), (8) and (C). The transltion metal compound having a group with conjugated ~ electron as a ligand, that is, the component (A) is exemplified by the compound represented by the general formula (III), (IV) or ~:
(V) and a derivative thereof.
Cp R eR fR g (III) Cp2M Re Rf (IV) (Cp-Ah-Cp)M2Re5Rf6 (V) wherein M2 is a transition metal belonging to the group IVB ~
of the Periodic Table such as a Ti atom, Zr atom or Hf atom; ~:
Cp is an unsaturated cyclic hydrocarbon radical or an ~ ~
unsaturated chain hydrocarhon radical such as : .
cyclopentadienyl gorup, substituted cyclopentadienyl group, indenyl group, substituted indenyl group, tetrahydroindenyl -group, substituted tetrahydroindenyl group, fluorenyl group or substituted fluorenyl group; R5, R6 and R7, independently of one another, are each a ligand such as a a-bonding ligand, a chelating ligand and a Lewis base, specifically exemplified as a ~-bonding ligand by a hydrogen atom, an oxygen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group each having 6 to 20 -. ` ~
21143~7 carbor, atoms, an acyloxy group having 1 to 20 carbon atoms, an all.yl group, a substituted allyl group and a substituent containing a silicon atom and, as a chelating ligand, by an acetylacetonato group and a substituted acetylacetonato group; A is crosslinkage by covalent bond: e, f and g, independently of one another, are each an integer from 0 to 4; h is an integer from 0 to 6; at least two out of R5, R6 and R may together form a ring; and when Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms.
Examples of the substituted cyclopentadienyl group in the above-mentioned formulae (III) to ~V) include methylcyclopentadienyl group; ethylcyclopentadienyl group;
isopropylcyclopentadienyl group; 1,2-dimethylcyclopentadienyl group: tetramethylcyclopentadienyl group; 1,3-dimethylcyclopentadienyl group; 1,2,3-trimethylcyclopentadienyl group; 1,2,4-trimethylcyclopentadienyl group; pentamethylcyclopentadienyl group and trimethylsilylcyclopentadienyl group. Specific examples of R5 to R7 in the aforesaid formulae (III) to ~V) includ~e fluorine atom, chlorine atom, bromine atom and iodine atom as halogen atom; methyl, ethyl, n-propyl, isopropyl, n-butyl, octyl and 2-ethylhexyl group as alkyl group having 1 to 20 carbon atoms; methoxy, ethoxy, propoxy, butoxy and phenoxy group as alkoxy group having 1 to 20 carbon atoms;
phenyl, tolyl, xylyl and benzyl group as aryl, alkylaryl or arylal'kyl group each having 6 to 20 carbon atoms;
heptadlecylcarbonyloxy group as acyloxy group having 1 to 20 21~4317 , _ carbon atoms; trimethylsilyl and (trimethylsilyl)methyl group as substituent containing silicon atom; as Lewis base, ethers such as dimethyl ether, diethyl ether and tetrahydrofuran;
thioethers such as tetrahydrothiophene; esters such as ethylbenzoate; nitriles such as acetonitrile and benzonltrile; amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, pyridine, 2,2'-bipyridine and phenanthroline; phosphine such as triethylphosphine and triphenylphosphine; unsaturated chain hydrocarbon such as ethylene, butadien, l-pentene, isoprene, pentadiene, l-hexene and derivatives thereof; unsaturated cyclic hydrocarbon such as benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and derivatives thereof. Examples of A, that is, crosslinkage by ~
covalent bond in the above formula (V) include methylene, ~ :
dimethylmethylene, ehtylene, 1,1'-cyclohexylene, dimethylsilylene, dimethylgermylene and dimethylstannylene crosslinkage.
Specific examples of the compound represented by the general formula (III) include pentamethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltriphenyltitanium, pentamethyloyclopentadienyltribenzyltitanium, pentam~ethylcyclopentadienyltrichlorotitanium, pentam~ethylcyclopentadienyltrimethoxytitanium, cyclop~entadienyltrimethyltitanium, cyclopentadienyltriphenyltitanium, cyclopentadienyltribenzyltitanium, cyclopentadienyltrichlorotitanium, cyclopentadienyltrimethoxytitanium, cyclopentadienyldimethylmethoxytitanium, methylcyclopentadienyltirmethyltitanium, methylcyclopentadienyltriphenyltitanium methylcyclopentadienyltribenzyltitanium, methylcyclopenadienyltrichlorotitanium, methylcyclopentadienyldimethylmethoxytitanium, dimethylcyclopentadienyltrichlorotitanium, trimethylcyclopentadienyltrichlorotitanium, trimethylcyclopetnadienyltrimethyltitanium, tetramethylcyclopentadienyltrichlorotitanium, and any of the above-exemplified compounds in which the titanium atom is replaced with a zirconium or a hafnium atom.
Specific examples of the compound represented by the general formula (IV) include bis(cyclopentadienyl)dimethyltianium;
bis(cyclopentadienyl)diphenyltitanium;
bis(cyclopentadienyl)diethyltianium;
bis(cyclopentadienyl)dibenzyltitanium;
bis(cyclopentadienyl)dimethoxytianium;
bis(cyclopentadienyl)dichlorotitanium;
bis(cyclopentadienyl)dihydridotianium;
bls(cyclopentadienyl)monochlorohydridotitanium;
bis(methylcyclopentadienyl)dimethyltitanium;
bis(methylcyclopentadienyl)dichlorotitanium;
bis(methylcyclopentadienyl)dibenzyltitanium; .
bis(pentamethylcyclopentadienyl)dimethyltitanium;
` :
211~317 bis(pentamethylcyclopentadienyl)dichlorotitanium;
bis(pentamethylcyclopentadienyl)dibenzyltitanium; ~:
bis(pentamethylcyclopentadienyl)chloromethyltitanium; ~:
bis(pentamethylcyclopentadienyl)hydridomethyltitanium;
(cyclopentadienyl)(pentamethylcyclopentadienyl)- :
dichlorotitanium; and any of the above-mentioned compounds in which the titanium atom is replaced with a zirconium or a hafnium atom. .
Specific examples of the compound represented by the formula (V) include ethylenebis(indenyl)dimethyltitanium;
ethylenebis(indenyl)dichlorotitanium;
ethylenebis(tetrahydroindenyl)dimethyltitanium;
ethylenebls(tetrahydroindenyl)dichlorotitanium;
dlmethylsllylenebis(cyclopentadienyl)dimethyltitanium;
dimethylsilylenebis(cyclopentadienyl)dichlorotitanium;
isopropylidene(cyclopentadienyl)(9-fluorenyl) dimethyltitanium; isopropylidene(cyclopentadienyl)(9-fluorenyl)dichlorotitanium;
[phenyl(methyl)methylene](9-fluorenyl)(cyclopentadienyl) dlmethyltitanium;
diphenylmethylene(cyclopentadienyl)(9-fluorenyl) dimethyltltanium;
ethylene(9-fluorenyl)(cyclopentadienyl)dimethyltitanium;
cyclohexalidene(9-fluorenyl)(cyclopentadienyl) dimethyltitanium;
cyclopentylidene(9-fluorenyl~(cyclopentadienyl) dimethyltitanium;
cyclobutylidene(9-fluorenyl)(cyclopentadienyl) dimethyltitanium;
dimethylsilylene(9-fluorenyl)(cyclopentadienyl) dimethyltitanium;
dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl) dichlorotitanium;
dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl) dimethyltitanium;
dimethylsilylenebis(indenyl)dichlorotitanium; any of the above-mentioned compounds in which the titanium atom is replaced with a zirconium or a hafnium atom.
Favorably usable titanium compound as the component (A) among those represented by the general formula (V) is a transition metal compound having a multidentate ligand in which two substituted or unsubsituted con~ugated cyclopentadienyl groups (at least one being substituted cyclopentadienyl group) are bonded to one another via an element selected from the group IVA of the Periodic Table.
By the use of such a compound, an isotactic polyolefin having enhanc~ed isotacticity, a high molecular weight and a high melting point is obtained.
E~amples of such compound include the compound repres,ented by the general formula (VI) and derivatives thereof (R t ~ C5H4-t)"~ / X
9 / "~ 2 R 2Y \ M \ (VI) (R u ~ C5H4-u) X
wherei;n M is a transition metal belonging to the group IV B
- . ' : . '.: , .': .' ' ' ~, ~ ' , ";'.. ' :. . '',, 211~3~7 of the Periodic Table, Y is a carbon atom, silicon atom, germanium atom or tin atom; R t-C5H4 t and R u~C5H4 u are each a substituted cyclopentadienyl group in which t and u are each an integer from 1 to 4; R8 iS a hydrogen atom, silyl ~ :
group or hydrocarbon radical, and may be the same or differ,ent, provided that at least one cyclopentadlenyl group has R8 on at least one carbon atom ad~acent to the carbon atom bonded to Y; R9 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group each having 6 to 20 carbon atoms;
X is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group each having 6 to 20 carbon atoms or an alkoxyl group having 1 to 20 carbon atoms and may be the same or different.
Examples of the substituted cyclopentadienyl group in the above-mentioned formula (VI) include methyl,cyclopentadienyl group; ethylcyclopentadienyl group;
i~opropylcyclopentadienyl group; 1,2-dimethylcyclopentadienyl group; 1,3-dimethylcyclopentadienyl group; 1,2,3-trimet:hylcyclopentadienyl group; and 1,2,4-trimethylcyalopentadienyl group. Specific examples of X
include F, Cl, Br and I as halogen atom; methyl, ehtyl n-propyl, isopropyl, n-butyl, octyl and 2-ethylhexyl group as alkyl group having 1 to 20 carbon atoms; methoxy, ethoxy, propoxy, butoxy and phenoxy group as alkoxy group having 1 to 20 carbon atoms; phenyl, tolyl, xylyl and benzyl group as aryl, alkylaryl or arylalkyl group each having 6 to 20 carbon -~` 21~43~7 atmos.
Specific Examples of R include methyl, ethyl, phenyl, toly, xylyl and benzyl group.
Examples of the compounds represented by the general formula (VI) include dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl)titanium dichloride and the compound in which a titanium atom is replaced with a zirconium atom or a hafnium atom.
In the present invention, the transition mstal compound may be employed alone or in combination with at least one other transition metal compound.
In the above-mentioned catalyst, an alumioxane is used as the component (B), and there are usable the previously known alumloxanes. Preferable examples thereof lnclude a cycllc alumlnoxane represented by the general formula (VII) ~, R10 - ~ Al - O ~ (VII) whereln R10 is a hydrocarbon radical having 1 to 8 carbon atoms and r ls an integer from 2 to 100, and a chain aluminoxane represented by the general formula (VIII) ~ ~12 R ~ Al O ~ Al R13 (VIII) wherein Rl1, R12 and R13, independently of one another, are each a hydrocarbon radical having 1 to 8 carbon atoms and S
i8 an integer from 2 to 100.
Preferable examples of R10 Rll R12 and R13 i 1 d alkyl group such as methyl group, ethyl group and isobutyl group, and r and s are each preferably 7 to 40. The - 2~43~
alumioxane as the component (B) in the catalyst may be employed alone or in combination with at least one other aluminoxane.
Moreover in the above-mentioned catalyst, there is used as the component (C), a magnesium compound represented by the general formula (I) Mg(OR)nX 2-n (I) wherein R, Xl and n are each as previously deflned.
Preferable examples of the aforementioned magnesium compound include dimethoxymagnesium, diethoxymagnesium, di-n-propoxymagnesium, dipheoxyma~nesium, dibenzyloxymagnesium, ethoxyphenoxymagnesium, chloromethoxymagnesium and chloroethoxymagnesium. The above-exemplified magnesium compound may be employed alone or in combination with at least one other magnesium compound.
As the magnesium compound represented by the foregoing general-formula (I), there is usable the reaction product among metallic magnesium, an alcohol and an halogen. The metallic magneslum to be employed in the reaction is not specifically limited with regard to its shape, but may be in any shape including granule, ribbon and powder. Likewise, the surface condition of the metallic magnesium i9 not specifically limited, but is preferably free from any coating such as magnesium oxide formed on the surface.
The alcohol to be employed in the reaction is not specifically limited with respect to its kind, but is -preferably a lower alcohol having 1 to 6 carbon atoms, especially ethanol because of its capability of providlng -- 21~431 ~
solid catalyst component which enhances the catalytic performance. There is no particular limitation to the purity and water content of the alcohol. However, the water content in the alocohol is desirably 1% by weight or less, more desirably 2,000 ppm or less, particularly desirably as low as possible, since the use of an alcohol having a high water content will lead to the formation of magnesium hydroxide on the surface of the metallic magnesium.
The usable halogen and/or halogen-containing compound are not specifically limited in regard to its kind, ~ut may be any compound provided that the chemical formula thereof has a halogen atom. In this case, the halogen atom is not speclfically limited in its ~ind, but is preferably a chlorine atom, a bromlne atom or an iodine atom. Among the hologen-containing compounds, a halogen-containing metallic compound is particularly desirable.
Specific examples of the halogen-containing compound includ,e MgCl2, MgI2, Mg(OC2H5)Cl, Mg(OC2H5)I, MgBr2, CaCl2, NaCl and KBr, among which MgCl2 and MgI2 are particularly dQsirable.
