CN1144821C - Procatalysts comprising bidentate ligands, catalyst systems, and use in olefin polymerization - Google Patents

Procatalysts comprising bidentate ligands, catalyst systems, and use in olefin polymerization Download PDF

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CN1144821C
CN1144821C CNB018035590A CN01803559A CN1144821C CN 1144821 C CN1144821 C CN 1144821C CN B018035590 A CNB018035590 A CN B018035590A CN 01803559 A CN01803559 A CN 01803559A CN 1144821 C CN1144821 C CN 1144821C
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acid
ester
methyl
compound
catalyst system
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CN1394212A (en
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D・S・威廉斯
D·S·威廉斯
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Westlake Longview Corp
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Eastman Chemical Co
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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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers

Abstract

There are described solid procatalysts, catalyst systems incorporating the solid procatalysts, anf the use of the catalyst systems in olefin polymerization and interpolymerization.

Description

Procatalyst, catalyst system and the purposes in olefinic polymerization thereof
Invention field
The invention belongs to the field of organometallic chemistry.Specifically, the present invention relates to organo-metallic solid procatalyst (procatalyst) and catalyst system on certain novel carriers that can be used in particular for olefinic polymerization or interpolymerization.
Background of invention
A kind of useful especially polymerization process for preparing polyethylene polymer is a vapor phase process.In United States Patent (USP) 3,709,853; 4,003,712,4,011,382,4,302,566,4,543,399,4,882,400,5,352,749 and 5,541,270 and Canadian Patent 991,798 and belgian patent 839,380 provided such example.
The well known Ziegler-natta catalyst systems that is used for olefin polymerization, and, just known this system after 115 issues at least from U.S. Patent number 3,113.Many patents about novel or improved Ziegler-natta catalyst have been issued thereafter.The example of these patents has U.S. Patent number 3,594, and 330,3,676,415,3,644,318,3,917,575,4,105,847,4,148,754,4,256,866,4,298,713,4,311,752,4,363,904,4,481,301 and again the issue 33,683.
These patent disclosures Ziegler-natta catalyst (this paper is called ZNCs), this class catalyzer is generally by comprising that the procatalyst (generally comprising titanium) that contains transition metal, the catalyst system of organo-metallic promotor (being generally organo-aluminium compound) form as everyone knows.Optional have activator (for example hydrogenate hydrocarbon) and an active modifier (for example electron donor(ED)) with what described catalyzer used.
In the patent that relates to ' Z-N ' catalyzer that is used for olefinic polymerization the earliest, for the reductive solid is provided, available metal alkylide is handled halogenated titanium, and described reductive solid is mainly by TiCl 3Form and generally admixed the by product of reaction.In these systems, formed and be mainly TiCl 3Solid, be used as the procatalyst of olefinic polymerization.There are a few class patents to describe solid TiCl 3Preparation.
The solubility Ziegler-Natta catalyst has also been described.United States Patent (USP) 4,366 has been described with reductive agent for No. 297 and have been handled TiCl 4The ether affixture so that soluble T iCl to be provided 3The method of species also proposes can not form throw out when having ether.United States Patent (USP) 3,862 has been described TiRCl No. 257 3.AlCl 3Hydrocarbon solution, wherein for low-molecular-weight wax is provided, can remove AlCl by adding properties-correcting agent in solution method 3United States Patent (USP) 4,319, described for No. 010 and be higher than 110 ℃ of solution methods of using soluble catalyst preparation olefin polymerization down, this method comprises makes titanium (IV) compound and reaction by the magnesium compound of aluminum alkyls solubilising, and United States Patent (USP) 4, proved alkyl aluminum activator and activity by the reaction product of the tetravalence transition metal salt of magnesium carboxylates solubilising for 540, No. 756, wherein the tetravalence transition metal salt specifically refers to TiCl 4United States Patent (USP) 5,037 has been described by Ti (OR) for No. 997 4+ AlR 3+ MgR 2The dimerization catalyst of the ethene that forms of reaction, its activity is less than 10Kg/g Ti.h.United States Patent (USP) 5,039,766 and 5,134, No. 104 solubility acid amides titanium (titanium amido) catalyzer has been described, when having substrate alkene and alkyl aluminum activator or aikyiaiurnirsoxan beta reaction.
Several patents has been described the soluble catalyst on other the carrier.United States Patent (USP) 3,634 has been described for No. 384 and have been prepared solubility halogenated titanium/aluminum alkyls species at low temperatures, toward wherein adding hydroxylated solid carrier, thereby has formed the Mg-O-Ti key.United States Patent (USP) 3,665 has been described similar methods No. 812, by generating the reduction titanium species and add magnesium halide carrier to increase activity in aromatic solvent.United States Patent (USP) 4,409 has been described the soluble reaction product of the hydrocarbon that obtains by the reaction that contains alkoxyl group transistion metal compound and organometallic compound No. 126, and this reaction product can be used for preparing olefin polymerization catalysis.At United States Patent (USP) 5,320, the variation of this catalyzer has been described in No. 994, wherein, add magnesium compound subsequently with titan-alkoxide and aluminum alkyls reaction, under reaction conditions, form MgCl 2This example also describes α in detail, ω-saturated dihalide is preventing that over reduction from becoming TiCl 2The importance of aspect.
United States Patent (USP) 2,981 has been discussed TiCl No. 725 4With the reaction of various carriers (as silicon carbide), then use promotor AlEt 2Cl handles.Supported catalyst and the precipitated catalyst on non-carrier relatively demonstrate the improvement that is less than aspect two.United States Patent (USP) 4,426, the preparation of describing similar supported catalyst No. 315 wherein is added to titanium and aluminum compound in the slurry of carrier simultaneously, and any reaction only takes place in the presence of described carrier.
Known some ziegler-natta catalyst systems solvable or " liquid " has utilized titanium chelate.For example, United States Patent (USP) 3,737,416 and 3,737, No. 417 the reaction of titanium chelate and halogenating agent has been described, then with the aluminum alkyls activation so that the catalyzer with alpha-olefin and butadiene copolymer to be provided.These activations are being low to moderate-78 ℃ temperature and are existing under the monomer to be implemented.United States Patent (USP) 3,652, No. 705 only claimed nitrile electron donor(ED) is being handled TiCl with organo-aluminium compound 4Before and TiCl 4The purposes of reaction.Preferably these catalyzer are used for aromatic hydrocarbons solution or slurry.United States Patent (USP) 4,482,639,4,603,185 and 4,727, No. 123 the bimetal complex that has single anion three tooth chelating ligands has been described, this complex compound adopts aluminum alkyls activation with olefin polymerization, alkynes and diene.United States Patent (USP) 5,021 has been described the catalyzer of solubility trivalent metal (particularly vanadium) complex compound based on the bidentate chelating ligand No. 595.These soluble complexes are reacted with the compound that comprises acidic hydrogen by trivalent metal halogenide and are prepared, and are used for olefin polymerization with the aluminum alkyls activation.United States Patent (USP) 5,378 has been reported for No. 778 acid amides titanium and the organic oxygen-containing compound reaction with acidic hydrogen, provides olefin polymerization catalysis on high reactivity, the non-carrier with aluminum alkyls by in-situ activation subsequently.United States Patent (USP) 5,840, reported for No. 646 have chela and two (alkoxyl group) (bis (alkoxides)) Ti, Zr of part or the dialkyl group complex compound of Hf, wherein limited (tethered) Lewis base is connected on the skeleton of described part.These compounds can be used for olefin polymerization under the activator that has the generation cationic complex, wherein the example of activator has trityl four (pentafluorophenyl group) borate or methylaluminoxane.
Aluminum alkyls is used as the activator or the promotor of Ziegler-Natta catalyst usually, and the example of some compounds has AlR 3-nL nThe form of (n=1 or 2), wherein the L single anion ligand of respectively doing for oneself.United States Patent (USP) 3,489 is for example understood the various purposes that comprise the aluminium nitrogen compound of carboxylic acid amide No. 736, its can with unite as Ziegler-Natta catalyst (as TiCl as lewis acidic aluminum halide 3) promotor.United States Patent (USP) 3,723 has been described the purposes of the vanadium compound of band activator for No. 348, and wherein said activator can be aluminum alkoxide, acid amides, carboxylate or acetylacetonate.United States Patent (USP) 3,786, No. 032 reaction product with organoaluminum or organic zinc and oxime or hydroxy ester is as activator.United States Patent (USP) 3,883 is united with carboxylamine aluminium and another kind of organo-aluminium compound for No. 493 and to be done promotor.With at United States Patent (USP) 3,948, report is the same in No. 869, the polymerization of mixtures conjugated diolefine of available titanium or vanadium halide, trialkylaluminium and a small amount of dithiocarbonic anhydride.United States Patent (USP) 4,129, disclose aluminium salt or the purposes of zinc salt in polymerization of vinyl halogenide or vinylidene dihalide for No. 702, pointed out that improvements are that aging promotor is to remove isocyanic ester as the carboxylic acid amide of the activator of Ziegler-Natta catalyst (optional be adsorbed on the carrier).United States Patent (USP) 5,468 has been described bidentate, two anionic the 13rd group element compounds purposes as promotor for No. 707.United States Patent (USP) 5,728 has also been described the purposes of catechuic acid aluminium (aluminum catecholate) compound as a component in four component catalysts No. 641, and wherein this system comprises the organic ring compound with two or more conjugated double bonds.
Aluminum chelate also can be used as external electronic donor.United States Patent (USP) 3,313 discloses the purposes of closing (acetylacetonato) aluminum alkoxide and titanous chloride and alkyllithium dihalide catalyst system as the methyl ethyl diketone acid group of external electronic donor No. 791.United States Patent (USP) 3,919, the purposes of No. 180 external electronic donor being discussed, described external electronic donor can be the bidentate that combines titanium catalyst or aluminum cocatalyst.United States Patent (USP) 5,777 has been described the purposes as the positively charged ion aluminum amidinate compound of single reactive site catalyzer of olefinic polymerization for No. 120.
United States Patent (USP) 3,534 has been described for No. 006 with two (dialkyl group alumina base (aluminoxy)) alkane activatory and has been comprised the catalyzer of 4-6 family metallic compound.The also claimed other external electronic donor of this patent or the purposes of promotor, wherein other external electronic donor or promotor comprise far-ranging nitrogenous compound.United States Patent (USP) 4,195 has been described the TiCl with complexing agent No. 069 4Complex compound and interaction with organic aluminium compound of complexing agent.This interaction causes TiCl 4Be reduced into TiCl 3
United States Patent (USP) 3,714 has been described a kind of catalyst system that high productivity prepares the alternating copolymer of high-molecular weight divinyl and alpha-olefin that is used for No. 133.Described catalyst system is made up of organo-aluminium compound, titanium tetrahalide and carbonyl containing compound.Described catalyst system also can comprise halogen-containing compound, metal oxide or nonmetal oxide, can improve the catalytic performance of described catalyst system thus.
Summary of the invention
By at least a empirical formula ML xX 4-xTransistion metal compound and at least a empirical formula L xER nY mH pAlkylating reagent at least a aprotic solvent, react so that soluble species to be provided, described soluble species is contacted with carrier prepare solid procatalyst subsequently, at formula ML xX 4-xIn, M is titanium, zirconium or hafnium, and independently for the atom that is selected from oxygen, sulphur, selenium, tellurium, nitrogen, phosphorus, arsenic, antimony and bismuth or its mixture by two is connected to single anion bidentate ligand on the M, X is fluorion, chlorion, bromide anion or iodide ion to L separately, and 0＜x≤4 are at formula L xER nY mH pIn, L independently is connected to single anion bidentate ligand on the E for the atom that is selected from oxygen, sulphur, selenium, tellurium, nitrogen, phosphorus, arsenic, antimony and bismuth or its mixture by two separately, E is boron, aluminium, gallium or indium, R independently is alkyl separately, and Y independently is the single anion unidentate ligand separately, 0＜x≤2, n＞0, m 〉=0, p 〉=0, and x+n+m+p=3.The solid procatalyst that obtains provides the catalyst system of suitable polymerization or copolyolefine with promotor.
The detailed description of invention
By at least a empirical formula ML xX 4-xTransistion metal compound and at least a empirical formula L xER nY mH pAlkylating reagent at least a aprotic solvent, react so that soluble species to be provided, described soluble species is contacted with carrier prepare solid procatalyst subsequently, at formula ML xX 4-xIn, M is titanium, zirconium or hafnium, and independently for the atom that is selected from oxygen, sulphur, selenium, tellurium, nitrogen, phosphorus, arsenic, antimony and bismuth or its mixture by two is connected to single anion bidentate ligand on the M, X is fluorion, chlorion, bromide anion or iodide ion to L separately, and 0＜x≤4 are at formula L xER nY mH pIn, L independently is connected to single anion bidentate ligand on the E for the atom that is selected from oxygen, sulphur, selenium, tellurium, nitrogen, phosphorus, arsenic, antimony and bismuth or its mixture by two separately, E is boron, aluminium, gallium or indium, R independently is alkyl separately, and Y independently is the single anion unidentate ligand separately, 0＜x≤2, n＞0, m 〉=0, p 〉=0, and x+n+m+p=3.Described soluble species contacted with carrier be included on the carrier the described soluble species of deposition.The solid procatalyst that obtains provides the catalyst system of suitable polymerization or copolyolefine with promotor.
The element of each family of all elements periodictable of herein mentioning can referring to 1985 at " Chemical and Engineering News ", the periodic table of elements of delivering in 63 (5), 27.In this version, family is numbered 1 to 18.This paper has used abbreviation Me (being used for methyl), Et (being used for ethyl), TMA (being used for trimethyl aluminium) and TEAL (being used for triethyl aluminum).
The present invention includes by empirical formula ML xX 4-xTransistion metal compound and formula L xER nY mH pThe reaction of alkylating reagent in aprotic solvent so that soluble species to be provided, the soluble species with gained contacts the solid procatalyst for preparing with carrier subsequently.If any precipitation takes place during generating soluble component, so must with soluble species with described precipitation is dissolved again, is filtered or is removed before carrier contacts.
The mol ratio of alkylating reagent and transistion metal compound is preferably about 0.1 to about 100.The mol ratio of preferred alkyl reagent and transistion metal compound is about 0.25 to about 15.More preferably the mol ratio of alkylating reagent and transistion metal compound is about 1 to about 5.
At least a transiting metal compound that is used for method of the present invention can be any empirical formula:
ML xX 4-xCompound or its mixture,
Wherein M is selected from titanium, zirconium and hafnium,
L is separately independently for the atom that is selected from oxygen, sulphur, selenium, tellurium, nitrogen, phosphorus, arsenic, antimony and bismuth or its mixture by two is connected to single anion bidentate ligand on the M,
X is separately independently for being selected from fluorion, chlorion, bromide anion or iodide ion, and
0＜x≤4，
Described transistion metal compound (ML xX 4-x) can with produce before alkylating reagent contacts and/or introduce in the aprotic solvent by any way, handle with alkylating reagent subsequently, wherein said introducing method comprises the dissolving pure substance or mixes for example metal halide and the conjugate acid of part (L), the complex compound of part or the salt of part by mixing.
The example that is connected to the single anion bidentate ligand L on the M has the conjugate base and the conjugate base that comprises the compound of acid C-H of the compound that comprises acidic hydrogen.
