CN1541229A - Olefin polymerization catalyst - Google Patents

Olefin polymerization catalyst Download PDF

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CN1541229A
CN1541229A CNA028084799A CN02808479A CN1541229A CN 1541229 A CN1541229 A CN 1541229A CN A028084799 A CNA028084799 A CN A028084799A CN 02808479 A CN02808479 A CN 02808479A CN 1541229 A CN1541229 A CN 1541229A
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hydrogen
perhaps
alkyl
another
halogen
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A・M・A・本内特
A·M·A·本内特
施菲诺
R·S·施菲诺
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/06—Cobalt compounds
    • C07F15/065—Cobalt compounds without a metal-carbon linkage
    • 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
    • C08F4/70—Iron group metals, platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/02—Iron compounds
    • C07F15/025—Iron compounds without a metal-carbon linkage
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/11—Compounds covalently bound to a solid support

Abstract

An olefin polymerization catalyst component is prepared by making a solution of a transition metal complex of a selected tridentate ligand, adsorbing the complex onto a silica or silica-alumina support, and separating the solution from the supported transition metal complex component, which is storage stable. Olefin polymerizations with this component may be carried out with high catalyst productivity using cocatalysts such as trialkylaluminum compounds.

Description

Olefin polymerization catalysis
FIELD OF THE INVENTION
The present invention relates to a kind of olefin polymerization catalysis, it contains the transition metal complex that is selected from tridentate ligand; The olefine polymerizing process that also relates to this catalyzer of methods and applications of making this class catalyzer.
Technical background
Polyolefine is the important commercial project, and many these class polyolefine are to use transition metal complex to make as the part of polymerisation catalyst system.Recently, many interest have been produced for the catalyzer that contains rear transition metal such as Fe, Co, Ni and Pd.A kind of olefin polymerization catalysis of special type contains a kind ofly believes it is the species of tridentate ligand, promptly 2, and 6-pyridine dicarbaldehyde diimine or 2,6-diacylpyridines diimine or their minor variant are typically as the complex compound of iron or cobalt.This class complex compound and they are as olefin polymerization catalysis, the particularly application of ethylene rolymerization catalyst aspect, be described in the patents such as US 5955555, WO 9912981, WO 9946302, WO 9946303, WO 9946304, WO 0069869, WO 0024788, WO 0032641, WO 0050470, WO 0069869 and WO 0069923, all these patents part are illustrated all purposes and are hereby incorporated by just as filling.
The variant of these complex compounds also has been found the dimerization or oligomeric " polymerization " catalyzer that can be used as ethene and other alpha-olefin, produces alpha-olefin and internal olefin.Referring to, for example US6063881, US 6103946, WO 0055216 and WO 0073249, all these patents part are illustrated all purposes and also are hereby incorporated by just as filling.
As to all olefin polymerization catalysis, important consideration is total cost of the required polymerisation catalyst system of per unit weight polyolefine that produces.Another important consideration is the form of the polymer product of acquisition, the particle of whether easy-to-use form such as the non-relatively dust-like that promptly obtains, latter's good fluidity also preferably has higher tap density, and whether can stain the phenomenon of polymerization reactor.
Sometimes the capital cost of polymerizing catalyst is not a transition metal complex itself, but prepares the expense of this catalyzer and/or need be used for the expense of other composition of this catalyst system.Latter event is for the single site catalysts of many what is called such as metallocenes and many catalyzer that contains rear transition metal particularly reality, aikyiaiurnirsoxan beta, particularly methylaluminoxane in a kind of catalyzer in back have confirmed to have good effect, but very expensive, thereby increased the polyolefinic total catalyst system expense of per unit weight that produces compared with other alkylaluminium cpd.
With 2,6-pyridine dicarbaldehyde diimine or 2, the filtering metal complex compound of 6-diacylpyridines diimine, situation generally also is like this when drawing in the reference those disclosed catalyzer in front.Noticed some exceptions, for example by modifying the carrier surface of carried catalyst, can be referring to for example WO 0020467, it part is illustrated all purposes and is hereby incorporated by just as filling.Though disclosed modified carrier allows to use aikyiaiurnirsoxan beta other alkylaluminium cpd in addition to reach good polymerization result in this patent specification.But modify carrier itself and but increased the required total polymerizing catalyst expense of per unit weight polyolefine that produces significantly.
Summary of the invention
The present invention relates to a kind of method for preparing the carrier polymerization catalyst component, it may further comprise the steps:
(a) in a kind of solvent, dissolve 2,6-pyridine dicarbaldehyde diimine or 2, the transition metal complex of 6-diacylpyridines diimine is to form its solution;
(b) said solution is contacted with carrier fill a part time, so that have at least a part of said metal complex to be attracted on the said carrier, this carrier is without the silica of modification or silica-alumina;
(c) alternatively separate said solution and solvent from said carrier; Precondition is not have activator to exist basically in implementation step (a) and (b) and process (c).
Also comprise a kind of the acquisition or catalyzer that available aforesaid method obtains in the present invention.
The present invention further comprises the method for one or more polymerizable olefins classes of polymerization, and it may further comprise the steps:
(a) 2,6-pyridine dicarbaldehyde diimine or 2, the transition metal complex of 6-diacylpyridines diimine are dissolved in a kind of organic solvent to form solution;
(b) said solution is contacted with carrier fill a part time, thereby form the carried catalyst component on the said carrier so that have at least a part of said metal complex to be attracted to, this carrier is silica or silica-alumina;
(c) alternatively from said carried catalyst component, separate said solution and solvent.
(d) under polymerizing condition, said carried catalyst component is contacted with said one or more polymerizable olefins classes and one or more activators, and precondition is not have activator to exist basically in implementation step (a) and (b) and process (c).
These and other characteristic of the present invention and advantage will be read following detailed specification sheets and more easily understanding by those skilled in the art.Be to be appreciated that characteristics more of the present invention are that the purpose of illustrating is described in the context of the embodiment of separating below, also can provide in conjunction with single embodiment.Conversely, for for purpose of brevity, various characteristics of the present invention are to be described in the context of single embodiment, also can be separated to provide or provide with any part bonded form.
Description of Preferred Embodiments
Some terms have been used at this.Wherein some have:
" alkyl " is the univalent perssad that only contains carbon and hydrogen.Example as alkyl can be mentioned unsubstituted alkyl, cycloalkyl and aryl.If not explanation separately, the alkyl here preferably contains 1 alkyl to about 30 carbon atoms.
" alkyl of replacement " here means and contains one or more (type) substituent alkyl, and these substituting groups can not disturb the running of polymerisation catalyst system basically.Suitable substituents can comprise some or all halogen, ester, ketone (oxo), amino, imido grpup, carboxyl, phosphorous acid base, phosphonous acid base, phosphine, phospho acid base, thioether, acid amides, nitrile and ether in some polyreaction.Preferred substituted has halogen, ester, amino, imido grpup, carboxyl, phosphorous acid base, phosphonous acid base, phosphine, phospho acid base, thioether and acid amides when existing.Any substituting group is that this useful problem can decide (for example US 5955555) by the patent disclosure that reference is introduced previously in some cases in what polyreaction, and US 5880241, the latter also illustrates and is hereby incorporated by all purposes as filling part.If not explanation separately, the preferred substituted hydrocarbon radical here contains 1 to about 30 carbon atoms.Comprise in " being substituted " speech and contain one or more heteroatomic chains or ring, heteroatoms has such as nitrogen, oxygen and/or sulphur, and the free valency of substituted hydrocarbon radical can be even to heteroatoms.In the alkyl that replaces, all hydrogen can be substituted, and is for example such in trifluoromethyl.
