CN1703430A - Preparation of catalyst compositions having improved activity - Google Patents

Preparation of catalyst compositions having improved activity Download PDF

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CN1703430A
CN1703430A CN 200380100985 CN200380100985A CN1703430A CN 1703430 A CN1703430 A CN 1703430A CN 200380100985 CN200380100985 CN 200380100985 CN 200380100985 A CN200380100985 A CN 200380100985A CN 1703430 A CN1703430 A CN 1703430A
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catalyst
compound
alkyl
halo
indenyl
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CN1319998C (en
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K·罗兰德
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Basell Polyolefine GmbH
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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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • 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
    • 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
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
    • 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
    • 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
    • C08F4/6592—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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The present invention relates to a process for preparing a catalyst composition for olefin polymerization, which comprises preparing a catalyst solid in a first step by bringing A) at least one support, B) at least one organic compound having at least one functional group containing active hydrogen, C) at least one organometallic compound and D) at least one organic transition metal compound into contact with one another, then bringing this catalyst solid into contact with E) at least one organoaluminum compound in a second step and then using this mixture for the polymerization without further work-up. In addition, the invention relates to catalyst system for the polymerization of olefins which comprise such catalyst compositions, to the use of the catalyst compositions or the catalyst systems for the polymerization of olefins and to a process of the polymerization of olefins.

Description

Preparation with active catalyst composition of raising
The present invention relates to the method that a kind of preparation is used for the catalyst composition of olefinic polymerization, wherein in first step by with at least a carrier, at least aly have at least one organic compound that contains the functional group of active hydrogen, at least a organometallic compound and at least a organo-transition metal compound and contact with each other and prepare catalyst solid, in second step, this catalyst solid is contacted with at least a organo-aluminium compound then, subsequently this mixture is used for polymerization and does not need further processing.The invention further relates to the catalyst system that is used for olefinic polymerization that comprises this catalyst composition, they are used for the purposes of olefinic polymerization and a kind of method of olefinic polymerization.
Organo-transition metal compound for example metallocene complex can synthesize the polyolefine that uses traditional ZieGler-Natta catalyzer not obtain of crucial importancely as the catalyzer that is used for olefinic polymerization because they make.For example, this single-point catalyst has obtained having narrow molar mass distribution and the even polymkeric substance that inserts of comonomer.For these can be successfully used to the polymerization process of gas phase or suspension, usually advantageously: metallocene will use with solid form, be about to them and be applied on the solid carrier.In addition, the catalyzer of the load polymkeric substance that should show high throughput and obtain having good form.
For make organo-transition metal compound for example metallocene complex be actively with acting on the catalyzer of olefinic polymerization, they must with other compound reaction as promotor.Often the promotor kind of using by aikyiaiurnirsoxan beta for example methylaluminoxane (MAO) form.Yet these have such shortcoming: they must big excessive use.In addition, the compound that organo-transition metal compound is changed into cationic complex also can be used as promotor, and these can use with stoichiometry or in fact stoichiometric ratio.
For example, WO99/40129, WO00/62928 and WO01/47635 disclosed can by with carrier, organic compound, organometallic compound and organo-transition metal compound with functional group of containing active hydrogen contact with each other the catalyst system of acquisition.This catalyst system shows high relatively polymerization activity and has obtained having the polymkeric substance of good polymer morphology.
EP-A 1153938 has described such catalyst system: wherein at first by carrier granule and organometallic compound are prepared the carrier of modification with organic compound with functional group of containing active hydrogen or Lewis base reaction.Then the carrier of modification and organo-transition metal compound are contacted with other organometallic compound.
Yet, need to realize that the activity that further improves the catalyst system that uses identical parent material keeps good polymer morphology simultaneously.
The objective of the invention is to find that a kind of preparation is used for the method for the catalyst composition of olefinic polymerization, it makes the catalyst system of the polymerization activity can obtain to have raising, and can not cause the defective about polymer morphology.
We have found that the method that is used for the catalyst composition of olefinic polymerization by a kind of preparation has realized this purpose, this method comprises: prepare catalyst solid by following material is contacted with each other in first step:
A) at least a carrier,
B) at least a have an organic compound that at least one contains the functional group of active hydrogen,
C) at least a organometallic compound and
D) at least a organo-transition metal compound,
In second step, this catalyst solid is contacted with following material then:
E) organo-aluminium compound of at least a formula (I)
AlR 1R 2R 3 (I)
Wherein
R 1Be C 1-C 10Alkyl, C 6-C 15Aryl, halo C 1-C 10Alkyl, halo C 6-C 15Aryl, C 7-C 40Aralkyl, C 7-C 40Alkaryl, C 1-C 10Alkoxyl group or halo C 7-C 40Alkaryl, halo C 7-C 40Aralkyl or halo C 1-C 10Alkoxyl group and
R 2And R 3Identical or different and be hydrogen, halogen, C separately independently of each other 1-C 10Alkyl, C 6-C 15Aryl, halo C 1-C 10Alkyl, halo C 6-C 15Aryl, C 7-C 40Aralkyl, C 7-C 40Alkaryl, C 1-C 10Alkoxyl group or halo C 7-C 40Alkaryl, halo C 7-C 40Aralkyl or halo C 1-C 10Alkoxyl group,
Then this mixture is used for polymerization and is not needed further processing, wherein except component A), B), C) and D) can use F) at least a Lewis base with the preparation catalyst solid, this catalyst solid and organo-aluminium compound E) contact.
In addition, we have found that the catalyst system that is used for olefinic polymerization that comprises this catalyst composition, this catalyst composition or catalyst system are used for purposes and a kind of olefine polymerizing process of olefinic polymerization.
Catalyst composition prepared in accordance with the present invention is applicable to olefinic polymerization and is particularly useful for alpha-olefin, promptly has the polymerization of the hydrocarbon of whole terminal double bond.Suitable monomers also comprises functionalized the alefinically unsaturated compounds for example ester or the amide derivatives of vinylformic acid or methacrylic acid, as acrylate, methacrylic ester or vinyl cyanide.Preferred nonpolar olefinic compounds comprises the alpha-olefin that aryl replaces.Particularly preferred alpha-olefin is the C of linearity or branching 2-C 12-1-alkene, particularly linear C 2-C 10-1-alkene is the C of ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-decene or branching for example 2-C 10-1-alkene is 4-methyl-1-pentene for example, and conjugation and unconjugated diene be 1,3-butadiene for example, and 1,4-hexadiene or 1,7-octadiene or vinyl aromatic compounds be the vinylbenzene of vinylbenzene or replacement for example.
Suitable alkene comprises that also wherein two keys are classes that can have the ring texture part of one or more member ring systems.Example is cyclopentenes, norbornylene, four-ring dodecylene or methyl norbornylene or diene for example 5-ethylidene-2-norbornene, norbornadiene or ethyl norbornadiene.
The mixture of all right two or more alkene of polymerization.
Catalyst composition of the present invention is particularly useful for the polymerization or the copolymerization of ethene or propylene.As the comonomer in the vinyl polymerization, preferably use C 3-C 8-alpha-olefin, particularly 1-butylene, 1-amylene, 1-hexene and/or 1-octene.Preferred comonomer is ethene and/or 1-butylene in the propylene polymerization.
Be used to prepare the component A of catalyst solid) be carrier.Preferred use carrier in small, broken bits, it can be any inert organic or inorganic solid.Especially, carrier component A) can be for example talcum, sheet silicate, inorganic oxide or polymer powder in small, broken bits of porous support.
Can in the middle of the oxide compound of 2,3,4,5,13,14,15 and 16 family's elements of the periodic table of elements, find to be suitable as the inorganic oxide of carrier.Preferred elements calcium, aluminium, silicon, magnesium or titanyl compound or mixed oxide and corresponding oxide mixture.Can be separately or other inorganic oxides that are used in combination with above-mentioned oxidation carrier be ZrO for example 2Or B 2O 3Preferred oxide compound is a silicon-dioxide, particularly with the form of silicon gel or fumed silica, and aluminum oxide.Preferably mixed oxide is, for example the incinerating hydrotalcite.
The solid support material that uses preferably specific surface area is 10-1000m 2/ G is preferably 50-500m 2/ G is in particular 200-400m 2/ G and pore volume are 0.1-5ml/G, are preferably 0.5-3.5ml/G, are in particular 0.8-3.0ml/G.The average particle size particle size of carrier in small, broken bits is generally 1-500 μ m, is preferably 5-350 μ m, is in particular 10-100 μ m.