The single anion bidentate ligand L that is connected on the M that can be used for herein is the conjugate base that comprises the compound of acidic hydrogen, and its example has carboxylic acid, carboxylic acid amide, the carboxylic acid phosphide, thiocarboxylic acid, dithionic acid, the thiocarboxylic acid acid amides, the thiocarboxylic acid phosphide, carbonic acid, carboxylamine, urea, thiocarbonic acid SOH, thiocarbamide, thiocarbamate, dithiocarbamic acid, hydroxycarboxylic acid esters, the hydroxycarboxylic acid acid amides, amino acid ester, the hydroxyl carbothioic acid ester, the hydroxyl dithiocarboxylic esters, hydroxyl thiocarboxylic acid acid amides, the hydroxycarboxylic acid thioester, hydroxyl thiocarboxylic acid thioester, hydroxyl dithionic acid thioester, mercapto-carboxylic ester, mercaptan carboxylic acid's acid amides, the sulfydryl carbothioic acid ester, the sulfydryl dithiocarboxylic esters, sulfydryl thiocarboxylic acid acid amides, mercaptan carboxylic acid's thioester, sulfydryl thiocarboxylic acid thioester, sulfydryl dithionic acid thioester, hydroxyketone, hydroxy aldehyde, hydroxyl imide, sulfydryl ketone, sulfydryl aldehyde, the sulfydryl imines, the hydroxyl thioketones, the hydroxyl thioaldehydes, the sulfydryl thioketones, the sulfydryl thioaldehydes, the 2-hydroxy benzaldehyde, 2-sulfydryl phenyl aldehyde, the 2-aminobenzaldehyde, 2-hydroxy phenyl thioaldehydes, the 2 hydroxybenzoic acid ester, the 2-hydroxybenzamide, 2 hydroxybenzoic acid thioester (2-hydroxybenzoate thioesters), 2-hydroxyl thiobenzoic acid ester, 2-hydroxyl thiobenzamide, 2-hydroxy phenyl thioaldehydes, 2-sulfydryl phenyl thioaldehydes, 2-aminophenyl thioaldehydes, the 2-hydroxyl arone, 2-sulfydryl arone, the amino arone of 2-, 2-hydroxyaryl imines, 2-sulfydryl aryl imine, 2-aminoaryl imines, 2-hydroxyaryl thioketones, 2-sulfydryl aryl thioketones, 2-aminoaryl thioketones, bitter almond oil camphor, 2-pyrroles's carboxyl aldehyde (2-pyrrolecarboxadehydes), 2-pyrrolidine dithiocarbamate carboxyl aldehyde (2-pyrrolthiocarboxadehydes), 2-pyrroles's carboxyl aldimine (2-pyrrolecarboxaldimine), alkyl 2-pyrrolyl ketone, alkyl 2-pyrryl imines, alkyl 2-pyrryl thioketones, 2-indoles carboxyl aldehyde, 2-indoles thiocarboxyl group aldehyde, 2-indoles carboxyl aldimine (2-indolecarboxaldimine), alkyl 2-indyl ketone, alkyl 2-indyl imines, alkyl 2-indyl thioketones, hydroxyquinoline, tropolone, amino tropolone, amino cycloheptatriene ketoimine.
The single anion bidentate ligand L that is connected on the M that can be used for herein is the conjugate base that comprises the compound of acid C-H; its example has 1; the 3-diketone; beta-ketoester; the beta-keto acid acid amides; the 3-nitroketone; 3-nitro acid esters; 3-nitroacid acid amides; phthalic monoester; two (2-furyl) alkane; it is two that (5-(2; 3-dihydrofuran base)) alkane; two (2-thio-phenyl) alkane; it is two that (5-(2; 3-dihydrogen phosphorothioate phenyl)) alkane; two (2-pyridyl) alkane; diester malonate; beta-ketimine; 1, the 3-diimine; β-imidic ester; β-imino-acid acid amides; the 3-nitro-imine; alkyl thionyl acetic ester; the alkyl sulfide ethyl sodio acetoacetic ester; two (alkyl sulfinyl) alkane; two (alkyl sulfide acyl group) alkane.
The preferred example that is connected to the single anion bidentate ligand L on the M that can be used for herein has 1, the conjugate base of 3-diketone, methyl ethyl diketone, 3 for example, 5-heptadione, 2,6-dimethyl-3,5-heptadione, 5,7-undecane diketone, benzoyl acetone, diphenylpropane-1,3-dione(DPPO), 1,1,1-trifluoroacetylacetone, 1,1,1,5,5,5-hexafluoroacetylacetone, 2,2,6,6-tetramethyl--3,5-heptadione, listed above 1, the list of 3-diketone-and the analogue of the imines of the analogue of two-imines, 2-hydroxybenzene carboxyl aldehyde, compound listed above.
Can will be connected to the mixture of the single anion bidentate ligand L on the M as the single anion bidentate ligand L that is connected on the M.
Above-mentioned empirical formula ML xX 4-xThe mixture of compound also can be used as transistion metal compound in this article.
At least aly be used for alkylating reagent of the present invention and can be any empirical formula:
L xER nY mH pOrganometallic compound or its mixture,
Wherein,
L independently is connected to single anion bidentate ligand on the E for the atom that is selected from oxygen, sulphur, selenium, tellurium, nitrogen, phosphorus, arsenic, antimony and bismuth or its mixture by two separately;
E is selected from boron, aluminium, gallium and indium;
R independently is alkyl separately,
Y independently is the single anion unidentate ligand separately,
0＜x≤2, n＞0, m 〉=0, p 〉=0, and
x+n+m+p＝3。
The unit price of the term of Shi Yonging " alkyl " expression herein, linearity, branching, ring-type or polycyclic comprise the group of carbon and hydrogen atom.Described alkyl can be chosen the atom that is selected from periodictable the 13rd, 14,15,16 and 17 families that comprises outside de-carbon and the hydrogen wantonly.The example of univalence hydrocarbyl comprises as follows: C 1-C 30Alkyl; By one or more C that are selected from 1-C 30Alkyl, C 3-C 15Cycloalkyl or the C that replaces of aryl 1-C 30Alkyl; C 3-C 15Cycloalkyl; By one or more C that are selected from 1-C 20Alkyl, C 3-C 15Cycloalkyl or the C that replaces of aryl 3-C 15Cycloalkyl; C 6-C 15Aryl; With by one or more C that are selected from 1-C 30Alkyl, C 3-C 15Cycloalkyl or the C that replaces of aryl 6-C 15Aryl, wherein aryl is preferably represented phenyl that replace or unsubstituted, naphthyl (napthyl) or anthryl (anthracenyl).
Described alkylating reagent (L xER nY mH p) can with produce before alkylating reagent contacts and/or introduce by any way in the aprotic solvent, handle with alkylating reagent subsequently, wherein said method comprises the dissolving pure substance or mixes for example empirical formula ER by original position N+1Y mH pWith the complex compound of part (L), part or the salt of part.
The example that is connected to the single anion bidentate ligand L on the E has the conjugate base and the conjugate base that comprises the compound of acid C-H of the compound that comprises acidic hydrogen.
The single anion bidentate ligand L that is connected on the E that can be used for herein is the conjugate base that comprises the compound of acidic hydrogen, and its example has carboxylic acid, carboxylic acid amide, the carboxylic acid phosphide, thiocarboxylic acid, dithionic acid, the thiocarboxylic acid acid amides, the thiocarboxylic acid phosphide, carbonic acid, carboxylamine, urea, thiocarbonic acid SOH, thiocarbamide, thiocarbamate, dithiocarbamic acid, hydroxycarboxylic acid esters, the hydroxycarboxylic acid acid amides, amino acid ester, the hydroxyl carbothioic acid ester, the hydroxyl dithiocarboxylic esters, hydroxyl thiocarboxylic acid acid amides, the hydroxycarboxylic acid thioester, hydroxyl thiocarboxylic acid thioester, hydroxyl dithionic acid thioester, mercapto-carboxylic ester, mercaptan carboxylic acid's acid amides, the sulfydryl carbothioic acid ester, the sulfydryl dithiocarboxylic esters, sulfydryl thiocarboxylic acid acid amides, mercaptan carboxylic acid's thioester, sulfydryl thiocarboxylic acid thioester, sulfydryl dithionic acid thioester, hydroxyketone, hydroxy aldehyde, hydroxyl imide, sulfydryl ketone, sulfydryl aldehyde, the sulfydryl imines, the hydroxyl thioketones, the hydroxyl thioaldehydes, the sulfydryl thioketones, the sulfydryl thioaldehydes, the 2-hydroxy benzaldehyde, 2-sulfydryl phenyl aldehyde, the 2-aminobenzaldehyde, 2-hydroxy phenyl thioaldehydes, the 2 hydroxybenzoic acid ester, the 2-hydroxybenzamide, the 2 hydroxybenzoic acid thioester, 2-hydroxyl thiobenzoic acid ester, 2-hydroxyl thiobenzamide, 2-hydroxy phenyl thioaldehydes, 2-sulfydryl phenyl thioaldehydes, 2-aminophenyl thioaldehydes, the 2-hydroxyl arone, 2-sulfydryl arone, 2-aminoaryl ketone, 2-hydroxyaryl imines, 2-sulfydryl aryl imine, 2-aminoaryl imines, 2-hydroxyaryl thioketones, 2-sulfydryl aryl thioketones, 2-aminoaryl thioketones, bitter almond oil camphor, 2-pyrroles's carboxyl aldehyde, 2-pyrrolidine dithiocarbamate carboxyl aldehyde, 2-pyrroles's carboxyl aldimine, alkyl 2-pyrrolyl ketone, alkyl 2-pyrryl imines, alkyl 2-pyrryl thioketones, 2-indoles carboxyl aldehyde, 2-indoles thiocarboxyl group aldehyde, 2-indoles carboxyl aldimine, alkyl 2-indyl ketone, alkyl 2-indyl imines, alkyl 2-indyl thioketones, hydroxyquinoline, tropolone, amino-tropolone, amino cycloheptatriene ketoimine.
The single anion bidentate ligand L that is connected on the E that can be used for herein is the conjugate base that comprises the compound of acid C-H; its example has 1; the 3-diketone; beta-ketoester; the beta-keto acid acid amides; the 3-nitroketone; 3-nitro acid esters; 3-nitroacid acid amides; phthalic monoester; two (2-furyl) alkane; it is two that (5-(2; 3-dihydrofuran base)) alkane; two (2-thio-phenyl) alkane; it is two that (5-(2; 3-dihydrogen phosphorothioate phenyl)) alkane; two (2-pyridyl) alkane; diester malonate; beta-ketimine; 1, the 3-diimine; β-imidic ester; β-imino-acid acid amides; the 3-nitro-imine; alkyl thionyl acetic ester; the alkyl sulfide ethyl sodio acetoacetic ester; two (alkyl sulfinyl) alkane; two (alkyl sulfide acyl group) alkane.
The preferred example that is connected to the single anion bidentate ligand L on the E that can be used for herein has 1, the conjugate base of 3-diketone, methyl ethyl diketone, 3 for example, 5-heptadione, 2,6-dimethyl-3,5-heptadione, 5,7-undecane diketone, benzoyl acetone, diphenylpropane-1,3-dione(DPPO), 1,1,1-trifluoroacetylacetone, 1,1,1,5,5,5-hexafluoroacetylacetone, 2,2,6,6-tetramethyl--3,5-heptadione, listed above 1, the list of 3-diketone-and the analogue of the imines of the analogue of two-imines, 2-hydroxybenzene carboxyl aldehyde, compound listed above.
Can will be connected to the mixture of the single anion bidentate ligand L on the E as the single anion bidentate ligand L that is connected on the E.
The example of single anion unidentate ligand Y comprise halogen anion ,-OR ,-OBR 2,-OSR ,-ONR 2,-OPR 2,-NR 2,-N (R) BR 2,-N (R) OR ,-N (R) SR ,-N (R) NR 2,-N (R) PR 2,-N (BR 2) 2,-N=CR 2,-N=NR ,-N=PR ,-SR ,-SBR 2,-SOR ,-SNR 2,-SPR 2,-PR 2R independently is the alkyl consistent with above-mentioned definition separately.The example of halogen anion has fluorion, chlorion, bromide anion and iodide ion.
The example of alkoxide has methylate, ethylate, n-propyl alcohol salt, isopropoxide, the ring propylate, propyl carbinol salt, the isobutyl alkoxide, sec-butyl alcohol salt, tert butoxide, cyclobutanol salt, Pentyl alcohol salt, the isoamyl alkoxide, sec.-amyl alcohol salt, tertiary amyl alcohol salt, neopentyl alcohol salt, cyclopentanol salt, n-hexyl alcohol salt, the cyclic group alkoxide, enanthol salt, octanol salt, nonyl alcohol salt, decyl alcohol salt, the undecane alkoxide, the dodecane alkoxide, 2-Ethylhexyl Alcohol salt, phenates, 2,6-dimethyl phenates, 2,6-di-isopropyl phenates, 2,6-phenylbenzene phenates, 2,6-two basic phenates, 2,4,6-trimethylammonium phenates, 2,4,6-triisopropyl phenates, 2,4,6-triphenyl phenates, 2,4,6-three basic phenates, benzylalcohol salt (benzyloxide), menthoxide, and haloalkane alkoxide, for example fluoroform alkoxide, trifluoroethanol salt, Trifluoroisoproanol salt, hexafluoroisopropanol salt, seven fluorine isopropoxides, the trifluoro tert butoxide, the hexafluoro tert butoxide, the fluoroform alkoxide, ethapon salt, isopral salt.
The example of thiolate has thiomethyl alcohol salt, sulfur alcohol salt, the n-propyl thiolate, isopropyl mercaptan salt, the cyclopropyl thiolate, the normal-butyl thiolate, the isobutyl-thiolate, the sec-butyl thiolate, tert-butyl mercaptan salt, the cyclobutyl thiolate, the n-pentyl thiolate, the isopentyl thiolate, the sec.-amyl sec-pentyl secondary amyl thiolate, the tert-pentyl thiolate, the neo-pentyl thiolate, the cyclopentyl thiolate, the n-hexyl thiolate, the cyclohexyl thiolate, phenyl mercaptan salt, 2,6-3,5-dimethylphenyl thiolate, 2,6-diisopropyl phenyl thiolate, 2,6-phenylbenzene phenyl thiolate, 2,6-two basic phenyl mercaptan salt, 2,4,6-trimethylphenyl thiolate, 2,4,6-triisopropyl phenyl thiolate, 2,4,6-triphenyl phenyl thiolate, 2,4,6-three basic phenyl mercaptan salt, the dibenzylsulfide alkoxide, the heptyl thiolate, octyl mercaptan salt, nonyl mercaptan salt, the decyl thiolate, the undecyl thiolate, lauryl mercaptan salt, 2-ethylhexyl thiolate,  base thiolate, and haloalkyl thiolate, for example trifluoromethyl mercaptan salt, the trifluoroethyl thiolate, trifluoro isopropyl mercaptan salt, hexafluoro isopropyl mercaptan salt, seven fluorine isopropyl mercaptan salt, trifluoro tert-butyl mercaptan salt, hexafluoro tert-butyl mercaptan salt, trifluoromethyl mercaptan salt, trichlorine ethanethio salt, trichlorine isopropyl mercaptan salt.
The example of acid amides has dimethylformamide, diethylamide, the di acid amides, diisopropylamide, two cyclopropyl amides, the di-n-butyl acid amides, the diisobutyl acid amides, the di-secondary butyl amide, di-te t-butylamide, two cyclobutylamides, two n-pentyl acid amides, the diisoamyl acid amides, the di-sec-amyl acid amides, two te t-amylamide, two cyclopentyl amides, the di neo-pentyl acid amides, the di-n-hexyl acid amides, the dicyclohexyl acid amides, the diheptyl acid amides, the dioctyl acid amides, the dinonyl acid amides, the didecyl acid amides, two (undecyl) acid amides, two (dodecyl) acid amides, two-2-ethylhexyl acid amides, the phenylbenzene acid amides, two-2,6-3,5-dimethylphenyl acid amides, two-2,6-diisopropyl phenyl acid amides, two-2,6-phenylbenzene phenyl acid amides, two-2,6-two basic phenyl amides, two-2,4,6-trimethylphenyl acid amides,-2,4,6-triisopropyl phenyl acid amides, two-2,4,6-triphenyl phenyl acid amides, two-2,4,6-three basic phenyl amides, the dibenzyl acid amides, the dihexyl acid amides, the dicyclohexyl acid amides, the dioctyl acid amides, the didecyl acid amides, two octadecyl acid amides, the phenylbenzene acid amides, the dibenzyl acid amides, two-2,6-3,5-dimethylphenyl acid amides, 2,6-pair-the isopropyl phenyl acid amides, two-2,6-phenylbenzene phenyl acid amides, the diallyl acid amides, the diallyl acid amides, methylphenylamine, N-ethylaniline, N propyl aniline, the N-isopropyl aniline, the N-butylaniline, isobutyl-aniline, the N-amyl aniline, the N-isoamyl aniline, N-octyl group aniline, N-cyclohexyl aniline; And silyl acid amides such as two (trimethylsilyl) acid amides, two (three second are for silyl) acid amides, two (3,5-dimethylphenyl silyl) acid amides, two (t-butyldimethylsilyl) acid amides, two (t-butyldiphenylsilyl) acid amides, phenyl (trimethylsilyl) acid amides, phenyl (three second are for silyl) acid amides, phenyl (trimethylsilyl) acid amides, methyl (trimethylsilyl) acid amides, ethyl (trimethylsilyl) acid amides, n-propyl (trimethylsilyl) acid amides, sec.-propyl (trimethylsilyl) acid amides, cyclopropyl (trimethylsilyl) acid amides, normal-butyl (trimethylsilyl) acid amides, isobutyl-(trimethylsilyl) acid amides, sec-butyl (trimethylsilyl) acid amides, the tertiary butyl (trimethylsilyl) acid amides, cyclobutyl (trimethylsilyl) acid amides, n-pentyl (trimethylsilyl) acid amides, isopentyl (trimethylsilyl) acid amides, sec.-amyl sec-pentyl secondary amyl (trimethylsilyl) acid amides, tert-pentyl (trimethylsilyl) acid amides, neo-pentyl (trimethylsilyl) acid amides, cyclopentyl (trimethylsilyl) acid amides, n-hexyl (trimethylsilyl) acid amides, cyclohexyl (trimethylsilyl) acid amides, heptyl (trimethylsilyl) acid amides and three second are for silyl trimethylsilyl acid amides, and heterocycleamide, for example pyrroles, pyridine, piperidines, piperazine, indoles, imidazoles, the pyrroles, thiazole, fast quinoline, phthalic imidine, the 1-azepan, the 1-Azacyclooctane, 1-nitrogen heterocyclic nonane, 1-nitrogen heterocyclic decane, the conjugate base of their substitutive derivative.