T,he halogen-containing compounds are not specifically limited with regard to the condition, shape and particle size, Ibut may be in an arbitrary form, for example, a solution thereof in an alcohol-based solvent such as ethanol.
The amount of the alcohol to be used in the reaction is u~ually in the range of 2 to 100 moles, preferably 5 to 50 moles ~er one mole of the metallic magnesium. An excessively large amount of alcohol to be used is apt to cause difficulty in providlng a magnesium compound having a faborable morphology, whereas the use of a too small amount thereof results in a possible failure to smoothly react wlth the metallic magnesium. On the other hand, the amount of the halogen and/or halogen-containing compound to be used in the reacti,on is usually O.OOO1 g-atom or more, desirably 0.0005 g-atom or more, more desirably 0.001 g-atom or more per one mole of the metallic magnesium. An amount of the halogen and/or halogen-containing compound to be used less than 0.0001 g-atom brings about deterioration of the amount of titaniumu to be supported, catalyst activity and the stereo~egularity of the polymer to be formed when the magnesium compound thus obtained is used as such without being crushed. The result is unfavorable, since the crushing of the magnesium compound is indispensably needed. The upper limit of the amount of the halogen and/or halogen-containing compound to be used is not specifically limited, but may be suitabLy selected in the range which enables the production of the desired magnesium compound. A suitahle selection of the above-mentioned amount of the halogen and/or halogen-containing compound to be used ma~e it possible to arbltrarily control the particle size of the magnesium compound to be produced.
The reaction among the metallic magnesium, the alcohol and the halogen and/or halogen-containing compound can be put into pxactice by using a conventional process, for example, a process in which the metallic magnesium, the alcohol and the halogen are reacted with each other under reflu~ usually for 2 to 30 hours until the generation of hydrogen gas is no longer observed, thus producing the desired magnesium product. Specifically usable process is exemplified by a process wherein solid iodine is used as the halogen and poured in a mixture of metallic magnesium and an alcohol, followed by heating with reflux, a process wherein a solution of iodine in an alcohol is added dropwise to a mixture of metallic magnesium and an alcohol, followed by heating with reflux, and a process wherein a solution of iodine in an alcohol is added dropwise to a mixture of metallic magnesium and an alcohol while being heated. In any of the above-mentioned processe~q, it is preferable that the reactlon be put into practice in an atmosphere of an inert gas such as nitrogen gas and argon gas and, as the case may be, by the use of an inert organic solvent such as a saturated hydrocarbon exemplified by n-hexane. There is no need to place the total amounts of both the metallic magnesium and the alcohol in a reaction vessel at the start of the reaction, but each of them may be dividedly placed therein, for example, by a method in which the total amount of the alcohol is placed at the start of the reaction, followed by the addition of the metallic magnesium dividadly into several times. The method is extremely desirable from the viewpoint of safety, since the sudden generation of a large amount of hydrogen gas is prevented thereby, and further it is advantageous in that it can miniaturize a reaction vessel and prevent the entrainment of the alcohol and halogen caused by the sudden generation of a large amount of hydrogen gas. The number of times of divided addition may be determined taking into consideration the scale and size of the reaction vessel without specifical limitation, but ls usually selected in the range of 5 to lO times in view of the tediousness in the operation.
The reaction system may be any of batchwise and continuous systems or a modified system in which a small amount of metallic magnesium is placed in the alcohol which has been put in a reaction vessel in a whole amount in advance, the reaction product is removed by separatin~ into another vessel, a small amout of metallic magnesium is again placed in the remaining alcohol, and the above-mentioned procedures are repeated.
The magnesium compound thus obtained can be used in the subsequent step with crushing or classification procedure for the purpose of uniformizing particle size.
By the use of the catalyst which comprises the aforestated components (A), (B) and (C), it is possible to contrive to improve the powder morphology of the polymer to be produced and facilitate the regulation of the molecular weight distribution of the polymer.
In the second aspect of the present lnvention, there is employed the catalyst composition which comprises an organoaluminum compound as the component (D) in addition to the components of the catalyst in the aforestated first aspect of the present invention. The combination of the organoaluminum compound can enhance the polymerization activity in addition to the above-mentioned properties.
:::
~ 21~317 Examples of the organoaluminum compound include the compound represented by the general formula (IX) R14mAlX 3 m (IX) wherein R14 is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, x2 is a halogen atom, an alkoxy group having 1 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms and m is a real number greater than 0 and not greater than 3. Specific examples of such organoaluminum compound include trimethylaluminum, triethylaluminum triisobutylaluminum, tri~
n-butylaluminum, tri-n-hexylaluminum, tri-n-octyl-aluminum, triisopropylaluminum, diethylaluminum ethoxide, diisobutylaluminum ethoxide, diethylaluminum chloride and ethylaluminum dichloride. The preferable compound among them i8 a trialkylaluminum represented by the general formula (X) AlRl 5R1 6R1 7 ( X ) wherein R15, R16 and R17are each an alkyl group having 1 to 20 carbon atoms and may be the same or different from one another. The organoaluminum compound may be used alone or in combination with at least one of the other ones.
Next, in the third aspect of the present invention, there Ls employed the catalyst composition which comprlses the above-mentioned components (E), (B) and (C). The transition metal compound as the component (E) is represented by the general formula (II) MlR1aR2bR3cR4d (II) wherein M1, Rl, R2, R3, R4, a, b, c, and d are each as ~
previously defined. In the general formula (II), M is a --: ::
' ~` 211~317 transition metal belonging to the group IVB of the Periodic Table such as Ti atom, Zr atom or Hf atom; R1, R , R and R , independently of one another, are each a a-bonding ligand, a chelating ligand or a Lewis base, specifically exempli~ied as a a-bonding ligand by a hydrogen atom, an oxygen atom, a halogen atom, an alkyl group havlng 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group each having 6 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, a substituted allyl group and a substituent containing a silicon atom and, as a chelating ligand, by an acetylacetonato group and a substituted acetylacetonato group, at least two out of R , R , R and R may together form a ring; and a, b, c and d, independently of one another, are each an integer from 0 to 4.
Specific examples of the compound represented by the general formula (II) inol~de tetramethyltitanium, tetrab~enzyltitanium, tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, titanium tetrachloride, titanium tetrabromide, butoxytitanium trichloride, butoxytitanium di.chlo:ride, bis(2,6-di-tert-butylphenoxy)dimethyltitanium, bis( 2,6-di-tert-butylphenoxy)titanium dichloride, titanium bis(ac,etylacetonato), bis(acetylacetonato)titanium dichlo:ride, bis(acetylacetonato)titanium dipropoxide and any of the above-mentioned compound in which titanium atom is replaced with a zirconium or a hafnium atom. The above-mentioned transition compound may be used alone or in combination with at least one of other one~1 14 3 The components (s) and (C) as described in the first aspect of the present inven-tion can be used as the component (B) and (C), respectively in the above-described catalyst.
The use of the catalyst comprising the aforesaid components (E), ~B) and (C) enables a high molecular weight polyolefin excellent in particle morphology to be effiaiently produced in a stable manner with minimized adhesion of the produced polymer to a polymerization reactor.
Next, in the fourth aspect of the present invention, there is employed the catalyst composition which comprlses an organoaluminum compound as the component (D) in addition to the component8 of the catalyst in the aforestated third aspect of the present invention. The combination of the organoaluminum compound can enhance the polymerization activi-ty in addition to the above-mentioned properties.
The component (D) as described in the second aspect of the present invention can be used as the component (D) in the catalyst of the fourth aspect thereof.
The amount of each of the components to be used in each catalyst ls not specifically limited, but may be 8uitably 8elected according to the situation. It is usually selected so that the amount of the component (A) or (E) is 10 4 to one (1) mole, preferably 10 3 to 10 1 mole per mole of the component (C), the amount of the component (B) is one (1) to 106 mo:les, preferably 10 to 105 moles per mole of the component (A) or (E) expressed in terms of aluminum atom, and the amount of the component (D) is 10 1 to 105 moles 21~ ~
preferably one (1) to 10 moles per mole of the component (A) or (E)- : ~
The order of bringing each o~ the components of the catalyst into contact with each other is not specifically limited, but may be arbitrarily selected. The reac~ion product after contact treatment may be used as such, or cleaned with an inert solvent prior to using, or distilled to distil away the preparation solvent and dispersed in another solvent, followed by using.
Examples of the inert solvent to be used in bringing each component into contact with one another include aliphatic hydrocarbons each having 5 to 18 carbon atoms, alicyclic hydrocarbons and aromatic hydrocarbons, whlch are specifically enumerated by n-pentate, isopentane, hexane, heptane, octane, nonane, decane, tetradecane, cyclohexane, benzene, toluene and xylene. Any of the above-enumerated solvents may be used alone or as a mixture with at least one other one. The contact temperature and reaction time are not specifically limited.
The contact treatment may be carried out in a manner similar to preliminary polymerization in the presence of a small amount of a monomer, or under the condition including a remarkably low rate of polymerization reactlon.
The contact-treated product thus prepared can be preserved in an atmosphere of an inert gas.
There is usable in the present invention, an arbitrary olefin as the monomer such as an a-olefin and a cyclic olefin, which are enumerated as a-olefin, ethylene, 21 ~31~
propylene, l-butene, 1-hexene, l-octene and 1-decene, and as cyclic olefin, cyclobutene, cyclopentene, cyclohexene, cycloheptene and cyclooctene. In the present invention, an olefin can be copolymerized with an unsaturated monomer component other than olefin which component is copolymerizable with the olefin.
The process according to the present invention is particularly preferably applicable to the production of an ethylenic polymer. In this case, ethylene may be homopolymerized or copolymerized with an a-olefin other than ethylene or a diene compound. Examples of such a-olefin include straigh-chain or branched monoolefin having 3 to 18 carbon atoms and a-olefin replaced with an aromatic group.
Specific examples of such a-olefin include straight-chain monoolefin such as propylene; butene-1; hexene-1; octene-1;
nonene-1; decene-1; undecene-1; and dodecene-1, branched monoolefin such as 3-methylbutene-1; 3-methylpentene-1; 4-methylpentene-l; 2-ethylhexene-1; and 2,2,4-trimethylpentene-1 and monoolefin replaced with a benzene ring such as styrene.
Examples of the preferable diene compound include a 8traight chain or branched non-con~ugated diolefin such as 1,5-hexadiene; 1,6-heptadiene; 1,7-octadiene; 1,8-nonadiene;
1,9-decadiene; 2,5-dimethyl-1,5-hexadiene; and 1,4-dimethyl-4-tert-butyl-2,6-heptadiene, polyene such as 1,5,9-decatriene and end-methylene series cyclic diene such as 5-vinyl-2-norbornene.
The polymerization method in the present invention is 2~431~
not specifically limited, but is usually any of slurry, hot solution, gas-phase or bulk polymerization method, etc.. As the polymerization solvent, an inert slovent such as an aliphatic hydrocarbon, an alicyclic hydrocarbon or an aromatic hydrocarbon is employed, among which is preferable an aliphatic hydrocarbon exemplified by hexane and heptane.
It is preferable that the amount of the polymerization catalyst to be used be selected in the range of 10 8 to 10 2 mole/liter, preferably 10 7 to 10 3 mole/liter expressed in terms of the atoms of the transition metal belonging to the group IVB of the Periodic Table.
The polymerization temperature is not specifically limited, but is usually selected in the range of O to 350C, prefer,ably 20 to 250C. On the other hand, the polymerization pressure is not specifically limited as well, but is usually selected in the range of O to 150 kg/cm2G, preferably O to 100 kg/cm2G.
The modification of the molecular weight and the molecular weight distribution of the polyolefin to be produced can be carried out with case by adding hydrogen into the re~sction system at the tlme of polymerization. The addition of hydrogen is effective particularly in the first and second aspects of the present invention.
In the following, the present invention will be described in more detail with reference to examples and comparative examples.
Preparation Example 1 : Preparation of solution of methylaluminoxane in toluene 21~317 A solution of mehtylaluminoxane (produced by TOSOH AKUZO
CORPORATION ) in toluene was made into the form of thick malt syrup by reducing the pressure at room temperature.
Subsequently, the pressure was further reduced at 90~C for one (1) hour to produce methylaluminoxane crystal in solid form, which was then dispersed in toluene to prepare 1.9 mole/liter solution of methylalumioxane in toluene expressed in terms of ~1 atom.
Preparation Example 2 : Preparation of dispersion liquid of methylalumioxane in hexane A solution of methylalumioxane (produced by Shelling Corporation) in toluene was made into the form of thick malt syrup by reducing the pressure at room temperature.
Subsequently, the pressure was further reduced at 90C for one (1) hour to produce methylaluminoxane crystal in solid ~`
form, wh$ch was then dispersed in hexane to prepare 1.0 mole/liter dispersion liguid of methylaluminoxane in hexane ;
expressed in terms of Al atom.
Example 1 (1) Preparation of solid product A 6 liter glass-made reactor equipped with a stirrer which had sufflciently been purged with nitrogen gas was charged with 2430 g of ethanol, 16 g of iodine and 160 g of metallic magnesium. The mixture in the reactor was allowed to react with stirring under heating and reflux condition until the generation of hydrogen gas was no longer observed to produce a reaction product in solid form. The reaction liquid containing the reaction product was dried under ~` 2ll43l7 reduced pressure to afford a solid product.