Inorganic carrier can carry out for example thermal treatment, to remove the water of absorption.This drying treatment is usually at 80-300 ℃, carries out under preferred 100-200 ℃.Preferably under reduced pressure and/or at inert gas flow for example carry out drying in nitrogen or the argon gas.Inorganic carrier can also be calcined, in this case, carrier 200-1000 ℃ handle down with the concentration of regulating OH group on the surface and, if wish, change the solid structure.Can also use for example metal alkyl class of conventional siccative, preferred aluminium alkyls, chlorosilane or SiCl 4, perhaps methylaluminoxane and the carrier chemical is handled.Suitable treatment process is described in, for example among the WO00/31090.
Inorganic carrier material can also chemical modification.For example, use NH 4SiF 6Handle the silicon gel and caused the silicon gel surface to be fluoridized, perhaps obtained the silicon gel surface of corresponding modification with the silane treatment silicon gel that contains nitrogenous, fluorine-containing or sulfur-containing group.
Possible in addition solid support material is a polymer powder in small, broken bits, for example polyolefine such as polyethylene or polyacrylic powder or polystyrene powder.They preferably before using by suitable purifying or drying operation and moisture-free, solvent residues thing or other impurity.Can also use functionalized polymer support, for example based on a class of polystyrene, by its functional group for example ammonium or hydroxyl, at least a catalyst component can be fixed or its functional group can be used as B component simultaneously) or F).
As the B component that is used to prepare catalyst solid), use at least a organic compound that at least one contains the functional group of active hydrogen that comprises.The example of suitable functional group is hydroxyl, primary and secondary amino, sulfydryl, silanol, carboxyl, amido and imino-, preferred hydroxyl.
Preferred compd B) is in particular the compound of formula (II)
(R 4) x-A-(OH) y (II)
Wherein
A is the main group 13,14 or 15 the atom of periodictable or the group that comprises 2-20 carbon atom, is preferably the atom of the main group 13 of periodictable, is in particular boron or aluminium, perhaps partially halogenated or fully halogenated C 1-C 20Alkyl or C 6-C 40Aryl is preferably the atom of the main group 13 of periodictable especially, is preferably boron or aluminium, is in particular boron,
R 4Identical or different and be hydrogen, halogen, C separately independently of each other 1-C 20Alkyl, C 1-C 20Haloalkyl, C 1-C 10Alkoxyl group, C 6-C 20Aryl, C 6-C 20Halogenated aryl, C 6-C 20Aryloxy, C 7-C 40Aralkyl, C 7-C 40Halo aralkyl, C 7-C 40Alkaryl or C 7-C 40Haloalkane aryl or OSiR 5 3Group, wherein
R 5Identical or different and respectively do for oneself hydrogen, halogen, C 1-C 20Alkyl, C 1-C 20Haloalkyl, C 1-C 10Alkoxyl group, C 6-C 20Aryl, C 6-C 20Halogenated aryl, C 6-C 20Aryloxy, C 7-C 40Aralkyl, C 7-C 40Halo aralkyl, C 7-C 40Alkaryl or C 7-C 40The haloalkane aryl,
R 4Be preferably hydrogen, halogen, C 6-C 14Aryl, C 6-C 14Halogenated aryl, C 1-C 14Alkyl, C 1-C 14Haloalkyl, C 7-C 30Aralkyl, C 7-C 30Halo aralkyl, C 7-C 30Alkaryl or C 7-C 30The haloalkane aryl is preferably C especially 6-C 10Aryl, C 6-C 10Halogenated aryl, C 1-C 6Alkyl, C 1-C 6Haloalkyl, C 7-C 20Alkaryl or C 7-C 20The haloalkane aryl,
Y is at least 1, is preferably 1-5, is in particular 1 or 2, very particularly preferably is 1
X is the integer of 0-41, is preferably 2 especially when y=1, is preferably 1 especially when y=2.
The example of preferred formula (II) compound is formula R 4 2The boric acid of B (OH) (borinic acid) or formula R 4B (OH) 2Boric acid (boronic acid).
Particularly preferred B component) also comprises the compound that contains partially fluorinated or whole fluorizated aryl, for example Pentafluorophenol or nine fluorine biphenyl-1-phenol or dihydroxyl octafluoro biphenyl.This compounds B) can also be to use with the adducts form of 1-10 part water.So these are preferably the compound that contains two OH groups, for example 4,4 '-dihydroxyl octafluoro biphenyl-(s-H 2O), 1,2-dihydroxyl octafluoro biphenyl-(s-H 2O), 1,8-dihydroxyl hexafluoro naphthalene-(s-H 2O) or 1,2-dihydroxyl hexafluoro naphthalene-(s-H 2O), wherein s is 1-10.
In addition, in the preparation catalyst solid, at least a organometallic compound is used as component C).
Suitable organometallic compound C) be the compound of formula (III),
M 1(R 6) r(R 7) s(R 8) t (III)
Wherein
M 1Be the metal of 13 families of basic metal, alkaline-earth metal or periodictable, i.e. boron, aluminium, gallium, indium or thallium,
R 6Be hydrogen, C 1-C 10Alkyl, C 6-C 15Aryl, halo C 1-C 10Alkyl, halo C 6-C 15Aryl, C 7-C 40Aralkyl, C 7-C 40Alkaryl, C 1-C 10Alkoxyl group or halo C 7-C 40Alkaryl, halo C 7-C 40Aralkyl or halo C 1-C 10Alkoxyl group,
R 7And R 8Difference hydrogen, halogen, C 1-C 10Alkyl, C 6-C 15Aryl, halo C 1-C 10Alkyl, halo C 6-C 15Aryl, C 7-C 40Aralkyl, C 7-C 40Alkaryl, C 1-C 10Alkoxyl group or halo C 7-C 40Alkaryl, halo C 7-C 40Aralkyl or halo C 1-C 10Alkoxyl group,
R is the integer of 1-3
S and t are the integers of 0-2, and summation r+s+t is corresponding to M 1Valency.
In the middle of the metallic compound of formula (III), preferred M wherein 1Be lithium, boron, magnesium or aluminium and R 6, R 7And R 8C respectively does for oneself 1-C 10Those of alkyl.
The metallic compound of particularly preferred formula (III) is n-Butyl Lithium, normal-butyl n-octyl magnesium, normal-butyl n-heptylmagnesium, triphenyl aluminum, three prenyl aluminium, three-octyl aluminum, three-n-hexyl aluminium, three-n-butylaluminum, triisobutyl aluminium, three-n-propyl aluminium, triisopropylaluminiuand, triethyl aluminum, three-pentafluorophenyl group borine and trimethyl aluminium and composition thereof.
Can also use the mixture of the various metallic compounds of formula (III).
In the preferred embodiment of the inventive method, with the mixture component C that acts on the preparation catalyst solid of at least two kinds of different organometallic compounds).It can be the mixture of the organometallic compound of at least a aluminiferous organometallic compound and at least a boracic.Yet, component C) and can also comprise at least two kinds of different aluminiferous organometallic compounds.In addition, in the preparation catalyst solid, can also will various aluminiferous organometallic compounds be used as component C) together with the mixture of the organometallic compound of boracic.
Can also once a little adds component C in a plurality of steps of preparation catalyst solid) or part component C), promptly can carry out multistep and add the independent organometallic compound or the mixture of organometallic compound.For example, the mixture of organometallic compound or organometallic compound can at first contact with the wherein a kind of of other components, this mixture can be combined with other component then, one or more of these other components can also be with one or more organometallic compound pre-treatment.Yet can also carry out, for example one or more organometallic compound multisteps be added total mixture.
Possible organo-transition metal compound D) be all periodictable 3-12 group 4 transition metals or all compounds of lanthanon in principle, its contain organic group and preferably with component A)-C) be formed for the active catalyst of olefinic polymerization after the reaction.Normally wherein at least one unidentate ligand or polydentate ligand are connected to the compound of central atom by σ or π key for these.Suitable part comprises part that contains cyclopentadienyl group and the part that does not contain cyclopentadienyl group.Chem.Rev.2000, Vol.10, No.4 have described many this Compound D that are applicable to olefinic polymerization).In addition, multinuclear cyclopentadiene base complex also is applicable to olefinic polymerization.