The example of phosphide has dimethyl phosphide, diethyl phosphide, dipropyl phosphide, dibutyl phosphide, diamyl phosphide, dihexyl phosphide, dicyclohexyl phosphide, phenylbenzene phosphatization thing, dibenzyl phosphide, two-2,6-3,5-dimethylphenyl phosphide, two-2,6-diisopropyl phenyl phosphide, 2,6-phenylbenzene phenyl phosphide, and the conjugate base of cyclic phosphines, for example phospholane, phospha cyclohexane, phosphorus heterocycle heptane, phosphorus heterocycle octane, phosphorus heterocycle nonane, phosphorus heterocycle decane.
The single anion unidentate ligand Y that is preferred for this paper is fluorion, chlorion, bromide anion, methylate, ethylate, n-propyl alcohol salt, isopropoxide, butanolate, neopentyl alcohol salt, benzylalcohol salt, fluoroform alkoxide and trifluoroethanol salt.
The mixture of single anion unidentate ligand Y can be used as single anion unidentate ligand Y.
This paper also can utilize the mixture of above-mentioned alkylating reagent to do alkylating reagent.
Described at least a aprotic solvent is the solvent of the hydrogen atom that do not contain any species that can be dissolved in the described solvent remove with the form of proton under working conditions.The example of this solvent comprises aliphatic hydrocrbon, aromatic hydrocarbon and halohydrocarbon and inorganic solvent, and wherein aliphatic hydrocrbon, aromatic hydrocarbon and halohydrocarbon can be chosen the element that comprises the 13rd, 14,15 or 16 families wantonly, and the example of inorganic solvent has CS 2, POCl 3, SO 2Preferred solvent is aliphatic hydrocrbon, aromatic hydrocarbon or halohydrocarbon.More preferably described solvent reaches as high as 10 heteroatomic aliphatic hydrocrbons, aromatic hydrocarbon and halohydrocarbon for comprising 4 to 40 carbon atoms, optional comprising.Most preferred solvent is pentane, heptane, hexane, benzene, toluene, methylene dichloride or 1, the 2-ethylene dichloride.
The present invention can use any inorganic or organic carrier.The example of the inorganic carrier that is fit to has clay, metal oxide, metal hydroxides, metal halide or other metal-salt, for example vitriol, carbonate, phosphoric acid salt, nitrate and silicate.Other example that is suitable for the inorganic carrier of this paper is the metallic compound of the periodic table of elements the 1st and 2 families, the for example oxide compound of the salt of sodium or potassium and magnesium or calcium or salt, as muriate, vitriol, carbonate, phosphoric acid salt or the silicate of sodium, potassium, magnesium or calcium, and for example oxide compound or the oxyhydroxide of magnesium or calcium.That be fit to use also can be inorganic oxide, for example silicon-dioxide, titanium dioxide, aluminum oxide, zirconium white, chromic oxide, boron oxide, silanized silica, silica hydrogel, silica xerogel, aerosil; With the blended oxide compound, for example talcum powder, silicon-dioxide/chromic oxide, silicon-dioxide/chromic oxide/titanium dioxide, silica/alumina, earth silicon/titanic oxide, silicon-dioxide/magnesium oxide, silicon-dioxide/magnesium oxide/titanium dioxide, phosphaljel, silica cogel.Described inorganic oxide can comprise carbonate, nitrate, vitriol and oxide compound, for example Na 2CO 3, K 2CO 3, CaCO 3, MgCO 3, Na 2SO 4, Al 2(SO 4) 3, BaSO 4, KNO 3, Mg (NO 3) 2, Al (NO 3) 3, Na 2O, K 2O and Li 2O.Preferred vector comprises at least a MgCl of being selected from 2, SiO 2, Al 2O 3Or its mixture is as the component of main ingredient.
The example of the organic carrier that is fit to comprises polymkeric substance, for example the multipolymer of the ethene of functional poly ethene, functional poly propylene, functionalization and alpha-olefin, polystyrene, functional polystyrene, polymeric amide and polyester.
The example of the polymeric inorganic carrier that is fit to comprises carbonization siloxanes (carbosiloxanes), phosphine piperazine, siloxanes and hybrid materials such as polymkeric substance/SiO 2 hybrid thing.
Be preferred for this paper for the halogenide of inorganic oxide, blended oxide compound, the 2nd family and contain deposition or be deposited in the inorganic oxide carrier of the magnesium chloride on the above-mentioned oxide surface, wherein the example of inorganic oxide has silicon-dioxide, titanium dioxide, aluminum oxide, the example of blended oxide compound has talcum, silicon-dioxide/chromic oxide, silicon-dioxide/chromic oxide/titanium dioxide, silica/alumina, earth silicon/titanic oxide, and the halid example of the 2nd family has magnesium chloride, magnesium bromide, calcium chloride and Calcium Bromide.
What more preferably be used for this paper is the inorganic oxide carrier that contains deposition or be deposited in the magnesium chloride on the above-mentioned oxide surface, for example magnesium chloride on the silicon-dioxide.
In another embodiment of the invention, discovery can prepare the aforesaid solid procatalyst that comprises electron donor(ED) at least one.By at least a empirical formula ML xX 4-xTransistion metal compound and at least a formula L xER nY mH pAlkylating reagent and at least a in electron donor(ED) at least a aprotic solvent, react so that soluble species to be provided, the soluble species of gained is contacted with carrier prepare solid procatalyst subsequently, at formula ML xX 4-xIn, M is titanium, zirconium or hafnium, and independently for the atom that is selected from oxygen, sulphur, selenium, tellurium, nitrogen, phosphorus, arsenic, antimony and bismuth or its mixture by two is connected to single anion bidentate ligand on the M, X is fluorion, chlorion, bromide anion or iodide ion to L separately, and 0＜x≤4 are at formula L xER nY mH pIn, L independently is connected to single anion bidentate ligand on the E for the atom that is selected from oxygen, sulphur, selenium, tellurium, nitrogen, phosphorus, arsenic, antimony and bismuth or its mixture by two separately, E is boron, aluminium, gallium or indium, R independently is alkyl separately, and Y independently is the single anion unidentate ligand separately, 0＜x≤2, n＞0, m 〉=0, p 〉=0, and x+n+m+p=3.Described soluble species contacted with described carrier comprise and to be deposited on the carrier by described dissolubility species.The solid procatalyst that obtains provides the catalyst system of suitable olefinic polymerization or copolymerization with promotor.
The mol ratio of interior electron donor(ED) and transistion metal compound is preferably about 0.1 to about 100.The mol ratio of electron donor(ED) and transistion metal compound is about 0.25 to about 15 in preferred.The mol ratio of more preferably interior electron donor(ED) and transistion metal compound is about 1 to about 5.
The example of interior electron donor(ED) has carboxylicesters; acid anhydrides; acyl halide; ether; thioether; aldehyde; ketone; imines; amine; acid amides; nitrile; isonitrile; cyanate; isocyanic ester; thiocyanic ester; lsothiocyanates; thioester; the dithio acid esters; carbonic ether; the alkyl carbamate; the alkyl thiocarbamate; the alkyl dithiocarbamate; urethanum; phosphine; sulfide; phosphine oxide; phosphamide; sulfoxide; sulfone; sulphonamide; comprise the silicoorganic compound of at least one Sauerstoffatom and link nitrogen on the organic group by carbon or Sauerstoffatom; phosphorus; arsenic or antimony compounds.
The example that can be used as the ether of interior electron donor(ED) in this article has any compound that comprises at least one C-O-C ehter bond.Be included in the scope of ether compound for comprising heteroatomic compound, wherein heteroatoms is the atom that is selected from the periodic table of elements the 13rd, 14,15,16 and 17 families outside the de-carbon.The example of ether has dialkyl ether, diaryl ether, two alkyl aryl ethers, two aralkyl ethers, alkyl aryl ether, alkyl-alkyl aryl ethers, alkyl aralkyl ether, aryl alkyl aryl ether, aryl aralkyl ethers and alkaryl aralkyl ethers.Be included in the ether scope for as following compound: dme, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, isoamyl ether, di-tert-butyl ether, phenyl ether, dibenzyl ether, divinyl ether, butyl methyl ether, the butyl ether, the sec-butyl methyl ether, t-butyl methyl ether, the cyclopentyl methyl ether, the cyclohexyl ether, tertiary amyl-methyl ether, the sec-butyl ether, chloromethyl methyl ether, trimethylsilyl methyl ether, two (trimethylsilyl methyl) ether, two (2,2, the 2-trifluoroethyl) ether, methyl phenyl ether, oxyethane, propylene oxide, 1, the 2-butylene oxide ring, cyclopentenes oxygen (cyclopentene oxide), Epicholorohydrin, furans, 2, the 3-dihydrofuran, 2, the 5-dihydrofuran, tetrahydrofuran (THF), the 2-methyltetrahydrofuran, 2, the 5-dimethyl-tetrahydrofuran, the 2-methyl furan, 2, the 5-dimethyl furan, tetrahydropyrans, 1,2-epoxy fourth-3-alkene, Styrene oxide 98min., 2-ethyl furan oxazole, 1,3, the 4-oxadiazole, 3,4-two chloro-1, the 2-butylene oxide ring, 3,4-two bromo-1, the 2-butylene oxide ring, Methylal(dimethoxymethane), 1, the 1-glycol dimethyl ether, 1,1, the 1-trimethoxy-methane, 1,1, the 1-trimethoxy-ethane, 1,1, the 2-trimethoxy-ethane, 1, the 1-Propanal dimethyl acetal, 1, the 2-Propanal dimethyl acetal, 2, the 2-Propanal dimethyl acetal, 1, the 3-Propanal dimethyl acetal, 1,1,3-trimethoxy propane, 1, the 4-dimethoxy-butane, 1, the 2-dimethoxy benzene, 1, the 3-dimethoxy benzene, 1, the 4-dimethoxy benzene, glycol dimethyl ether, diglyme, diethyl carbitol, diethylene glycol dibutyl ether, the glycol ether t-butyl methyl ether, triglyme, the triglycol diethyl ether, tetraethylene glycol dimethyl ether, 2,2-diethyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-ethyl-1, the 3-Propanal dimethyl acetal, 2-methoxyl group furans, 3-methoxyl group furans, 1, the 3-dioxolane, the 2-methyl isophthalic acid, the 3-dioxolane, 2,2-dimethyl-1, the 3-dioxolane, 2-ethyl-2-methyl isophthalic acid, the 3-dioxolane, 2,2-tetramethylene-1, the 3-dioxolane, 2,2-pentamethylene-1, the 3-dioxolane, 1, the 3-dioxane, 1, the 4-dioxane, the 4-methyl isophthalic acid, the 3-dioxane, 1,3,5-trioxane and 3,4-epoxy tetrahydrofuran (THF).
The preferred ether compound that is used as interior electron donor(ED) herein is tetrahydrofuran (THF), diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dioctyl ether, t-butyl methyl ether, trimethylene oxide, 1,2-glycol dimethyl ether, 1,2-Propanal dimethyl acetal, 1,3-Propanal dimethyl acetal, 1,2-dimethoxy-butane, 1,3-dimethoxy-butane, 1,4-dimethoxy-butane and tetrahydropyrans.
The example that can be used as the thioether of interior electron donor(ED) in this article has any compound that comprises at least one C-S-C thioether bond.Be included in the scope of sulfide compound for comprising heteroatomic compound, wherein heteroatoms is the atom that is selected from the periodic table of elements the 13rd, 14,15,16 and 17 families outside the de-carbon.The example of thioether has dialkyl sulfide, diaryl sulfide, dioxane aryl thioethers, two aralkyl thioethers, alkylaryl thioether, alkyl-alkyl aryl thioethers, alkyl aralkyl thioether, aryl alkaryl thioether, aryl aralkyl thioether and alkaryl aralkyl thioether.Comprise as following compound: dimethyl sulphide, the diethyl thioether, propyl thioether, the di-isopropyl thioether, dibutyl sulfide ether, the diamyl thioether, two own thioethers, two hot thioethers, isoamyl sulfide, the di-t-butyl thioether, diphenyl sulfide, dibenzyl sulfide, vinyl thioether, diallyl thioether, the dipropargyl thioether, two cyclopropyl thioethers, two cyclopentyl thioethers, the dicyclohexyl thioether, the allyl methyl thioether, the allyl group ethyl thioether, allyl group cyclohexyl thioether, the allyl phenyl thioether, allyl group benzyl thioether, allyl group 2-tolyl thioether, allyl group 3-tolyl thioether, benzyl methyl thioether, the benzyl ethyl thioether, the benzyl isoamyl sulfide, benzyl chloride methyl thioether, benzyl rings hexyl thioether, the benzyl phenyl thioether, benzyl 1-naphthyl thioether, benzyl 2-naphthyl thioether, the butyl methyl thioether, the butyl ethyl thioether, sec-butyl methyl thioether, tertiary butyl methyl thioether, butyl cyclopentyl thioether, butyl 2-chloroethyl thioether, the cyclopentyl-methyl thioether, the cyclohexyl ethyl thioether, cyclohexyl vinyl thioether, uncle-amyl group methyl thioether, the sec-butyl ethyl thioether, tertiary butyl ethyl thioether, the tert-pentyl ethyl thioether, cyclododecane ylmethyl thioether, two (2-cyclopentenes-1-yl) sulphur, 1-methylthio group-1, the 3-cyclohexadiene, 1-methylthio group-1, the 4-cyclohexadiene, chloromethyl methyl thioether, the chloromethyl ethyl thioether, two (2-tolyl) thioether, trimethylsilyl methyl thioether, Thietane, thiophene, 2, the 3-dihydro-thiophene, 2, the 5-dihydro-thiophene, tetramethylene sulfide, 2-methyl tetramethylene sulfide, 2,5-dimethyl tetrahydro thiophene, 4,5-dihydro-2-thiotolene, the 2-thiotolene, 2, the 5-thioxene, 3 bromo thiophene, 2, the 3-thionaphthene, 2-methylbenzene thiophthene, dibenzothiophene, different thionaphthene, 1, two (methylthio group) ethane of 1-, 1,1,1-three (methylthio group) ethane, 1,1,2-three (methylthio group) ethane, 1, two (methylthio group) propane of 1-, 1, two (methylthio group) propane of 2-, 2, two (methylthio group) propane of 2-, 1, two (methylthio group) propane of 3-, 1,1,3-three (methylthio group) propane, 1, two (methylthio group) butane of 4-, 1, two (methylthio group) benzene of 2-, 1, two (methylthio group) benzene of 3-, 1, two (methylthio group) benzene of 4-, the ethylene glycol dimethyl thioether, the ethylene glycol bisthioglycolate ethyl thioether, the ethylene glycol bisthioglycolate thio-allyl ether, the ethylene glycol diphenylsulfide, ethylene glycol tertiary butyl methyl thioether, ethylene glycol tertiary butyl ethyl thioether, 2, two (methylthio group) thiophene of 5-, 2-methylthio group thiophene, 3-methylthio group thiophene, 2-methylthio group tetrahydropyrans, 3-methylthio group tetrahydropyrans, 1, the 3-dithiolane, the 2-methyl isophthalic acid, the 3-dithiolane, 2,2-dimethyl-1,3-dithiolane, 2-ethyl-2-methyl isophthalic acid, the 3-dithiolane, 2,2-tetramethylene-1, the 3-dithiolane, 2,2-pentamethylene-1, the 3-dithiolane, 2-vinyl-1, the 3-dithiolane, 2-chloromethyl-1, the 3-dithiolane, 2-methylthio group-1, the 3-dithiolane, 1, the 3-dithiane, 1, the 4-dithiane, the 4-methyl isophthalic acid, the 3-dithiane, 1,3, the 5-trithian, 2-(2-ethylhexyl)-1, two (methylthio group) propane of 3-, 2-sec.-propyl-1, two (methylthio group) propane of 3-, 2-butyl-1, two (methylthio group) propane of 3-, 2-sec-butyl-1, two (methylthio group) propane of 3-, the 2-tertiary butyl-1, two (methylthio group) propane of 3-, 2-cyclohexyl-1, two (methylthio group) propane of 3-, 2-phenyl-1, two (methylthio group) propane of 3-, 2-cumyl-1, two (methylthio group) propane of 3-, 2-(2-phenylethyl)-1, two (methylthio group) propane of 3-, 2-(2-cyclohexyl ethyl)-1, two (methylthio group) propane of 3-, 2-(rubigan)-1, two (methylthio group) propane of 3-, 2-(to fluorophenyl)-1, two (methylthio group) propane of 3-, 2-(diphenyl methyl)-1, two (methylthio group) propane of 3-, 2,2-dicyclohexyl-1, two (methylthio group) propane of 3-, 2,2-diethyl-1, two (methylthio group) propane of 3-, 2,2-dipropyl-1, two (methylthio group) propane of 3-, 2,2-di-isopropyl-1, two (methylthio group) propane of 3-, 2,2-dibutyl-1, two (methylthio group) propane of 3-, 2,2-diisobutyl-1, two (methylthio group) propane of 3-, 2-methyl-2-ethyl-1, two (methylthio group) propane of 3-, 2-methyl-2-propyl group-1, two (methylthio group) propane of 3-, 2-methyl-2-butyl-1, two (methylthio group) propane of 3-, 2-methyl-2-benzyl-1, two (methylthio group) propane of 3-, 2-methyl-2-methylcyclohexyl-1, two (methylthio group) propane of 3-, 2-sec.-propyl-2-isopentyl-1, two (methylthio group) propane of 3-, 2, two (the 2-cyclohexyl methyls)-1 of 2-, two (methylthio group) propane of 3-.