(2) Preparation of solid catalyst components To 10 g of the solid product (62 ~m average particle size) as produced in the preceding item (1) were added in turn a solution of 0.17 mmol of bis (cyclopentadienyl)zirconium dichloride in 50 ml of tol~ene and 1.9 mole/liter solution of methylaluminoxane in toluene in an amount of 35 mmol in terms of methylaluminoxane. The mixture was allowed to react at room temperature with gentle stirring for one hour. Then, the toluene solvent was removed by reducing the pressure with gentle stirring at room temperature. Subsequently heptane was added to the reaction system to form a slurry in a total amount of 400 ml. All o$
the aforesaid procedure was carried out in an atmosphere of dry nitrogen.
-- 1:~ TRANSLATION 2114 317 PROCESS FOR PRODUCING POLYOLEFIN
TECHNICAL FIELD
" :
The present invention relates to a process for producing -a polyolefin. More particularly, it pertains to a process for producing a polyolefin capable of enhancin~ the powder morphology of the resultant polymer and facilitating the regulation of the molecular weight distribution of the polymer, a process for efficiently producing in a stable manner a high-molecular weight polyolefin having excellent particle shapes, and a process for efficiently producing a polyolefin characterized by any of the aforestated process by the use of a catalyst enhanced in polymerization activity.
BACKGROVND ART
There has heretofore been known a process for producing a polyolefin by the use of a solid titanium-based catalyst and an organoaluminum compound. However, the polyolefin produced by the above-mentioned process generally has involved the problem that its transparency is poor when formed into films because of its being broad in the molecular weight distribution and compositional distribution.
orl the other hand, there has recently been proposed a homogeneous catalyst having high activity and capable of producing a polymer witll narrow molecular-weight ~ ;~
distribution, which catalyst is exemplified by a catalyst composed of a metallocene compound of a transition metal and an aluminoxane. (Refer to Japanese Patent Application Laid-Open No. 19303/1983.) Nevertheless, the aforesaid process for producing a polyolefin by the use of the above-mentioned -- 21~4317 : ~
homogeneous catalyst involves the problems that ~1) the resultant polymer dissolves in a solvent or becomes gel, thereby making it difficult to separate the polymer from the solvent, (2~ The polymer is likely to adhere to a reaction vessel and (3) a high-molecular weight polymer is difficult to produce.
There is proposed, as a process for producing a high-molecular weight polymer, a method in which a homogeneous catalyst composed of an oxygen-containing titanium compound and an aluminoxane is employed. (~efer to Japanese Patent Application Laid-Open No.3008/1988). However, the above-mentioned process suffers the disadvantage that the formed polymer adheres to a polymerization reactor, thus making it dlfficult to proceed with the reaction in a stable manner.
As a means for regulating the molecular weight distribution in the case of a homogeneous catalyst being used, there are proposed (1) a method in which at least two kinds of metallocene compounds are employed (Japanese Patent Application Laid-Open Nos. 35006/1985 and 35008/1985) and (2) a method in which polymerization is carried out at a specific temperature by the use of a hafnocene compound (Japane8e Patent Application Laid-Open No. 75605/1990). However, any of the aforesaid methods suffers the disadvantage that the operat:Lon is troublesome or only a specific condition is utilizable for the method.
On the other hand, there is proposed a technique by using a solid substance which is obtained by allowing a homogeneous catalyst to be supported on an inorganic oxide --" 21143~7 carrier (Japanese Patent Application Laid-Open No.
108610/1985). Nevertheless, the above-proposed technique involv,es the problems of low activity of the catalyst per unit a~ount of the carrier and frequent occurrence of film gelling due to the carrier remainlng in the polymer. There is also disclosed a catalyst composed of a non-metallocene transition metal compound and an aluminoxane that are supported on silica (Japanese Patent Application Laid-Open No. 503715/1989 through PCT). However, the above-mentioned catalyst involves the problem of low polymerization-activity in spite of a high-molecular weight of the polymer to be obtained.
DISCLOSURE OF THE INVENTION
Under such circumstances, intensive research and investigation were made by the present inventors in order to develop a process for producing a polyolefin capable of ~
enhancing the powder morphology of the resultant polymer and ~;
facilitating the regulation of the molecular weight distribution of the polymer, a process for efficiently producing in a stable manner a high-molecular weight polyolefin having excellent particle shapes, and process for efflciently producing a polyolefin characterized by any of the above-mentioned process by the use of a catalyst enhanced in polymerization activity. `~
As a result, it has been found by the present inventors that the foregoing ob;ects are attained by the use of the catalyst comprising a specific transition-metal compound, an ~;
aluminoxane and a specific magnesium compound or the catalyst further comprising an organoaluminum compound in addition thereto. The present invention has been accomplished on the basis of the above-mentioned finding and information.
Specifically, the first aspect of the present invention provides a process for producing a polyolefin which comprises polymerizing an olefin by the use of a catalyst comprising (A) a transition metal compound having a group with conjugated ~ electron as a ligand, (B) an aluminoxane and (C) a magnesium compound represented by the general formula g( )n 2-n (I) wherein R is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group; X1 is a halogen atom; and n is a number from 1 to 2, the second aspect thereof provides a process for producing a polyolefin which comprises polymerizing an olefin by the use of a catalyst comprising the above-mentioned components (A), (B), (C) and (D) an organoaluminum compound, the third aspect thereof provides a process for producing a polyolefin which comprises polymerizing an olefin by the use of a catalyst comprising (E) a transition metal compound represented by the general formula MlRlaR2bR3CR4d (II) wherein M1 is a transition metal belonging to the group IVB
in the Periodic table; Rl, R2, R3 and R4 are each a a-bonding ligand, a chelating ligand or a Lewis base and may be the same o:r different from each other; and a, b, c and d are each an integer from 1 to 4, and the aforesaid components (B) and (C), and the fourth aspects thereof provides a process for -~~~` 21~1317 produci~g as polyolefin which comprises polymerizing an olefin by the use of a castalyst comprising the aforesaid components (E), (B), (C) and (D).
THE MOST PREFERRED EM~ODIMENT TO CARRY OUT THE INVENTION
In the first aspect of the present invention, there is used as the catalyst the composition comprising the above-mentioned components (A), (8) and (C). The transltion metal compound having a group with conjugated ~ electron as a ligand, that is, the component (A) is exemplified by the compound represented by the general formula (III), (IV) or ~:
(V) and a derivative thereof.
Cp R eR fR g (III) Cp2M Re Rf (IV) (Cp-Ah-Cp)M2Re5Rf6 (V) wherein M2 is a transition metal belonging to the group IVB ~
of the Periodic Table such as a Ti atom, Zr atom or Hf atom; ~:
Cp is an unsaturated cyclic hydrocarbon radical or an ~ ~
unsaturated chain hydrocarhon radical such as : .
cyclopentadienyl gorup, substituted cyclopentadienyl group, indenyl group, substituted indenyl group, tetrahydroindenyl -group, substituted tetrahydroindenyl group, fluorenyl group or substituted fluorenyl group; R5, R6 and R7, independently of one another, are each a ligand such as a a-bonding ligand, a chelating ligand and a Lewis base, specifically exemplified as a ~-bonding ligand by a hydrogen atom, an oxygen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group each having 6 to 20 -. ` ~
21143~7 carbor, atoms, an acyloxy group having 1 to 20 carbon atoms, an all.yl group, a substituted allyl group and a substituent containing a silicon atom and, as a chelating ligand, by an acetylacetonato group and a substituted acetylacetonato group; A is crosslinkage by covalent bond: e, f and g, independently of one another, are each an integer from 0 to 4; h is an integer from 0 to 6; at least two out of R5, R6 and R may together form a ring; and when Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms.
Examples of the substituted cyclopentadienyl group in the above-mentioned formulae (III) to ~V) include methylcyclopentadienyl group; ethylcyclopentadienyl group;
isopropylcyclopentadienyl group; 1,2-dimethylcyclopentadienyl group: tetramethylcyclopentadienyl group; 1,3-dimethylcyclopentadienyl group; 1,2,3-trimethylcyclopentadienyl group; 1,2,4-trimethylcyclopentadienyl group; pentamethylcyclopentadienyl group and trimethylsilylcyclopentadienyl group. Specific examples of R5 to R7 in the aforesaid formulae (III) to ~V) includ~e fluorine atom, chlorine atom, bromine atom and iodine atom as halogen atom; methyl, ethyl, n-propyl, isopropyl, n-butyl, octyl and 2-ethylhexyl group as alkyl group having 1 to 20 carbon atoms; methoxy, ethoxy, propoxy, butoxy and phenoxy group as alkoxy group having 1 to 20 carbon atoms;
phenyl, tolyl, xylyl and benzyl group as aryl, alkylaryl or arylal'kyl group each having 6 to 20 carbon atoms;
heptadlecylcarbonyloxy group as acyloxy group having 1 to 20 21~4317 , _ carbon atoms; trimethylsilyl and (trimethylsilyl)methyl group as substituent containing silicon atom; as Lewis base, ethers such as dimethyl ether, diethyl ether and tetrahydrofuran;
thioethers such as tetrahydrothiophene; esters such as ethylbenzoate; nitriles such as acetonitrile and benzonltrile; amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, pyridine, 2,2'-bipyridine and phenanthroline; phosphine such as triethylphosphine and triphenylphosphine; unsaturated chain hydrocarbon such as ethylene, butadien, l-pentene, isoprene, pentadiene, l-hexene and derivatives thereof; unsaturated cyclic hydrocarbon such as benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and derivatives thereof. Examples of A, that is, crosslinkage by ~
covalent bond in the above formula (V) include methylene, ~ :
dimethylmethylene, ehtylene, 1,1'-cyclohexylene, dimethylsilylene, dimethylgermylene and dimethylstannylene crosslinkage.
Specific examples of the compound represented by the general formula (III) include pentamethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltriphenyltitanium, pentamethyloyclopentadienyltribenzyltitanium, pentam~ethylcyclopentadienyltrichlorotitanium, pentam~ethylcyclopentadienyltrimethoxytitanium, cyclop~entadienyltrimethyltitanium, cyclopentadienyltriphenyltitanium, cyclopentadienyltribenzyltitanium, cyclopentadienyltrichlorotitanium, cyclopentadienyltrimethoxytitanium, cyclopentadienyldimethylmethoxytitanium, methylcyclopentadienyltirmethyltitanium, methylcyclopentadienyltriphenyltitanium methylcyclopentadienyltribenzyltitanium, methylcyclopenadienyltrichlorotitanium, methylcyclopentadienyldimethylmethoxytitanium, dimethylcyclopentadienyltrichlorotitanium, trimethylcyclopentadienyltrichlorotitanium, trimethylcyclopetnadienyltrimethyltitanium, tetramethylcyclopentadienyltrichlorotitanium, and any of the above-exemplified compounds in which the titanium atom is replaced with a zirconium or a hafnium atom.
Specific examples of the compound represented by the general formula (IV) include bis(cyclopentadienyl)dimethyltianium;
bis(cyclopentadienyl)diphenyltitanium;
bis(cyclopentadienyl)diethyltianium;
bis(cyclopentadienyl)dibenzyltitanium;
bis(cyclopentadienyl)dimethoxytianium;
bis(cyclopentadienyl)dichlorotitanium;
bis(cyclopentadienyl)dihydridotianium;
bls(cyclopentadienyl)monochlorohydridotitanium;
bis(methylcyclopentadienyl)dimethyltitanium;
bis(methylcyclopentadienyl)dichlorotitanium;
bis(methylcyclopentadienyl)dibenzyltitanium; .
bis(pentamethylcyclopentadienyl)dimethyltitanium;
` :
211~317 bis(pentamethylcyclopentadienyl)dichlorotitanium;
bis(pentamethylcyclopentadienyl)dibenzyltitanium; ~:
bis(pentamethylcyclopentadienyl)chloromethyltitanium; ~:
bis(pentamethylcyclopentadienyl)hydridomethyltitanium;
(cyclopentadienyl)(pentamethylcyclopentadienyl)- :
dichlorotitanium; and any of the above-mentioned compounds in which the titanium atom is replaced with a zirconium or a hafnium atom. .
Specific examples of the compound represented by the formula (V) include ethylenebis(indenyl)dimethyltitanium;
ethylenebis(indenyl)dichlorotitanium;
ethylenebis(tetrahydroindenyl)dimethyltitanium;
ethylenebls(tetrahydroindenyl)dichlorotitanium;
dlmethylsllylenebis(cyclopentadienyl)dimethyltitanium;
dimethylsilylenebis(cyclopentadienyl)dichlorotitanium;
isopropylidene(cyclopentadienyl)(9-fluorenyl) dimethyltitanium; isopropylidene(cyclopentadienyl)(9-fluorenyl)dichlorotitanium;
[phenyl(methyl)methylene](9-fluorenyl)(cyclopentadienyl) dlmethyltitanium;
diphenylmethylene(cyclopentadienyl)(9-fluorenyl) dimethyltltanium;
ethylene(9-fluorenyl)(cyclopentadienyl)dimethyltitanium;
cyclohexalidene(9-fluorenyl)(cyclopentadienyl) dimethyltitanium;
cyclopentylidene(9-fluorenyl~(cyclopentadienyl) dimethyltitanium;
cyclobutylidene(9-fluorenyl)(cyclopentadienyl) dimethyltitanium;
dimethylsilylene(9-fluorenyl)(cyclopentadienyl) dimethyltitanium;
dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl) dichlorotitanium;
dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl) dimethyltitanium;
dimethylsilylenebis(indenyl)dichlorotitanium; any of the above-mentioned compounds in which the titanium atom is replaced with a zirconium or a hafnium atom.