Suitable organo-transition metal compound D) particularly contains those of at least one cyclopentadiene base class part; The compound that contains two cyclopentadiene base class parts is commonly referred to as metallocene complex.The useful especially organo-transition metal compound D that contains at least one cyclopentadiene base class part) is those of formula (IV)
Figure A20038010098500101
Wherein substituting group and index have following implication:
M 1ABe titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, the perhaps element and the lanthanon of periodictable 3 families,
X 1AIdentical or different and be fluorine, chlorine, bromine, iodine, hydrogen, C separately independently of each other 1-C 10Alkyl, C 2-C 10Alkenyl, C 6-C 15Aryl, C 6-C 40Alkaryl, C 7-C 40Aralkyl ,-OR 6AOr-NR 6AR 7APerhaps two radicals X AInterconnection and form, for example replace or unsubstituted diene ligand, particularly 1, the 3-diene ligand, perhaps two aryloxy, wherein
R 6AAnd R 7AEach is C naturally 1-C 10Alkyl, C 6-C 15Aryl, C 7-C 40Aralkyl, C 7-C 40Contain 1-16 carbon atom in alkaryl, each comfortable alkyl and in aryl, contain the fluoro-alkyl or the fluorinated aryl of 6-21 carbon atom,
n ABe 1,2 or 3, n AHave the valent numerical value that depends on M, make the metallocene complex neutral of formula (IV),
R 1A-R 5ABe hydrogen, C separately independently of each other 1-C 22Alkyl, can have C conversely 1-C 10Alkyl is as substituent 5 to 7 yuan cycloalkyl or cycloalkenyl, C 2-C 22Alkenyl, C 6-C 22Aryl, C 7-C 40Aralkyl, C 7-C 40Alkaryl ,-NR 8A 2,-N (SiR 8A 3) 2,-OR 8A,-OSiR 8A 3,-SiR 8A 3, radicals R wherein 1A-R 5ACan also be replaced by halogen and/or two radicals R 1A-R 5A, particularly Lin Jin group can connect so that they form with the atom that connects them and is preferably 5,6 or 7 yuan of rings, perhaps is preferably 5,6 or 7 yuan of heterocycles that contain at least one atom that derives from N, P, O and S, wherein
R 8ACan the identical or different and C that can respectively do for oneself 1-C 10Alkyl, C 3-C 10Cycloalkyl, C 6-C 15Aryl, C 1-C 4Alkoxyl group or C 6-C 10Aryloxy,
Z AAs X ADefine or
Group wherein
R 9A-R 13ABe hydrogen, C separately independently of each other 1-C 22Alkyl, can have C conversely 1-C 10Alkyl is as substituent 5 to 7 yuan cycloalkyl or cycloalkenyl, C 2-C 22Alkenyl, C 6-C 22Aryl, C 7-C 40Aralkyl, C 7-C 40Alkaryl ,-NR 14A 2,-N (SiR 14A 3) 2,-OR 14A,-OSiR 14A 3,-SiR 14A 3, radicals R wherein 1A-R 5ACan also be replaced by halogen and/or two radicals R 1A-R 5A, particularly Lin Jin group can connect so that they form with the atom that connects them and is preferably 5,6 or 7 yuan of rings, perhaps is preferably 5,6 or 7 yuan of heterocycles that contain at least one atom that derives from N, P, O and S, wherein
R 14ACan the identical or different and C that can respectively do for oneself 1-C 10Alkyl, C 3-C 10Cycloalkyl, C 6-C 15Aryl, C 1-C 4Alkoxyl group or C 6-C 10Aryloxy,
Perhaps radicals R 4AAnd Z AFormation-R together 15A vA-A AGroup, wherein
R 15AFor
Figure A20038010098500121
-BR 16A-、-(BNR 16AR 17A)-、-AlR 16A-、-Ge-、-Sn-、-O-、
-S-,-SO-,-SO 2-,-NR 16A-,-CO-,-PR 16A-or-(POR 16A)-,
Wherein
R 16A, R 17AAnd R 18AIdentical or different and respectively do for oneself hydrogen atom, halogen atom, trimethyl silyl, C 1-C 10Alkyl, C 1-C 10Fluoro-alkyl, C 6-C 10Fluorinated aryl, C 6-C 10Aryl, C 1-C 10Alkoxyl group, C 7-C 15Alkyl-aryloxy, C 2-C 10Alkenyl, C 7-C 40Aralkyl, C 8-C 40Aromatic yl alkenyl or C 7-C 40Alkaryl or two adjacent groups form the saturated or undersaturated ring of 4-15 carbon atom with the atom that connects them,
M 2ABe silicon, germanium or tin, preferred silicon,
A ABe-O-,-S-,-NR 19A-,-PR 19A-,-O-R 19A,-NR 19A 2,-PR 19A 2Or do not replace, replacement or condensed heterocycle system, wherein
R 19ABe C separately independently of each other 1-C 10Alkyl, C 6-C 15Aryl, C 3-C 10Cycloalkyl, C 7-C 18Alkaryl or-Si (R 20A) 3,
R 20ABe hydrogen, C 1-C 10Alkyl can have C conversely 1-C 4Alkyl is as substituent C 6-C 15Aryl or C 3-C 10Cycloalkyl,
v ABe 1, if perhaps A AFor do not replace, replacement or condensed heterocycle system, then be 1 or 0,
Perhaps radicals R 4AAnd R 12AFormation-R together 15A-group.
Radicals X in the formula (IV) APreferably identical and be preferably fluorine, chlorine, bromine, C 1-C 7Alkyl or aralkyl are in particular chlorine, methyl or benzyl.
In the middle of the organo-transition metal compound of formula (IV), preferred
Figure A20038010098500132
With
Figure A20038010098500133
In the middle of the compound of formula (IVa), especially preferably wherein
M 1ABe titanium or chromium,
X ABe chlorine, C 1-C 4Alkyl, phenyl, alkoxyl group or aryloxy,
n ABe 1 or 2, and
R 1A-R 5AEach is hydrogen or C naturally 1-C 4Alkyl or two adjacent group R 1A-R 5AForm with the atom that connects them and to replace or those of unsubstituted unsaturated six-ring.
In the middle of the metallocene of formula (IVb), preferably wherein
M 1ABe titanium, zirconium, hafnium or chromium,
X AEach is chlorine, C naturally 1-C 4Alkyl or benzyl, perhaps two radicals X form and replace or unsubstituted divinyl part,
n ABe 1 or 2, be preferably 2, if perhaps M 1ABeing chromium, then is 0,
R 1A-R 5AEach is hydrogen, C naturally 1-C 8Alkyl, C 6-C 10Aryl ,-NR 8A 2,-OSiR 8A 3,-SiR 8A 3Or-Si (R 8A) 3
R 9A-R 13AEach is hydrogen, C naturally 1-C 8Alkyl, C 6-C 10Aryl ,-NR 8A 2,-OSiR 8A 3,-SiR 8A 3Or-Si (R 8A) 3
Perhaps two radicals R 1A-R 5AAnd/or R 9A-R 13AForm those of indenyl system of indenyl or replacement with cyclopentadienyl rings.
Useful especially formula (IVb) compound is identical those of cyclopentadienyl group wherein.
The example of specially suitable formula (IVb) compound is
Two (cyclopentadienyl) zirconium dichloride,
Two (pentamethyl-cyclopentadienyl) zirconium dichloride,
Two (methyl cyclopentadienyl) zirconium dichloride,
Two (ethyl cyclopentadienyl) zirconium dichloride,
Two (n-butyl cyclopentadienyl) zirconium dichloride,
Two (1-normal-butyl-3-methyl cyclopentadienyl) zirconium dichloride,
Two (indenyl) zirconium dichloride,
Two (tetrahydro indenyl) zirconium dichloride and
Two (trimethyl silyl cyclopentadienyl) zirconium dichloride
And corresponding zirconium dimethyl compound.
The metallocene of useful especially formula (IVc) is wherein
R 1AAnd R 9AIdentical or different and respectively do for oneself hydrogen or C 1-C 10Alkyl,
R 5AAnd R 13AIdentical or different and respectively do for oneself hydrogen or methyl, ethyl, sec.-propyl or the tertiary butyl,
R 3AAnd R 11AC respectively does for oneself 1-C 4Alkyl and
R 2AAnd R 10AThe hydrogen of respectively doing for oneself
Perhaps
Two adjacent group R 2AAnd R 3APerhaps R 10AAnd R 11AForm the saturated of 4-44 carbon atom or unsaturated cyclic group together,
R 15ABe-M 2AR 16AR 17A-or-CR 16AR 17A-CR 16AR 17A-or-BR 16A-or-BNR 16AR 17A-,
M 1ABe titanium, zirconium or hafnium,
X AIdentical or different and each chlorine, C naturally 1-C 4Alkyl, benzyl, phenyl or C 7-C 15Those of alkyl-aryloxy.