Any amine can be used as interior electron donor(ED) herein.Comprise containing heteroatomic amine compound that wherein heteroatoms is the atom that is selected from the periodic table of elements the 13rd, 14,15,16 and 17 families outside the de-carbon.The amine that the example of amine has by primary, the second month in a season and tertiary alkyl, aryl, alkaryl and aralkyl replace.The example of amine has ammonia, methylamine, ethamine, propylamine, Isopropylamine, butylamine, isobutylamine, amylamine, isobutylcarbylamine, octylame, hexahydroaniline, aniline, dimethylamine, diethylamine, dipropyl amine, Diisopropylamine, dibutylamine, diisobutylamine, diamylamine, di-iso-amylamine, Di-Octyl amine, dicyclohexyl amine, Trimethylamine 99, triethylamine, tripropyl amine, tri-isopropyl amine, Tributylamine, tri-isobutylamine, triamylamine, tri-isoamylamine, trioctylamine, tricyclohexyltin amine, methylphenylamine, N-ethylaniline, N propyl aniline, the N-isopropyl aniline, the N-butylaniline, isobutyl-aniline, the N-amyl aniline, the N-isoamyl aniline, N-octyl group aniline, N-cyclohexyl aniline, N, accelerine, N, the N-Diethyl Aniline, N, N-dipropyl aniline, N, the N-diisopropyl aniline, N, the N-dibutyl aniline, N, N-diisobutyl aniline, N, N-diamyl aniline, N, N-diisoamyl aniline, N, N dimethylamine, N, N-dicyclohexyl aniline, azetidine, the 1-methyl azetidine, 1-ethyl azetidine, 1-propyl group azetidine, 1-sec.-propyl azetidine, 1-butyl azetidine, 1-isobutyl-azetidine, 1-amyl group azetidine, 1-isopentyl azetidine, tetramethyleneimine, the N-Methylimidazole, the 1-crassitude, the 1-ethyl pyrrolidine, 1-propyl pyrrole alkane, 1-sec.-propyl tetramethyleneimine, the 1-butyl pyrrolidine, 1-isobutyl-tetramethyleneimine, 1-amyl group tetramethyleneimine, 1-isopentyl tetramethyleneimine, 1-octyl group tetramethyleneimine, 1-cyclohexyl tetramethyleneimine, the 1-Phenylpyrrolidine, piperidines, the 1-methyl piperidine, the 1-ethyl piperidine, 1-propyl group piperidines, 1-sec.-propyl piperidines, the 1-butyl piperidine, 1-isobutyl-piperidines, the 1-amyl piperidine, 1-isopentyl piperidines, 1-octyl group piperidines, 1-cyclohexyl piperidines, the 1-Phenylpiperidine, piperazine, the 1-methylpiperazine, the 1-ethyl piperazidine, 1-propyl group piperazine, 1-sec.-propyl piperazine, 1-butyl piperazine, the 1-isobutyl piperazine, 1-amyl group piperazine, 1-isopentyl piperazine, 1-octyl group piperazine, 1-cyclohexyl piperazine, the 1-phenylpiperazine, 1, the 4-lupetazin, 1,4-diethyl piperazine, 1,4-dipropyl piperazine, 1,4-di-isopropyl piperazine, 1,4-dibutyl piperazine, 1,4-diisobutyl piperazine, 1,4-diamyl piperazine, 1,4-diisoamyl piperazine, 1,4-dioctyl piperazine, 1,4-dicyclohexyl piperazine, 1,4-phenylbenzene piperazine, pyridine, the 2-picoline, the 4-picoline, hexamethyldisilazane, morpholine, N-methylmorpholine.
In being used as in can be herein the example of the carboxylicesters of electron donor(ED) have any comprise at least one C (=O)-carbonate of O-C ester bond.The example of carboxylicesters has and contains the saturated or undersaturated aliphatic series of ester bond, alicyclic or aromatic substance.Be included in the scope of carboxylicesters for comprising heteroatomic compound, wherein heteroatoms is the atom that is selected from the periodic table of elements the 13rd, 14,15,16 and 17 families outside the de-carbon.Other example of carboxylicesters has methyl-formiate, methyl acetate, ethyl acetate, vinyl-acetic ester, propyl acetate, butylacetate, isopropyl acetate, isobutyl acetate, octyl acetate, hexalin acetate, ethyl propionate, Valeric acid ethylester, the Mono Chloro Acetic Acid methyl ester, the Mono Chloro Acetic Acid ethyl ester, methyl methacrylate, butenoic acid ethyl, the PIVALIC ACID CRUDE (25) ethyl ester, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isobutyl benzoate, isopropyl benzoate, n-octyl benzoate, the phenylformic acid cyclohexyl, phenol benzoate, peruscabin, the 2-methyl-toluate, 2-tolyl acid ethyl ester, 2-tolyl acid propyl ester, 2-tolyl acid isopropyl ester, 2-tolyl acid butyl ester, 2-tolyl acid isobutyl ester, 2-tolyl acid monooctyl ester, 2-tolyl acid cyclohexyl, 2-tolyl acid 2-methyl phenyl ester, 2-tolyl acid benzyl ester, the 3-methyl-toluate, 3-tolyl acid ethyl ester, 3-tolyl acid propyl ester, 3-tolyl acid isopropyl ester, 3-tolyl acid butyl ester, 3-tolyl acid isobutyl ester, 3-tolyl acid monooctyl ester, 3-tolyl acid cyclohexyl, 3-tolyl acid 3-methyl phenyl ester, 3-tolyl acid benzyl ester, methyl 4 methylbenzoate, 4-tolyl acid ethyl ester, 4-tolyl acid propyl ester, 4-tolyl acid isopropyl ester, 4-tolyl acid butyl ester, 4-tolyl acid isobutyl ester, 4-tolyl acid monooctyl ester, 4-tolyl acid cyclohexyl, 4-tolyl acid 4-methyl phenyl ester, 4-tolyl acid benzyl ester, neighbour-chloro benzoic ether, neighbour-chloro-benzoic acid ethyl ester, neighbour-chloro-benzoic acid propyl ester, neighbour-chloro-benzoic acid isopropyl ester, neighbour-chloro-benzoic acid butyl ester, neighbour-chloro-benzoic acid isobutyl ester, neighbour-chloro-benzoic acid pentyl ester, neighbour-chloro-benzoic acid isopentyl ester, neighbour-chloro-benzoic acid monooctyl ester, neighbour-chloro-benzoic acid cyclohexyl, neighbour-chloro-benzoic acid phenyl ester, neighbour-chloro-benzoic acid benzyl ester, between-chloro benzoic ether, between-the chloro-benzoic acid ethyl ester, between-the chloro-benzoic acid propyl ester, between-the chloro-benzoic acid isopropyl ester, between-the chloro-benzoic acid butyl ester, between-the chloro-benzoic acid isobutyl ester, between-the chloro-benzoic acid pentyl ester, between-the chloro-benzoic acid isopentyl ester, between-the chloro-benzoic acid monooctyl ester, between-the chloro-benzoic acid cyclohexyl, between-the chloro-benzoic acid phenyl ester, between-chloro-benzoic acid benzyl ester, right-chloro benzoic ether, right-the chloro-benzoic acid ethyl ester, right-the chloro-benzoic acid propyl ester, right-the chloro-benzoic acid isopropyl ester, right-the chloro-benzoic acid butyl ester, right-the chloro-benzoic acid isobutyl ester, right-the chloro-benzoic acid pentyl ester, right-the chloro-benzoic acid isopentyl ester, right-the chloro-benzoic acid monooctyl ester, right-the chloro-benzoic acid cyclohexyl, right-the chloro-benzoic acid phenyl ester, right-chloro-benzoic acid benzyl ester, dimethyl maleate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, phthalic acid methylethyl ester, phthalic acid methyl-propyl ester, phthalic acid methyl butyl ester, phthalic acid methyl-isobutyl ester, phthalic acid ethyl propyl ester, phthalic acid ethyl-butyl ester, phthalic acid ethyl isobutyl, phthalic acid propyl group butyl ester, phthalic acid propyl group isobutyl, dimethyl terephthalate (DMT), diethyl terephthalate, the terephthalic acid dipropyl, dibutyl terephthalate, isobutyl terephthalate, terephthalic acid methylethyl ester, terephthalic acid methyl-propyl ester, terephthalic acid methyl butyl ester, terephthalic acid methyl-isobutyl ester, terephthalic acid ethyl propyl ester, terephthalic acid ethyl-butyl ester, terephthalic acid ethyl isobutyl, terephthalic acid propyl group butyl ester, terephthalic acid propyl group isobutyl, dimethyl isophthalate, dimethyl isophthalate, the m-phthalic acid dipropyl, the m-phthalic acid dibutylester, the m-phthalic acid diisobutyl ester, m-phthalic acid methylethyl ester, m-phthalic acid methyl-propyl ester, m-phthalic acid methyl butyl ester, m-phthalic acid methyl-isobutyl ester, m-phthalic acid ethyl propyl ester, m-phthalic acid ethyl-butyl ester, m-phthalic acid ethyl isobutyl, m-phthalic acid propyl group butyl ester, m-phthalic acid propyl group isobutyl, rhodia, cellulose butyrate, cellulosic mixed ester.
Can be herein as the example of the thioester of interior electron donor(ED) have comprise at least one C (=O)-compound of S-C thioic acid sulfoacid ester bond.The example of thioester has and comprises the saturated or undersaturated aliphatic series of thioic acid sulfoacid ester bond, alicyclic or aromatic substance.Interior the having of scope that is included in thioester comprises heteroatomic compound, and wherein heteroatoms is the atom that is selected from the periodic table of elements the 13rd, 14,15,16 and 17 families outside the de-carbon.The example of thioester has the thiol-acetic acid methyl esters, the thiol-acetic acid ethyl ester, the thiol-acetic acid propyl ester, the thiol-acetic acid isopropyl ester, the thiol-acetic acid butyl ester, the thiol-acetic acid isobutyl ester, the thiol-acetic acid pentyl ester, the thiol-acetic acid isopentyl ester, the thiol-acetic acid monooctyl ester, the thiol-acetic acid cyclohexyl, the thiol-acetic acid phenyl ester, thiol-acetic acid 2-chloroethene ester, thiol-acetic acid 3-chlorine propyl ester, the thiobenzoic acid methyl esters, the thiobenzoic acid ethyl ester, the thiobenzoic acid propyl ester, the thiobenzoic acid isopropyl ester, the thiobenzoic acid butyl ester, the thiobenzoic acid isobutyl ester, the thiobenzoic acid pentyl ester, the thiobenzoic acid isopentyl ester, the thiobenzoic acid monooctyl ester, the thiobenzoic acid cyclohexyl, the thiobenzoic acid phenyl ester, thiobenzoic acid 2-chloroethene ester, thiobenzoic acid 3-chlorine propyl ester.
Can be herein as the example of the acid amides of interior electron donor(ED) have comprise at least one C (=O)-compound of N amido linkage.The example of acid amides has and contains the saturated or undersaturated aliphatic series of amido linkage, alicyclic or aromatic substance.Interior the having of scope that is included in acid amides comprises heteroatomic compound, and wherein heteroatoms is the atom that is selected from the periodic table of elements the 13rd, 14,15,16 and 17 families outside the de-carbon.The example of acid amides has methane amide; ethanamide; propionic acid amide; isobutyramide; pivalyl amine; hexanamide; stearylamide; the hexanaphthene acid amides; 1-diamantane acid amides; acrylamide; Methacrylamide; the 2-monofluoroacetamide; the 2-chlor(o)acetamide; the 2-bromoacetamide; 2; the 2-dichloro acetamide; 2; 2; the 2-trifluoroacetamide; 2; 2; the 2-trichloroacetamide; 2-chlorine propionic acid amide; benzamide; the N-methylformamide; the N-ethyl-formamide; N-propyl group methane amide; N-butyl methane amide; N-isobutyl-methane amide; N-amyl group methane amide; N-cyclohexyl methane amide; formylaniline; the N-methylacetamide; the N-ethyl acetamide; the N-propyl acetamide; N-butyl ethanamide; N-isobutyl-ethanamide; N-amyl group ethanamide; N-cyclohexyl ethanamide; Acetanilide; the N-methyl propanamide; N-ethyl propionic acid amide; N-propyl group propionic acid amide; N-butyl propionic acid amide; N-isobutyl-propionic acid amide; N-amyl group propionic acid amide; N-cyclohexyl propionic acid amide; the N-Phenylpropionamide; N-methyl isobutyramide; N-methyl trimethoxy yl acetamide; N-methyl hexanamide; N-methyl stearylamide; N methacrylamide; N-methyl acrylamide; N-methyl-2-monofluoroacetamide; N-methyl-2-chlor(o)acetamide; N-methyl-2-bromoacetamide; N-methyl-2; the 2-dichloro acetamide; N-methyl-2; 2; the 2-trifluoroacetamide; N-methyl-2; 2; the 2-trichloroacetamide; N-methyl-2-chlorine propionic acid amide; N; dinethylformamide; N; the N-diethylformamide; N; the N-diisopropyl formamide; N; the N-dibutyl formamide; the N-methyl formyl aniline; N; the N-N,N-DIMETHYLACETAMIDE; N; the N-diethyl acetamide; N; N-di-isopropyl ethanamide; N; the N-dibutyl acetamide; the N-exalgine; N; N-dimethyl propylene acid amides; N; N-diethyl propionic acid amide; N; N-di-isopropyl propionic acid amide; N; N-dibutyl propionic acid amide; N; N-dimethyl isobutyramide; N; N-dimethyl pivalyl amine; N; N-dimethyl hexanamide; N; N-dimethyl stearylamide; N; the N-DMAA; N; the N-dimethylmethacryl amide; N; N-dimethyl-2-monofluoroacetamide; N; N-dimethyl-2-chlor(o)acetamide; N; N-dimethyl-2-bromoacetamide; N; N-dimethyl-2; the 2-dichloro acetamide; N; N-dimethyl-2; 2; the 2-trifluoroacetamide; N; N-diethyl-2; 2; the 2-trifluoroacetamide; N; N-di-isopropyl-2; 2; the 2-trifluoroacetamide; N; N-dibutyl-2; 2; the 2-trifluoroacetamide; N; N-dimethyl-2; 2; the 2-trichloroacetamide; N; N-diethyl-2; 2; the 2-trichloroacetamide; N; N-di-isopropyl-2; 2; the 2-trichloroacetamide; N; N-dibutyl-2; 2; the 2-trichloroacetamide; N; N-dimethyl-2-chlorine propionic acid amide; 1-ethanoyl azetidine; the 1-acetyl-pyrrolidine; 1-ethanoyl piperidines; 1-ethanoyl piperazine; 1-ethanoyl piperazine; 1,4-diacetyl piperazine.