" (inert) functional group " here is the alkyl group in addition that means alkyl or replacement, it is except that participating in complex compound " absorption " on the carrier (definition below), containing in present method under the residing condition of compound of this group, is inert.This functional group can not disturb basically yet any this functional group described herein be present in wherein compound may with reference to process.Functional group's example comprises halogen (fluorine, chlorine, bromine and iodine) and ether such as-OR 30, OR wherein 30It is the alkyl of alkyl or replacement.May be the functional group near under the situation of transition metal atoms (such as iron atom), this functional group should not have the compound of coordination stronger to transition metal atoms than those demonstrations to the coordination situation of transition metal atoms, and they should not substitute those required part groups in other words.
" alkyl " and " alkyl of replacement " has their common meanings (referring to above-mentioned explanation to replacement one speech in the alkyl that replaces).Unless otherwise indicated, the alkyl of alkyl and replacement preferably contains 1 to about 30 carbon atoms.
" aryl " is to mean the univalent aromatic group, and free valency wherein is to be connected on the carbon atom of aromatic nucleus.The aryl that contains one or more aromatic nucleus can be a condensed, perhaps links together by singly-bound or other group.
" aryl of replacement " mean univalent, by the defined aromatic group that substituting group replaced that those are enumerated in above-mentioned " alkyl of replacement ".Similar in appearance to aryl, the aryl of replacement also can contain one or more aromatic nucleus, condenses mutually together or links together by singly-bound or other group; But, when containing assorted aromatic nucleus in the aryl that replaces, the free valency in the aryl of replacement can be to connect on the heteroatoms (such as nitrogen-atoms) of assorted aromatic nucleus, rather than on the carbon atom.
" activator ", " promotor " or " catalyst activator " be mean one and or multiple compound, they and a kind of transistion metal compound form can the polymerization polymerizable olefins catalyst species.Useful activator comprises alkylaluminium cpd, some boron compound and other alkylating or hydrogenant compound.Typically, be used for the step (a) and (b) of first method and second method and (c) in transistion metal compound be not just can initiated polymerization by the effect of itself, but need just can make activated olefin polymerization catalysis with one or more activators.
" do not have basically activator exist " be mean except, for example, do not have activator to exist beyond being present in the extremely low impurity of concentration in the various components usually.Mean the activatory catalyzer that in upload process, can not produce meaningful quantity, the latter be by transition metal complex and a kind of activator interact and this reactivation process of producing should be preferably when catalyzer is applied in the polymerization process or close on when using and carry out.
" unmodified " carrier (silica or silica-alumina) means carrier and does not contain (no matter be by bonding or be in simply on its surface) such material, and the latter is designed to bonding or causes that transition metal complex sticks on the carrier.This class material comprises the alkylating or hydrogenant compound of alkylaluminium cpd and other, Louis's acids (bonding or be not bonded on the carrier surface) and other similar compounds.Preferably this transition metal, more preferably wherein tridentate ligand do not contain and have been bonded on a kind of like this group, latter's meeting or may react with carrier, thus covalently be bonded on the carrier.For example, hydroxyl (alcohol) not in the preferred part, the latter will react with silica surface.
" alkylaluminium cpd " means has at least an alkyl to be bonded directly to compound on the aluminium.Also can other group of bonding in this compound, such as, for example alkoxyl group, hydride and halogen.Alkylaluminium cpd is an activator.
" silica " or " silica-alumina " is meant such silica or silica-alumina, and they may be dehydrated by heating, also may not have.Preferred this material passes through before any technology as described herein participating in, preferably, and heating and being dewatered to a certain degree.These materials are well-known in polyalcohol catalyst carrier field, and often preferably have high porosity and/or surface-area.They also often have little and/or controllable granular size.
" polyreaction " is to mean on its wide significance, comprises dimerization, oligomeric and polymerization (comprise homopolymerization and copolymerization the two).
" polymerizing condition " here is the condition that means the alkene " polyreaction " that causes with catalyzer, the identical transition metal tridentate ligand complex compound that this catalyzer uses method as described herein to modify.In other words, the used similarity condition of identical complex compound can former report crossed of polymerization catalyst system described herein uses down.This class condition comprises temperature, pressure, suspension medium, polymerization process such as gas phase, liquid phase, continous way, intermittent type etc.Carried catalyst is particularly useful in liquid suspension polymerization and gas phase polymerization.
" absorption " only means first kind of material quilt " attraction " here to second kind of material, thereby make first kind of material " glue " on second kind of material (being partially at least), even, for example, the first kind of material that is adsorbed is also to be like this under the condition that the solvent that first kind of material arranged exists.Here " absorption " speech is not related to any first kind of material and can be adhered to second kind of culvert meaning on the material.
" relatively not coordinate " (or weak coordinate) negatively charged ion is to mean those general negatively charged ion of indication in this field by this way, and the coordination ability of this anionoid is known, and came into question in the literature, referring to, for example people such as W.Beck is at Chem.Rev., the 88th volume (405-1421 page or leaf (1988) and S.H.Stares, at Chem.Rev., the article of the 93rd volume 927-942 page or leaf (1993), both part illustrate all purposes and all are hereby incorporated by just as filling.In these negatively charged ion, have by those aluminum compound and X in the chapters and sections in front just -The negatively charged ion that forms comprises R 9 3AlX -, R 9 2AlClX -, R 9AlCl 2X -, " R 9AlOX ", R wherein 9It is alkyl.Other useful not coordinate negatively charged ion comprises BAF{BAF=four [3, two (trifluoromethyl) phenyl of 5-] borate }, SbF 6 -, PF 6 -And BF 4 -, trifluoromethyl sulfonic acid, tosilate, (R fSO 2) 2N -And (C 6F 5) 4B -
" three teeth " part is to mean a kind of part that can become tridentate ligand, and promptly it has three positions, often is the heteroatoms position, can be coordinated to simultaneously on the transition metal atoms.Preferred all these three positions are coordinated on the transition metal exactly.
" primary carbon base " here is to mean a general formula to be-CH 2---group, free valency wherein---can link on any other atom, the key of solid line representative then is to be connected on the ring atom of the substituted aryl that the primary carbon base connected.Like this, free valency---can link above hydrogen atom, halogen atom, carbon atom, Sauerstoffatom, the sulphur atom etc. by key.In other words, on the free valency---alkyl can be even got to hydrogen, alkyl, generation or the functional group.The example of primary carbon base comprises-CH 3,-CH 2CH (CH 3) 2,-CH 2Cl ,-CH 2C 6H 5,-OCH 3With-CH 2OCH 3
" secondary carbon back " means group The key of wherein solid line representative is on the atom that is connected on the ring of the substituted aryl that secondary carbon back connects, and two free linkages that dotted line is represented then are connected on the atom or some atoms beyond the dehydrogenation.These atoms or group can be identical or different.In other words, the free valency of dotted line representative can be the alkyl or the inert functional group of alkyl, replacement.The example of secondary carbon back comprises-CH (CH 3) 2,-CHCl 2,-CH (C 6H 5) 2, cyclohexyl ,-CH (CH 3) CH 3And-CH=C CH 3
" tertiary carbon base " means group
Figure A0280847900152
Wherein the key of solid line representative is on the atom that is connected on the ring of the substituted aryl that the tertiary carbon base connected, and three free linkages that dotted line is represented then are connected on the atom or some atoms beyond the dehydrogenation.In other words, these keys of dotted line representative are to be connected on the alkyl or inert functional group of alkyl, replacement.The example of tertiary carbon base comprises-C (CH 3) 3,-C (C 6H 5) 3,-CCl 3,-CF 3,-C (CH 3) 2OCH 3,-C ≡ CH ,-C (CH 3) 2CH=CH 2, aryl and replacement aryl such as phenyl and 1-adamantyl.