The formula that is particularly useful (IVc) compound is those of formula (IVc ')
Wherein
Radicals R ' AIdentical or different and respectively do for oneself hydrogen, C 1-C 10Alkyl or C 3-C 10Cycloalkyl, preferable methyl, ethyl, sec.-propyl or cyclohexyl, C 6-C 20Aryl, preferred phenyl, naphthyl or Lay base, C 7-C 40Aralkyl, C 7-C 40Alkaryl, preferred 4-tert-butyl-phenyl or 3,5-di-tert-butyl-phenyl, perhaps C 8-C 40Aromatic yl alkenyl,
R 5AAnd R 13AIdentical and different and respectively do for oneself hydrogen, C 1-C 6Alkyl, preferable methyl, ethyl, sec.-propyl, n-propyl, normal-butyl, n-hexyl or the tertiary butyl,
Ring S and T are saturated, unsaturated or fractional saturation separately independently of each other.
The indenyl of the metallocene of formula (IVc ') or tetrahydro indenyl part be preferably at 2,2,4,4,7,2,4, and 7,2,6,2,4,6,2,5,6,2,4,5,6 or 2,4,5,6,7, be in particular 2,4 replacements, below numbering is used for the position of substitution:
Figure A20038010098500161
As complex compound (IVc '), the preferred two indenyl complex compounds that use with the bridge joint of racemization or vacation-racemization form, vacation-racemization form is wherein when ignoring the every other substituting group of complex compound, two indenyl ligands are relative to each other with the complex compounds of racemization arrangement.
The example of useful especially metallocene (IVc) and (IVc ') comprises
Two (cyclopentadienyl) zirconium dichlorides of dimethylsilane two bases,
Two (indenyl) zirconium dichlorides of dimethylsilane two bases,
Two (tetrahydro indenyl) zirconium dichlorides of dimethylsilane two bases,
Ethylenebis (cyclopentadienyl) zirconium dichloride,
Ethylenebis (indenyl) zirconium dichloride,
Ethylenebis (tetrahydro indenyl) zirconium dichloride,
Tetramethyl-ethylidene-9-fluorenyl cyclopentadiene base zirconium dichloride,
Two (the 3-tertiary butyl-5-methyl cyclopentadienyl) zirconium dichlorides of dimethylsilane two bases,
Two (the 3-tertiary butyl-5-ethyl cyclopentadienyl) zirconium dichlorides of dimethylsilane two bases,
Two (the 2-methyl indenyl) zirconium dichlorides of dimethylsilane two bases,
Two (the 2-sec.-propyl indenyl) zirconium dichlorides of dimethylsilane two bases,
Two (the 2-tertiary butyl indenyl) zirconium dichlorides of dimethylsilane two bases,
Two (2-methyl indenyl) the dibrominated zirconiums of diethylsilane two bases,
Two (3-methyl-5-methyl cyclopentadienyl) zirconium dichlorides of dimethylsilane two bases,
Two (3-ethyl-5-sec.-propyl cyclopentadienyl) zirconium dichlorides of dimethylsilane two bases,
Two (2-ethyl-indenyl) zirconium dichlorides of dimethylsilane two bases,
Two (2-methyl-4, the 5-benzo indenyl) zirconium dichlorides of dimethylsilane two bases,
Two (2-ethyl-4, the 5-benzo indenyl) zirconium dichlorides of dimethylsilane two bases,
Two (2-methyl-4, the 5-benzo indenyl) zirconium dichlorides of aminomethyl phenyl silane two bases,
Two (2-ethyl-4, the 5-benzo indenyl) zirconium dichlorides of aminomethyl phenyl silane two bases,
Two (2-methyl-4, the 5-benzo indenyl) zirconium dichlorides of diphenyl silane two bases,
Two (2-ethyl-4, the 5-benzo indenyl) zirconium dichlorides of diphenyl silane two bases,
Two (the 2-methyl indenyl) hafnium dichloride of diphenyl silane two bases,
Two (the 2-methyl 4-phenyl indenyl) zirconium dichlorides of dimethylsilane two bases,
Two (the 2-ethyl 4-phenyl indenyl) zirconium dichlorides of dimethylsilane two bases,
Two (2-methyl-4-(1-naphthyl) indenyl) zirconium dichlorides of dimethylsilane two bases,
Two (2-ethyl 4-(1-naphthyl) indenyl) zirconium dichlorides of dimethylsilane two bases,
Two (2-propyl group-4-(1-naphthyl) indenyl) zirconium dichlorides of dimethylsilane two bases,
Two (2-isobutyl--4-(1-naphthyl) indenyl) zirconium dichlorides of dimethylsilane two bases,
Two (2-propyl group-4-(9-phenanthryl) indenyl) zirconium dichlorides of dimethylsilane two bases,
Two (2-methyl-4-sec.-propyl indenyl) zirconium dichlorides of dimethylsilane two bases,
Two (2, the 7-dimethyl-4-sec.-propyl indenyl) zirconium dichlorides of dimethylsilane two bases,
Two (2-methyl-4, the 6-di-isopropyl indenyl) zirconium dichlorides of dimethylsilane two bases,
Dimethylsilane two base two (2-methyl-4-[is right-trifluoromethyl] indenyl) zirconium dichloride,
Dimethylsilane two base two (2-methyl-4-[3 ', 5 '-3,5-dimethylphenyl] indenyl) zirconium dichloride,
Dimethylsilane two base two (2-methyl-4-[4 '-tert-butyl-phenyl] indenyl) zirconium dichloride,
Diethylsilane two base two (2-methyl-4-[4 '-tert-butyl-phenyl] indenyl) zirconium dichloride,
Dimethylsilane two base two (2-ethyl-4-[4 '-tert-butyl-phenyl] indenyl) zirconium dichloride,
Dimethylsilane two base two (2-propyl group-4-[4 '-tert-butyl-phenyl] indenyl) zirconium dichloride,
Dimethylsilane two base two (2-sec.-propyl-4-[4 '-tert-butyl-phenyl] indenyl) zirconium dichloride,
Dimethylsilane two base two (2-normal-butyl-4-[4 '-tert-butyl-phenyl] indenyl) zirconium dichloride,
Dimethylsilane two base two (2-hexyl-4-[4 '-tert-butyl-phenyl] indenyl) zirconium dichloride,
Dimethylsilane two bases (2-sec.-propyl-4-phenyl indenyl)-(2-methyl-4-phenyl indenyl) zirconium dichloride,
Dimethylsilane two bases (2-sec.-propyl-4-(1-naphthyl) indenyl)-(2-methyl-4-(1-naphthyl) indenyl) zirconium dichloride,
Dimethylsilane two bases (2-sec.-propyl-4-[4 '-tert-butyl-phenyl] indenyl)-(2-methyl-4-[4 '-tert-butyl-phenyl] indenyl) zirconium dichloride,
Dimethylsilane two bases (2-sec.-propyl-4-[4 '-tert-butyl-phenyl] indenyl)-(2-ethyl-4-[4 '-tert-butyl-phenyl] indenyl) zirconium dichloride,
Dimethylsilane two bases (2-sec.-propyl-4-[4 '-tert-butyl-phenyl] indenyl)-(2-methyl-4-[3 ', 5 '-the dual-tert-butyl phenyl] indenyl) zirconium dichloride,
Dimethylsilane two bases (2-sec.-propyl-4-[4 '-tert-butyl-phenyl] indenyl)-(2-methyl-4-[1 '-naphthyl] indenyl) zirconium dichloride and
Ethylidene (2-sec.-propyl-4-[4 '-tert-butyl-phenyl] indenyl)-(2-methyl-4-[4 '-tert-butyl-phenyl] indenyl) zirconium dichloride
And corresponding zirconium dimethyl, monochloro list (alkyl-aryloxy) zirconium and two (alkyl-aryloxy) zirconium compounds.
The compound of useful especially formula (IVd) be those wherein
M 1AFor titanium or zirconium, be in particular titanium,
X AChlorine, C respectively do for oneself 1-C 4Alkyl or phenyl or two radicals X are to replace or unsubstituted divinyl part,
R 15AFor-SiR 16AR 17A-or-CR 16AR 17A-CR 16AR 17A-,
A AFor-O-,-S-or-NR 19A-,
R 1A-R 3AAnd R 5AHydrogen, C respectively do for oneself 1-C 10Alkyl preferable methyl, C 3-C 10Cycloalkyl, C 6-C 15Aryl or-Si (R 8A) 3, perhaps two adjacent groups form the cyclic group of 4-12 carbon atom, especially preferably all R 1A-R 3AAnd R 5ABe methyl.