Can be herein as the example of the acid anhydrides of interior electron donor(ED) have comprise at least one C (=O)-compound of O-(C=O) anhydride bond.The example of acid anhydrides has and contains the saturated or undersaturated aliphatic series of anhydride bond, alicyclic or aromatic substance.Interior the having of scope that is included in acid anhydrides comprises heteroatomic compound, and wherein heteroatoms is the atom that is selected from the periodic table of elements the 13rd, 14,15,16 and 17 families outside the de-carbon.The example of acid anhydrides has diacetyl oxide, propionic anhydride, butyryl oxide, isobutyric anhydride, valeric anhydride, trimethyl acetic anhydride, caproic anhydride, heptylic anhydride, capric anhydride, lauric anhydride, myristic anhydride, the palmitic acid acid anhydride, the stearic acid acid anhydride, the docosane acid anhydrides, crotonic anhydride, methacrylic anhydride, oil anhydride, the linolic acid acid anhydride, sym-dichloroacetic anhydride, the iodoacetic acid acid anhydride, the dichloro acetic acid acid anhydride, trifluoroacetic anhydride, the chlorodifluoroacetic acid acid anhydride, Trichloroacetic anhydride, PFPA, heptafluorobutyric anhydride, succinyl oxide, the methylsuccinic acid acid anhydride, 2, the 2-dimethyl succinic anhydride, itaconic anhydride, maleic anhydride, Pyroglutaric acid, the di-alcohol acid anhydrides, benzoyl oxide, the phenyl succinyl oxide, the phenyl maleic anhydride, the homophthalic acid acid anhydride, isatoic anhydride, Tetra hydro Phthalic anhydride, ptfe phthalic anhydride, tetrabromophthalic anhydride, mixed acid anhydride.
Can be herein as the example of the acyl halide of interior electron donor(ED) have comprise at least one C (=O)-compound of X acyl halide group, wherein X is a halogen.Example has and contains the saturated or undersaturated aliphatic series of chloride of acid group, alicyclic or aromatic substance.Interior the having of scope that is included in chloride of acid contains heteroatomic compound, and wherein heteroatoms is the atom that is selected from the periodic table of elements the 13rd, 14,15,16 and 17 families outside the de-carbon.The example of acyl halide has Acetyl Chloride 98Min.; acetyl bromide; chloroacetyl chloride; dichloroacetyl chloride; trichoroacetic chloride; trifluoroacetyl chloride; tribromo-acetyl chloride; propionyl chloride; propionyl bromide; butyryl chloride; isobutyryl chloride; trimethyl-acetyl chloride; 3-cyclopentyl propionyl chloride; the 2-chlorpromazine chloride; the 3-chlorpromazine chloride; tertiary butyl Acetyl Chloride 98Min.; isoveryl chloride; caproyl chloride; oenanthyl chloro; decanoyl chloride; lauroyl chloride; myristyl chloride; hexadecanoyl chloride; stearoyl chlorine; oleoyl chloride; the pentamethylene formyl chloride; oxalyl chloride; malonyl chloride; succinyl dichloride glutaryl chlorine; hexanedioyl chlorine; pimeloyl chloride; suberoyl chlorine; azelaoyl chloride; sebacoyl chloride; the dodecane diacid chloride; methoxyacetyl chloride; the oxyethyl group Acetyl Chloride 98Min..
Can be herein as the example of the aldehyde of interior electron donor(ED) have comprise at least one C-C (=O)-compound of H aldehyde radical.Example has and contains the saturated or undersaturated aliphatic series of aldehyde radical, alicyclic or aromatic substance.Interior the having of scope that is included in aldehyde comprises heteroatomic compound, and wherein heteroatoms is the atom that is selected from the periodic table of elements the 13rd, 14,15,16 and 17 families outside the de-carbon.The example of aldehyde has formaldehyde, acetaldehyde, propionic aldehyde, isobutyric aldehyde, trimethyl-acetaldehyde, butyraldehyde, 2 methyl butyraldehyde, valeral, isovaleric aldehyde, hexanal, the 2-ethyl hexanal, enanthaldehyde, capraldehyde, crotonaldehyde, propenal, methacrylaldehyde, 2-ethyl acrylic aldehyde, monochloroacetaldehyde, Jod-acetaldehyd, dichloro acetaldehyde, trifluoro acetaldehyde, one chlorine difluoro acetaldehyde, trichoro-aldehyde, five fluorine propionic aldehyde, seven fluorine butyraldehyde, phenyl acetaldehyde, phenyl aldehyde, neighbour-toluic aldehyde, between-toluic aldehyde, right-toluic aldehyde, instead-Nei cinnamic aldehyde, instead-the 2-nitro cinnamaldehyde, the 2-bromobenzaldehyde, the 2-chlorobenzaldehyde, the 3-chlorobenzaldehyde, the 4-chlorobenzaldehyde.
Can be herein as the example of the ketone of interior electron donor(ED) have comprise at least one C-C (=O)-compound of C ketonic bond.Example has and contains the saturated or undersaturated aliphatic series of ketonic bond, alicyclic or aromatic substance.Interior the having of scope that is included in ketone contains heteroatomic compound, and wherein heteroatoms is the atom that is selected from the periodic table of elements the 13rd, 14,15,16 and 17 families outside the de-carbon.The example of ketone has acetone, 2-butanone, 3-methyl-2-butanone, Pinacolone, 2 pentanone, propione, 3-methyl-2 pentanone, 4-methyl-2 pentanone, 2-methyl-propione, 4,4-dimethyl-2 pentanone, 2,4-dimethyl-propione, 2,2,4,4-tetramethyl--propione, methyl-n-butyl ketone, the 3-hexanone, 5 methy 12 hexanone, 2-methyl-3-hexanone, 2-heptanone, the 3-heptanone, dipropyl ketone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2, the 6-valerone, methyln-hexyl ketone, the 3-octanone, the 4-octanone, methyl phenyl ketone, benzophenone, mesityl oxide, Perfluoroacetone, perfluor-2-butanone, 1,1, the 1-trichloroacetone.
The example that can be used as the nitrile of interior electron donor(ED) herein has the compound that comprises at least one C-C ≡ N itrile group.Example has the saturated or undersaturated aliphatic series of nitrile group-containing, alicyclic or aromatic substance.Interior the having of scope that is included in nitrile contains heteroatomic compound, and wherein heteroatoms is the atom that is selected from the periodic table of elements the 13rd, 14,15,16 and 17 families outside the de-carbon.The example of nitrile has acetonitrile, propionitrile, different propionitrile, butyronitrile, isopropyl cyanide, valeronitrile, isovaleronitrile, trimethylacetonitrile, own nitrile, heptonitrile, caprylic nitrile (heptyl cyanide), octyl group cyanogen (octyl cyanide), undecanonitrile, propane dinitrile, succinonitrile, trimethylene cyanide, adiponitrile, sebaconitrile, allyl cyanide, vinyl cyanide, propenyl cyanide, methacrylonitrile, flumaronitrile, tetracyanoethylene, the pentamethylene nitrile, cyclohexane nitrile, two chloromethyl cyanides, fluoride acetonitrile, Trichloroacetonitrile, benzonitrile, Bian Jiqing, 2-methyl-benzyl cyanogen, 2-benzyl chloride nitrile, 3-benzyl chloride nitrile, 4-benzyl chloride nitrile, neighbour-tolunitrile, between-tolunitrile, right-tolunitrile.
The example that can be used as the isocyanides of interior electron donor(ED) herein has the compound that comprises at least one C-N ≡ C isonitrile base.Example has and contains the saturated or undersaturated aliphatic series of isonitrile base, alicyclic or aromatic substance.Interior the having of scope that is included in isocyanides contains heteroatomic compound, and wherein heteroatoms is the atom that is selected from the periodic table of elements the 13rd, 14,15,16 and 17 families outside the de-carbon.The example of isocyanides have methyl-isocyanide, ethyl isonitrile, propyl carbylamine, isopropyl isonitrile, positive fourth isocyanides, uncle's fourth isocyanides, Zhong Ding isocyanides, capronitrile, own isocyanides, heptan isocyanides, hot isocyanides, ninth of the ten Heavenly Stems isocyanides, last of the ten Heavenly stems isocyanides, 11 isocyanides, benzyl isocyanides, 2-methyl benzyl isocyanides, 2-chlorobenzene and isocyanides, 3-chlorobenzene and isocyanides, 4-chlorobenzene and isocyanides, neighbour-methylbenzene methyl-isocyanide ,-methylbenzene methyl-isocyanide, right-the methylbenzene methyl-isocyanide, dichlorophenyl isocyanides, 1,4-phenylene two isocyanides.
The example that can be used as the thiocyanate-of interior electron donor(ED) herein has the compound that comprises at least one C-SCN thiocyanate ion.Example has and contains the saturated or undersaturated aliphatic series of thiocyanate ion, alicyclic or aromatic substance.Interior the having of scope that is included in thiocyanate-contains heteroatomic compound, and wherein heteroatoms is the atom that is selected from the periodic table of elements the 13rd, 14,15,16 and 17 families outside the de-carbon.The example of thiocyanate-has methylthiocyanide methylthiocyanate; Thiocyanic Acid Ethyl ester; propyl thiocyanide; isopropyl thiocyanate; the positive butyl ester of thiocyanic acid; the thiocyanic acid tert-butyl ester; the secondary butyl ester of thiocyanic acid; amyl thiocyanide; the own ester of thiocyanic acid; the thiocyanic acid heptyl ester; the thiocyanic acid monooctyl ester; thiocyanic acid ester in the ninth of the ten Heavenly Stems; thiocyanic acid ester in the last of the ten Heavenly stems; thiocyanic acid undecyl ester; benzyl thiocyanide; the thiocyanic acid phenylester; thiocyanic acid 4 '-bromophenyl acyl ester; thiocyanic acid 2-methyl-benzyl ester; 2-chlorobenzene and thiocyanic ester; 3-chlorobenzene and thiocyanic ester; 4-chlorobenzene and thiocyanic ester; neighbour-methylbenzene first thiocyanic ester; between-methylbenzene first thiocyanic ester; right-methylbenzene first thiocyanic ester.
The example that can be used as the isothiocyanate of interior electron donor(ED) herein has the compound that contains at least one C-NCS isosulfocyanate radical.Example has and contains the saturated or undersaturated aliphatic series of isosulfocyanate radical, alicyclic or aromatic substance.Interior the having of scope that is included in isothiocyanate contains heteroatomic compound, and wherein heteroatoms is the atom that is selected from the periodic table of elements the 13rd, 14,15,16 and 17 families outside the de-carbon.The example of isothiocyanate has Trapex; ethyl mustard oil; propyl isothiocyanide; isopropyl isothiocyanate; n-butyl isothiocyanate; tert.-butyl isothiocyanate; sec.-butyl isothiocyanate; amyl mustard oil; the own ester of isothiocyanic acid; the isothiocyanic acid heptyl ester; the isothiocyanic acid monooctyl ester; isothiocyanic acid ester in the ninth of the ten Heavenly Stems; isothiocyanic acid ester in the last of the ten Heavenly stems; isothiocyanic acid undecyl ester; the isothiocyanic acid phenylester; benzyl isothiocyanide; isothiocyanic acid styroyl ester; isothiocyanic acid neighbour-tolyl ester; isothiocyanic acid 2-fluorophenyl ester; isothiocyanic acid 3-fluorophenyl ester; isothiocyanic acid 4-fluorophenyl ester; isothiocyanic acid 2-nitrophenyl ester; isothiocyanic acid 3-nitrophenyl ester; isothiocyanic acid 4-nitrophenyl ester; isothiocyanic acid 2-chloro-phenyl-ester; isothiocyanic acid 2-bromophenyl ester; isothiocyanic acid 3-chloro-phenyl-ester; isothiocyanic acid 3-bromophenyl ester; isothiocyanic acid 4-chloro-phenyl-ester; isothiocyanic acid 2; 4-dichlorophenyl ester; isothiocyanic acid R-(+)-α-Jia Jibianji ester; isothiocyanic acid S-(-)-α-Jia Jibianji ester; isothiocyanic acid 3-pseudoallyl-α; the α-Er Jiajibianji ester; anti-(formula)-2-phenycyclopropyl lsothiocyanates; 1; two (isocyanato-the methyl)-benzene of 3-; 1; two (1-isocyanato--1-the methylethyl)-benzene of 3-; isothiocyanic acid 2-ethyl phenyl ester; the isothiocyanic acid benzoyl ester; isothiocyanic acid 1-naphthyl ester; the isothiocyanic acid benzoyl ester; isothiocyanic acid 4-bromophenyl ester; isothiocyanic acid 2-p-methoxy-phenyl ester; between isothiocyanic acid-the tolyl ester; α; α; between α-three fluoro--the tolyl lsothiocyanates; 3-fluorophenyl lsothiocyanates; 3-chloro-phenyl-lsothiocyanates; 3-bromophenyl lsothiocyanates; 1,4-phenylene diisothio-cyanate; 1-isothiocyanato-4-(anti--4-propyl group cyclohexyl) benzene; 1-(anti--4-hexyl cyclohexyl)-4-isothiocyanato benzene; 1-isothiocyanato-4-(anti--4-octyl group cyclohexyl) benzene; isothiocyanic acid 2-methyl-benzyl ester; 2-chlorobenzene and lsothiocyanates; 3-chlorobenzene and lsothiocyanates; 4-chlorobenzene and lsothiocyanates; between-methylbenzene first lsothiocyanates; right-methylbenzene first lsothiocyanates.
Can be herein as the example of the sulfoxide of interior electron donor(ED) have contain at least one C-S (=O)-compound of Csulfoxo group.Example has and contains the saturated or undersaturated aliphatic series of sulfoxo group, alicyclic or aromatic substance.Interior the having of scope that is included in sulfoxide contains heteroatomic compound, and wherein heteroatoms is the atom that is selected from the periodic table of elements the 13rd, 14,15,16 and 17 families outside the de-carbon.The example of sulfoxide has methyl sulfoxide; ethyl-sulfoxide; the propyl group sulfoxide; the butyl sulfoxide; the amyl group sulfoxide; the hexyl sulfoxide; the heptyl sulfoxide; the octyl group sulfoxide; the nonyl sulfoxide; the decyl sulfoxide; the phenyl sulfoxide; right-the tolyl sulfoxide; between-the tolyl sulfoxide; neighbour-tolyl sulfoxide; methyl phenyl sulfoxide; (R)-(+)-and methyl is right-the tolyl sulfoxide; (S)-(-)-methyl phenyl sulfoxide; the phenyl vinyl sulfoxide; 4-chloro-phenyl-sulfoxide; methyl (phenyl sulfinyl) acetic ester; the benzyl sulfoxide; tetramethylene sulfoxide; methyl sulfinyl methyl thioether; the dl-methionine sulfoxide; dl-methionine(Met) sulfinyl imines (sulfoximine).