Favorably usable titanium compound as the component (A) among those represented by the general formula (V) is a transition metal compound having a multidentate ligand in which two substituted or unsubsituted con~ugated cyclopentadienyl groups (at least one being substituted cyclopentadienyl group) are bonded to one another via an element selected from the group IVA of the Periodic Table.
By the use of such a compound, an isotactic polyolefin having enhanc~ed isotacticity, a high molecular weight and a high melting point is obtained.
E~amples of such compound include the compound repres,ented by the general formula (VI) and derivatives thereof (R t ~ C5H4-t)"~ / X
9 / "~ 2 R 2Y \ M \ (VI) (R u ~ C5H4-u) X
wherei;n M is a transition metal belonging to the group IV B
- . ' : . '.: , .': .' ' ' ~, ~ ' , ";'.. ' :. . '',, 211~3~7 of the Periodic Table, Y is a carbon atom, silicon atom, germanium atom or tin atom; R t-C5H4 t and R u~C5H4 u are each a substituted cyclopentadienyl group in which t and u are each an integer from 1 to 4; R8 iS a hydrogen atom, silyl ~ :
group or hydrocarbon radical, and may be the same or differ,ent, provided that at least one cyclopentadlenyl group has R8 on at least one carbon atom ad~acent to the carbon atom bonded to Y; R9 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group each having 6 to 20 carbon atoms;
X is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group each having 6 to 20 carbon atoms or an alkoxyl group having 1 to 20 carbon atoms and may be the same or different.
Examples of the substituted cyclopentadienyl group in the above-mentioned formula (VI) include methyl,cyclopentadienyl group; ethylcyclopentadienyl group;
i~opropylcyclopentadienyl group; 1,2-dimethylcyclopentadienyl group; 1,3-dimethylcyclopentadienyl group; 1,2,3-trimet:hylcyclopentadienyl group; and 1,2,4-trimethylcyalopentadienyl group. Specific examples of X
include F, Cl, Br and I as halogen atom; methyl, ehtyl n-propyl, isopropyl, n-butyl, octyl and 2-ethylhexyl group as alkyl group having 1 to 20 carbon atoms; methoxy, ethoxy, propoxy, butoxy and phenoxy group as alkoxy group having 1 to 20 carbon atoms; phenyl, tolyl, xylyl and benzyl group as aryl, alkylaryl or arylalkyl group each having 6 to 20 carbon -~` 21~43~7 atmos.
Specific Examples of R include methyl, ethyl, phenyl, toly, xylyl and benzyl group.
Examples of the compounds represented by the general formula (VI) include dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl)titanium dichloride and the compound in which a titanium atom is replaced with a zirconium atom or a hafnium atom.
In the present invention, the transition mstal compound may be employed alone or in combination with at least one other transition metal compound.
In the above-mentioned catalyst, an alumioxane is used as the component (B), and there are usable the previously known alumloxanes. Preferable examples thereof lnclude a cycllc alumlnoxane represented by the general formula (VII) ~, R10 - ~ Al - O ~ (VII) whereln R10 is a hydrocarbon radical having 1 to 8 carbon atoms and r ls an integer from 2 to 100, and a chain aluminoxane represented by the general formula (VIII) ~ ~12 R ~ Al O ~ Al R13 (VIII) wherein Rl1, R12 and R13, independently of one another, are each a hydrocarbon radical having 1 to 8 carbon atoms and S
i8 an integer from 2 to 100.
Preferable examples of R10 Rll R12 and R13 i 1 d alkyl group such as methyl group, ethyl group and isobutyl group, and r and s are each preferably 7 to 40. The - 2~43~
alumioxane as the component (B) in the catalyst may be employed alone or in combination with at least one other aluminoxane.
Moreover in the above-mentioned catalyst, there is used as the component (C), a magnesium compound represented by the general formula (I) Mg(OR)nX 2-n (I) wherein R, Xl and n are each as previously deflned.
Preferable examples of the aforementioned magnesium compound include dimethoxymagnesium, diethoxymagnesium, di-n-propoxymagnesium, dipheoxyma~nesium, dibenzyloxymagnesium, ethoxyphenoxymagnesium, chloromethoxymagnesium and chloroethoxymagnesium. The above-exemplified magnesium compound may be employed alone or in combination with at least one other magnesium compound.
As the magnesium compound represented by the foregoing general-formula (I), there is usable the reaction product among metallic magnesium, an alcohol and an halogen. The metallic magneslum to be employed in the reaction is not specifically limited with regard to its shape, but may be in any shape including granule, ribbon and powder. Likewise, the surface condition of the metallic magnesium i9 not specifically limited, but is preferably free from any coating such as magnesium oxide formed on the surface.
The alcohol to be employed in the reaction is not specifically limited with respect to its kind, but is -preferably a lower alcohol having 1 to 6 carbon atoms, especially ethanol because of its capability of providlng -- 21~431 ~
solid catalyst component which enhances the catalytic performance. There is no particular limitation to the purity and water content of the alcohol. However, the water content in the alocohol is desirably 1% by weight or less, more desirably 2,000 ppm or less, particularly desirably as low as possible, since the use of an alcohol having a high water content will lead to the formation of magnesium hydroxide on the surface of the metallic magnesium.
The usable halogen and/or halogen-containing compound are not specifically limited in regard to its kind, ~ut may be any compound provided that the chemical formula thereof has a halogen atom. In this case, the halogen atom is not speclfically limited in its ~ind, but is preferably a chlorine atom, a bromlne atom or an iodine atom. Among the hologen-containing compounds, a halogen-containing metallic compound is particularly desirable.
Specific examples of the halogen-containing compound includ,e MgCl2, MgI2, Mg(OC2H5)Cl, Mg(OC2H5)I, MgBr2, CaCl2, NaCl and KBr, among which MgCl2 and MgI2 are particularly dQsirable.
T,he halogen-containing compounds are not specifically limited with regard to the condition, shape and particle size, Ibut may be in an arbitrary form, for example, a solution thereof in an alcohol-based solvent such as ethanol.
The amount of the alcohol to be used in the reaction is u~ually in the range of 2 to 100 moles, preferably 5 to 50 moles ~er one mole of the metallic magnesium. An excessively large amount of alcohol to be used is apt to cause difficulty in providlng a magnesium compound having a faborable morphology, whereas the use of a too small amount thereof results in a possible failure to smoothly react wlth the metallic magnesium. On the other hand, the amount of the halogen and/or halogen-containing compound to be used in the reacti,on is usually O.OOO1 g-atom or more, desirably 0.0005 g-atom or more, more desirably 0.001 g-atom or more per one mole of the metallic magnesium. An amount of the halogen and/or halogen-containing compound to be used less than 0.0001 g-atom brings about deterioration of the amount of titaniumu to be supported, catalyst activity and the stereo~egularity of the polymer to be formed when the magnesium compound thus obtained is used as such without being crushed. The result is unfavorable, since the crushing of the magnesium compound is indispensably needed. The upper limit of the amount of the halogen and/or halogen-containing compound to be used is not specifically limited, but may be suitabLy selected in the range which enables the production of the desired magnesium compound. A suitahle selection of the above-mentioned amount of the halogen and/or halogen-containing compound to be used ma~e it possible to arbltrarily control the particle size of the magnesium compound to be produced.
The reaction among the metallic magnesium, the alcohol and the halogen and/or halogen-containing compound can be put into pxactice by using a conventional process, for example, a process in which the metallic magnesium, the alcohol and the halogen are reacted with each other under reflu~ usually for 2 to 30 hours until the generation of hydrogen gas is no longer observed, thus producing the desired magnesium product. Specifically usable process is exemplified by a process wherein solid iodine is used as the halogen and poured in a mixture of metallic magnesium and an alcohol, followed by heating with reflux, a process wherein a solution of iodine in an alcohol is added dropwise to a mixture of metallic magnesium and an alcohol, followed by heating with reflux, and a process wherein a solution of iodine in an alcohol is added dropwise to a mixture of metallic magnesium and an alcohol while being heated. In any of the above-mentioned processe~q, it is preferable that the reactlon be put into practice in an atmosphere of an inert gas such as nitrogen gas and argon gas and, as the case may be, by the use of an inert organic solvent such as a saturated hydrocarbon exemplified by n-hexane. There is no need to place the total amounts of both the metallic magnesium and the alcohol in a reaction vessel at the start of the reaction, but each of them may be dividedly placed therein, for example, by a method in which the total amount of the alcohol is placed at the start of the reaction, followed by the addition of the metallic magnesium dividadly into several times. The method is extremely desirable from the viewpoint of safety, since the sudden generation of a large amount of hydrogen gas is prevented thereby, and further it is advantageous in that it can miniaturize a reaction vessel and prevent the entrainment of the alcohol and halogen caused by the sudden generation of a large amount of hydrogen gas. The number of times of divided addition may be determined taking into consideration the scale and size of the reaction vessel without specifical limitation, but ls usually selected in the range of 5 to lO times in view of the tediousness in the operation.
The reaction system may be any of batchwise and continuous systems or a modified system in which a small amount of metallic magnesium is placed in the alcohol which has been put in a reaction vessel in a whole amount in advance, the reaction product is removed by separatin~ into another vessel, a small amout of metallic magnesium is again placed in the remaining alcohol, and the above-mentioned procedures are repeated.
The magnesium compound thus obtained can be used in the subsequent step with crushing or classification procedure for the purpose of uniformizing particle size.
By the use of the catalyst which comprises the aforestated components (A), (B) and (C), it is possible to contrive to improve the powder morphology of the polymer to be produced and facilitate the regulation of the molecular weight distribution of the polymer.
In the second aspect of the present lnvention, there is employed the catalyst composition which comprises an organoaluminum compound as the component (D) in addition to the components of the catalyst in the aforestated first aspect of the present invention. The combination of the organoaluminum compound can enhance the polymerization activity in addition to the above-mentioned properties.
:::
~ 21~317 Examples of the organoaluminum compound include the compound represented by the general formula (IX) R14mAlX 3 m (IX) wherein R14 is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, x2 is a halogen atom, an alkoxy group having 1 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms and m is a real number greater than 0 and not greater than 3. Specific examples of such organoaluminum compound include trimethylaluminum, triethylaluminum triisobutylaluminum, tri~
n-butylaluminum, tri-n-hexylaluminum, tri-n-octyl-aluminum, triisopropylaluminum, diethylaluminum ethoxide, diisobutylaluminum ethoxide, diethylaluminum chloride and ethylaluminum dichloride. The preferable compound among them i8 a trialkylaluminum represented by the general formula (X) AlRl 5R1 6R1 7 ( X ) wherein R15, R16 and R17are each an alkyl group having 1 to 20 carbon atoms and may be the same or different from one another. The organoaluminum compound may be used alone or in combination with at least one of the other ones.
Next, in the third aspect of the present invention, there Ls employed the catalyst composition which comprlses the above-mentioned components (E), (B) and (C). The transition metal compound as the component (E) is represented by the general formula (II) MlR1aR2bR3cR4d (II) wherein M1, Rl, R2, R3, R4, a, b, c, and d are each as ~
previously defined. In the general formula (II), M is a --: ::
' ~` 211~317 transition metal belonging to the group IVB of the Periodic Table such as Ti atom, Zr atom or Hf atom; R1, R , R and R , independently of one another, are each a a-bonding ligand, a chelating ligand or a Lewis base, specifically exempli~ied as a a-bonding ligand by a hydrogen atom, an oxygen atom, a halogen atom, an alkyl group havlng 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group each having 6 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, a substituted allyl group and a substituent containing a silicon atom and, as a chelating ligand, by an acetylacetonato group and a substituted acetylacetonato group, at least two out of R , R , R and R may together form a ring; and a, b, c and d, independently of one another, are each an integer from 0 to 4.
Specific examples of the compound represented by the general formula (II) inol~de tetramethyltitanium, tetrab~enzyltitanium, tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, titanium tetrachloride, titanium tetrabromide, butoxytitanium trichloride, butoxytitanium di.chlo:ride, bis(2,6-di-tert-butylphenoxy)dimethyltitanium, bis( 2,6-di-tert-butylphenoxy)titanium dichloride, titanium bis(ac,etylacetonato), bis(acetylacetonato)titanium dichlo:ride, bis(acetylacetonato)titanium dipropoxide and any of the above-mentioned compound in which titanium atom is replaced with a zirconium or a hafnium atom. The above-mentioned transition compound may be used alone or in combination with at least one of other one~1 14 3 The components (s) and (C) as described in the first aspect of the present inven-tion can be used as the component (B) and (C), respectively in the above-described catalyst.
The use of the catalyst comprising the aforesaid components (E), ~B) and (C) enables a high molecular weight polyolefin excellent in particle morphology to be effiaiently produced in a stable manner with minimized adhesion of the produced polymer to a polymerization reactor.
Next, in the fourth aspect of the present invention, there is employed the catalyst composition which comprlses an organoaluminum compound as the component (D) in addition to the component8 of the catalyst in the aforestated third aspect of the present invention. The combination of the organoaluminum compound can enhance the polymerization activi-ty in addition to the above-mentioned properties.