Another compound of organizing useful especially formula (IVd) comprises wherein
M 1ABe preferred titanium or chromium with oxidation state III,
X AChlorine, C respectively do for oneself 1-C 4Alkyl or phenyl or two radicals X AForm replacement or unsubstituted divinyl part,
R 15AFor-SiR 16AR 17A-or-CR 16AR 17A-CR 16AR 17A-,
A AFor-O-R 19A,-NR 19A 2,-PR 19A 2,
R 1A-R 3AAnd R 5AHydrogen, C respectively do for oneself 1-C 10Alkyl, C 3-C 10Cycloalkyl, C 6-C 15Aryl or-Si (R 8A) 3, perhaps two adjacent groups form those of cyclic group of 4-12 carbon atom.
Can be by known method itself, preferably by the cyclic hydrocarbon negatively charged ion of replacement suitably and synthetic these complex compounds of halide reaction of titanium, zirconium, hafnium, vanadium, niobium, tantalum or chromium.
Suitable preparation method's example especially is described in Journal of OrGanometallicChemistry, and 369 (1989), among the 359-370.
Suitable in addition organo-transition metal compound D) be such metallocene: its contain at least one part that forms by cyclopentadienyl or heterocyclic pentylene base and condense, wherein at least one carbon atom is by heteroatoms, the heterocycle of the heteroatoms of preferred cycle table 15 or 16 families, particularly nitrogen or sulfur.This compound is described in, for example among the WO98/22486.These particularly,
Dimethylsilane two bases (2-methyl-4-phenyl indenyl) (2,5-dimethyl-N-phenyl-4-azepine pentalene) zirconium dichloride,
Two (2-methyl-4-phenyl-4-hydrogen Azulene base) zirconium dichlorides of dimethylsilane two base and
Two (2-ethyl-4-phenyl-4-hydrogen Azulene base) zirconium dichlorides of dimethylsilane two bases.
Be applicable to the other organo-transition metal compound D of the object of the invention) be the transition metal complex that has at least one part in the formula (Va)-(Ve),
Figure A20038010098500201
Wherein transition metal is selected from element ti, Zr, Hf, Sc, V, Nb, Ta, Cr, Mo, W, Fe, Co, Ni, Pd, Pt and thulium.Preferably contain nickel, iron, cobalt or palladium compound as central metal.
E BBe the periodic table of elements 15 family's elements, be preferably N or P, preferred especially N.Two or three atom E in the molecule BCan be identical or different.
Radicals R that can be identical or different in the ligand system of formula (Va)-(Ve) 1B-R 19BAs follows:
R 1BAnd R 4BBe the hydrocarbyl group of hydrocarbyl group or replacement separately independently of each other, preferred adjacent elements E wherein BCarbon atom be connected to hydrocarbyl group at least two carbon atoms,
R 2BAnd R 3BBe the hydrocarbyl group of hydrogen, hydrocarbyl group or replacement, wherein R separately independently of each other 2BAnd R 3BCan also form together and wherein can have one or more heteroatomic member ring systems,
R 6BAnd R 8BBe the hydrocarbyl group of hydrocarbyl group or replacement separately independently of each other,
R 5BAnd R 9BBe the hydrocarbyl group of hydrogen, hydrocarbyl group or replacement separately independently of each other,
R wherein 6BAnd R 5BPerhaps R 8BAnd R 9BCan also form member ring systems together.
R 7BBe the hydrocarbyl group of hydrogen, hydrocarbyl group or replacement, wherein two R separately independently of each other 7ACan also form member ring systems together,
R 10BAnd R 14BBe the hydrocarbyl group of hydrocarbyl group or replacement separately independently of each other,
R 11B, R 12B, R 12B 'And R 13B is the hydrocarbyl group of hydrogen, hydrocarbyl group or replacement separately independently of each other, wherein two or more paired or contiguous radicals R 11B, R 12B, R 12B 'And R 13BCan also form member ring systems together,
R 15BAnd R 18BBe the group of hydrogen, hydrocarbyl group or replacement separately independently of each other,
R 16BAnd R 17BBe the group of hydrogen, hydrocarbyl group or replacement separately independently of each other,
R 19BBe organic group, it forms that 5-7 unit replaces or is unsubstituted, and the heterocyclic system of particularly unsaturated or aromatics is especially with E BForm the pyridine system together,
n 1BBe 0 or 1, work as n 1BThe compound that is 0 up-to-date style (Vc) is a negative charge,
n 2BBe the integer of 1-4, preferred 2 or 3.
The useful especially transition metal complex that has formula (Va)-(Vd) part is for example to have the complex compound of transition-metal Fe, Co, Ni, Pd and the Pt of formula (Va) part.The diimine complex compound of preferred especially Ni or Pd, for example:
Two (2, the 6-diisopropyl phenyl)-2,3-dimethyl diaza divinyl palladium chloride,
Two (diisopropyl phenyl)-2,3-dimethyl diaza divinyl Nickel Chloride,
Two (2, the 6-diisopropyl phenyl)-2,3-dimethyl diaza divinyl dimethyl palladium,
Two (2, the 6-diisopropyl phenyl)-2,3-dimethyl diaza divinyl dimethyl nickel,
Two (2, the 6-3,5-dimethylphenyl)-2,3-dimethyl diaza divinyl palladium chloride,
Two (2, the 6-3,5-dimethylphenyl)-2,3-dimethyl diaza divinyl Nickel Chloride,
Two (2, the 6-3,5-dimethylphenyl)-2,3-dimethyl diaza divinyl dimethyl palladium,
Two (2, the 6-3,5-dimethylphenyl)-2,3-dimethyl diaza divinyl dimethyl nickel,
Two (2-aminomethyl phenyls)-2,3-dimethyl diaza divinyl palladium chloride,
Two (2-aminomethyl phenyls)-2,3-dimethyl diaza divinyl Nickel Chloride,
Two (2-aminomethyl phenyls)-2,3-dimethyl diaza divinyl dimethyl palladium,
Two (2-aminomethyl phenyls)-2,3-dimethyl diaza divinyl dimethyl nickel,
Phenylbenzene-2,3-dimethyl diaza divinyl palladium chloride,
Phenylbenzene-2,3-dimethyl diaza divinyl Nickel Chloride,
Phenylbenzene-2,3-dimethyl diaza divinyl dimethyl palladium,
Phenylbenzene-2,3-dimethyl diaza divinyl dimethyl nickel,
Two (2, the 6-3,5-dimethylphenyl) azacycloalkyl palladium chloride,
Two (2, the 6-3,5-dimethylphenyl) azacycloalkyl Nickel Chloride,
Two (2, the 6-3,5-dimethylphenyl) azacycloalkyl dimethyl palladium,
Two (2, the 6-3,5-dimethylphenyl) azacycloalkyl dimethyl nickel,
1,1 '-the bipyridyl palladium chloride,
1,1 '-the bipyridyl Nickel Chloride,
1,1 '-bipyridyl (dimethyl) palladium or
1,1 '-bipyridyl (dimethyl) nickel.
Useful especially compound (Ve) is to be described in J.Am.Chem.Soc.120, p.4049ff. (1998), J.Chem.Soc., Chem.Commun.1998, those in 849.As the complex compound that preferably has part (Ve), can use 2 of transition-metal Fe, Co, Ni, Pd or Pt, particularly Fe, two (imino-) pyridyl complex compounds of 6-.
Can be used as organo-transition metal compound D) other compound be imino-phenoxide complex compound, its part can be for example by replacing or unsubstituted salicylic aldehyde and primary amine, particularly replace or the preparation of unsubstituted arylamine.Have and in the π system, contain one or more heteroatomic π parts for example assorted (borata) benzene part of boron, pyrryl negatively charged ion or the anionic transition metal complex of phosphorus base also can be used as organo-transition metal compound D).
Be applicable to the transistion metal compound D of the object of the invention) also comprise the monocyclopentadienyl of the replacement of chromium, molybdenum or tungsten, single indenyl, single fluorenyl or heterocyclic pentylene base complex, wherein at least one substituting group on the cyclopentadienyl rings have (rigid) by force give the body official can, it does not pass through sp separately 3The carbon of-hydridization or Siliciumatom combination.Here to containing at least one sp-or sp for the functional main straight key of body 2The carbon atom of-hydridization, preferred 1-3 sp 2The carbon atom of-hydridization.This straight key preferably contains undersaturated pair of key, aromatics or with the heterocyclic system that forms the undersaturated or aromatics of part to body.