Can be herein as the example of the sulfone of interior electron donor(ED) have comprise at least one C-S (=O) 2The compound of-C sulfuryl.Example has and contains the saturated or undersaturated aliphatic series of sulfuryl, alicyclic or aromatic substance.Interior the having of scope that is included in sulfone contains heteroatomic compound, and wherein heteroatoms is the atom that is selected from the periodic table of elements the 13rd, 14,15,16 and 17 families outside the de-carbon.The example of sulfone has the first sulfone; the second sulfone; third sulfone; the fourth sulfone; the methyl ethylene sulfone; the ethyl vinyl sulfone; divinylsulfone; the phenyl vinyl sulfone; the allyl phenyl sulfone; suitable-1; two (phenyl sulphonyl) ethene of 2-; 2-(phenyl sulphonyl) tetrahydropyrans; the chloromethyl phenyl sulfone; the 2-bromomethylphenyl sulfone; phenyl trisbromomethyl sulfone; 2-chloroethyl phenylsulfone; the methylthiomethyl phenylsulfone; (phenyl sulphonyl) acetonitrile; chloromethyl is right-tolyl sulfone; N; two (right-the tolylsulfonyl-the methyl)-ethamine of N-; methylthiomethyl is right-tolyl sulfone; 2-(phenyl sulphonyl) phenyl methyl ketone; aminomethyl phenyl sulphonyl acetic ester; 4-fluorophenyl methyl sulfone; 4-chloro-phenyl-2-chloro-1; 1; 2-trifluoroethyl sulfone; the tosyl group methyl carbylamine; phenylsulfone; the benzyl sulfone; phenyl is anti--the styryl sulfone; 1-methyl-2-((phenyl sulphonyl) methyl)-benzene; 1-brooethyl-2-((phenyl sulphonyl)-methyl) benzene; right-tolyl sulfone; two (phenyl sulphonyl) methane; the 4-chlorophenyl phenyl sulfone; 4-fluorophenyl sulfone; 4-chloro-phenyl-sulfone; 4; 4 '-alkylsulfonyl two (methyl benzoic acid ester); 9-oxo-9H-thioxanthene-3-nitrile 10; the 10-dioxide; the tetramethylene sulfone; the 3-methyl sulfolane; 2; the 4-dimethylsulfolane; instead-3; 4-dichloro tetramethylene sulfide 1; the 1-dioxide; instead-3; 4-dibromo tetramethylene sulfide 1; the 1-dioxide; 3; 4 one epoxy tetramethylene sulfides-1; the 1-dioxide; butadiene sulfone; 3-ethyl-2; 5-dihydro-thiophene-1, the 1-dioxide.
Can be herein as the example of the phosphorus compound of interior electron donor(ED) have saturated or undersaturated aliphatic series, alicyclic or aromatics, have 2 to 50 carbon atoms, comprise the compound of at least one phosphorus atom.Interior the having of scope that is included in phosphorus compound contains heteroatomic compound, and wherein heteroatoms is the atom that is selected from the periodic table of elements the 13rd, 14,15,16 and 17 families outside the de-carbon.The example of phosphorus compound has trimethyl-phosphine, triethyl phosphine, trimethyl phosphite, triethyl-phosphite, hexamethylphosphorictriamide, hexamethylphosphoramide, oxidation three piperidines phosphines, triphenylphosphine, three-p-methylphenyl phosphine, a three-tolylphosphine, three-o-tolyl phosphine, methyldiphenyl base phosphine, the ethyl diphenylphosphine, isopropyl diphenyl base phosphine, the allyl group diphenylphosphine, the cyclohexyl diphenylphosphine, the benzyl diphenylphosphine, two-tertiary butyl dimethyl phosphoramidite, two-tertiary butyl diethyl phosphoramidite, two-tertiary butyl diisopropylphosphoramidite; The diallyl diisopropylphosphoramidite.
Can be herein as the example of the silicoorganic compound of interior electron donor(ED) have saturated or undersaturated aliphatic series, alicyclic or aromatics, have 2 to 50 carbon atoms, comprise the compound of at least one Sauerstoffatom.Interior the having of scope that is included in silicoorganic compound contains heteroatomic compound, and wherein heteroatoms is the atom that is selected from the periodic table of elements the 13rd, 14,15,16 and 17 families outside the de-carbon.The example of silicoorganic compound has the tetramethyl-ortho-silicate, tetraethylorthosilicise, the tetrapropyl ortho-silicate, tetrabutyl ortho-silicate, the trichlorine methoxy silane, the trichlorine Ethoxysilane, trichlorine propoxy-silane, trichlorine isopropoxy silane, the trichlorine butoxy silane, trichlorine isobutoxy silane, dichloro dimethoxy silane, the dichloro diethoxy silane, dichloro dipropoxy silane, dichloro diisopropoxy silane, dichloro dibutoxy silane, dichloro two isobutoxy silane, one chlorine Trimethoxy silane, one chlorine triethoxyl silane, one chlorine tripropoxy silane, one chlorine, three isopropoxy silane, one chlorine, three butoxy silanes, one chlorine, three isobutoxy silane, the dimethyl methyl TMOS, the diethyl methoxy silane, the dipropyl methoxy silane, the di-isopropyl methoxy silane, the dibutyl methoxy silane, the diisobutyl methoxy silane, the diamyl methoxy silane, two cyclopentyl methoxy silane, the dihexyl methoxy silane, the dicyclohexyl methoxy silane, the diphenylmethyl TMOS, dimethylethoxysilane, the diethyl Ethoxysilane, the dipropyl Ethoxysilane, the di-isopropyl Ethoxysilane, the dibutyl Ethoxysilane, the diisobutyl Ethoxysilane, the diamyl Ethoxysilane, two cyclopentyl Ethoxysilanes, the dihexyl Ethoxysilane, the dicyclohexyl Ethoxysilane, the phenylbenzene Ethoxysilane, the trimethylammonium methoxy silane, the triethyl methoxy silane, the tripropyl methoxy silane, the triisopropyl methoxy silane, the tributyl methoxy silane, the triisobutyl methoxy silane, three amyl group methoxy silane, three cyclopentyl methoxy silane, three hexyl methoxy silane, the thricyclohexyl methoxy silane, the triphenyl methoxy silane, trimethylethoxysilane, triethyl-ethoxy-silicane alkane, the tripropyl Ethoxysilane, the triisopropyl Ethoxysilane, the tributyl Ethoxysilane, the triisobutyl Ethoxysilane, three amyl group Ethoxysilanes, three cyclopentyl Ethoxysilanes, three hexyl Ethoxysilanes, the thricyclohexyl Ethoxysilane, the triphenyl Ethoxysilane, dimethyldimethoxysil,ne, diethyl dimethoxy silane, dipropyl dimethoxy silane, diisopropyl dimethoxy silane, dibutyl dimethoxy silane, second, isobutyl dimethoxy silane, diamyl dimethoxy silane, dicyclopentyl dimethoxyl silane, dihexyl dimethoxy silane, dicyclohexyl dimethoxy silane, dimethoxydiphenylsilane, dimethyldiethoxysilane, the diethyl diethoxy silane, the dipropyl diethoxy silane, the di-isopropyl diethoxy silane, the dibutyl diethoxy silane, the diisobutyl diethoxy silane, the diamyl diethoxy silane, two cyclopentyl diethoxy silanes, the dihexyl diethoxy silane, the dicyclohexyl diethoxy silane, the phenylbenzene diethoxy silane, cyclopentyl-methyl dimethoxy silane, cyclopentyl ethyl dimethoxy silane, cyclopentyl propyl group dimethoxy silane, the cyclopentyl-methyl diethoxy silane, cyclopentyl ethyl diethoxy silane, cyclopentyl propyl group diethoxy silane, cyclohexyl methyl dimethoxy silane, cyclohexyl ethyl dimethoxy silane, cyclohexyl propyl group dimethoxy silane, the cyclohexyl methyl diethoxy silane, cyclohexyl ethyl diethoxy silane, cyclohexyl propyl group diethoxy silane, methyltrimethoxy silane, ethyl trimethoxy silane, vinyltrimethoxy silane, propyl trimethoxy silicane, the sec.-propyl Trimethoxy silane, butyl trimethoxy silane, the isobutyl-Trimethoxy silane, tert-butyl trimethoxy silane, phenyltrimethoxysila,e, the norbornane Trimethoxy silane, Union carbide A-162, ethyl triethoxysilane, vinyltriethoxysilane, propyl-triethoxysilicane, the sec.-propyl triethoxyl silane, the butyl triethoxyl silane, the isobutyl-triethoxyl silane, tertiary butyl triethoxyl silane, phenyl triethoxysilane, the norbornane triethoxyl silane, 2,3-dimethyl-2-(trimethoxysilyl) butane, 2,3-dimethyl-2-(triethoxysilyl) butane, 2,3-dimethyl-2-(tripropoxy-sil(ic)ane base) butane, 2,3-dimethyl-2-(three isopropoxy silyls) butane, 2,3-dimethyl-2-(trimethoxysilyl) pentane, 2,3-dimethyl-2-(triethoxysilyl) pentane, 2,3-dimethyl-2-(tripropoxy-sil(ic)ane base) pentane, 2,3-dimethyl-2-(three isopropoxy silyls) pentane, 2-methyl-3-ethyl-2-(trimethoxysilyl) pentane, 2-methyl-3-ethyl-2-(triethoxysilyl) pentane, 2-methyl-3-ethyl-2-(tripropoxy-sil(ic)ane base) pentane, 2-methyl-3-ethyl-2-(three isopropoxy silyls) pentane, 2,3,4-trimethylammonium-2-(trimethoxysilyl) pentane, 2,3,4-trimethylammonium-2-(triethoxysilyl) pentane, 2,3,4-trimethylammonium-2-(tripropoxy-sil(ic)ane base) pentane, 2,3,4-trimethylammonium-2-(three isopropoxy silyls) pentane, 2,3-dimethyl-2-(trimethoxysilyl) hexane, 2,3-dimethyl-2-(triethoxysilyl) hexane, 2,3-dimethyl-2-(tripropoxy-sil(ic)ane base) hexane, 2,3-dimethyl-2-(three isopropoxy silyls) hexane, 2,4-dimethyl-3-ethyl-2-(trimethoxysilyl) pentane, 2,4-dimethyl-3-ethyl-2-(triethoxysilyl) pentane, 2,4-dimethyl-3-ethyl-2-(tripropoxy-sil(ic)ane base) pentane, 2,4-dimethyl-3-ethyl-2-(three isopropoxy silyls) pentane, 2,4-dimethyl-3-sec.-propyl-2-(trimethoxysilyl) pentane, 2,4-dimethyl-3-sec.-propyl-2-(triethoxysilyl) pentane, 2,4-dimethyl-3-sec.-propyl-2-(tripropoxy-sil(ic)ane base) pentane, 2,4-dimethyl-3-sec.-propyl-2-(three isopropoxy silyls) pentane, hexamethyldisiloxane, 1,1,1,3,3, the 3-hexamethyldisilazane.
The present invention also provides the catalyst system that comprises following material:
(A) at least a aforesaid solid procatalyst; With
(B) at least a promotor
Electron donor(ED) in described solid procatalyst can or can not comprise as described here.
In described solid procatalyst, the mol ratio of preferred promoter and transition metal is about 0.1 to about 1000.In described solid procatalyst, the mol ratio of preferred described promotor and transition metal is about 1 to about 250.In described solid procatalyst, most preferably the mol ratio of promotor and described transition metal is about 5 to about 100.
Be used at least a promotor of the present invention can be any can be in olefinic polymerization or copolymerization with described solid procatalyst activatory organometallic compound or its mixture.For example, described cocatalyst component can comprise the element of the 1st, 2,11,12,13 and/or 14 families of the above referenced periodic table of elements.The example of these elements has lithium, magnesium, copper, zinc, boron, aluminium, silicon, tin.
Preferably described promotor is at least a empirical formula:
R nEY mH pOr (QER) qCompound, or its mixture,
Wherein,
R independently is alkyl separately;
E is selected from boron, aluminium, gallium and indium;
Y independently is the single anion unidentate ligand separately;
Q is selected from-O-,-S-,-N (R)-,-N (OR)-,-N (SR)-,-N (NR 2)-,-N (PR 2)-,-P (R)-,-P (OR)-,-P (SR)-and-P (NR 2)-;
N＞0, m 〉=0, p 〉=0, and n+m+p=3; And
q≥1。
Term used herein " alkyl " expression comprises unit price, linearity, branching, ring-type or the polycyclic group of carbon and hydrogen atom.Described alkyl can be chosen the atom that comprises the 13rd, 14,15,16 and 17 families that are selected from periodictable outside de-carbon and the hydrogen wantonly.The example of univalence hydrocarbyl comprises following group: C 1-C 30Alkyl; By one or more C that are selected from 1-C 30Alkyl, C 3-C 15Cycloalkyl or the C that replaces of the group of aryl 1-C 30Alkyl; C 3-C 15Cycloalkyl; By one or more C that are selected from 1-C 20Alkyl, C 3-C 15Cycloalkyl or the C that replaces of the group of aryl 3-C 15Cycloalkyl; C 6-C 15Aryl; With by one or more C that are selected from 1-C 30Alkyl, C 3-C 15Cycloalkyl or the C that replaces of the group of aryl 6-C 15Aryl; Wherein aryl is preferably represented phenyl that replace or unsubstituted, naphthyl or anthryl.
The example of single anion unidentate ligand Y comprise halogen anion ,-OR ,-OBR 2,-OSR ,-ONR 2,-OPR 2,-NR 2,-N (R) BR 2,-N (R) OR ,-N (R) SR ,-N (R) NR 2,-N (R) PR 2,-N (BR 2) 2,-N=CR 2,-N=NR ,-N=PR ,-SR ,-SBR 2,-SOR ,-SNR 2,-SPR 2,-PR 2R independently is alkyl as defined above separately.The example of halogen anion comprises fluorion, chlorion, bromide anion and iodide ion.
The example of alkoxide has methylate, ethylate, n-propyl alcohol salt, isopropoxide, the ring propylate, propyl carbinol salt, the isobutyl alkoxide, sec-butyl alcohol salt, tert butoxide, cyclobutanol salt, Pentyl alcohol salt, the isoamyl alkoxide, sec.-amyl alcohol salt, tertiary amyl alcohol salt, neopentyl alcohol salt, cyclopentanol salt, n-hexyl alcohol salt, dissident's alkoxide, enanthol salt, octanol salt, nonyl alcohol salt, decyl alcohol salt, the undecane alkoxide, the dodecane alkoxide, 2-Ethylhexyl Alcohol salt, phenates, 2,6-dimethyl phenates, 2,6-two-sec.-propyl phenates, 2,6-phenylbenzene phenates, 2,6-two basic phenates, 2,4,6-trimethylammonium phenates, 2,4,6-triisopropyl phenates, 2,4,6-triphenyl phenates, 2,4,6-three basic phenates, benzyl oxide, menthoxide, and halo alkoxide, for example fluoroform alkoxide, trifluoroethanol salt, Trifluoroisoproanol salt, hexafluoroisopropanol salt, seven fluorine isopropoxides, the trifluoro tert butoxide, the hexafluoro tert butoxide, the fluoroform alkoxide, ethapon salt, isopral salt.
The example of mercaptan has methyl mercaptan salt, ethanethio salt, the n-propyl thiolate, isopropyl mercaptan salt, the cyclopropyl thiolate, the normal-butyl thiolate, the isobutyl-thiolate, the sec-butyl thiolate, tert-butyl mercaptan salt, the cyclobutyl thiolate, the n-pentyl thiolate, the isopentyl thiolate, the sec.-amyl sec-pentyl secondary amyl thiolate, the tert-pentyl thiolate, the neo-pentyl thiolate, the cyclopentyl thiolate, the n-hexyl thiolate, the cyclohexyl thiolate, phenyl mercaptan salt, 2,6-3,5-dimethylphenyl thiolate, 2,6-two-isopropyl phenyl thiolate, 2,6-phenylbenzene phenyl thiolate, 2,6-two basic phenyl mercaptan salt, 2,4,6-trimethylphenyl thiolate, 2,4,6-triisopropyl phenyl thiolate, 2,4,6-triphenyl phenyl thiolate, 2,4,6-three basic phenyl mercaptan salt, the dibenzylsulfide alkoxide, the heptyl thiolate, octyl mercaptan salt, nonyl mercaptan salt, the decyl thiolate, the undecyl thiolate, lauryl mercaptan salt, 2-ethylhexyl thiolate,  base thiolate, and halogenated alkyl sulfide alkoxide, for example trifluoromethyl mercaptan salt, the trifluoroethyl thiolate, trifluoro isopropyl mercaptan salt, hexafluoro isopropyl mercaptan salt, seven fluorine isopropyl mercaptan salt, three fluoro-tert-butyl thiolate, hexafluoro-tert-butyl thiolate, trifluoromethyl mercaptan salt, trichlorine ethanethio salt, three chloro-isopropyl mercaptan salt.