The component (D) as described in the second aspect of the present invention can be used as the component (D) in the catalyst of the fourth aspect thereof.
The amount of each of the components to be used in each catalyst ls not specifically limited, but may be 8uitably 8elected according to the situation. It is usually selected so that the amount of the component (A) or (E) is 10 4 to one (1) mole, preferably 10 3 to 10 1 mole per mole of the component (C), the amount of the component (B) is one (1) to 106 mo:les, preferably 10 to 105 moles per mole of the component (A) or (E) expressed in terms of aluminum atom, and the amount of the component (D) is 10 1 to 105 moles 21~ ~
preferably one (1) to 10 moles per mole of the component (A) or (E)- : ~
The order of bringing each o~ the components of the catalyst into contact with each other is not specifically limited, but may be arbitrarily selected. The reac~ion product after contact treatment may be used as such, or cleaned with an inert solvent prior to using, or distilled to distil away the preparation solvent and dispersed in another solvent, followed by using.
Examples of the inert solvent to be used in bringing each component into contact with one another include aliphatic hydrocarbons each having 5 to 18 carbon atoms, alicyclic hydrocarbons and aromatic hydrocarbons, whlch are specifically enumerated by n-pentate, isopentane, hexane, heptane, octane, nonane, decane, tetradecane, cyclohexane, benzene, toluene and xylene. Any of the above-enumerated solvents may be used alone or as a mixture with at least one other one. The contact temperature and reaction time are not specifically limited.
The contact treatment may be carried out in a manner similar to preliminary polymerization in the presence of a small amount of a monomer, or under the condition including a remarkably low rate of polymerization reactlon.
The contact-treated product thus prepared can be preserved in an atmosphere of an inert gas.
There is usable in the present invention, an arbitrary olefin as the monomer such as an a-olefin and a cyclic olefin, which are enumerated as a-olefin, ethylene, 21 ~31~
propylene, l-butene, 1-hexene, l-octene and 1-decene, and as cyclic olefin, cyclobutene, cyclopentene, cyclohexene, cycloheptene and cyclooctene. In the present invention, an olefin can be copolymerized with an unsaturated monomer component other than olefin which component is copolymerizable with the olefin.
The process according to the present invention is particularly preferably applicable to the production of an ethylenic polymer. In this case, ethylene may be homopolymerized or copolymerized with an a-olefin other than ethylene or a diene compound. Examples of such a-olefin include straigh-chain or branched monoolefin having 3 to 18 carbon atoms and a-olefin replaced with an aromatic group.
Specific examples of such a-olefin include straight-chain monoolefin such as propylene; butene-1; hexene-1; octene-1;
nonene-1; decene-1; undecene-1; and dodecene-1, branched monoolefin such as 3-methylbutene-1; 3-methylpentene-1; 4-methylpentene-l; 2-ethylhexene-1; and 2,2,4-trimethylpentene-1 and monoolefin replaced with a benzene ring such as styrene.
Examples of the preferable diene compound include a 8traight chain or branched non-con~ugated diolefin such as 1,5-hexadiene; 1,6-heptadiene; 1,7-octadiene; 1,8-nonadiene;
1,9-decadiene; 2,5-dimethyl-1,5-hexadiene; and 1,4-dimethyl-4-tert-butyl-2,6-heptadiene, polyene such as 1,5,9-decatriene and end-methylene series cyclic diene such as 5-vinyl-2-norbornene.
The polymerization method in the present invention is 2~431~
not specifically limited, but is usually any of slurry, hot solution, gas-phase or bulk polymerization method, etc.. As the polymerization solvent, an inert slovent such as an aliphatic hydrocarbon, an alicyclic hydrocarbon or an aromatic hydrocarbon is employed, among which is preferable an aliphatic hydrocarbon exemplified by hexane and heptane.
It is preferable that the amount of the polymerization catalyst to be used be selected in the range of 10 8 to 10 2 mole/liter, preferably 10 7 to 10 3 mole/liter expressed in terms of the atoms of the transition metal belonging to the group IVB of the Periodic Table.
The polymerization temperature is not specifically limited, but is usually selected in the range of O to 350C, prefer,ably 20 to 250C. On the other hand, the polymerization pressure is not specifically limited as well, but is usually selected in the range of O to 150 kg/cm2G, preferably O to 100 kg/cm2G.
The modification of the molecular weight and the molecular weight distribution of the polyolefin to be produced can be carried out with case by adding hydrogen into the re~sction system at the tlme of polymerization. The addition of hydrogen is effective particularly in the first and second aspects of the present invention.
In the following, the present invention will be described in more detail with reference to examples and comparative examples.
Preparation Example 1 : Preparation of solution of methylaluminoxane in toluene 21~317 A solution of mehtylaluminoxane (produced by TOSOH AKUZO
CORPORATION ) in toluene was made into the form of thick malt syrup by reducing the pressure at room temperature.
Subsequently, the pressure was further reduced at 90~C for one (1) hour to produce methylaluminoxane crystal in solid form, which was then dispersed in toluene to prepare 1.9 mole/liter solution of methylalumioxane in toluene expressed in terms of ~1 atom.
Preparation Example 2 : Preparation of dispersion liquid of methylalumioxane in hexane A solution of methylalumioxane (produced by Shelling Corporation) in toluene was made into the form of thick malt syrup by reducing the pressure at room temperature.
Subsequently, the pressure was further reduced at 90C for one (1) hour to produce methylaluminoxane crystal in solid ~`
form, wh$ch was then dispersed in hexane to prepare 1.0 mole/liter dispersion liguid of methylaluminoxane in hexane ;
expressed in terms of Al atom.
Example 1 (1) Preparation of solid product A 6 liter glass-made reactor equipped with a stirrer which had sufflciently been purged with nitrogen gas was charged with 2430 g of ethanol, 16 g of iodine and 160 g of metallic magnesium. The mixture in the reactor was allowed to react with stirring under heating and reflux condition until the generation of hydrogen gas was no longer observed to produce a reaction product in solid form. The reaction liquid containing the reaction product was dried under ~` 2ll43l7 reduced pressure to afford a solid product.
(2) Preparation of solid catalyst components To 10 g of the solid product (62 ~m average particle size) as produced in the preceding item (1) were added in turn a solution of 0.17 mmol of bis (cyclopentadienyl)zirconium dichloride in 50 ml of tol~ene and 1.9 mole/liter solution of methylaluminoxane in toluene in an amount of 35 mmol in terms of methylaluminoxane. The mixture was allowed to react at room temperature with gentle stirring for one hour. Then, the toluene solvent was removed by reducing the pressure with gentle stirring at room temperature. Subsequently heptane was added to the reaction system to form a slurry in a total amount of 400 ml. All o$
the aforesaid procedure was carried out in an atmosphere of dry nitrogen.
(3) Polymerization of ethylene A one (1) liter dry polymerization reactor equipped with a stirrer the inside of which had been purged with dry nitrogen was charged with 400 ml of dry heptane and further with 2.6 ml of solution of methylaluminoxane in toluene (1.9 mmol/llter) and 0.003 mmol of the solid catalyst component as prepared in the preceding item (2) expres~ed in terms of zirconium.
Subsequently the reaction system was heated to raise the temperature up to 80C, charged with hydrogen so as to attain a hydrogen partial pressure of 0.06 kg/cm2G and pressurized with ethylene so as to maintain the internal pressure in the polymerization reactor at 8 kg/cm2G, and ethylene was further 2114~7 introduced there$n so as to maintain the internal pressure at 8 kg/cm2G to proceed wi~h polymerization at 80C for one hour.
After the completion of polymerization, the reactor was opened and the resultant polymer slurry was poured in 2 liter of mixed liquid of methanol and hydrochloric acid. The polymer was filtered off, washed with methanol and dried at 80C under reduced pressure for 4 hours.
As the result, there was obtained 23.0 g of polymer powder with favorable fluidity at a polymerization activity :. :
of 84 kg/g-Zr, which polymer had an apparent bulk density of 0.17 g/ml, a weight-average molecular weight (Mw) of 46000 and a ratio of welght-average molecular weight(Mw) to number-average molecular weight(Mn)(Mw/Mn) of 4.9.
Comparative Example 1 The procedure in Example 1 was repeated to polymerize ethylene except that 0.003 mmol of bis(cyclopentadienyl)zirconium dichloride expressed in terms of zirconium(Zr) and 1.3 ml of 1.9 mol/liter solution of methylaluminoxane in toluene were added to the reaction system at the time of polymerization without preparing a solid catalyst component, and hydrogen partial pressure was set to 0.10 kg/cm2G.
As a result, 23.7 g of polymer was obtained in the form of agglomerate and had a Mw of 38000 and a Mw/Mn ratio of 2.6.
Example 2 The procedure in Example 1 was repeated to polymerize ~ 26 -21~ 4317 ethylene except that the solid catalyst component in an amount of 0.0015 mmol expressed in terms of zr and 1.3 ml of 1.9 mole/liter solution of methylaluminoxane in toluene were used and hydrogen was not added to the reaction system.
As a result, 22.4 g of polymer was obtalned at a polymerlzation activity of 164 kg/g-Zr and had an apparent bulk density of 0.07 g/ml, a Mw of 220,000 and a Mw/Mn ratio Of 2.6.
Comparative Example 2 (1) Preparation of catalyst components The procedure in Example 1 (2) was repeated to prepare catalyst components except that the solid product was not lncorporated.
(2) Polymerization of ethylene The procedure in Example 2 was repeated to polymerlze ethylene except that the catalyst components as prepared in the preceding item (1) were used in place of the solid catalyst components.
However, after an elapse of 25 minutes from the start of polymerization, the polymerization was discontinued because of impossibility of the temperature control. On opening the polymerization reactor, there was observed remarkable adhesion of the polymer to the inside wall of the reactor.
Example 3 Tlhe procedure in Example 2 was repeated to polymerize ethylene except that 5.3 ml of l.9 mole/liter solution of methylaluminoxane in toluene was used.
A~3 a result, 32.0 g of polymer was obtained at a 21~ 4317 ~
polymerization activity of 234 kg/g-Zr and had a Mw of 220,000 and a Mw/Mn ratio of 2.6.
Examplle 4 (1) Preparation of solid catalyst components The procedure in Example 1 (2) was repeated to prepare solid catalyst components except that methylaluminoxane was not incorporated. ;~
(2) Polymerization of ethylene The procedure in Example 3 was repeated to polymerize ethylene except that the solid catalyst components as prepared in the preceding item (l) were used in place of ~
those ln Example 3.
A~3 a result, 25.3g of polymer was obtained at a polymerlzation activity of 185 kg/g-Zr and had an lntrinsic viscosity [nl of 3.1 dl/g.
Example 5 (l) Preparation of solid catalyst components The procedure in Example 1 (2) was repeated to prepare solid aatalyst components except that one (1) g of the solid product was used.
t2) PoLymerization of ethylene The procedure in Example 3 was repeated to polymerlze ethylene except that the solid catalyst components as prepared in the preceding item (1) were used in place of those :Ln Example 3 and that the polymerization was carried out for 30 minutes.
As a result, 47.7 g of polymer was obtained at a polyme:rization activity of 349 kg/g-Zr and had an intrinsic - 2~ -21i4317 viscosity [ n ] of 4.1 dl/g.
Example 6 Ethylene was polymerized through preliminary polymerization.
A one (1) liter dry polymerization reactor equipped with a stirrer the inside of which had been purged with dry nitrogen was charged with 400 ml of dry heptane and further with 1.3 ml of solution of methylaluminoxane in toluene (1.9 mmol/liter) and 0.0015 mmol of the solid catalyst component as prepared in Example 1 (2) expressed in terms of zirconium.
Then, 0.17 Nl of ethylene was introduced into the reactor to carry out preliminary polymeri7ation at 17C for 30 minutes.
Subsequently the reaction system was heated to raise the temperature up to 80C and pressurized with ethylene so as to maintain the internal pressure in the polymerization reactor at 8 kg/cm2G, and ethylene was further introduced therein so as to maintain the internal pressure at 8 kg/cm2G to proceed with polymerization at 80C for one hour.
After the completion of polymerization, the reactor was opened and the resultant polymer slurry was poured in 2 liter of mix~ed liquid of methanol and hydrochloric acid. The polymer was filtered off, washed with methanol and dried at 80C under reduced pressure for 4 hours.
As the result, there was obtained 9.5 g of polymer powder with favorable fluidity at a polymerization activity of 69 kg/g-Zr.
Exampl~e 7 Ethylene was copolymerized with 1-octene.
'~
-` 21~43~7 A one (1) liter dry polymerization reactor equipped with a stirrer the inside of which had been purged with dry nitrogen was charged with 370 ml of dry heptane and further with 30 ml of 1-octene, 1.3 ml of solution of methylaluminoxane in toluene (1.9 mmol/liter) and 0.0015 mmol of the solid catalyst component as prepared in Example 1 (2) expressed in terms of zirconium. Immediately thereafter, the reaction system was heated to raise the temperature up to 60C and pressurized with ethylene so as to maintain the internal pressure in the polymerization rea~tor at 8 kg/cm2G, and ethylene was further introduced therein so as to maintain the internal pressure at 8 kg/cm G to proceed with polymerization at 60C for one hour.