In these transistion metal compounds, cyclopentadienyl rings also can be the heterocyclic pentylene ylidene ligands, and promptly at least one carbon atom can be derived from the heteroatoms replacement of 15 or 16 families.In this case, a preferred C 5-ring carbon atom is replaced by phosphorus.Especially, cyclopentadienyl rings is replaced by other alkyl, and it can also form 5 or 6 yuan of rings, for example tetrahydro indenyl, indenyl, benzo indenyl or fluorenyl.
Possible is to contain periodictable 15 or 16 family's elements, not charged functional group to body, for example amine, imines, carboxamide, carboxylicesters, ketone (oxo), ether, thioketones, phosphine, phosphite, phosphine oxide, sulphonyl, sulfanilamide (SN) or do not replace, replacement or undersaturated heterocycle of condensed part or hetero-aromatic ring system.
Here preferably use the monocyclopentadienyl of the replacement of formula (VI), single indenyl, single fluorenyl or heterocyclic pentylene base complex
Figure A20038010098500231
Wherein
M CBe chromium, molybdenum or tungsten
Z CHas formula (VIa)
Wherein variable has following implication:
E 1C-E 5CEach is carbon or be no more than the E of 1 atom naturally 1C-E 5CBe phosphorus or nitrogen,
A CBe-NR 5CR 6C,-PR 5CR 6C,-OR 5C,-SR 5CPerhaps do not replace, replacement or undersaturated heterocycle of condensed part or hetero-aromatic ring system,
R CBe one of them of following groups:
Figure A20038010098500241
And, if A CBe do not replace, replacement or the undersaturated heterocycle of condensed part or aromatic ring system, then R CCan also be
Wherein
L 1C, L 2CBe silicon or carbon,
K CBe 1 or work as A CBe do not replace, when replacement or undersaturated heterocycle of condensed part or aromatic ring system, can also be 0,
X CBe fluorine, chlorine, bromine, iodine, hydrogen, C separately independently of each other 1-C 10Alkyl, C 2-C 10Alkenyl, C 6-C 20Aryl, C 7-C 40Alkaryl ,-NR 15CR 16C,-OR 15C,-SR 15C,-SO 3R 15C,-OC (O) R 15C,-CN ,-SCN, beta-diketon hydrochlorate ,-CO, BF 4 -, PF 6 -Or the not coordination anion of large volume,
R 1C-R 16CBe hydrogen, C separately independently of each other 1-C 20Alkyl, C 2-C 20Alkenyl, C 6-C 20Aryl, C 7-C 40Alkaryl, in moieties, contain 1-10 carbon atom and in aryl moiety, contain alkaryl, the SiR of 6-20 carbon atom 17C 3, organic group R wherein 1B-R 16BCan also be replaced by halogen and radicals R that two paired or contiguous 1C-R 16CCan also connect forming 5 or 6 yuan of rings,
R 17CBe hydrogen, C separately independently of each other 1-C 20Alkyl, C 2-C 20Alkenyl, C 6-C 20Aryl, C 7-C 40Alkaryl and two paired R 17CCan also connect forming 5 or 6 yuan of rings,
n cBe 1,2 or 3
m cBe 1,2 or 3.
Transition metal M cBe preferably chromium especially.
The example of the organo-transition metal compound of formula (VI) is
1-(8-quinolyl)-2-methyl-4-methyl cyclopentadienyl chromium dichloride (III),
1-(8-quinolyl)-3-sec.-propyl-5-methyl cyclopentadienyl chromium dichloride (III),
1-(8-the quinolyl)-3-tertiary butyl-5-methyl cyclopentadienyl chromium dichloride (III),
1-(8-quinolyl)-2,3,4,5-tetramethyl-ring pentadienyl chromium dichloride (III),
1-(8-quinolyl) tetrahydro indenyl chromium dichloride (III),
1-(8-quinolyl) indenyl chromium dichloride (III),
1-(8-quinolyl)-2-methyl indenyl chromium dichloride (III),
1-(8-quinolyl)-2-sec.-propyl indenyl chromium dichloride (III),
1-(8-quinolyl)-2-ethyl-indenyl chromium dichloride (III),
1-(8-quinolyl)-2-tertiary butyl indenyl chromium dichloride (III),
1-(8-quinolyl) benzo indenyl chromium dichloride (III),
1-(8-quinolyl)-2-methyl benzo indenyl chromium dichloride (III),
1-(8-(2-toluquinoline base))-2-methyl-4-methyl cyclopentadienyl chromium dichloride (III),
1-(8-(2-toluquinoline base))-2,3,4,5-tetramethyl-ring pentadienyl chromium dichloride (III),
1-(8-(2-toluquinoline base)) tetrahydro indenyl chromium dichloride (III),
1-(8-(2-toluquinoline base)) indenyl chromium dichloride (III),
1-(8-(2-toluquinoline base))-2-methyl indenyl chromium dichloride (III),
1-(8-(2-toluquinoline base))-2-sec.-propyl indenyl chromium dichloride (III),
1-(8-(2-toluquinoline base))-2-ethyl-indenyl chromium dichloride (III),
1-(8-(2-toluquinoline base))-2-tertiary butyl indenyl chromium dichloride (III),
1-(8-(2-toluquinoline base)) benzo indenyl chromium dichloride (III) or
1-(8-(2-toluquinoline base))-2-methyl benzo indenyl chromium dichloride (III).
It is known for a long time to prepare functional cyclopentadienyl ligands.Various synthesis paths to the part of these complexings for example are described in Chem.Ber. (1996) by M.Enders etc., and 129,459-463 perhaps is described in J.OrGmet.Chem. (1995) by P.Jutzi and U.SiemelinG, and 500, among the 175-185.
Metal complex, particularly chromium complex can by make suitable metal-salt for example metal chloride and part anionic reactive (for example, by with DE-A 19710615 in the similar method of embodiment) and obtain in simple mode.
Be applicable to the other transistion metal compound D of the object of the invention) be the imino-chromium cpd of formula (VII):
Figure A20038010098500261
Wherein variable has following implication:
R DBe R 1DC=NR 2D, R 1DC=O, R 1DC=O (OR 2D), R 1DC=S, (R 1D) 2P=O, (OR 1D) 2P=O, SO 2R 1D, R 1DR 2DC=N, NR 1DR 2DOr BR 1DR 2D, C 1-C 20Alkyl, C 1-C 20Cycloalkyl, C 2-C 20Alkenyl, C 6-C 20Aryl, C 7-C 40Alkaryl, hydrogen, if it is connected on the carbon atom, organic group R wherein 1DAnd R 2DCan also have inert substituent,
X DBe independently of each other separately fluorine, chlorine, bromine, iodine ,-NR 3DR 4D,-NP (R 3D) 3,-OR 3D,-OSi (R 3D) 3,-SO 3R 3D,-OC (O) R 3D, beta-diketon hydrochlorate, BF 4 -, PF 6 -Or the weak coordination of large volume or coordinate negatively charged ion not,
R 1D-R 4DBe C separately independently of each other 1-C 20Alkyl, C 2-C 20Alkenyl, C 6-C 20Aryl, C 7-C 40Alkaryl, hydrogen, if it is connected on the carbon atom, organic group R wherein 1D-R 4DCan also have inert substituent,
n DBe 1 or 2,
m DBe 1,2 or 3 and depend on the valency of Cr and make that the metallocene complex of formula (VII) is not electrically charged,
L DIt is the not charged body of giving
y DBe 0-3.
The preparation of these compounds and they for example is described among the WO01/09148.
Suitable organo-transition metal compound D in addition) be the transition metal complex that has three tooth macrocyclic ligands, for example
[1,3,5-three (methyl)-1,3,5-Trianacyclohexane] chromium trichloride,
[1,3,5-three (ethyl)-1,3,5-Trianacyclohexane] chromium trichloride,
[1,3,5-three (octyl group)-1,3,5-Trianacyclohexane] chromium trichloride,
[1,3,5-three (dodecyl)-1,3,5-Trianacyclohexane] chromium trichloride and
[1,3,5-three (benzyl)-1,3,5-Trianacyclohexane] chromium trichloride.
The mixture that can also use various organo-transition metal compounds is as component D).