The example of acid amides has dimethylformamide, diethylamide, two-n-propyl acid amides, two-sec.-propyl acid amides, two cyclopropyl amides, the di-n-butyl acid amides, the Di-Isobutyl acid amides, two-sec-butyl acid amides, two-tert-butylamides, two cyclobutylamides, two-n-pentyl acid amides, two-isopentyl acid amides, two-sec.-amyl sec-pentyl secondary amyl acid amides, two-te t-amylamide, two cyclopentyl amides, the di neo-pentyl acid amides, two-n-hexyl acid amides, the dicyclohexyl acid amides, the diheptyl acid amides, the dioctyl acid amides, two-nonyl acid amides, the didecyl acid amides, two (undecyl) acid amides, two (dodecyl) acid amides, two-2-ethylhexyl acid amides, the phenylbenzene acid amides, two-2,6-3,5-dimethylphenyl acid amides, two-2,6-two-isopropyl phenyl acid amides, two-2,6-phenylbenzene phenyl acid amides, two-2,6-two Lay base phenyl amides, two-2,4,6-trimethylphenyl acid amides, two-2,4,6-triisopropyl phenyl acid amides, two-2,4,6-triphenyl phenyl acid amides, two-2,4,6-three basic phenyl amides, the dibenzyl acid amides, the dihexyl acid amides, the dicyclohexyl acid amides, the dioctyl acid amides, the didecyl acid amides, two (octadecyl) acid amides, the phenylbenzene acid amides, the dibenzyl acid amides, two-2,6-3,5-dimethylphenyl acid amides, 2,6-two-isopropyl phenyl acid amides, two-2,6-phenylbenzene phenyl acid amides, the diallyl acid amides, the diallyl acid amides, methylphenylamine; N-ethylaniline; N propyl aniline; The N-isopropyl aniline; The N-butylaniline; Isobutyl-aniline; The N-amyl aniline; The N-isoamyl aniline; N-octyl group aniline; N-cyclohexyl aniline; And silyl acid amides such as two (trimethylsilyl) acid amides, two (three second are for silyl) acid amides, two (3,5-dimethylphenyl silyl) acid amides, two (tertiary butyl diformazan is for silyl) acid amides, two (t-butyldiphenylsilyl) acid amides, phenyl (trimethylsilyl) acid amides, phenyl (three second are for silyl) acid amides, phenyl (trimethylsilyl) acid amides, methyl (trimethylsilyl) acid amides, ethyl (trimethylsilyl) acid amides, n-propyl (trimethylsilyl) acid amides, sec.-propyl (trimethylsilyl) acid amides, cyclopropyl (trimethylsilyl) acid amides, normal-butyl (trimethylsilyl) acid amides, isobutyl-(trimethylsilyl) acid amides, sec-butyl (trimethylsilyl) acid amides, the tertiary butyl (trimethylsilyl) acid amides, cyclobutyl (trimethylsilyl) acid amides, n-pentyl (trimethylsilyl) acid amides, isopentyl (trimethylsilyl) acid amides, sec.-amyl sec-pentyl secondary amyl (trimethylsilyl) acid amides, tert-pentyl (trimethylsilyl) acid amides, neo-pentyl (trimethylsilyl) acid amides, cyclopentyl (trimethylsilyl) acid amides, n-hexyl (trimethylsilyl) acid amides, cyclohexyl (trimethylsilyl) acid amides, heptyl (trimethylsilyl) acid amides and three second are for silyl trimethylsilyl acid amides, and heterocycleamide, for example pyrroles, pyridine, piperidines, piperazine, indoles, imidazoles, the pyrroles, thiazole, fast quinoline, phthalimide, the 1-azepan, the 1-Azacyclooctane, 1-nitrogen heterocyclic nonane, 1-nitrogen heterocyclic decane, the conjugate base of their substitutive derivative.
The example of phosphide has dimethyl phosphide, diethyl phosphide, dipropyl phosphide, dibutyl phosphide, diamyl phosphide, dihexyl phosphide, dicyclohexyl phosphide, phenylbenzene phosphatization thing, dibenzyl phosphide, two-2,6-3,5-dimethylphenyl phosphide 2,6-diisopropyl phenyl phosphide, 2,6-phenylbenzene phenyl phosphide, and the conjugate base of cyclic phosphines, for example phospholane, phospha cyclohexane, phosphorus heterocycle heptane, phosphorus heterocycle octane, phosphorus heterocycle nonane, phosphorus heterocycle decane.
The group of the single anion unidentate ligand Y that is preferably used as is fluorion, chlorion, bromide anion, methylate, ethylate, n-propyl alcohol salt, isopropoxide, butanolate, neopentyl alcohol salt, benzylalcohol salt, fluoroform alkoxide and trifluoroethanol salt.
The mixture of single anion unidentate ligand Y can be used as single anion unidentate ligand Y.
Available promotor in the method for the invention is wherein at formula R nEY mH pIn E be that the example of boron comprises the trimethylammonium borine, boron triethyl, three n-propyl borines, three normal-butyl borines, three n-pentyl borines, three prenyl borines, three n-hexyl borines, three n-heptyl borines, three n-octyl borines, the triisopropyl borine, the triisobutyl borine, three (cyclohexyl methyl) borine, triphenylborane, three (pentafluorophenyl group) borine, the dimethyl borine, the diethyl borine, the di borine, the di-n-butyl borine, two n-pentyl borines, diisoamyl dialkylene borine, the di-n-hexyl borine, two n-heptyl borines, the di-n-octyl borine, the di-isopropyl borine, the diisobutyl borine, two (cyclohexyl methyl) borine, the phenylbenzene borine, two (pentafluorophenyl group) borine, chlorination dimethyl boron, chlorination diethyl boron, chlorination di boron, chlorination di-n-butyl boron, chlorination two n-pentyl boron, chlorination diisoamyl dialkylene boron, chlorination di-n-hexyl boron, chlorination two n-heptyl boron, chlorination di-n-octyl boron, chlorination di-isopropyl boron, chlorination diisobutyl boron, two (cyclohexyl methyl) boron of chlorination, diphenyl antimony chloride base boron, two (pentafluorophenyl group) boron of chlorination, fluoridize diethyl boron, bromination diethyl boron, iodate diethyl boron, methoxyl group dimethyl boron, oxyethyl group dimethyl boron, oxyethyl group diethyl boron, methoxyl group dimethyl boron, oxyethyl group dimethyl boron, oxyethyl group diethyl boron, the dichloride methyl boron, dichloride ethyl boron, dichloride n-propyl boron, dichloride normal-butyl boron, dichloride n-pentyl boron, dichloride prenyl boron, dichloride n-hexyl boron, dichloride n-heptyl boron, dichloride n-octyl boron, dichloride sec.-propyl boron, isobutyl dichloride boron, dichloride (cyclohexyl methyl) boron, dichloride phenyl boron, dichloride pentafluorophenyl group boron, one chloromethane oxygen ylmethyl boron, one chloroethoxy methyl boron, one chloroethoxy ethyl boron.
Available promotor in the method for the invention is wherein at formula R nEY mH pMiddle E is that aluminium comprises trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, three n-butylaluminum, three n-pentyl aluminium, three prenyl aluminium, tri-n-hexyl aluminum, three n-heptyl aluminium, tri-n-octylaluminium, triisopropylaluminiuand, triisobutyl aluminium, three (cyclohexyl methyl) aluminium, dimethyl hydrogenation aluminium, ADEH, the di aluminum hydride, the di-n-butyl aluminum hydride, two n-pentyl aluminum hydride, diisoamyl dialkylene aluminum hydride, the di-n-hexyl aluminum hydride, two n-heptyl aluminum hydride, the di-n-octyl aluminum hydride, the di-isopropyl aluminum hydride, diisobutyl aluminium hydride, chlorodimethylalumiu, diethylaluminum chloride, chlorination di aluminium, chlorination di-n-butyl aluminium, chlorination two n-pentyl aluminium, chlorination diisoamyl dialkylene aluminium, chlorination di-n-hexyl aluminium, chlorination two n-heptyl aluminium, chlorination di-n-octyl aluminium, chlorination di-isopropyl aluminium, di-isobutyl aluminum chloride, two (cyclohexyl methyl) aluminium of chlorination, fluoridize diethyl aluminum, the bromination diethyl aluminum, the iodate diethyl aluminum, methoxyl group dimethyl aluminium, oxyethyl group dimethyl aluminium, the oxyethyl group diethyl aluminum, methylaluminium dichloride, ethylaluminium dichloride, dichloride n-propyl aluminium, the dichloride n-butylaluminum, dichloride n-pentyl aluminium, dichloride prenyl aluminium, dichloride n-hexyl aluminium, dichloride n-heptyl aluminium, the dichloride octyl aluminum, dichloride sec.-propyl aluminium, aluminium isobutyl dichloride, dichloride (cyclohexyl methyl) aluminium, chloromethane oxygen ylmethyl aluminium, the chloroethoxy aluminium trimethide, the chloroethoxy aluminium triethyl.
The example of the promotor that other is fit to comprises aikyiaiurnirsoxan beta, particularly methylaluminoxane.The formula (QER) that other is fit to qThe example of promotor comprise alumimines.
What be preferably used as herein promotor is trialkylaluminium, for example trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-hexyl aluminum, three isohexyl aluminium, three-2-methyl amyl aluminium, tri-n-octylaluminium, three positive decyl aluminium; And aluminum dialkyl monohalide, for example chlorodimethylalumiu, diethylaluminum chloride, chlorination dibutyl aluminium, di-isobutyl aluminum chloride, bromination diethyl aluminum and iodate diethyl aluminum; And the sesquihalide of aluminum alkyls, for example the sesquialter iodide of the sesquialter bromide of the sesquialter fluorochemical of the sesquichloride of the sesquichloride of the sesquichloride of the sesquichloride of aluminium trimethide, aluminium triethyl, n-butylaluminum, aluminium isobutyl, aluminium triethyl, aluminium triethyl and aluminium triethyl.
Most preferably the promotor that is used as herein is a trialkylaluminium, for example trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, triisobutyl aluminium, tri-n-octylaluminium; And aluminum dialkyl monohalide, for example sesquihalide of chlorodimethylalumiu, diethylaluminum chloride, di-isobutyl aluminum chloride and aluminum alkyls, for example sesquichloride of the sesquichloride of aluminium trimethide and aluminium triethyl.
The mixture of above-mentioned promotor also can be used as promotor herein.
Another aspect of the present invention provides the method for using catalyst system of the present invention to come polymerization or copolyolefine, and wherein said catalyst system comprises the solid procatalyst and the promotor of setting forth herein.
Preferred method provided by the invention is used for polymerising ethylene and/or copolymerization of ethylene and at least a or multiple other alkene, and this method is included under the polymerizing condition ethene and/or ethene are contacted with catalyst system of the present invention with at least a or multiple alkene.
Polymerization of the present invention or copolymerization method can use the method for any routine to implement.For example, can utilize polymerization or copolymerization in suspended substance, solution, supercutical fluid or gas phase media.Well known these all polymerizations or the method for copolymerization.
According to the present invention, satisfactory especially be used to prepare polyethylene polymer and multipolymer method be gaseous polymerization, preferably use fluidized-bed reactor.The working method of such reactor and reactor is known and at United States Patent (USP) 3,709,853,4,003,712,4,011,382,4,012,573,4,302,566,4,543,399,4,882,400,5,352,749,5,541, No. 270; Carried out describing completely in No. 839,380, No. 991,798, Canadian Patent and the belgian patent.These patent disclosures gaseous polymerization, wherein polymerisation medium can be carried out mechanical stirring or come fluidisation by the Continuous Flow of gas phase monomer and thinner.Full content with these patents is attached to herein by reference.
Generally speaking, polymerization of the present invention can be implemented as continuous vapor phase process (as fluidized bed process).The fluidized-bed reactor that is used for method of the present invention generally comprises reaction zone and so-called deceleration area.Described reaction zone comprises the bed that makes the polymer beads growth, and the polymer beads of formation and minor amount of catalyst particles can be come fluidisation by the Continuous Flow of gas phase monomer and thinner, thereby heat of polymerization is removed from reaction zone.When circulating current is sent into reaction zone again, choose wantonly and can cool off and compress some recycle gas to have formed liquid, can improve the heat-removal capability of circulating current like this.Can easily determine satisfactory airflow rate by simple experiment.Gaseous monomer adds to the speed that speed in the circulating current equals the granulated polymer product and the monomer carried secretly is discharged from described reactor, and regulate the composition of the gas of the described reactor of flowing through, form the basicly stable state that is in to keep the gas phase in the described reaction zone.The gas that leaves reaction zone is sent into deceleration area, remove the particle of deentrainment there.Thinner entrained particles and dust can be removed in cyclonic separator and/or fine filtrator.Described gas stream is removed heat of polymerization through heat exchanger in heat exchanger, compress in compressor, gets back to described reaction zone then.
In more detail, the temperature of reactor of fluidized bed process herein is about 30 ℃ to about 110 ℃.Usually reactor is thought after the sintering temperature of having considered the polymer product in the reactor and is operated under the feasible top temperature.
Method of the present invention is applicable to the polymkeric substance of preparation alkene and/or the multipolymer of alkene and at least a or multiple other alkene.Preferred method of the present invention is applicable to the polymkeric substance of preparation ethene and/or the multipolymer of ethene and at least a or multiple other alkene.Preferred alkene is alpha-olefin.Described alkene can for example comprise 2 to 16 carbon atoms.Be the polymkeric substance and the multipolymer of linear polyethylene especially preferably by method preparation of the present invention.This linear polyethylene polymkeric substance or multipolymer are preferably the linear homopolymer of ethene and the linear copolymer of ethene and at least a alpha-olefin, and the content of wherein said ethene accounts for about at least 50% of the monomer weight that all relates to.The example of available alpha-olefin has propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 4-methylpent-1-alkene, 1-decene, 1-laurylene, 1-hexadecylene herein.Also can use polyenoid herein, for example 1,3-hexadiene, 1,4-hexadiene, cyclopentadiene, Dicyclopentadiene (DCPD), 4-vinyl hexamethylene-1-alkene, 1,5-cyclooctadiene, 5-vinylidene-2-norbornylene and 5-vinyl-2-norbornylene, and can be in polymerization or copolymerization medium the alkene that forms of original position.When alkene original position in polymerization or copolymerization medium forms, can form the linear polyethylene polymkeric substance or contain the multipolymer of long-chain branch.
The polymkeric substance of available method preparation of the present invention or the example of multipolymer comprise polymkeric substance and the ethene and at least a or multiple multipolymer with alpha-olefin of 3 to 16 carbon atoms of ethene, and the content of wherein said ethene accounts for about at least 50% of all monomer weights that relate to.
Olefin polymer of the present invention or multipolymer can be made film by any technology well known in the art.For example, can prepare film by cast film, inflation film and the extrusion coating technology of knowing.
In addition, can olefin polymer or multipolymer be made other goods, for example moulded parts by any technology of knowing.
In the method for the invention, available any method well known in the art is introduced described solid procatalyst, promotor or catalyst system.For example, solid procatalyst directly can be introduced among polymerization or the copolymerization medium with the form of slurry or exsiccant free flowing powder.Form that also can performed polymer is used described solid procatalyst, and wherein said performed polymer obtains by solid procatalyst is contacted with one or more alkene when having promotor.
Can for example control with any method of knowing by the olefin polymer of the present invention's preparation or the molecular weight of multipolymer by use hydrogen.When the mol ratio of hydrogen and ethene in polymerization or copolymerization medium improves, by the melt index (I of described polymkeric substance or multipolymer 2) the provable molecular weight of increase be subjected to control.
Can more easily understand the present invention with reference to the following examples.Certainly, when fully openly of the present invention, for a person skilled in the art, the present invention will become apparent, and will appreciate that therefore these embodiment only are that explanation and not meaning imposes any restrictions scope of the present invention.