Preferred 2,6-pyridine dicarbaldehyde diimine and 2,6-diacylpyridines diamine is the compound with following formula (I):
Wherein:
R 1, R 2, R 3, R 4And R 5Be alkyl or an inertia group of hydrogen, alkyl, replacement independently of one another, precondition is R 1, R 2And R 3In any two groups adjacent one another are can form a ring together;
R 6And R 7Be aryl or a functional group of aryl, replacement.
Typically, the transition metal complex of formula (I) has general formula L MX mY n, wherein L is 2,6-pyridine dicarbaldehyde diimine or 2, and 6-diacylpyridines diimine part, M is a transition metal, and X is single anion (being with a negative charge), and Y is a coordinate single anion not relatively, and m+n equals the oxidation state of M.Typically, if all X are the monodentate negatively charged ion, then the n value is zero, and the m value equals the oxidation state of M.If, for example there is one to be the bidentate single anion among the X, then the n value is 1 (if m+n=2) usually.Like this, m may be 1 or bigger integer, and then the n value can be zero or 1 or bigger integer, and preferred n value is 0 or 1.
The monodentate single anion comprises halogenide and carboxylate radical, and the bidentate single anion comprises acetylacetonate, allyl group and benzyl single anion.The coordinate negatively charged ion does not define in front relatively.
When X and Y are not alkyl negatively charged ion or hydride, typically can form living polymerization (in the second approach), X must be converted into alkyl negatively charged ion a such as alkyl or hydride (other negatively charged ion also may be active) at least.This normally uses a kind of activator (promotor) to reach, the latter can, for example, metal alkyl.Here " alkylation " is to mean promotor and LMX mY nReact so that metal alkyl (for example provides LM (alkyl) mY n), simultaneously alternatively forms relatively not coordinate negatively charged ion (if particularly the n value is zero) by capturing in the alkyl one." hydrogenation " is to be similar to alkylation, just replaces an alkyl negatively charged ion with a hydride negatively charged ion.For alternatively,, can add a kind of neutral Lewis acid and capture alkyl as second kind of promotor and form relatively not coordinate negatively charged ion as the some of catalyst system.Notice that this only is a kind of scheme that can be used to form the active olefin polymerisation catalysts, and will depend on employed special metal complex compound and employed promotor.
Preferably, this activator (promotor) or (1), a kind of neutral Lewis acid, it can capture a negatively charged ion to form weak coordinate negatively charged ion by (i) transition metal from said transition metal complex, (ii), can alkylation or the said transition metal of hydrogenation; Or (2), i.e. (i) a kind of neutral Lewis acid, it can capture a negatively charged ion to form weak coordinate negatively charged ion from the transition metal the said transition metal complex, (ii), another compound, it can alkylation or the said transition metal of hydrogenation, both combinations.More preferably this promotor is a kind of alkylating compound and a kind of Lewis acid, and it can form weak coordinate negatively charged ion.
Useful alkylating compound comprises alkylaluminium cpd (it also may be the hydrogenant compound, if they comprise the hydrogen that is bonded on the aluminium), alkyl zinc compound, and Grignard reagent.Preferably can alkylation can form again relatively not that the anionic compound of coordinate has alkylaluminium cpd such as trialkyl aluminium compound, comprise trimethyl aluminium, triethyl aluminum, three n-butylaluminum and triisobutyl aluminium; Alkyl halide aluminum compound such as diethyl aluminum chloride, ethyl aluminum chloride and ethyl sesquialter aluminum chloride; And (alkoxyl group) (alkyl) aluminum compound is such as the oxyethyl group diethyl aluminum.Alumina alkane such as methylaluminoxane, also can use, but because their expense costliness (even they may be very effective), they are not preferred.
General preferred in formula (I) compound have:
R 1, R 2And R 3Be hydrogen; And/or
R 1And R 3Be hydrogen, R 2It is trifluoromethyl; And/or
R 4And R 5Be halogen, sulfane base, hydrogen or the alkyl that contains 1 to 6 carbon atom, more preferably R independently of one another 4And R 5Be hydrogen or methyl independently of one another.
In a kind of preferred form of (I), R 6And R 7Be the aryl of a replacement independently of one another, be more preferably the phenyl of a replacement.More preferably R also 6Be the base of following formula (VI):
Figure A0280847900171
And R 7Be the base of following formula (VII):
Figure A0280847900181
R wherein 8, R 12, R 13And R 17Be alkyl or an inert functional group of alkyl, replacement independently of one another.
R 9, R 10, R 11, R 14, R 15And R 16Be alkyl or an inertia functional group of hydrogen, alkyl, replacement independently of one another;
Precondition is R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16And R 17In any two groups adjacent one another are can form a ring together.
In formula (VI) and formula (VII), preferred:
R 9, R 10, R 11, R 14, R 15And R 16Be hydrogen, halogen or an alkyl that contains 1 to 6 carbon atom independently of one another, more preferably these groups each all be hydrogen; And/or
R 10And R 15It is the phenyl (adding the phenyl that alkyl replaces) of methyl, phenyl or replacement; And/or
R 8, R 12, R 13And R 17Be the phenyl of halogen, phenyl, replacement or the alkyl that contains 1 to 6 carbon atom independently of one another, more preferably each group is that the phenyl (for example the phenyl that replaces of alkyl is such as the contraposition tert-butyl-phenyl) of phenyl, replacement or the alkyl (such as the sec.-propyl or the tertiary butyl) that contains 1 to 6 carbon atom be not (though preferably work as R independently 8And R 12The two or R 13And R 17The two all is the tertiary butyl in same compound).
Particularly preferred compound has (in conjunction with above-mentioned R 1, R 2, R 3, R 4And R 5In any variant), R wherein 6And R 7Be respectively formula (VI) and formula (VII), and:
R 9, R 11, R 14And R 16Be hydrogen, R 8, R 10, R 12, R 13, R 15And R 17It is methyl;
R 9, R 10, R 11, R 14, R 15And R 16Be hydrogen, R 8And R 18Be chlorine, R 12And R 17It is methyl;
R 9, R 10, R 11, R 14, R 15, R 16And R 17Be hydrogen, R 8And R 18It is phenyl;
R 9, R 10, R 11, R 14, R 15, R 16And R 17Be hydrogen, R 8And R 13It is the contraposition tert-butyl-phenyl;
R 9, R 10, R 11, R 14, R 15And R 16Be hydrogen, R 8, R 12, R 13And R 17It is phenyl;
R 9, R 10, R 11, R 14, R 15And R 16Be hydrogen, R 8, R 12, R 13And R 17It is the contraposition tert-butyl-phenyl;
R 9, R 10, R 11, R 14, R 15And R 16Be hydrogen, R 8And R 13Be phenyl, R 12And R 17It is halogen;
R 9, R 10, R 11, R 14, R 15And R 16Be hydrogen, R 8, R 13Be the contraposition tert-butyl-phenyl, R 12And R 17It is halogen;
R 9, R 10, R 11, R 14, R 15And R 16Be hydrogen, R 8, R 12, R 13And R 17It is sec.-propyl;
R 9, R 10, R 11, R 12, R 14, R 15, R 16And R 17Be hydrogen, R 8And R 13It is the tertiary butyl.