In preferred embodiments, Lewis base is used as the other component F that is used for preparing catalyst solid), this catalyst solid and organo-aluminium compound E) contact.Suitable Lewis base F) have formula (VIII),
M 2R 9R 10R 11 (VIII)
Wherein
R 9, R 10And R 11Identical or different and respectively do for oneself hydrogen atom, C 1-C 20Alkyl, C 1-C 20Haloalkyl, C 6-C 40Aryl, C 6-C 40Halogenated aryl, C 7-C 40Alkaryl or C 7-C 40Aralkyl, and two groups or three all radicals R 9, R 10And R 11Can pass through C 2-C 20Carbon unit is interconnection,
M 2It is the element of the periodic table of elements 15 families.
R 9, R 10And R 11C preferably respectively does for oneself 1-C 20Alkyl, C 6-C 40Aryl or C 7-C 40Alkaryl.Preferred especially at least one radicals R 9, R 10Or R 11Be C 7-C 40Aralkyl, for example benzyl.
M 2Be preferably nitrogen or phosphorus, be in particular nitrogen.
As component F) the example of Lewis base be methylamine, aniline, dimethylamine, diethylamine, methylphenylamine, pentanoic, Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine, N, accelerine, N, N-Diethyl Aniline and N, N-dimethylcyclohexylamine.Particularly preferred Lewis base is, for example benzylamine, N-benzyldimethylamine, N-benzyl diethylamine, N-benzyl butylamine, N-benzyl TERTIARY BUTYL AMINE, N '-benzyl-N, N-dimethyl ethylene diamine, N-benzyl ethylene diamine, N-benzyl Isopropylamine, N-benzyl methylamine, N-benzyl ethamine, N-benzyl-1-phenyl-ethyl amine, N-benzyl-2-phenyl-ethyl amine and N-benzyl diethylenediamine.
According to the present invention, preparation and organo-aluminium compound E) method of the catalyst solid that contacts is by with component A)-D) and if you are using, and F in addition then) contact with each other and carry out with any order.All components can add separately continuously, but also single component can be mixed at first mutually, then these mixtures is contacted with other mixture and/or single component.
The optimal way that component is contacted with each other comprises: at first make the organic compound B with at least one functional group of containing active hydrogen) with organometallic compound C), with part organometallic compound C) or, when using the mixture of various organometallic compounds, with at least a component C) composition contact.
Usually carrier A therein), the organic solvent that suspends of the catalyst solid of the reaction product of carrier or formation exists down the component combination.Suitable solvent is aromatics or aliphatic solvents, and for example hexane, heptane, toluene or dimethylbenzene, perhaps halogenated hydrocarbon is methylene dichloride or halogenated aromatic hydrocarbon neighbour-dichlorobenzene for example for example.
Usually at-20 ℃-150 ℃, under preferred 0 ℃-100 ℃ temperature with the component combination.When not all component simultaneously in conjunction with the time, in each case, can be identical with the temperature in the component bonded single step.Yet the temperature of single step also can be different.
Allow the time of the component reaction that contacted with each other to be generally 1 minute-48 hours.Preferred 10 minutes-6 hours reaction times.When component in a step-wise fashion in conjunction with the time, the reaction times of single step was generally 1 minute-6 hours, preferred 10 minutes-2 hours.
Any employed Lewis base F) and compd B) mol ratio be preferably 0.05: 1-2: 1, be in particular 0.1: 1-1: 1.
Organo-transition metal compound D) and compd B) the mol ratio of the functional group of containing active hydrogen be preferably 1: 0.1-1: 1000, be in particular 1: 1-1: 100.
At component A) if-D) and use, then also have F) in conjunction with after the reaction product that obtains can be solid, wet solid or suspension.In second step that is used to prepare catalyst composition, i.e. reaction product and organo-aluminium compound E) contact, if suitable, this reaction product former state ground can be used with the other component of catalyst system.This reaction product is usually preferred by with solid drying and preprocess.Solid can for example separate from liquid phase by filtering and/or cleaning in advance.Yet, also can solvent be taken out fully by evaporation.Dry carry out being higher than under the temperature of room temperature usually.Preferably during drying use vacuum.In second step of preparation catalyst composition, the exsiccant catalyst solid can former state or the form use to suspend again.
In second step of preparation catalyst composition, by making component A) if-D) and use, then also have F) contact with each other the catalyst solid of acquisition and the organo-aluminium compound E of at least a formula (I)) contact.
Organo-aluminium compound E in preferred formula (I)) in, R 1Be C 1-C 10Alkyl is in particular C 3-C 10Alkyl.In addition, preferred R wherein 2And R 3Hydrogen, halogen or C respectively do for oneself 1-C 10Alkyl is in particular hydrogen or C 3-C 10The organo-aluminium compound E of the formula of alkyl (I)).Especially preferred R wherein 1, R 2And R 3Identical and the C that respectively does for oneself 3-C 10The organo-aluminium compound E of the formula of alkyl (I)).
Can also use the organo-aluminium compound E of various formulas (I)) mixture.
The organo-aluminium compound E of particularly preferred formula (I)) is three prenyl aluminium, tri-n-octylaluminium, tri-n-hexyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-n-propyl aluminum, triisopropylaluminiuand and its mixture.
Allow by with component A) if-D) and use, then also have F) contact with each other the catalyst solid and the organo-aluminium compound E of acquisition) time of interreaction was generally 0.5 minute-10 hours.Preferred 1 minute-2 hours reaction times.Catalyst solid and organo-aluminium compound E) usually at-10 ℃-80 ℃, contact with each other under preferred 15 ℃-75 ℃ temperature.
In addition, can be at first with catalyst solid at itself and organo-aluminium compound E) contact before or after and and alpha-olefin, preferred linear C 2-C 10Gained pre-polymerized catalyst solid is used in-1-alkene, particularly ethene or propylene prepolymerization then in actual polymerization.The catalyst solid that in prepolymerization, uses be aggregated to above monomeric mass ratio be generally 1: 0.1-1: 200.
In addition, a small amount of alkene as modified component, preferred alpha-olefin is vinyl cyclohexane, vinylbenzene or phenyl dimethyl vinyl silanes for example, and antistatic compound or suitable inert compound for example wax or oil can or add as additive during the preparation catalyst composition afterwards.Additive and organo-transition metal compound D) mol ratio be generally 1: 1000-1000: 1, preferred 1: 5-20: 1.
Catalyst composition prepared in accordance with the present invention can former state or with the catalyst system of other component as for olefines polymerization.If this catalyst system comprises the other component except catalyst composition prepared in accordance with the present invention, then they comprise further that preferably at least a scavenging agent is as component G).For the purposes of the present invention, term " scavenging agent " is meant: monomer with by component A) if-E) and use, then also have F) join the organometallic compound that is used for the polymeric monomer before the catalyst composition contact of preparation.Suitable organometallic compound G) be in particular the organometallic compound of formula (III), promptly be used to prepare the organometallic compound C of catalyst solid) also can be used as scavenging agent G), preferred organometallic compounds C) also be preferred scavenging agent G).
Can be used for the popular response device of olefinic polymerization, in body, suspension, gas phase or supercritical medium, carry out polymerization in known manner.Can or preferably carry out continuously in one or more stage discontinuous.The gas phase process of solution methods, suspension process, stirring or phase fluidised bed processes all are possible.As solvent or suspension medium, can use for example Trimethylmethane of unreactive hydrocarbons, perhaps monomer they itself.
Can under the pressure of-60-300 ℃ and 0.5-3000 crust, carry out polymerization.Preferred 50-200 ℃ temperature is in particular the pressure of 60-100 ℃ and 5-100 crust, is in particular the 15-70 crust.Mean residence time is generally 0.5-5 hour, preferred 0.5-3 hour.Can also be with molar mass regulator hydrogen for example, perhaps conventional additives for example static inhibitor be used for polymerization.
The inventive method that is used to prepare the catalyst composition of for olefines polymerization makes and can obtain to have highly active catalyst system, and impact polymer form on the contrary not.