After the completion of polymerization, the reactor was opened and the resultant polymer slurry was poured ln 2 liter of mixed liquid of methanol and hydrochloric acid. The polymer was filtered off, washed with methanol and dried at 80C under reduced pressure for 4 hours.
As the result, there was obtained 25.4 g of polymer powdsr with favorable fluidity at a polymerization activity of 186 kg/g-Zr, which polymer had a density of 0.925 g/ml, 1-octene unit content of 4% by weight, a weight-average molecular weight (Mw) of 140,000 and a ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn)(Mw/Mn) of 2.7.
Example 8 (l) Preparation of solid catalyst To 32 ml of toluene were added l.0 ml of l.0 mole/liter _ 30 -2~317 solution of triisobutylaluminum in toluene, 10.7 ml of 1.9 mole/liter solution of methylaluminoxane in toluene and 7.6 ml of 13 mmol/liter solution of bis(cyclopentadienyl)zirconium dichloride in toluene with stirring for 20 minutes. To the resultant mixture was further added 50 ml of the dispersion liquid (1.0 mole/liter) of the solid product which was obtained in Example 1 (1) in toluene as the dispersant with further stirring for 2 hours.
The toluene contained in the slurry thus obtained was distilled away and 100 ml of hexane was added to the remaining slurry to prepare solid catalyst slurry.
(2) Polymerization of ethylene A one (1) liter dry polymerization reactor equipped with a stirrer the inside of which had been purged with dry nitrogen was charged with 400 ml of dry heptane and further with 1.3 ml of solution of methylaluminoxane in toluene (1.9 mmol/liter) and 2.0 ml of the solid catalyst slurry as prepared in the preceding item (1)(2 micromol of Zr).
Immediately thereafter the reaction system was heated to raise the temperature up to 80C and pressurized with ethylene so as to maintain the total internal pressure in the polymerization reactor at 8 kg/cm2G to proceed with polymerization a 80C for one hour.
After the completion of polymerization, the reactor was immediately depressurized and charged with methanol to arrest polymerization, and the resultant polymer slurry was poured in a large amount of mixed liquid of methanol and hydrochloric acid for deashing. The polymer was filtered off - 31 ~
' . ; , . ' : . : ~ ` . ' 2~4317 and dried at 80C under reduced pressure for 4 hours.
As the result, there was obtained 31.9 g of polymer granul,e. Table 1 gives the polymerization activity, apparent bulk density [ n ]and Mw/Mn.
Examplle 9 :
(1) Preparation of solid catalyst The procedure in Example 8 (1) was repeated to prepare solid ,-atalyst slurry except that 1.0 ml of 1.0 mole/liter solution of triisobutylaluminum in toluene was not incorporated.
(2) Polymerization of ethylene The procedure in Example 8 was repeated to polymerize ethyle;ne except that the solid catalyst slurry as prepared in the pr~eceding item (1) was used. The results are given in Table 1.
Compar,ative Example 3 The procedure in Example 8 was repeated to polymerize ethylene except that the preparation of the solid catalyst slurry was omitted and there were used bis(cyclopentadienyl)zirconium dichloride in an amount of 0.5 micromol as Zr and 1.3 ml of 1.9 mole/liter solution of methylaluminoxane in toluene at the time of polymerization.
The results are given in Table 1. Afte the polymerization there was observed the polymer which adhered to the agitation impellers and the walls of the reactor.
Example 10 ~ ~;
(l) Polymerization of ethylene The procedure in Example 8 was repeated to polymerize ~ -- 3~
ethylene except that hydrogen was introduced in the reaction system so as to attain 0.10 kg/cm2G. The results are glven in Table 1.
Comparative Example 4 The procedure in Example 10 was repeated to polymerize ethylene except that the preparation of the solid catalyst slurry was omitted and there were used bis(cyclopentadienyl)zirconium dichloride in an amount of 1.0 micromol as zr and 1.3 ml of 1.9 mole/liter solution of methylaluminoxane in toluene at the time of polymerization.
The re~ults are given in Table 1.
Example ll (1) Preparation of solid catalyst The procedure in Example 8 was repeated to prepare solid oatalyst slurry except that 6.7 ml of 15 mmol/liter solution of cyclopentadienylzirconium trichloride in toluene was used in place of 7.6 ml of 13 mmol/liter solution of bis(cyclopentadienyl)zirconium dichloride in toluene.
(2) Polymerization of ethylene ~ -The procedure in Example 8 was repeated to polymerize ethylene except that there was used 10.0 ml of the solid catalyst slurry (10 micromol as Zr) as prepared in the preced:ing item (1). The results are given in Table 1.
Example 12 (1) Preparation of solid catalyst rhe procedure in Example ll (1) was repeated to prepare solid catalyst slurry except that 1.0 ml of 1.0 mol/liter solution of trilsobutylaluminum in toluene was not - . .. . . . . . ..
incorporated.
(2) Pc,lymerization of ethylene The procedure in Example 11 was repeated to polymerize ethylene except that the solid catalyst slurry as prepared in the preceding item (1) was used. The results are given in Table 1.
Example 13 The procedure in Example 11 was repeated to polymerize ethylene except that hydrogen was introduced in the reaction system so as to attain 0.10 kg/cm2G. The results are given in Table 1.
Comparative Example 5 The procedure in Example 10 was repeated to polymerize ethylene except that the preparation of the solid catalyst slurry was omitted and there were used cyclopentadienylzirconium trichloride in an amount of 3.0 micromol as Zr and 1.3 ml of 1.9 mole/liter solution of methylaluminoxane in toluene at the time of polymerization.
The results are given in Table 1. ~ -:, ~ ~'' ,.
''' Table 1 21~3~ 7 Polymer yield Polymer.ization Bulk density [ ]
activity n (g)(kQ /~-Zr) (g/ml) (dl/g) Example 8 31.9 175 0.08 3.8 Example 9 24.1 132 0.06 3.3 Comparative 21.8 478 0.03 3.9 Example 3 Example 10 15.1 83 0.18 1.0 Comparative 29.6 325 not measurable 0.9 Example 4 Example 11 34.5 38 0.06 4.2 Example 12 19.2 21 0.06 3.8 Example 13 22.8 25 0.15 1.1 Comparative 18.1 66 not measurable 1.0 Example 5 Table 1 (continued) Mw/Mn Remarks :
Example 8 2.5 Example 9 2.6 - ,: .. . .::
Comparative 2.6 adhesion of polymer to agitation Example 3 impellers, etc. : ;
Example 10 4.5 Comparative 2.6 agglomerate polymer Example 4 Example 11 2.5 Example 12 2.6 Example 13 4.8 Comparative 2.5 agglomerate polymer Example 5 ~ :
Example 14 (1) Preparation of solid catalyst To 129 ml of toluene were added 3 ml of 0.1 mole/liter solution of tetra-n-butoxytitanium in hexane and 15 ml of 1.0 mole/liter dispersion liquid of the above-mentioned methylaluminoxane in hexane with stirring for one (1) hour.
To the resultant mixture was further added 34.3 ml of the dispersion liquid (lOOgJliter) of the solid product which was obtained in Example 1 (1) in hexane as the dispersant with further stirring for one (1) hour. The slurry thus obtained was washed three times each with 400 ml of hexane and diluted with hexane to a total volume of 150 ml to prepare solid catalyst slurry, which had a titanium concentration of 1.9 ~;
mmol-T:L/liter. No titanium component was detected in the supernatant hexane of the slurry. ~ ~
(2) Po:Lymerization of ethyLene ~ -A one (1) liter dry polymerization reactor equipped with a stirrer the inside of which had been purged with dry nitrogen was charged with 400 ml of dry n-hexane, and the mixture was heated to raise the temperature to 60C.
Subsequently 21.0 ml (40 micromol of Ti) of the solid catalyst slurry as prepared in the preceding item (1) was placed in the polymerization reactor, immediately followed by raisin~a the temperature of the mixture in the reactor to 80C. Then ethylene was introduced into the reactor to carry out po:Lymerization at 80C for one (1) hour so as to maintain the total internal pressure in the polymerization reactor at 8 kg/cm2G.
21 14 ~ t I
After the completion of polymerization, the reactor was immediately depressurized and charged with methanol to arrest polymerization, and the content in the reactor was poured in a large amount of mixed liquid of methanol and hydrochloric acid. The polymer was filtered off, and dried at 80C under reduced pressure for 4 hours. There was not observed any polymer adhesion to the reactor.
As the result, there was obtained 5.6 g of polyethylene powder in particulate form having a [ n ] of 35 dl/g.
Example 15 A one (1) liter dry polymerization reactor equipped with a stirrer the inside of which had been purged with dry nitrog~en was charged with 400 ml of dry n-hexane and 1.0 ml of 1.0 mol/liter solution of triisobutylaluminum in hexane, and thle resultant mixture was heated to raise the temperature up to 60C.
Then, by the use of the solid catalyst slurry as prepared in Example 14 (1), ethylene was polymerized in the same manner as in Example 14. There was not observed any polymer adhesion to the walls of the reactor.
As the result, there was obtained 7.0 g of polyethylene powder in particulate form having a [ n ] of 39 dl/g.
Comparative Example 6 (1) Pr,sparation of mixed liquid of catalyst components To 132 ml of toluene were added 3 ml of 0.1 mol/liter solution of tetra-n-butoxytitanium in hexane and 15 ml of 1.0 mol/liter dispersion liquid of the above-mentioned methylaluminoxane in hexane as the dispersant, with stirring :
. ~
- 37 - ~
211~317 for one (1) hour.
(2) Polymerization of ethylene A one (1) liter dry polymerization reactor equipped with a stirrer the inside of which had been purged with dry nitrogen was charged with 400 ml of dry n-hexane and 1.0 ml of 1.0 mole/liter of triisobutylaluminum in hexane followed by raising the temperature of the mixture in the reactor to 60C. Subsequently 20.0 ml (40 micromol of Ti) of the mixed liquid of the catalyst component as prepared in the preceding item (1) was placed in the polymerization reactor.
Immediately thereafter the reaction system was heated to raise the temperature up to 80C and pressurized with ethylene so as to maintain the total internal pressure in the .
polymerization reactor at 8 kg/cm2G to proceed with polymerizatlon at 80C for one hour.
After the completion of polymerization, the reactor was immediately depressurized and charged with methanol to arrest polymerizaiton.
As the result, there was obtained 8.0 g of agglomerate polymer whlch adhered to the agitation impellers and the walls of the reactor.
Example 16 (1) Preparation of solid catalyst To 126 ml of toluene were added 3.0 ml of 1.0 mole/liter solution of triisobutylaluminum in hexane and 3 ml of 0.1 mole/liter solution of tetra-n-butoxytitanium in hexane with stirring for 10 minutes, and then 15 ml of 1.0 mole/liter dispersion liquid of the above-mentioned ~ 21~3~ ~
methylaluminoxane in hexane as the dispersant with stirring for one (1) hour. To the resultant mlxture was fur-ther added 34.3 mmol of the dispersion liquid (100 g/liter) of the solid product which was obtained in Example 1 (1) in hexane as the dispersant with further stirring for one (1) hour. The slurry thus obtained was washed three times each with 400 ml of hexane and diluted with hexane to a total volume of 150 ml to prepare solid catalyst slurry, which had a titanium concentration of 1.6 mmol-Ti/liter. No titanium component was detected in the supernatant hexane of the slurry.
(2) Polymerization of ethylene The procedure in Example 15 was repeated except the use of 25.0 ml (40 micromol of Ti) of the solid catalyst slurry as prepared in the preceding item (1).
There was not observed any polymer adhesion to the reactor.
As a result, there was obtained 43.6 g of polyethylene powder in particulate form~having a [ n ] Of 46 dl/g a bulk density of 0.13 g/ml.
Examp_e 17 (1) Copolymerization of ethylene and 1-octene A one (1) liter dry polymerization reactor equipped with a stirrer the inside of which had been purged with dry nitrogen was charged with 360 ml of dry n-hexane, A0 ml of 1-octene and 1.0 ml of 1.0 mol/liter of triisobutylaluminum in hexane, followed by raising the temperature of the mixture in the reactor to 60~C. Subsequently, 25.0 ml (40 micromol of Ti) of the solid catalyst slurry as prepared in Example 16 - 39 ~
~ 21 ~43~r~
(1) was placed in the polymeriæation reactor. Immediately thereafter, the reaction system was heated to raise the temperature up to 80C and pressurized with ethylene so as to maintaln the total internal pressure in the polymerization reactor at 8 kg/cm G, to proceed with polymerization at 80C
for one hour.
After the completion of polymerization, the reactor was immediately depressurized and charged with methanol to arrest polymerization.
There was not observed any polymer adhesion to the reactor.
As a result, there was obtained 42.9 g of ethylene/octene copolymer in particulate form having a [ n ] f 41 dl/g, a bulk density of 0.15 g/ml, 1-octene unit content of 0.5 mole% and a melting point of 127C.
Comparative Example 7 (1) Pr~aparation of mixed liquid of catalyst components To 129 ml of toluene were added 3.0 ml of 1.0 mole/liter solution of triisobutylaluminum in hexane and 3 ml of 0.1 mole/liter solution of tetra-n-butoxytitanium in hexane with stirring for 10 minutes, and then 15 ml of 1.0 mole/lLter dispersion liquid of the above-mentioned methylaluminoxane in hexane as the dispersant wlth stirring for one (1) hour.