In the variant of another preferred embodiment of (I), R 6And R 7Be the 1-pyrryl that replaces independently of one another.More preferably R in this example 6And R 7Be respectively the base of following formula (VIII) and formula (IX) representative:
Figure A0280847900191
With
Figure A0280847900192
Wherein
R 18And R 21Corresponding to R in the formula (VI) 8And R 12Definition and preferred property;
R 22And R 25Corresponding to R in the formula (VII) 13And R 17Definition and preferred property;
R 19And R 20Corresponding to R in the formula (VI) 9And R 11Definition and preferred property;
R 23And R 24Corresponding to R in the formula (VII) 14And R 16Definition and preferred property;
In " polyreaction " that have dipolymer and oligopolymer to produce, R 6And R 7Preferred is the aryl of a replacement independently of one another, and first ring atom that it has is bonded on the nitrogen of imido grpup, and precondition is:
At R 6In, be to be bonded on halogen, primary carbon base, secondary carbon back or the tertiary carbon base adjacent to second ring atom of said first ring atom; And further precondition is:
At R 6In, when said second ring atom is when being bonded on halogen or the primary carbon base, at R 6And R 7In not have, have one or two in other ring atom adjacent to said first ring atom be to be bonded on halogen or the primary carbon base, remaining ring atom adjacent to said first ring atom then is to be bonded on the hydrogen atom; Perhaps
At R 6In, when said second ring atom is when being bonded on the secondary carbon back, at R 6And R 7In not have, have one or two in other ring atom adjacent to said first ring atom be to be bonded on halogen, primary carbon base or the secondary carbon back, remaining ring atom adjacent to said first ring atom then is to be bonded on the hydrogen atom; Perhaps
At R 6In, when said second ring atom is when being bonded on the tertiary carbon base, at R 6And R 7In not have, have one or two in other ring atom adjacent to said first ring atom be to be bonded on the tertiary carbon base, then be to be bonded on the hydrogen atom adjacent to all the other ring atoms of said first ring atom;
" at R 6And R 7In be bonded to first ring atom on the imido grpup nitrogen-atoms " be to mean the ring atom that is presented in these groups that are bonded in (I) on the imido grpup nitrogen, for example, in formula below (II) or the formula (III):
Figure A0280847900201
Or
Figure A0280847900202
The shown atom in 1-position is exactly first ring atom (other gene that may replace on aryl is not shown) that is bonded on the imido grpup nitrogen-atoms in ring.Other ring atom adjacent to first ring atom is displayed on, for example, in formula (IV) and the formula V, dotted line wherein show the opening of the ring atom that these are adjacent valency [in (IV) 2, the 6-position and in (V) 2, the 5-position].
Or
In preferred dimerization/oligomerization embodiment, R 6Be following formula (VIa):
And R 7Be following formula (VIIa):
Figure A0280847900211
Wherein:
R 8Be halogen, primary carbon base, secondary carbon back or tertiary carbon base; And
R 9, R 10, R 11, R 14, R 15, R 16And R 17Be alkyl or a functional group of hydrogen, alkyl, replacement independently of one another; Precondition is:
Work as R 8When being halogen or primary carbon base, R 12, R 13And R 17In not have, have one or two be halogen or primary carbon base, R 12, R 13, R 17In all the other groups be hydrogen; Perhaps
Work as R 8When being secondary carbon back, R 12, R 13And R 17In not or have one to be halogen, primary carbon base or secondary carbon back, R 12, R 13And R 17All the other groups be hydrogen; Perhaps
Work as R 8When being the tertiary carbon base, R 12, R 13And R 17In not or have one to be the tertiary carbon base, R 12, R 13And R 17All the other groups be hydrogen; Further precondition is R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16And R 17In any two groups adjacent each other can form a ring together.
In superincumbent formula (VIa) and the formula (VIIa), R 8Corresponding to second the adjacent ring atom of first ring atom that is bonded on the imino-nitrogen, R 12, R 13And R 17Ring atom corresponding to other adjacent with first ring atom.
In comprising (VIa) and compound (VIIa) (I), preferred especially:
If R 8Be primary carbon base, then R 18Be the primary carbon base, and R 12And R 17Be hydrogen; Perhaps
If R 8Be secondary carbon back, then R 13Be primary carbon base or secondary carbon back, be more preferably a secondary carbon back, and R 12And R 17Be hydrogen; Perhaps
If R 8Be tertiary carbon base (more preferably three halo tertiary carbon bases are such as trihalogenmethyl), then R 13Be tertiary carbon base (more preferably three halos and carbon back are such as trihalogenmethyl), and R 12And R 17Be hydrogen; Perhaps
If R 8Be halogen, R then 18Be halogen, and R 12And R 17Be hydrogen.
Wherein have in (VIa) and the particularly preferred compound (I) (VIIa) preferred R at all 1And R 2And R 3Be hydrogen, and/or R 4And R 5It is methyl.Further preferred:
R 9, R 10, R 11, R 12, R 14, R 15, R 16And R 17All be hydrogen; R 13It is methyl; And R 8Be the primary carbon base, be more preferably methyl; Perhaps
R 9, R 10, R 11, R 12, R 14, R 15, R 16And R 17All be hydrogen; R 13It is ethyl; And R 8Be the primary carbon base, be more preferably ethyl; Perhaps
R 9, R 10, R 11, R 12, R 14, R 15, R 16And R 17All be hydrogen; R 13It is sec.-propyl; And R 8Be the primary carbon base, be more preferably sec.-propyl; Perhaps
R 9, R 10, R 11, R 12, R 14, R 15, R 16And R 17All be hydrogen; R 18It is n-propyl; And R 8Be the primary carbon base, be more preferably n-propyl; Perhaps
R 9, R 10, R 11, R 12, R 14, R 15, R 16And R 17All be hydrogen; R 13Be chlorine; And R 8Be halogen, be more preferably chlorine; Perhaps
R 9, R 10, R 11, R 12, R 14, R 15, R 16And R 17All be hydrogen; R 13It is trihalomethyl group; Be more preferably trifluoromethyl; And R 8Be trihalomethyl group, more preferably trifluoromethyl.
In the other preferred embodiment of (I), R 6And R 7Be respectively following formula (VIIIa) and (IXa):
With
Wherein:
R 18Corresponding to R in (VIa) 8Definition and preferred property:
R 19, R 20And R 21Respectively corresponding to R in (VIa) 9, R 10And R 12Definition and preferred property;
R 22, R 23, R 24And R 25Respectively corresponding to R in (VIIa) 13, R 14, R 16And R 17Definition and preferred property.
Superincumbent formula (VIIIa) and (IXa) in, R 18Corresponding to second the adjacent ring atom of first ring atom that is bonded on the imino-nitrogen, R 21, R 22And R 25Then corresponding to other ring atom adjacent with first ring atom.
Any can use with the transition metal of (I) formation active polymerization reaction catalyst.The example of the suitable transition metal that can mention has those in the 3-12 family in the periodictable (IUPAC).The transition metal of preferred 8-10 family.The more preferably transition metal of 8-9 family, preferred especially Fe and Co.And Fe most preferably.
Compound (I) and its transition metal complex can prepare by disclosed the whole bag of tricks in the document that is incorporated herein by reference in front, also can be with being disclosed in, for example, experimental implementation method among WO9950273 and the WO 00/08034 prepares, and these two pieces of patents also are hereby incorporated by as all purposes that it throws a flood of light on.
It is R that the monomer of preferred polyreaction (comprising oligomeric) has ethene and general formula 18-CH=CH 2Alpha-olefin, R wherein 18Be positive alkyl, particularly contain the positive alkyl of 1 to 10 carbon atom.Preferred separately with ethene to provide Alathon (or under the situation of oligomerization, a series of alpha-olefins that contain the even carbon atom), or ethene combine to provide ethylene copolymer with one or more alpha-olefins (such as propylene, 1-hexene, 1-octene, 1-decene and/or 1-dodecylene).