Embodiment
Embodiment 1
A) preparation catalyst solid
In 13ml toluene, the trimethyl aluminium solution of 20% weight concentration of 1ml in the hydrocarbon mixture of high boiling point dearomatization at room temperature reacts with two (pentafluorophenyl group) boric acid (borinicacid) of 1.5G.After stirring 1 hour, solution is added in 0.3ml dimethyl benzylamine and the suspension of 1.5G silica gel (deriving from the XPO2107 of Grace) in 30ml toluene.After stirring 1 hour, by filtering supernatant liquor is separated, with 20ml toluene solid is cleaned twice, then under reduced pressure 50 ℃ of dryings.After solid has been suspended in the 10ml toluene again, add the triisobutyl aluminum solutions of 50mG dimethylsilane two bases two (2-methyl-4-(4 '-tert-butyl-phenyl) indenyl) solution of zirconium dichloride, the triethyl aluminium solution of 20% weight concentration of 0.25ml in the hydrocarbon mixture of high boiling point dearomatization and 20% weight concentration of 0.44ml in the hydrocarbon mixture of high boiling point dearomatization.Be under the room temperature to stir after 1 hour, under reduced pressure at 50 ℃ with solid drying.
B) activation
With 55mG embodiment 1a) in the triisobutyl aluminum solutions of catalyst solid 20% weight concentration in the hydrocarbon mixture of high boiling point dearomatization of preparation with 10ml heptane and 8ml mix, and under 20 ℃ with gained suspension stirring 10 minutes.
C) polymerization
At first with propylene exsiccant 51 reactors are washed the hydrogen that 31 liquid propenes and 1.5 standards of packing into then rise subsequently with nitrogen.Subsequently by lock with embodiment 1b) in the catalyst composition suspension of preparation do not need further processing to introduce reactor, and wash with the 10ml heptane.Reaction mixture was heated to 65 ℃ polymerization temperature and polymerization 1 hour.This has obtained 750G powdered polypropylene, corresponding to the productivity of 13.6kGPP/G catalyst solid.
Comparative example
At first with propylene exsiccant 51 reactors are washed the hydrogen that 3l liquid propene and 1.5 standards of packing into then rise subsequently with nitrogen.The triisobutyl aluminum solutions that adds 20% weight concentration of 8ml in the hydrocarbon mixture of high boiling point dearomatization, and with this mixture stirring 15 minutes.Subsequently by lock with 55mG embodiment 1a) in the suspension of catalyst solid in the 10ml heptane of preparation add reactor, and wash with the 10ml heptane.Reaction mixture was heated to 65 ℃ polymerization temperature and polymerization 1 hour.This has obtained 374G powdered polypropylene, corresponding to the productivity of 6.8kGPP/G catalyst solid.
Embodiment 2
Repeat embodiment 1, except in the preparation catalyst solid, two (2-methyl-4-phenyl indenyl) zirconium dichlorides of 42mG dimethylsilane two bases being used as metallocene and using the trimethyl aluminium solution of 20% weight concentration of 0.32ml in the hydrocarbon mixture of high boiling point dearomatization to replace triethyl aluminum and the triisobutyl aluminium.
This has obtained 870G powdered polypropylene, corresponding to the productivity of 14.1kGPP/G catalyst solid.
Embodiment 3
Repeat embodiment 2, except in activation, using the triisobutyl aluminum solutions of 20% weight concentration of 12ml in the hydrocarbon mixture of high boiling point dearomatization.
This has caused the productivity of 15.8kGPP/G catalyst solid.
Embodiment 4
Repeat embodiment 2, carry out the polymerization except not adopting hydrogen.
This has caused the productivity of 8.6kGPP/G catalyst solid.
Embodiment 5
Repeat embodiment 2, except in activation, using the tri-n-octylaluminium solution of 20% weight concentration of 12.9ml in hexane.
This has caused the productivity of 7.23kGPP/G catalyst solid.
Embodiment 6
Repeat embodiment 2, except the triisobutyl aluminum solutions that in activation, only uses 20% weight concentration of 6ml in the hydrocarbon mixture of high boiling point dearomatization and in polymerization with remaining 2ml as the scavenging agent, this 2ml triisobutyl aluminum solutions is introduced reactor after reactor has been packed liquid propene and hydrogen into, before adding catalyst composition mixture was stirred 15 minutes.
This has caused the productivity of 15.5kGPP/G catalyst solid.

Claims (10)

1. method for preparing the catalyst composition that is used for olefinic polymerization, it comprises: prepare catalyst solid by following material is contacted with each other in first step:
A) at least a carrier,
B) at least a have an organic compound that at least one contains the functional group of active hydrogen,
C) at least a organometallic compound and
D) at least a organo-transition metal compound,
In second step, this catalyst solid is contacted with following material then:
E) organo-aluminium compound of at least a formula (I)
AlR 1R 2R 3 (I)
Wherein
R 1Be C 1-C 10Alkyl, C 6-C 15Aryl, halo C 1-C 10Alkyl, halo C 6-C 15Aryl, C 7-C 40Aralkyl, C 7-C 40Alkaryl, C 1-C 10Alkoxyl group or halo C 7-C 40Alkaryl, halo C 7-C 40Aralkyl or halo C 1-C 10Alkoxyl group and
R 2And R 3Identical or different and be hydrogen, halogen, C separately independently of each other 1-C 10Alkyl, C 6-C 15Aryl, halo C 1-C 10Alkyl, halo C 6-C 15Aryl, C 7-C 40Aralkyl, C 7-C 40Alkaryl, C 1-C 10Alkoxyl group or halo C 7-C 40Alkaryl, halo C 7-C 40Aralkyl or halo C 1-C 10Alkoxyl group,
Then this mixture is used for polymerization and does not further process.
2. preparation as claimed in claim 1 is used for the method for the catalyst composition of olefinic polymerization, wherein before reaction product is used for polymerization, down will be by making component A at-10 ℃-80 ℃), B), C) and D) contact with each other the catalyst solid and the organo-aluminium compound E of acquisition) contacted with each other 0.5 minute-10 hours.
3. preparation as claimed in claim 1 or 2 is used for the method for the catalyst composition of olefinic polymerization, wherein except component A), B), C) and D) also will
F) at least a Lewis base
Be used to prepare catalyst solid, this catalyst solid and organo-aluminium compound E) contact.
4. each described preparation is used for the method for the catalyst composition of olefinic polymerization as claim 1-3, wherein at the organo-aluminium compound E of formula (I)) in, R 1Be C 3-C 10Alkyl, R 2And R 3Each is hydrogen or C naturally 3-C 10Alkyl.
5. catalyst system that is used for olefinic polymerization comprises the catalyst composition as claim 1-4 preparation as described in each.
6. the catalyst system that is used for olefinic polymerization as claimed in claim 5, it further comprises:
G) at least a other organometallic compound is as scavenging agent,
Monomer they with as claim 1-4 as described in each catalyst composition of preparation contact with this scavenging agent before contacting.
As claim 1-4 as described in each catalyst composition of preparation be used for the purposes of olefinic polymerization.
8. the purposes that is used for olefinic polymerization as claim 5 or 6 described catalyst systems.
9. olefine polymerizing process wherein uses the catalyst composition as claim 1-4 preparation as described in each.
10. an olefine polymerizing process wherein uses as claim 5 or 6 described catalyst systems.
CNB2003801009855A 2002-11-04 2003-11-03 Preparation of catalyst compositions having improved activity Expired - Fee Related CN1319998C (en)

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DE2002151491 DE10251491A1 (en) 2002-11-04 2002-11-04 Olefin polymerization catalyst production involves mixing carrier, active hydrogen compound, organometallic compound and organo-transition metal compound to give a solid which is contacted with organoaluminum compound
US60/429,495 2002-11-27

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105764931A (en) * 2014-11-06 2016-07-13 株式会社Lg化学 Metallocene catalyst for preparing high-molecular polyolefin, and method for preparing same

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IT1264680B1 (en) * 1993-07-07 1996-10-04 Spherilene Srl SUPPORTED CATALYSTS FOR THE POLYMERIZATION OF OLEFINS
GB9918668D0 (en) * 1999-08-06 1999-10-13 Bp Chem Int Ltd Polymerisation catalysts
DE19962814A1 (en) * 1999-12-23 2001-06-28 Targor Gmbh Catalyst system, useful for the production of polyolefins, comprises a metallocene, a Lewis base, a support and a compound containing at least one Group 3 element

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105764931A (en) * 2014-11-06 2016-07-13 株式会社Lg化学 Metallocene catalyst for preparing high-molecular polyolefin, and method for preparing same
US9884926B2 (en) 2014-11-06 2018-02-06 Lg Chem, Ltd. Metallocene catalyst for preparing a high molecular weight polyolefin and a preparation method thereof
CN105764931B (en) * 2014-11-06 2018-05-25 株式会社Lg化学 It is used to prepare metallocene catalyst of high molecular polyolefine and preparation method thereof

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