(2) Copolylmerization of ethylene and 1-octene The procedure in Example 17 was repeated except the use of 20.0 ml (40 micromol of Ti) of the mixed liquid of catalyst components as prepared in the preceding item (1~.
-- ~0 --However, after an elapse of 30 minutes from the start of the polymerization, the polymerization was discontinued because of impossibility of the temperature control. On opening the polymerization reactor, there was observed 35.2 g of agg:Lomerate polymer which adhered to the walls and impellers of the reactor.
INDUSTRIAL APPLICABILITY
As described hereinbefore, the present invention enables to contrive to improve the powder morphology of the produced polymer and facilitate the regulation of the molecular weight distribution thereof and besides to efficiently and stably produce a high molecular weight polyolefin having excellent particle shape with minimized adhesion of the resultant polymer to the polymerization reactor.
Thus, the process according to the present invention is preferably applicable to the production of ethylenic polymers such as polyolefin, especially low-density linear polyolefin, thereby rendering itself extremely valueable in utilization.
Subsequently the reaction system was heated to raise the temperature up to 80C, charged with hydrogen so as to attain a hydrogen partial pressure of 0.06 kg/cm2G and pressurized with ethylene so as to maintain the internal pressure in the polymerization reactor at 8 kg/cm2G, and ethylene was further 2114~7 introduced there$n so as to maintain the internal pressure at 8 kg/cm2G to proceed wi~h polymerization at 80C for one hour.
After the completion of polymerization, the reactor was opened and the resultant polymer slurry was poured in 2 liter of mixed liquid of methanol and hydrochloric acid. The polymer was filtered off, washed with methanol and dried at 80C under reduced pressure for 4 hours.
As the result, there was obtained 23.0 g of polymer powder with favorable fluidity at a polymerization activity :. :
of 84 kg/g-Zr, which polymer had an apparent bulk density of 0.17 g/ml, a weight-average molecular weight (Mw) of 46000 and a ratio of welght-average molecular weight(Mw) to number-average molecular weight(Mn)(Mw/Mn) of 4.9.
Comparative Example 1 The procedure in Example 1 was repeated to polymerize ethylene except that 0.003 mmol of bis(cyclopentadienyl)zirconium dichloride expressed in terms of zirconium(Zr) and 1.3 ml of 1.9 mol/liter solution of methylaluminoxane in toluene were added to the reaction system at the time of polymerization without preparing a solid catalyst component, and hydrogen partial pressure was set to 0.10 kg/cm2G.
As a result, 23.7 g of polymer was obtained in the form of agglomerate and had a Mw of 38000 and a Mw/Mn ratio of 2.6.
Example 2 The procedure in Example 1 was repeated to polymerize ~ 26 -21~ 4317 ethylene except that the solid catalyst component in an amount of 0.0015 mmol expressed in terms of zr and 1.3 ml of 1.9 mole/liter solution of methylaluminoxane in toluene were used and hydrogen was not added to the reaction system.
As a result, 22.4 g of polymer was obtalned at a polymerlzation activity of 164 kg/g-Zr and had an apparent bulk density of 0.07 g/ml, a Mw of 220,000 and a Mw/Mn ratio Of 2.6.
Comparative Example 2 (1) Preparation of catalyst components The procedure in Example 1 (2) was repeated to prepare catalyst components except that the solid product was not lncorporated.
(2) Polymerization of ethylene The procedure in Example 2 was repeated to polymerlze ethylene except that the catalyst components as prepared in the preceding item (1) were used in place of the solid catalyst components.
However, after an elapse of 25 minutes from the start of polymerization, the polymerization was discontinued because of impossibility of the temperature control. On opening the polymerization reactor, there was observed remarkable adhesion of the polymer to the inside wall of the reactor.
Example 3 Tlhe procedure in Example 2 was repeated to polymerize ethylene except that 5.3 ml of l.9 mole/liter solution of methylaluminoxane in toluene was used.
A~3 a result, 32.0 g of polymer was obtained at a 21~ 4317 ~
polymerization activity of 234 kg/g-Zr and had a Mw of 220,000 and a Mw/Mn ratio of 2.6.
Examplle 4 (1) Preparation of solid catalyst components The procedure in Example 1 (2) was repeated to prepare solid catalyst components except that methylaluminoxane was not incorporated. ;~
(2) Polymerization of ethylene The procedure in Example 3 was repeated to polymerize ethylene except that the solid catalyst components as prepared in the preceding item (l) were used in place of ~
those ln Example 3.
A~3 a result, 25.3g of polymer was obtained at a polymerlzation activity of 185 kg/g-Zr and had an lntrinsic viscosity [nl of 3.1 dl/g.
Example 5 (l) Preparation of solid catalyst components The procedure in Example 1 (2) was repeated to prepare solid aatalyst components except that one (1) g of the solid product was used.
t2) PoLymerization of ethylene The procedure in Example 3 was repeated to polymerlze ethylene except that the solid catalyst components as prepared in the preceding item (1) were used in place of those :Ln Example 3 and that the polymerization was carried out for 30 minutes.
As a result, 47.7 g of polymer was obtained at a polyme:rization activity of 349 kg/g-Zr and had an intrinsic - 2~ -21i4317 viscosity [ n ] of 4.1 dl/g.
Example 6 Ethylene was polymerized through preliminary polymerization.
A one (1) liter dry polymerization reactor equipped with a stirrer the inside of which had been purged with dry nitrogen was charged with 400 ml of dry heptane and further with 1.3 ml of solution of methylaluminoxane in toluene (1.9 mmol/liter) and 0.0015 mmol of the solid catalyst component as prepared in Example 1 (2) expressed in terms of zirconium.
Then, 0.17 Nl of ethylene was introduced into the reactor to carry out preliminary polymeri7ation at 17C for 30 minutes.
Subsequently the reaction system was heated to raise the temperature up to 80C and pressurized with ethylene so as to maintain the internal pressure in the polymerization reactor at 8 kg/cm2G, and ethylene was further introduced therein so as to maintain the internal pressure at 8 kg/cm2G to proceed with polymerization at 80C for one hour.
After the completion of polymerization, the reactor was opened and the resultant polymer slurry was poured in 2 liter of mix~ed liquid of methanol and hydrochloric acid. The polymer was filtered off, washed with methanol and dried at 80C under reduced pressure for 4 hours.
As the result, there was obtained 9.5 g of polymer powder with favorable fluidity at a polymerization activity of 69 kg/g-Zr.
Exampl~e 7 Ethylene was copolymerized with 1-octene.
'~
-` 21~43~7 A one (1) liter dry polymerization reactor equipped with a stirrer the inside of which had been purged with dry nitrogen was charged with 370 ml of dry heptane and further with 30 ml of 1-octene, 1.3 ml of solution of methylaluminoxane in toluene (1.9 mmol/liter) and 0.0015 mmol of the solid catalyst component as prepared in Example 1 (2) expressed in terms of zirconium. Immediately thereafter, the reaction system was heated to raise the temperature up to 60C and pressurized with ethylene so as to maintain the internal pressure in the polymerization rea~tor at 8 kg/cm2G, and ethylene was further introduced therein so as to maintain the internal pressure at 8 kg/cm G to proceed with polymerization at 60C for one hour.
After the completion of polymerization, the reactor was opened and the resultant polymer slurry was poured ln 2 liter of mixed liquid of methanol and hydrochloric acid. The polymer was filtered off, washed with methanol and dried at 80C under reduced pressure for 4 hours.
As the result, there was obtained 25.4 g of polymer powdsr with favorable fluidity at a polymerization activity of 186 kg/g-Zr, which polymer had a density of 0.925 g/ml, 1-octene unit content of 4% by weight, a weight-average molecular weight (Mw) of 140,000 and a ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn)(Mw/Mn) of 2.7.
Example 8 (l) Preparation of solid catalyst To 32 ml of toluene were added l.0 ml of l.0 mole/liter _ 30 -2~317 solution of triisobutylaluminum in toluene, 10.7 ml of 1.9 mole/liter solution of methylaluminoxane in toluene and 7.6 ml of 13 mmol/liter solution of bis(cyclopentadienyl)zirconium dichloride in toluene with stirring for 20 minutes. To the resultant mixture was further added 50 ml of the dispersion liquid (1.0 mole/liter) of the solid product which was obtained in Example 1 (1) in toluene as the dispersant with further stirring for 2 hours.
The toluene contained in the slurry thus obtained was distilled away and 100 ml of hexane was added to the remaining slurry to prepare solid catalyst slurry.
(2) Polymerization of ethylene A one (1) liter dry polymerization reactor equipped with a stirrer the inside of which had been purged with dry nitrogen was charged with 400 ml of dry heptane and further with 1.3 ml of solution of methylaluminoxane in toluene (1.9 mmol/liter) and 2.0 ml of the solid catalyst slurry as prepared in the preceding item (1)(2 micromol of Zr).
Immediately thereafter the reaction system was heated to raise the temperature up to 80C and pressurized with ethylene so as to maintain the total internal pressure in the polymerization reactor at 8 kg/cm2G to proceed with polymerization a 80C for one hour.
After the completion of polymerization, the reactor was immediately depressurized and charged with methanol to arrest polymerization, and the resultant polymer slurry was poured in a large amount of mixed liquid of methanol and hydrochloric acid for deashing. The polymer was filtered off - 31 ~
' . ; , . ' : . : ~ ` . ' 2~4317 and dried at 80C under reduced pressure for 4 hours.
As the result, there was obtained 31.9 g of polymer granul,e. Table 1 gives the polymerization activity, apparent bulk density [ n ]and Mw/Mn.
Examplle 9 :
(1) Preparation of solid catalyst The procedure in Example 8 (1) was repeated to prepare solid ,-atalyst slurry except that 1.0 ml of 1.0 mole/liter solution of triisobutylaluminum in toluene was not incorporated.
(2) Polymerization of ethylene The procedure in Example 8 was repeated to polymerize ethyle;ne except that the solid catalyst slurry as prepared in the pr~eceding item (1) was used. The results are given in Table 1.
Compar,ative Example 3 The procedure in Example 8 was repeated to polymerize ethylene except that the preparation of the solid catalyst slurry was omitted and there were used bis(cyclopentadienyl)zirconium dichloride in an amount of 0.5 micromol as Zr and 1.3 ml of 1.9 mole/liter solution of methylaluminoxane in toluene at the time of polymerization.
The results are given in Table 1. Afte the polymerization there was observed the polymer which adhered to the agitation impellers and the walls of the reactor.
Example 10 ~ ~;
(l) Polymerization of ethylene The procedure in Example 8 was repeated to polymerize ~ -- 3~
ethylene except that hydrogen was introduced in the reaction system so as to attain 0.10 kg/cm2G. The results are glven in Table 1.
Comparative Example 4 The procedure in Example 10 was repeated to polymerize ethylene except that the preparation of the solid catalyst slurry was omitted and there were used bis(cyclopentadienyl)zirconium dichloride in an amount of 1.0 micromol as zr and 1.3 ml of 1.9 mole/liter solution of methylaluminoxane in toluene at the time of polymerization.
The re~ults are given in Table 1.
Example ll (1) Preparation of solid catalyst The procedure in Example 8 was repeated to prepare solid oatalyst slurry except that 6.7 ml of 15 mmol/liter solution of cyclopentadienylzirconium trichloride in toluene was used in place of 7.6 ml of 13 mmol/liter solution of bis(cyclopentadienyl)zirconium dichloride in toluene.
(2) Polymerization of ethylene ~ -The procedure in Example 8 was repeated to polymerize ethylene except that there was used 10.0 ml of the solid catalyst slurry (10 micromol as Zr) as prepared in the preced:ing item (1). The results are given in Table 1.
Example 12 (1) Preparation of solid catalyst rhe procedure in Example ll (1) was repeated to prepare solid catalyst slurry except that 1.0 ml of 1.0 mol/liter solution of trilsobutylaluminum in toluene was not - . .. . . . . . ..
incorporated.
(2) Pc,lymerization of ethylene The procedure in Example 11 was repeated to polymerize ethylene except that the solid catalyst slurry as prepared in the preceding item (1) was used. The results are given in Table 1.
Example 13 The procedure in Example 11 was repeated to polymerize ethylene except that hydrogen was introduced in the reaction system so as to attain 0.10 kg/cm2G. The results are given in Table 1.
Comparative Example 5 The procedure in Example 10 was repeated to polymerize ethylene except that the preparation of the solid catalyst slurry was omitted and there were used cyclopentadienylzirconium trichloride in an amount of 3.0 micromol as Zr and 1.3 ml of 1.9 mole/liter solution of methylaluminoxane in toluene at the time of polymerization.
The results are given in Table 1. ~ -:, ~ ~'' ,.