(polymerization of preparation carrier catalyst component and one or more alkene the two) in the method for the invention, transition metal complex preferably is dissolved in a kind of solvent at first.Preferred this solvent can not decompose this complex compound basically, though this solvent may be extraly and metal complex generation complexing action.Preferred this solvent is a kind of aprotic solvent, rather than the protonic solvent as water, alcohol or carboxylic acid.Preferably, this complex compound should have at least approximately solubleness of about 0.0001 gram of per 100 milliliters of solvents, more preferably per 100 milliliters of solubleness at least about 0.01 gram.
Preferably, then the combination of this solvent/complex compound and silica or silica-alumina (collectively, carrier) are contacted, preferably under agitation condition, at this moment complex compound is to be attracted on the carrier partially at least.Adsorption may be quick relatively, if particularly complex compound has in solvent than higher solubleness.Contact process can be finished in less than one hour in this case.If the solubleness of complex compound in solvent very low (for example not every transition metal can dissolve immediately), (perhaps about 10 hours or longer time) dissolves complex compound and it is adsorbed on carrier then may to need the more time.Preferably carry out gentle stirring and guarantee mixing of carrier and solution.Usually complex compound is coloured, and at this moment people can judge that with range estimation complex compound is adsorbed onto the process on the carrier.Sometimes not all transition metal complex all can be adsorbed on the carrier.In the preferred complex compound that exists at least about have 50%, more preferably at least about having 80% to be adsorbed.The complex compound that is not adsorbed can circulate again so that it is attracted on the more carrier.
After contact procedure, the method of available any standard is separated solution and/or solvent with carrier (and by complex compound of its absorption), for example from solvent, leach carrier (still containing the complex compound that is dissolved in wherein in the solvent), perhaps that mixture is centrifugal, decantation goes out supernatant liquor from solid, by evaporation, for example under vacuum, remove and desolvate.Preferred solution separates with carrier as liquid, as by above-mentioned filtration or centrifugation method.If desired, carrier and by its absorption complex compound can be with solvent wash to remove any complex compound that is not adsorbed (at this moment some complex compound that has been adsorbed also may be washed off), and/or carrier and by its absorption complex compound can be dried, such as under vacuum condition, evaporating.But preferably most of, optional＞90% solvents are not by the mode of evaporating solvent and (in other words, should implement the physical sepn of solid carrier and liquid solvent (solution)) of carrier clathrate separation.Carried catalyst also can still had better separate it earlier before being used for polyreaction without directly being used in the polymerization process with just separating of solvent/solution with solvent/solution.
Transition metal complex to the ratio of carrier preferably like this in step (a), promptly on carried catalyst final levels of transition metals (pressing the transition metal metering) for the carrier catalyst component gross weight about 0.01 to about 5.0 weight percentage, preferably approximately 0.02 is to about 1.0 weight percentage.May need to carry out experiment in a small amount and measure the accurate condition that must obtain concrete transiting metal concentration in carrier catalyst component, this carrier catalyst component can contain any specific transition metal complex series, solvent and carrier; But, this experiment is in those of ordinary skills' limit of power.In general, transition metal complex is higher to the ratio that is present in the carrier in the first method, and then the amount of transition metal is also bigger in carrier catalyst component.
For guaranteeing that carried catalyst has activity as well as possible, preferably all exist the operation steps (and store) (be not adsorbed and adsorbed) of transition metal complex all will (nitrogen or argon gas) implement under inert atmosphere.
Have been found that at room temperature can stablize and deposit considerable time with the produced carrier catalyst component of this experimental implementation.Also have, this catalyzer does not need to contain those materials that are considered to combustibility or incendivity yet, thereby makes it implement transportation and to need not special careful with comparatively cheap method.
Now carrier catalyst component can be used as the some of the catalyst system of olefinic polyreaction, the various disclosures that have been incorporated herein by reference as the front are described.
In above-mentioned polymerization technology, alkylation or hydrogenation promotor (preferred a kind of alkylaluminium cpd or dialkyl zinc compounds) are about 1 to about 2000 to the preferred molar ratio of transition metal " mole " number, more preferably about 5 to about 1000, and special preferably approximately 30 is to about 500 (in these minimum and maximum rates any can be in to).Typically, this promotor also is used as scavenging agent simultaneously, can remove the compound of the impurity of harm polymerization process in polyreaction.Like this, this promotor also depends on the concentration of detrimental impurity in second kind of technology to a certain extent to the ratio of transition metal.
Other if desired Lewis acid is captured, such as, an alkyl, and form relatively not coordinate negatively charged ion, this in general Lewis acid typically is about 1 to about 5 to the molar ratio of transition metal.
Any promotor that is preferred in the polymerization technique contacts with the carried catalyst of making in first kind of technology under the condition that olefinic monomer exists, perhaps with contacting of promotor be contact in addition with olefinic monomer soon before (be less than 6 hours, more preferably less than 1 hour, especially preferably be less than 5 minutes).Particularly preferred in fact way is that promotor and carried catalyst contact in the molten device of polyreaction itself, perhaps contacts leading on the processing line of polymerization container.If polymerization technology is implemented in liquid phase, for example for suspension polymerization, then carried catalyst and any promotor can be added in the liquid medium of suspension.If polyreaction is a vapour phase polymerization, then granular carried catalyst can be fluidized by gas, and promotor such as trialkyl aluminium compound then adds with the steam form.Usually preference uses more volatile alkylaluminium cpd such as trimethyl aluminium for this purpose.
Can use more than the catalyzer of a kind of transistion metal compound as polyreaction, wherein one or both can be loaded in on a kind of carrier or the different carrier.More information for this class blended catalyzer, can be referring to the patent WO 9946302 that is incorporated herein by reference previously, and WO 9838228, WO 9950318 and WO 9957159, all these patents are being incorporated herein by reference just as filling part all purposes of illustrating.Can use typical polymeric reaction condition, for example, hydrogen can be used to control polyolefinic molecular weight.Referring to, for example, WO9946302 that introduces previously and WO 9962963, they also are hereby incorporated by just as filling part all purposes of explanation.
In a kind of preferred form of polymerization technique, the transition metal complex of tridentate ligand is used to oligomerisation of ethylene to form more purified alpha-olefin.For the more information of this class oligomerization process can referring to, for example, the US 6063881 of aforementioned introducing, US 6103946, WO 0055216, WO 0073249 and WO 0076659, they also are hereby incorporated by just as filling all purposes that part illustrates.If also have second kind of transistion metal compound that ethene and alpha-olefin copolymer are closed in addition, then will obtain branched polyethylene.Referring to, for example, WO 9950318 that introduces previously and WO 0055216.Preferred second kind of transistion metal compound is to be loaded in picture to be used for same a kind of carrier of first kind of technology in this example, and oligomeric and polymerisation catalysts can side by side be placed on the carrier (in first kind of technological process when also having other polymerizing catalyst to exist).
As the morphology of the silica granule of carrier usually is to be replicated in polymer beads (comprising silica) and to obtain.Product below many among the embodiment promptly shows such duplicating.Silica carrier is morphologic duplicates and believes and demonstrate catalyst species without any the uniform deposition under sedimentary activation al-alkyl compound, the condition that exists such as methylaluminoxane.
Abbreviation below in embodiment and experiment, having used:
The acac-acetylacetonate
ICP-inductively coupled plasma spectrum
The r.b.-round bottom
The THF-tetrahydrofuran (THF)
In an embodiment, all force value all refer to gauge pressure.Used following transition metal complex in an embodiment:
Figure A0280847900261
Complex compound with structural formula 1 and 3 is to make by the experimental implementation method described in the US 5955555 that introduces previously.