Embodiment
In the following embodiments, used the testing method of listing below to estimate the analysis and the physicals of polymkeric substance herein.
A) molecular weight distribution of ethylene/olefin interpolymers (MWD), i.e. M w/ M nRatio is measured with the Waters Gel PermeationChromatograph Series150 that has equipped Ultrastyrogel chromatographic column and refractive index detector.The service temperature of device is arranged on 140 ℃, and eluting solvent is an orthodichlorobenzene, the calibration standard thing comprise 10 known accurate molecular weight, molecular weight ranges is at 1000 to 1.3 hundred ten thousand polystyrene, and polyethylene standard thing NBS1475;
B) melt flow index (MI), I 2According to ASTM D-1238, condition E, 190 ℃ of following mensuration, and the unit of report is decigram/minute;
C) high-load melt flow index (HLMI), I 21According to ASTM D-1238, in condition F mensuration, used weight is 10.0 times of above-mentioned melt flow index;
D) ratio of melt flow index (MFR)=I 21/ I 2Or the melt flow index/melt flow index under the high-load.
Embodiment 1 to 12 fills in the Vacuum Atmospheres He-43-2 glove box at nitrogen and implements.Before entering described glove box, under the nitrogen pressure of 172kPa (25psi), with solvent and the hexene bed by the activatory aluminum oxide, the bed by BASF R-311 copper catalyst carries out purifying subsequently.Before entering described glove box, ethene and the hydrogen bed by the BASFR-311 copper catalyst is carried out purifying.Steel pipe with the end of 3.2mm (1/8 inch) dribbling valve is introduced solvent and gas in the glove box.All other reagent is obtained by commercial sources and does not process when using.In embodiment 2,4 and 11-12, used the Sylopol of Grace Davison TM5550 carriers.
Embodiment 1 (contrast)
By with 0.0981mL 2,2,6, the 6-dipivaloylmethane is added to 0.0590mL Et 2Prepare solution in the solution of AlCl in the toluene of 2mL.With the solution stirring that obtains 30 minutes.
Under agitation, above-mentioned solution is added in 114mg dichloride (2,2,6,6-tetramethyl-heptane diketone acid group closes (the tetramethylheptanedionate)) solution of titanium in 2.0mL toluene, adds 1.0mL toluene subsequently.With the solution stirring that obtains 120 seconds.
Embodiment 2 (contrast)
By with 0.0981mL 2,2,6, the 6-dipivaloylmethane is added to 0.0590mL Et 2Prepare solution in the solution of AlCl in 2mL toluene.With the solution stirring that obtains 30 minutes.
Under agitation, above-mentioned solution is added in dichloride (2,2,6, the 6-tetramethyl-heptane diketone acid group closes) solution of titanium in 2.0mL toluene of 114mg, adds 1.0mL toluene subsequently.With the solution stirring that obtains 120 seconds.The solution that 1.0mL is obtained is added to the 500mgSylopol that is stirring TMIn the slurry of 5550 carriers in 6.0mL toluene.The slurry that obtains was stirred 30 minutes and used the sintered glass funnel filtration.Clean the solid procatalyst powder of gained and dry 30 minutes in a vacuum with pentane then.
Embodiment 3 (contrast)
By with 2,2,6 of 5mL 0.196mL, the solution of 6-dipivaloylmethane in toluene with 2-4 drip/second speed be added to 0.090mL Me 3Prepare solution in the solution of Al in 4mL toluene.With the solution stirring that obtains 60 minutes.Then, the solution that obtains is added in the volumetric flask of 10mL, adds the solution that toluene is made 10.0mL subsequently.
Under agitation, dichloride (2,2,6, the 6-tetramethyl-heptane diketone acid group closes) titanium with 114mg is added in the above-mentioned solution of 5.0mL.With the solution stirring that obtains 120 seconds.
Embodiment 4
By with 2,2,6 of 5mL 0.196mL, the solution of 6-dipivaloylmethane in toluene with 2-4 drip/second speed be added to the Me of 0.090mL 3Prepare solution in the solution of Al in 4mL toluene.With the solution stirring that obtains 60 minutes.Then, the solution that obtains is added in the volumetric flask of 10mL, adds the solution that toluene is made 10.0mL subsequently.
Under agitation, dichloride (2,2,6, the 6-tetramethyl-heptane diketone acid group closes) titanium with 114mg is added in the above-mentioned solution of 5.0mL.With the solution stirring that obtains 120 seconds.The solution that 1.0mL is obtained is added to the 500mg Sylopol that is stirring TMIn the slurry of 5550 carriers in 6.0mL toluene.The slurry that obtains was stirred 30 minutes and used the sintered glass funnel filtration.Clean the powder of solid procatalyst of gained and dry 30 minutes in a vacuum with pentane then.
Embodiment 5-10
Among the embodiment 5-10 below, use the material for preparing among the embodiment 1-4 to implement polyreaction.In 12 ounces of Fischer-Porter aerosol reactors, implement polyreaction.This is a doleiform design, has used the rubber of salable glass to seal.The reactor head of loading onto can provide the sealing that can keep 690kPa (100psi) pressure safely.By around stainless metal protection online 1 " wide heating brings heating.When needs, can add head by porous and add gas or liquid monomer.Before adding container, the place can all keep pressure and volume in the source.
Comparative examples 5 and 8
Use following procedure to implement comparative examples 5 and 8.The trimethyl aluminium of 0.0075mL is added in the solution of 15mL hexene in the 100mL heptane, and the solution that obtains is heated to 90 ℃.The solution and the sealed reactor that add embodiment 1 then.Unnecessary pressure is discharged from described reaction vessel.The hydrogen that adds pressure 55.2kPa (8psi).Add ethene up to the total pressure that provides 662kPa (96psi), and this pressure was kept 1 hour by adding ethene continuously.After this, get rid of the pressure of reaction vessel and described container taken out from glove box.To be added in the slurry of gained near the reagent grade acetone of 300mL and cool off slurry to room temperature.Mix described slurry, filtration with blending machine, and use washing with acetone.With the powder that obtains drying at least 4 hours in 40-50 ℃ vacuum drying oven.
Embodiment 6,7,9 and 10
Use following procedure to implement embodiment 6,7,9 and 10.The 100mL heptane is added in the reactor.Described heptane 1.0mL is added in the solid procatalyst of embodiment 2 and forms slurry, and add the trimethyl aluminium of 0.0075mL.The slurry that obtains is added in the described reactor.With described container sealing, and be heated to 90 ℃.From described reaction vessel, discharge unnecessary pressure.The hydrogen that adds pressure 55.2kPa (8psi).Pressure with ethene adds hexene up to the total pressure that provides 662kPa (96psi).And this pressure was kept 1 hour by adding ethene continuously.After this, get rid of the pressure of reaction vessel and described container taken out from glove box.To be added in the slurry near the reagent grade acetone of 300mL and cool off slurry to room temperature.Mix described slurry, filtration with blending machine, and use washing with acetone.With the powder that obtains drying at least 4 hours in 40-50 ℃ vacuum drying oven.
In table 1, reported other details about embodiment 5-10.
Table 1. aggregated data
Embodiment Catalyzer from following examples Catalyst consumption The output of polymkeric substance (g) Kg polymkeric substance/gTi hr Mg polymkeric substance/mol Ti hr MWD Mw/ Mn Mn K Mw K
5 1 1.0mL 0.3 0.13 0.006 41 1.1 44
6 2 4.5mg 6.0 296 14.2 4.7 24.8 117
7 2 4.5mg 5.3 262 12.5 5.2 26.3 137
8 3 1.0mL 0.0 - - - - -
9 4 4.5mg 6.2 306 14.7 4.4 25.2 112
10 4 4.5mg 5.3 262 12.5 4.7 26.7 125
From top data as can be seen, the activity of using activity (Kg polymkeric substance/gTi hr) that the solid procatalyst on the carrier produces and solid procatalyst on using the non-carrier of solubility to produce is compared and is improved.In addition, the molecular weight distribution (Mw/Mn) that can see the polymkeric substance of the solid procatalyst preparation of using on the carrier is compared with the molecular weight distribution of polymkeric substance of solid procatalyst preparation on using the non-carrier of solubility and is reduced.
Among the embodiment 11 and 12 below, the preparation of other solid procatalyst has been described.The solid procatalyst of expecting embodiment 11 and 12 can be used for preparation useful catalysts system in olefinic polymerization and copolymerization.
Embodiment 11
By with 0.0981mL 2,2,6, the 6-dipivaloylmethane is added to 0.0590mL Et 2Prepare solution in the solution of AlCl in 2mL toluene.With the solution stirring that obtains 30 minutes.
Under agitation, above-mentioned solution is added in 114mg dichloride (2,2,6, the 6-tetramethyl-heptane diketone acid group closes) solution of titanium in 2.0mL toluene, adds the toluene of 1.0mL subsequently.With the solution stirring that obtains 120 seconds.The 0.0381mL tetrahydrofuran (THF) is added in this solution.With the solution stirring that obtains 120 seconds.The solution that 1.0mL is obtained is added to the 500mgSylopol that is stirring TMIn the slurry of 5550 carriers in 6.0mL toluene.The slurry that obtains was stirred 30 minutes and used the sintered glass funnel filtration.Clean the powder of solid procatalyst of gained and dry 30 minutes in a vacuum with pentane then.
Embodiment 12
By with 2,2,6 of the 0.196mL of 5mL, the solution of 6-dipivaloylmethane in toluene with 2-4 drip/second speed be added to the Me of 0.090mL 3Prepare solution in the solution of Al in 4mL toluene.With the solution stirring that obtains 60 minutes.Then, the solution that obtains is added in the volumetric flask of 10mL, adds the solution that toluene is made 10.0mL subsequently.
Under agitation, 114mg dichloride (2,2,6,6-tetramethyl-heptane diketone acid group closes) titanium is added in the above-mentioned solution.With the solution stirring that obtains 120 seconds.The 0.0381mL tetrahydrofuran (THF) is added in this solution.With the solution stirring that obtains 120 seconds.The solution that 1.0mL is obtained is added to the 500mg Sylopol that is stirring TMIn the slurry of 5550 carriers in 6.0mL toluene.The slurry that obtains was stirred 30 minutes and used the sintered glass funnel filtration.Clean the powder of solid procatalyst of gained and dry 30 minutes in a vacuum with pentane then.
Should be understood that to be understood that the present invention's form herein only has exemplary, be not used for limiting the scope of the invention.The present invention includes all various changes that belong in the following claim scope.

Claims (20)

1. one kind by making following i) with the ii) solid procatalyst of contact preparation, wherein:
I) by making at least a empirical formula ML xX 4-xTransistion metal compound and at least a formula L xER nY mH pAlkylating reagent at least a aprotic solvent, react and the soluble species that obtains, wherein, at formula ML xX 4-xIn, M is titanium, zirconium and hafnium, L independently is the single anion bidentate ligand separately, two atoms that are selected from oxygen, sulphur, selenium, tellurium, nitrogen, phosphorus, arsenic, antimony and bismuth or its mixture by described bidentate ligand are connected on the M, X is the halogen that is selected from fluorine, chlorine, bromine and iodine, and 0＜x≤4, at formula L xER nY mH pIn, L independently is the single anion bidentate ligand separately, and two atoms that are selected from oxygen, sulphur, selenium, tellurium, nitrogen, phosphorus, arsenic, antimony and bismuth or its mixture by described bidentate ligand are connected on the E, and E is selected from boron, aluminium, gallium and indium, R independently is alkyl separately, Y independently is the single anion unidentate ligand separately, 0＜x≤2, n＞0, m 〉=0, p 〉=0, and x+n+m+p=3 and
Ii) carrier.
2. the solid procatalyst of claim 1, the amount of wherein said alkylating reagent make that the mol ratio of itself and transistion metal compound is 0.1 to 100.
3. the solid procatalyst of claim 1, wherein said M is a titanium.
4. the solid procatalyst of claim 1, wherein said at least a alkylating reagent is an organometallic compound.
5. the solid procatalyst of claim 4, wherein said E is an aluminium.
6. the solid procatalyst of claim 1 wherein is deposited on described soluble species on the carrier.
7. the solid procatalyst of claim 1, wherein said carrier is selected from inorganic oxide and inorganic halides.
8. one kind by making following i) with the ii) solid procatalyst of contact preparation, wherein:
I) by making at least a empirical formula ML xX 4-xTransistion metal compound and at least a formula L xER nY mH pAlkylating reagent and at least a in electron donor(ED) at least a aprotic solvent, react and the soluble species that obtains, wherein, at formula ML xX 4-xIn, M is titanium, zirconium and hafnium, L independently is the single anion bidentate ligand separately, two atoms that are selected from oxygen, sulphur, selenium, tellurium, nitrogen, phosphorus, arsenic, antimony and bismuth or its mixture by described bidentate ligand are connected on the M, X is the halogen that is selected from fluorine, chlorine, bromine or iodine, and 0＜x≤4, at formula L xER nY mH pIn, L independently is the single anion bidentate ligand separately, and two atoms that are selected from oxygen, sulphur, selenium, tellurium, nitrogen, phosphorus, arsenic, antimony and bismuth or its mixture by described bidentate ligand are connected on the E, and E is selected from boron, aluminium, gallium and indium, R is alone alkyl independently, Y independently is the single anion unidentate ligand separately, 0＜x≤2, n＞0, m 〉=0, p 〉=0, and x+n+m+p=3 and
Ii) carrier,
Electron donor(ED) is selected from carboxylicesters in described; acid anhydrides; acyl halide; ether; thioether; aldehyde; ketone; imines; amine; acid amides; nitrile; isonitrile; cyanate; isocyanic ester; thiocyanic ester; lsothiocyanates; thioester; the dithio acid esters; carbonic ether; the alkyl carbamate; the alkyl thiocarbamate; the alkyl dithiocarbamate; urethanum; phosphine; sulfide; phosphine oxide; phosphamide; sulfoxide; sulfone; sulphonamide; comprise the silicoorganic compound of at least one Sauerstoffatom and link nitrogen on the organic group by carbon or Sauerstoffatom; phosphorus; arsenic or antimony compounds and composition thereof.
9. catalyst system, described catalyst system comprises:
I) solid procatalyst of claim 1 and
Ii) at least a promotor.
10. the catalyst system of claim 9, the M of the transistion metal compound of wherein said solid procatalyst is a titanium.
11. the catalyst system of claim 9, at least a alkylating reagent of wherein said solid procatalyst is an organometallic compound.
12. the catalyst system of claim 11, wherein said E are aluminium.
13. the catalyst system of claim 9, wherein said at least a promotor are the organometallic compound that can activate described solid procatalyst in olefinic polymerization or copolymerization.
14. the catalyst system of claim 13, wherein said at least a promotor is selected from the organometallic compound of following empirical formula:
R nEY mH p(QER) q,
Wherein,
R independently is alkyl separately;
E is selected from boron, aluminium, gallium and indium;
Y independently is the single anion unidentate ligand separately;
Q is selected from-O-,-S-,-N (R)-,-N (OR)-,-N (SR)-,-N (NR 2)-,-N (PR 2)-,-P (R)-,-P (OR)-,-P (SR)-and-P (NR 2)-;
N＞0, m 〉=0, p 〉=0, and n+m+p=3; With
q≥1。
15. the catalyst system of claim 14, wherein said E are aluminium.
16. the catalyst system of claim 15, wherein said promotor are trialkyl aluminium compound.
17. the catalyst system of claim 9, the amount of wherein said promotor make that the mol ratio of transition metal of itself and described solid procatalyst is 0.1 to 1000.
18. a catalyst system, described catalyst system comprises:
I) solid procatalyst of claim 8 and
Ii) at least a promotor.
19. one kind is used for the polymerization method of one or more alkene at least, described method is included under the polymerizing condition, and one or more alkene are at least contacted with the catalyst system of claim 9.
20. one kind is used for the polymerization method of one or more alkene at least, described method is included under the polymerizing condition, and one or more alkene are at least contacted with the catalyst system of claim 18.
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Patentee after: Westlake Longview Corp.

Address before: Tennessee

Patentee before: Eastman Chem Co.

CX01 Expiry of patent term
CX01 Expiry of patent term

Granted publication date: 20040407