''' Table 1 21~3~ 7 Polymer yield Polymer.ization Bulk density [ ]
activity n (g)(kQ /~-Zr) (g/ml) (dl/g) Example 8 31.9 175 0.08 3.8 Example 9 24.1 132 0.06 3.3 Comparative 21.8 478 0.03 3.9 Example 3 Example 10 15.1 83 0.18 1.0 Comparative 29.6 325 not measurable 0.9 Example 4 Example 11 34.5 38 0.06 4.2 Example 12 19.2 21 0.06 3.8 Example 13 22.8 25 0.15 1.1 Comparative 18.1 66 not measurable 1.0 Example 5 Table 1 (continued) Mw/Mn Remarks :
Example 8 2.5 Example 9 2.6 - ,: .. . .::
Comparative 2.6 adhesion of polymer to agitation Example 3 impellers, etc. : ;
Example 10 4.5 Comparative 2.6 agglomerate polymer Example 4 Example 11 2.5 Example 12 2.6 Example 13 4.8 Comparative 2.5 agglomerate polymer Example 5 ~ :
Example 14 (1) Preparation of solid catalyst To 129 ml of toluene were added 3 ml of 0.1 mole/liter solution of tetra-n-butoxytitanium in hexane and 15 ml of 1.0 mole/liter dispersion liquid of the above-mentioned methylaluminoxane in hexane with stirring for one (1) hour.
To the resultant mixture was further added 34.3 ml of the dispersion liquid (lOOgJliter) of the solid product which was obtained in Example 1 (1) in hexane as the dispersant with further stirring for one (1) hour. The slurry thus obtained was washed three times each with 400 ml of hexane and diluted with hexane to a total volume of 150 ml to prepare solid catalyst slurry, which had a titanium concentration of 1.9 ~;
mmol-T:L/liter. No titanium component was detected in the supernatant hexane of the slurry. ~ ~
(2) Po:Lymerization of ethyLene ~ -A one (1) liter dry polymerization reactor equipped with a stirrer the inside of which had been purged with dry nitrogen was charged with 400 ml of dry n-hexane, and the mixture was heated to raise the temperature to 60C.
Subsequently 21.0 ml (40 micromol of Ti) of the solid catalyst slurry as prepared in the preceding item (1) was placed in the polymerization reactor, immediately followed by raisin~a the temperature of the mixture in the reactor to 80C. Then ethylene was introduced into the reactor to carry out po:Lymerization at 80C for one (1) hour so as to maintain the total internal pressure in the polymerization reactor at 8 kg/cm2G.
21 14 ~ t I
After the completion of polymerization, the reactor was immediately depressurized and charged with methanol to arrest polymerization, and the content in the reactor was poured in a large amount of mixed liquid of methanol and hydrochloric acid. The polymer was filtered off, and dried at 80C under reduced pressure for 4 hours. There was not observed any polymer adhesion to the reactor.
As the result, there was obtained 5.6 g of polyethylene powder in particulate form having a [ n ] of 35 dl/g.
Example 15 A one (1) liter dry polymerization reactor equipped with a stirrer the inside of which had been purged with dry nitrog~en was charged with 400 ml of dry n-hexane and 1.0 ml of 1.0 mol/liter solution of triisobutylaluminum in hexane, and thle resultant mixture was heated to raise the temperature up to 60C.
Then, by the use of the solid catalyst slurry as prepared in Example 14 (1), ethylene was polymerized in the same manner as in Example 14. There was not observed any polymer adhesion to the walls of the reactor.
As the result, there was obtained 7.0 g of polyethylene powder in particulate form having a [ n ] of 39 dl/g.
Comparative Example 6 (1) Pr,sparation of mixed liquid of catalyst components To 132 ml of toluene were added 3 ml of 0.1 mol/liter solution of tetra-n-butoxytitanium in hexane and 15 ml of 1.0 mol/liter dispersion liquid of the above-mentioned methylaluminoxane in hexane as the dispersant, with stirring :
. ~
- 37 - ~
211~317 for one (1) hour.
(2) Polymerization of ethylene A one (1) liter dry polymerization reactor equipped with a stirrer the inside of which had been purged with dry nitrogen was charged with 400 ml of dry n-hexane and 1.0 ml of 1.0 mole/liter of triisobutylaluminum in hexane followed by raising the temperature of the mixture in the reactor to 60C. Subsequently 20.0 ml (40 micromol of Ti) of the mixed liquid of the catalyst component as prepared in the preceding item (1) was placed in the polymerization reactor.
Immediately thereafter the reaction system was heated to raise the temperature up to 80C and pressurized with ethylene so as to maintain the total internal pressure in the .
polymerization reactor at 8 kg/cm2G to proceed with polymerizatlon at 80C for one hour.
After the completion of polymerization, the reactor was immediately depressurized and charged with methanol to arrest polymerizaiton.
As the result, there was obtained 8.0 g of agglomerate polymer whlch adhered to the agitation impellers and the walls of the reactor.
Example 16 (1) Preparation of solid catalyst To 126 ml of toluene were added 3.0 ml of 1.0 mole/liter solution of triisobutylaluminum in hexane and 3 ml of 0.1 mole/liter solution of tetra-n-butoxytitanium in hexane with stirring for 10 minutes, and then 15 ml of 1.0 mole/liter dispersion liquid of the above-mentioned ~ 21~3~ ~
methylaluminoxane in hexane as the dispersant with stirring for one (1) hour. To the resultant mlxture was fur-ther added 34.3 mmol of the dispersion liquid (100 g/liter) of the solid product which was obtained in Example 1 (1) in hexane as the dispersant with further stirring for one (1) hour. The slurry thus obtained was washed three times each with 400 ml of hexane and diluted with hexane to a total volume of 150 ml to prepare solid catalyst slurry, which had a titanium concentration of 1.6 mmol-Ti/liter. No titanium component was detected in the supernatant hexane of the slurry.
(2) Polymerization of ethylene The procedure in Example 15 was repeated except the use of 25.0 ml (40 micromol of Ti) of the solid catalyst slurry as prepared in the preceding item (1).
There was not observed any polymer adhesion to the reactor.
As a result, there was obtained 43.6 g of polyethylene powder in particulate form~having a [ n ] Of 46 dl/g a bulk density of 0.13 g/ml.
Examp_e 17 (1) Copolymerization of ethylene and 1-octene A one (1) liter dry polymerization reactor equipped with a stirrer the inside of which had been purged with dry nitrogen was charged with 360 ml of dry n-hexane, A0 ml of 1-octene and 1.0 ml of 1.0 mol/liter of triisobutylaluminum in hexane, followed by raising the temperature of the mixture in the reactor to 60~C. Subsequently, 25.0 ml (40 micromol of Ti) of the solid catalyst slurry as prepared in Example 16 - 39 ~
~ 21 ~43~r~
(1) was placed in the polymeriæation reactor. Immediately thereafter, the reaction system was heated to raise the temperature up to 80C and pressurized with ethylene so as to maintaln the total internal pressure in the polymerization reactor at 8 kg/cm G, to proceed with polymerization at 80C
for one hour.
After the completion of polymerization, the reactor was immediately depressurized and charged with methanol to arrest polymerization.
There was not observed any polymer adhesion to the reactor.
As a result, there was obtained 42.9 g of ethylene/octene copolymer in particulate form having a [ n ] f 41 dl/g, a bulk density of 0.15 g/ml, 1-octene unit content of 0.5 mole% and a melting point of 127C.
Comparative Example 7 (1) Pr~aparation of mixed liquid of catalyst components To 129 ml of toluene were added 3.0 ml of 1.0 mole/liter solution of triisobutylaluminum in hexane and 3 ml of 0.1 mole/liter solution of tetra-n-butoxytitanium in hexane with stirring for 10 minutes, and then 15 ml of 1.0 mole/lLter dispersion liquid of the above-mentioned methylaluminoxane in hexane as the dispersant wlth stirring for one (1) hour.
(2) Copolylmerization of ethylene and 1-octene The procedure in Example 17 was repeated except the use of 20.0 ml (40 micromol of Ti) of the mixed liquid of catalyst components as prepared in the preceding item (1~.
-- ~0 --However, after an elapse of 30 minutes from the start of the polymerization, the polymerization was discontinued because of impossibility of the temperature control. On opening the polymerization reactor, there was observed 35.2 g of agg:Lomerate polymer which adhered to the walls and impellers of the reactor.
INDUSTRIAL APPLICABILITY
As described hereinbefore, the present invention enables to contrive to improve the powder morphology of the produced polymer and facilitate the regulation of the molecular weight distribution thereof and besides to efficiently and stably produce a high molecular weight polyolefin having excellent particle shape with minimized adhesion of the resultant polymer to the polymerization reactor.
Thus, the process according to the present invention is preferably applicable to the production of ethylenic polymers such as polyolefin, especially low-density linear polyolefin, thereby rendering itself extremely valueable in utilization.
Claims
CLAIMS:
(1) A process for producing a polyolefin which comprises polymerizing an olefin by the use of a catalyst comprising (A) a transition metal compound having a group with conjugated .pi. electron as a ligand; (B) an aluminoxane; and (C) a magnesium compound represented by the general formula Mg(OR)nX12-n wherein R is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, X1 is a halogen atom, and n is a number from 1 to 2.
(2) A process for producing a polyolefin which comprises polymerizing an olefin by the use of a catalyst comprising (A) a transition metal compound having a group with conjugated .pi. electron as a ligand; (B) an aluminoxane; (C) a magnesium compound represented by the general formula Mg(OR)nX12-n wherein R is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, X1 is a halogen atom, and n is number from 1 to 2; and (D) an organoaluminum compound.
(3) The process according to Claim 1 or 2 wherein hydrogen is added in the reaction system at the time of the polymelrization reaction.
(4) A process for producing a polyolefin which comprises polymerizing an olefin by the use of a catalyst comprising (E) a transition metal compound represented by the general formula M1R1aR2bR3cR4d wherein M1 is a transition metal belonging to the group IVB
in the Periodic table; R1, R2, R3 and R4 are each a .sigma.-bonding ligand, a chelating ligand or a Lewis base and may be the same or different from each other; and a, b, c and d are each an integer from 1 to 4; (B) an aluminoxane; and (C) a magnesium compound represented by the general formula Mg(OR)nX12-n wherein R is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, X1 is a halogen atom, and n is number from 1 to 2.
(5) A process for producing a polyolefin which comprises polymerizing an olefin by the use of a catalyst comprising (E) a transition metal compound represented by the general formula M1R1aR2bR3cR4d wherein M1 is a transition metal belonging to the group IVB
in the Periodic table; R1, R2, R3 and R4 are each a .sigma.-bonding ligand, a chelating ligand or a Lewis base and may be the same or different from each other; and a, b, c and d are each an integer from 1 to 4; (B) an aluminoxane; (C) a magnesium compound represented by the general formula Mg(OR)nX12-n wherein R is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, X1 is a halogen atom, and n is number from 1 to 2; and (D) an organoaluminum compound.
(6) The process according to Claim 1, 2, 4 or 5 wherein the polyolefin is an ethylenic polymer.
(1) A process for producing a polyolefin which comprises polymerizing an olefin by the use of a catalyst comprising (A) a transition metal compound having a group with conjugated .pi. electron as a ligand; (B) an aluminoxane; and (C) a magnesium compound represented by the general formula Mg(OR)nX12-n wherein R is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, X1 is a halogen atom, and n is a number from 1 to 2.
(2) A process for producing a polyolefin which comprises polymerizing an olefin by the use of a catalyst comprising (A) a transition metal compound having a group with conjugated .pi. electron as a ligand; (B) an aluminoxane; (C) a magnesium compound represented by the general formula Mg(OR)nX12-n wherein R is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, X1 is a halogen atom, and n is number from 1 to 2; and (D) an organoaluminum compound.
(3) The process according to Claim 1 or 2 wherein hydrogen is added in the reaction system at the time of the polymelrization reaction.
(4) A process for producing a polyolefin which comprises polymerizing an olefin by the use of a catalyst comprising (E) a transition metal compound represented by the general formula M1R1aR2bR3cR4d wherein M1 is a transition metal belonging to the group IVB
in the Periodic table; R1, R2, R3 and R4 are each a .sigma.-bonding ligand, a chelating ligand or a Lewis base and may be the same or different from each other; and a, b, c and d are each an integer from 1 to 4; (B) an aluminoxane; and (C) a magnesium compound represented by the general formula Mg(OR)nX12-n wherein R is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, X1 is a halogen atom, and n is number from 1 to 2.
(5) A process for producing a polyolefin which comprises polymerizing an olefin by the use of a catalyst comprising (E) a transition metal compound represented by the general formula M1R1aR2bR3cR4d wherein M1 is a transition metal belonging to the group IVB
in the Periodic table; R1, R2, R3 and R4 are each a .sigma.-bonding ligand, a chelating ligand or a Lewis base and may be the same or different from each other; and a, b, c and d are each an integer from 1 to 4; (B) an aluminoxane; (C) a magnesium compound represented by the general formula Mg(OR)nX12-n wherein R is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, X1 is a halogen atom, and n is number from 1 to 2; and (D) an organoaluminum compound.
(6) The process according to Claim 1, 2, 4 or 5 wherein the polyolefin is an ethylenic polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002114317A CA2114317A1 (en) | 1992-08-26 | 1992-08-26 | Process for producing polyolefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002114317A CA2114317A1 (en) | 1992-08-26 | 1992-08-26 | Process for producing polyolefin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2114317A1 true CA2114317A1 (en) | 1994-03-03 |
Family
ID=4152801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002114317A Abandoned CA2114317A1 (en) | 1992-08-26 | 1992-08-26 | Process for producing polyolefin |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2114317A1 (en) |
-
1992
- 1992-08-26 CA CA002114317A patent/CA2114317A1/en not_active Abandoned
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