Embodiment 1
Wushu 1 compound (following simple and easy be 1,2,3 be equal to) is by CH 2Cl 2Middle recrystallization.Dissolving 1 (7.0 milligrams) are in anhydrous CH 2Cl 2In (7 milliliters) and add silica (0.5 gram is 948 silicas after the Grace dehydration, and rank is XPO-2402, is dewatered to every gram silica and contains 1 mmole OH yl).The mazarine mixture that obtains was stirred 30 minutes, from very light blue filtrate, leach the solid and the drying that obtain then.Output 0.5 gram is light blue solid.The mass percent of Fe (recording with the ICP method) is 0.14%.
Embodiment 2
1 by CH 2Cl 2Middle recrystallization.Dissolving 1 (7.0 milligrams) are in anhydrous CH 2Cl 2In (7 milliliters) and add the silica aluminum oxide [0.5 the gram, Grace M513-1.10 is at 200 ℃ of dehydration (mobile N 2Under the gas)].The navy blue mixture that obtains stirred 60 minutes.From colourless filtrate, leach the solid that obtains then, use CH 2Cl 2The washing after drying.Produce the light blue/gray solid of 0.5 gram.
Embodiment 3
1 from CH 2Cl 2Middle recrystallization.Dissolving 1 (7.0 milligrams) are in anhydrous CH 2Cl 2In (7 milliliters) and add the silica aluminum oxide [0.5 the gram, Grace M513-1.10 is at 500 ℃ of dehydration (mobile N 2Under the gas)].The navy blue mixture that obtains stirred 60 minutes.From colourless filtrate, leach the solid that obtains then, use CH 2Cl 2The washing after drying.Produce 0.5 gram light orange solid.
Embodiment 4
1 from CH 2Cl 2Middle recrystallization.Dissolving 1 (4.0 milligrams) are in dry toluene CH 2Cl 2In (15 milliliters) and add silica [0.25 gram, 948 silicas of Grace XPO-2402 dehydration].The mixture that obtains stirs and spends the night.From almost colourless filtrate, leach the solid that obtains then, with toluene and pentane washing after drying.Produce the light blue solid of 0.5 gram.
Embodiment 5
Be dissolved in 1 (4.0 milligrams) without recrystallization in the dry toluene (15 milliliters) and add silica [0.25 gram, 948 silicas of Grace XPO-2402 dehydration].The mixture that obtains stirs and spends the night.From almost colourless filtrate, leach the solid that obtains then, with toluene and pentane washing after drying.Produce the light blue solid of 0.5 gram.
Experiment 1
2 be prepared as follows:
In phial, be weighed into C 27H 31N 3(1.00 grams, 397.56 gram/moles, 2.515 mmoles), Fe (acac) 2(644 milligrams, 253.15 gram/moles, 2.516 mmoles) and [Na] [BAF] (2.24 grams, 890 gram/moles, 2.517 mmoles, BAF=B[3,5-(CF 3) 2C 6H 2] 4), put it into then in 50 milliliters of round-bottomed flasks that have stirring rod.Add THF (25 milliliters) and obtain wine-colored solution, it was stirred 24 hours.Remove THF (product can not be dissolved among the THF fully), product is suspended in the toluene, and passes through Celite Filter.From dark red solution, remove and desolvate, add pentane and promptly provide red precipitate, rinsing after it is leached, and drying promptly provides 2 under vacuum.
Ultimate analysis: C 64H 50BF 24FeN 3O 2(1415.72 gram/mole), theoretical value: C, 54.30; H, 3.56; N, 2.97. experimental result: C, 54.37; H, 3.58; N, 2.96.
Embodiment 6
2 (19.6 milligrams) are dissolved in orange-yellow solution of formation and the past silica aluminum oxide [0.5 gram, Grace is at the silica (under nitrogen gas stream) of 200 ℃ of dehydrations] that wherein adds in the dry toluene (7 milliliters).The mixture that obtains stirred 60 minutes, leached then to consolidate from almost colourless filtrate, with toluene and pentane washing after drying.Produce the solid of the shallow orange/beige of 0.5 gram.
Embodiment 7
3 (7.5 milligrams) are dissolved in anhydrous CH 2Cl 2In (7 milliliters) forming jonquilleous solution, and toward wherein adding silica (0.5 gram, 948 silicas of Grace dehydration).The mixture that obtains stirred 60 minutes, leached solid then from faint yellow filtrate, with toluene and pentane washing and dry.Produce the solid of 0.5 gram lemon yellow.
Embodiment 8
In glove box,, in an other cylinder, add 10 milliliters of triisobutyl aluminiums (the 1M solution in hexane that Aldrich reagent company produces) toward the middle product (75.8 milligrams) that adds embodiment 1 of a stainless steel cylinder (25 to 40 milliliters of volumes).Cylinder is connected to the inlet of autoclave reactor under the condition with the nitrogen purging junctor.The pressurized line of cylinder also connects under the nitrogen purging condition.
Trimethylmethane (1200 grams, the C.P level reagent that Matheson produces) is transferred in the autoclave of cooling (30 ℃) by pressure reduction.In case shift and to finish, promptly autoclave (AutoclaveEngineers produces, belt stirrer, 1 gallon (made in U.S.A), about 3.8 liters) is heated to 20 ℃ and stir with the speed of 1000rpm.Solvent is saturated with hydrogen down at 0.36 MPa (total pressure comprises hydrogen pressure) pressure.After saturated, reactor is heated to 80 ℃ and be pressurized to 1.4 MPas with ethene.The triisobutyl aluminum solutions is pushed in the reactor with ethene, then is the catalyzer of embodiment 1, also pushes with ethene.Pressure in the end reaction device is 2.41 MPas, and ethylene feed is turned to the side inlet of autoclave by feed containers.Reaction enters 3 hours.At the end of polyreaction,, and before opening reactor, then use nitrogen purging reactor emptying at leisure.The polymkeric substance drying is spent the night.Polymer output is 353 grams, and causing catalyst efficiency is 4.65 kilograms of PE/ gram catalyzer (comprising carrier), or rate of polymerization is 1.55 kilograms of PE/ gram catalyzer hour or 1109 kilograms of PE/ grams Fe hour.
Embodiment 9
According to the experimental implementation identical with embodiment 8, but carried catalyst with 5 milliliters of triisobutyl aluminum solutions and 75.5 milligrams of embodiment 1, polymer output is 316 grams, causing catalyst efficiency is 4.18 kilograms of PE/ gram catalyzer, or rate of polymerization is 1.40 kilograms of PE/ gram catalyzer hour or 997 kilograms of PE/ grams Fe hour.
Embodiment 10
According to the experimental implementation identical with embodiment 8, but carried catalyst with 15 milliliters of triisobutyl aluminum solutions and 78.0 milligrams of embodiment 1 preparations, polymer output is 256 grams as a result, and causing catalyst efficiency is that 3.28 kilograms of PE/ gram catalyzer or rate of polymerization are 1.09 kilograms of PE/ gram catalyzer hour or 781 kilograms of PE/ grams Fe hour.
Embodiment 11
According to the experimental implementation identical with embodiment 8, but carried catalyst with 10 milliliters of triisobutyl aluminum solutions and 75.8 milligrams of embodiment 2 preparations, polymer output is 182 grams as a result, and causing catalyst efficiency is that 2.4 kilograms of PE/ gram catalyzer or rate of polymerization are 0.8 kilogram of PE/ gram catalyzer hour or 572 kilograms of PE/ grams Fe hour.
Embodiment 12
According to the experimental implementation identical with embodiment 8, but carried catalyst with 10 milliliters of triisobutyl aluminum solutions and 74.2 milligrams of embodiment 4 preparations, polymer output is 380 grams as a result, causing catalyst efficiency is 5.12 kilograms of PE/ gram catalyzer, or rate of polymerization is 1.71 kilograms of PE/ gram catalyzer hour or 1219 kilograms of PE/ grams Fe hour.
Embodiment 13
According to the experimental implementation identical with embodiment 8, but carried catalyst with 10 milliliters of triisobutyl aluminum solutions and 75.4 milligrams of embodiment 4 preparations, polymer output is 374 grams as a result, causing catalyst efficiency is 4.96 kilograms of PE/ gram catalyzer, or rate of polymerization is 1.65 kilograms of PE/ gram catalyzer hour or 1181 kilograms of PE/ grams Fe hour.
Embodiment 14
According to the experimental implementation identical with embodiment 8, but carried catalyst with 5 milliliters of triisobutyl aluminum solutions and 79.8 milligrams of embodiment 3 preparations, polymer output is 51 grams as a result, causing catalyst efficiency is 0.64 kilogram of PE/ gram catalyzer, or rate of polymerization is 0.21 kilogram of PE/ gram catalyzer hour or 152 kilograms of PE/ grams Fe hour.
Embodiment 15
Weighing 1 (7.0 milligrams) is in the flicker phial and it is dissolved in about 10 milliliters of toluene, adds 0.5 gram and is dewatered to the silica gel (Grace Daridson948) of 0.76 mmole OH/ gram in phial.Phial is shaken 30 minutes, mixture filtered by the frit filtration procedure, and solid is dried overnight under vacuum and room temperature condition.
Embodiment 16-28
According to the experimental implementation identical with embodiment 8, but with the hydrogen of prepared catalyzer among the embodiment 15 and different quantities, the polymer output that obtains is listed in the following table
Embodiment Amounts of hydrogen Catalyst weight Output, dry weight Active Tap density
Numbering KPa ??mg ??g ????Kg?PE/g ????Fe/hr
??16 ????125 ??80.0 ??88.0 ????282 ????0.316
??17 ????35 ??78.2 ??32.0 ????105
??18 ????35 ??73.9 ??234.0 ????812 ????0.316
??19 ????276 ??72.3 ??19.0 ????67
??20 ????125 ??76.2 ??232.0 ????781 ????0.3097
??21 ????- ??74.9 ??260.0 ????890 ????0.404
??22 ????35 ??75.5 ??154.0 ????523 ????0.304
??23 ????125 ??75.2 ??174.0 ????593 ????0.313
??24 ????245 ??76.1 ??118.0 ????398 ????0.289
??25 ????572 ??76.9 ??31.0 ????103 ????0.259
??26 ????125 ??79.9 ??273.0 ????876 ????0.325
??27 ????207 ??76.7 ??230.0 ????769 ????0.319
??28 ????69 ??75.0 ??400.0 ????1368 ????0.367

Claims (17)

1. one kind prepares the method for being with the carrier polymerization catalyst component, and it may further comprise the steps:
(a) in a kind of solvent, dissolve 2,6-pyridine dicarbaldehyde diimine or 2, the transition metal complex of 6-diacylpyridines diimine is to form solution;
(b) said solution is contacted with carrier, the latter is the silica or silica one aluminum oxide of non-modified, and contact is filled part time so that the said metal complex of at least one part is attracted on the said carrier;
(c) alternatively separate said solution and solvent from said carrier;
Precondition is not have activator to exist basically in carrying out step (a) and (b) and process (c).
2. the process of claim 1 wherein that step (b) implements under agitation condition.
3. the general formula of the transition metal complex that the process of claim 1 wherein is LMx mY n, wherein L is 2,6-pyridine dicarbaldehyde diimine or 2, and 6-diacylpyridines diimine part, M is a transition metal, and X is single positively charged ion, and Y is a coordinate single anion not relatively, and m+n equals the oxidation state of M.
4. the method for claim 3, part wherein has following formula (I):
Figure A028084790002C1
Wherein:
R 1, R 2, R 3, R 4And R 5Be alkyl or an inert functional groups of hydrogen, alkyl, replacement independently of one another, precondition is R 1, R 2And R 3In any two groups adjacent one another are can form a ring together;
R 6And R 7Be aryl or a functional group of aryl, replacement.
5. the method for claim 4, wherein:
R 1, R 2And R 3Be hydrogen, perhaps R 1And R 3Be hydrogen and R 2It is trifluoromethyl;
R 4And R 5Be hydrogen or methyl independently of one another;
R 6Be following formula (VI)
Figure A028084790003C1
R 7Be following formula (VII)
Figure A028084790003C2
Wherein:
R 8, R 12, R 13And R 17Be alkyl or an inert functional group of alkyl, replacement independently of one another;
R 9, R 10, R 14, R 15And R 16Be alkyl or an inertia group of hydrogen, alkyl, replacement independently of one another;
Precondition is R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16And R 17In any two adjacent groups can form a ring together.
6. the method for claim 5, wherein:
R 1, R 2And R 3Be hydrogen;
R 4And R 5Be hydrogen or methyl;
R 9, R 11, R 14And R 16Be hydrogen, R 8, R 10, R 12, R 13, R 15And R 17It is methyl; Perhaps R 9, R 10, R 11, R 14, R 15And R 16Be hydrogen, R 8And R 13Be chlorine, R 12And R 17It is methyl; Perhaps
R 9, R 10, R 11, R 14, R 15, R 16And R 17Be hydrogen, R 8And R 13It is phenyl; Perhaps
R 9, R 10, R 11, R 14, R 15, R 16And R 17Be hydrogen, R 8And R 13It is the contraposition tert-butyl-phenyl; Perhaps R 9, R 10, R 11, R 14, R 15And R 16Be hydrogen, R 8, R 12, R 13And R 17It is phenyl; Perhaps
R 9, R 10, R 11, R 14, R 15And R 16Be hydrogen, R 8, R 12, R 13And R 17It is the contraposition tert-butyl-phenyl; Perhaps R 9, R 10, R 11, R 14, R 15And R 16Be hydrogen, R 8And R 13Be phenyl, R 12And R 17It is halogen; Perhaps R 9, R 10, R 11, R 14, R 15And R 16Be hydrogen, R 8And R 13Be the contraposition tert-butyl-phenyl, R 12And R 17It is halogen; Perhaps
R 9, R 10, R 11, R 14, R 15And R 16Be hydrogen, R 8, R 2, R 13And R 17It is sec.-propyl; Perhaps
R 9, R 10, R 11, R 12, R 14, R 15, R 16And R 17Be hydrogen, R 8And R 13It is the tertiary butyl.
7. the method for claim 4, wherein:
R 1, R 2And R 3Be hydrogen, or R 1And R 3Be hydrogen, R 2It is trifluoromethyl;
R 4And R 5Be hydrogen or methyl independently of one another;
R 6Be following formula (VIa):
Figure A028084790004C1
R 7Be following formula (VIIa):
Wherein: R 8Be halogen, primary carbon base, secondary carbon back or tertiary carbon base; And
R 9, R 10, R 11, R 14, R 15, R 16And R 17Be hydrogen independently of one another, alkyl, the alkyl of replacement or a functional group;
Precondition is:
Work as R 8When being halogen or primary carbon base, R 12, R 13And R 17In not or one or two is arranged is halogen or primary carbon base, all the other R 12, R 13And R 17All be hydrogen; Perhaps
Work as R 8When being secondary carbon back, R 12, R 13And R 17In not or have one to be halogen, primary carbon base or secondary carbon back, all the other R 12, R 13And R 17All be hydrogen; Perhaps
Work as R 8When being the tertiary carbon base, R 12, R 13And R 17In not or have one to be the tertiary carbon base, all the other R 12, R 13And R 17All be hydrogen;
Further precondition is R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16And R 17Central any two adjacent groups can form a ring together.
8. the method for claim 7, wherein:
R 9, R 10, R 11, R 12, R 14, R 15, R 16And R 17All be hydrogen, R 13And R 8It is methyl; Perhaps
R 9, R 10, R 11, R 12, R 14, R 15, R 16And R 17All be hydrogen, R 8And R 13It is ethyl; Perhaps
R 9, R 10, R 11, R 12, R 14, R 15, R 16And R 17All be hydrogen, R 8And R 13It is sec.-propyl; Perhaps
R 9, R 10, R 11, R 12, R 14, R 15, R 16And R 17All be hydrogen, R 8And R 13It is n-propyl; Perhaps
R 9, R 10, R 11, R 12, R 14, R 15, R 16And R 17All be hydrogen, R 8And R 13Be chlorine; Perhaps
R 9, R 10, R 11, R 12, R 14, R 15, R 16And R 17All be hydrogen, R 8And R 13It is trifluoromethyl.
9. polymerisation catalysts component that obtains with the method for claim 1.
10. the method for one or more polymerizable olefins of polymerization, it may further comprise the steps:
(a) in a kind of organic solvent, dissolve 2,6-pyridine dicarbaldehyde diimine or 2, the transition metal complex of 6-diacylpyridines diimine is to form solution;
(b) said solution is contacted with a kind of carrier, the latter is silica or silica-alumina, and contact is filled part time so that the said metal complex of at least one part is attracted on the said carrier, thereby forms carrier catalyst component;
(c) alternatively from said carrier catalyst component, separate said solution and solvent;
(d) contact with said one or more polymerizable olefins and one or more activators at following said carrier catalyst component of polymerizing condition, precondition is not have activator to exist basically in implementation step (a) and (b) and process (c).
11. the method for claim 6, wherein step (b) is implemented under agitation condition.
12. the method for claim 6, the general formula that transition metal complex wherein has are LMX mY n, wherein L is 2,6-pyridine dicarbaldehyde diimine or 2, and 6-diacylpyridines diimine part, M is a transition metal, and X is a single anion, and Y is a coordinate single anion not relatively, and the value of m+n equals the oxidation state of M.
13. the method for claim 7, coordination wherein have following formula (I):
Wherein:
R 1, R 2, R 3, R 4And R 5Be alkyl or an inert functional groups of hydrogen, alkyl, replacement independently of one another, precondition is R 1, R 2And R 3In any two groups adjacent one another are can form a ring together;
R 6And R 7Be aryl, the aryl of replacement or a functional group.
14. the method for claim 12, wherein:
R 1, R 2And R 3Be hydrogen, perhaps R 1And R 3Be hydrogen, R 2It is trifluoromethyl;
R 4And R 5Be hydrogen or methyl independently of one another;
R 6Be following formula (VI):
R 7Be following formula (VII):
Wherein: R 8, R 12, E 13And R 17Be alkyl independently of one another, the alkyl of replacement or an inertia functional group;
R 9, R 10, R 11, R 14, R 15And R 16Be alkyl or an inertia functional group of hydrogen, alkyl, replacement independently of one another;
Precondition is R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16And R 17Central any two groups adjacent one another are can form a ring together.
15. the method for claim 13, wherein:
R 1, R 2And R 3Be hydrogen;
R 4And R 5Be hydrogen or methyl;
R 9, R 11, R 14And R 16Be hydrogen, R 8, R 10, R 12, R 13, R 15And R 17It is methyl; Perhaps
R 9, R 10, R 11, R 14, R 15And R 16Be hydrogen, R 8And R 13Be chlorine, R 12And R 17Be methyl, perhaps
R 9, R 10, R 11, R 14, R 15, R 16And R 17Be hydrogen, R 8And R 13It is phenyl; Perhaps
R 9, R 10, R 11, R 14, R 15, R 16And R 17Be hydrogen, R 8And R 13It is the contraposition tert-butyl-phenyl; Perhaps R 9, R 10, R 11, R 14, R 15, R 16Be hydrogen, R 8, R 12, R 13And R 17It is phenyl; Perhaps R 9, R 10, R 11, R 14, R 15, R 16Be hydrogen, R 8, R 12, R 13And R 17It is the contraposition tert-butyl-phenyl; Perhaps
R 9, R 10, R 11, R 14, R 15And R 16Be hydrogen, R 8And R 13Be phenyl, R 12And R 17Be halogen, perhaps
R 9, R 10, R 11, R 14, R 15And R 16Be hydrogen, R 8And R 13Be the contraposition tert-butyl-phenyl, R 12And R 17It is halogen; Perhaps
R 9, R 10, R 11, R 14, R 15And R 16Be hydrogen, R 8, R 12, R 13And R 17It is sec.-propyl; Perhaps
R 9, R 10, R 11, R 12, R 14, R 15, R 16And R 17Be hydrogen, R 8And R 13It is the tertiary butyl.
16. the method for claim 12, wherein:
R 1, R 2And R 3Be hydrogen, or R 1Or R 3Be hydrogen, R 2It is trifluoromethyl;
R 4And R 5Be hydrogen or methyl independently of one another;
R 6Be following formula (VIa):
Figure A028084790008C1
R 7Be following formula (VIIa):
Figure A028084790008C2
Wherein:
R 8Be halogen, primary carbon base, secondary carbon back or tertiary carbon base;
R 9, R 10, R 11, R 14, R 15, R 16And R 17Be alkyl or a functional group of hydrogen, alkyl, replacement independently of one another;
Precondition is:
Work as R 8When being halogen or primary carbon base, R 12, R 13And R 17In the middle of not have, have one or two be halogen or primary carbon base, wherein R 12, R 13And R 17All be hydrogen; Perhaps
Work as R 8When being secondary carbon back, R 12, R 13And R 17In the middle of do not have or have one to be halogen, primary carbon base or secondary carbon back, all the other R 12, R 13And R 17All be hydrogen; Perhaps
Work as R 8When being the tertiary carbon base, R 12, R 13And R 17In the middle of do not have or have one to be the tertiary carbon base, all the other R 12, R 13And R 17All be hydrogen;
Further precondition is R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16And R 17Central any two groups adjacent one another are can form a ring together.
17. the method for claim 15, wherein:
R 9, R 10, R 11, R 12, R 14, R 15, R 16And R 17All be hydrogen, R 13And R 8It is methyl; Perhaps R 9, R 10, R 11, R 12, R 14, R 15, R 16And R 17All be hydrogen, R 8And R 13It is ethyl; Perhaps
R 9, R 10, R 11, R 12, R 14, R 15, R 16And R 17All be hydrogen, R 8And R 13It is sec.-propyl; Perhaps
R 9, R 10, R 11, R 12, R 14, R 15, R 16And R 17All be hydrogen, R 8And R 13It is n-propyl; Perhaps
R 9, R 10, R 11, R 12, R 14, R 15, R 16And R 17All be hydrogen, R 8And R 13Be chlorine; Perhaps
R 9, R 10, R 11, R 12, R 14, R 15, R 16And R 17All be hydrogen, R 8And R 13It is trifluoromethyl.
CNA028084799A 2001-04-17 2002-04-16 Olefin polymerization catalyst Pending CN1541229A (en)

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