CN1268951A - Metallocene, ligands and olefin polymerization - Google Patents
Metallocene, ligands and olefin polymerization Download PDFInfo
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- CN1268951A CN1268951A CN99800705A CN99800705A CN1268951A CN 1268951 A CN1268951 A CN 1268951A CN 99800705 A CN99800705 A CN 99800705A CN 99800705 A CN99800705 A CN 99800705A CN 1268951 A CN1268951 A CN 1268951A
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- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6596—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having atoms other than oxygen, sulfur, selenium, tellurium, nitrogen or phosphorus as ring hetero atoms
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- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
Abstract
A class of metallocene compounds is disclosed having the following general formula (I): Rn(Cp)(A)MLp wherein Rn is a structural bridge; Cp is a heterocyclic cyclopentadienyl group of formula (II) wherein R<1> and R<2> are hydrogen or hydrocarbon groups; M is a transition metal of group 3, 4, 5 or 6 or to the lanthanides or the actinides in the Periodic Table or the Elements (new IUPAC version); L is a monoanionic ligand; Z is NR<3> or O; X and Y are selected from (CR<4>2)n, BR<4>2, PR<4>, SiR<4>2 or GeR<4>2; and substituents R<4> are hydrogen atoms or hydrocarbon radicals, with the proviso that both X and Y cannot be carbon atoms at the same time; A is a group selected from substituted or unsubstituted cyclopentadienyls, which may carry one or more condensed cycles, =NR<5>, -O-, -S- and =PR<5> groups, R<5> being defined as substituents R<1> and R<2>, and groups corresponding to formula (II); p is an integer from 0 to 3. These metallocene compounds are useful as catalyst components for the polymerization of olefins.
Description
Invention field
The present invention relates to the new metallocene compound of a class, and contain their olefin polymerization catalysis and in the presence of described catalyzer, carry out the polymeric method.The present invention also relates to corresponding ligand as the intermediate product of synthetic described metallocene compound, and the method for preparing described ligand and described metallocene compound.
The description of prior art
The known catalyst component that can be used as olefinic polymerization of the metallocene compound that has two cyclopentadienyls.
European patent 0129368 for example, has been described and has been contained (a) and have the bicyclic pentadiene co-ordination complex of transition metal and (b) catalyst system of the olefinic polymerization of aikyiaiurnirsoxan beta.Two cyclopentadienyls can connect by an abutment, and this abutment normally contains one or more carbon atoms or heteroatomic divalent group.The metallocene compound of bridging, wherein to be condensed into the ring of aromatics or non-aromatics also be known to cyclopentadienyl group.
For example, European patent application EP 0185918 described use dichloride ethylenebis (4,5,6,7-tetrahydrochysene-1-indenyl) zirconium with the promotor that is fit to prepare complete with polyolefine.
Metallocene compound, wherein the cyclopentadienyl catalyzer that contains substituent heteroatoms and contain them also is known.
From European patent application EP-A2-0743317 known have contain the metallocene compound of heteroatomic cyclopentadienyl as a part that replace or the condensed member ring systems.The example that illustrates is the indenyl that replaces with quinoline or pyridyl.These catalyzer that contain described metallocene can be used for the polymerization of alkene.
United States Patent (USP) 5489659 relates to the siliceous metallocene compound that is used for alpha-olefine polymerizing of a class, and wherein Siliciumatom is a part that is fused to the non-aromatic ring on the cyclopentadienyl rings, as dichloride ethylenebis (4,4-dimethyl-4,5,6,7-tetrahydrochysene-4-sila indenyl) zirconium.
European patent application EP 0590486 has been described and has been contained the metallocene compound that contains heteroatomic cyclopentadienyl in system not and be used to prepare polyolefine.Only case illustrated is molybdenyl dichloride (1-phospha-2,3,4,5-tetramethyl-ring pentadienyl) zirconium and four (2, a 5-dimethyl pyrrole) zirconium.International Patent Application PCT/EP97/6297, the applicant of same name discloses the class bridging and a non-bridged heterocyclic metallocene compounds, and this metallocene compound contains and is contained heteroatomic ring condensed cyclopentadienyl.The catalyst system that contains described metallocene is used to the polymerization of alkene.
Hope can provide a class new metallocene, when being used for the catalyzer of olefinic polymerization, can be suitable for preparing polyolefine.
The invention summary
The inventor has found the metallocene compound that contains specific cyclopentadienyl ligand system that a class is new beyond expectationly, and it can be advantageously used for the catalyst component of olefinic polymerization.
According to first aspect, the invention provides the metallocene compound of formula (I):
R
n(Cp)(A)ML
p
R wherein
nIt is structure bridge;
Cp is the heterocyclic ring pentadienyl of formula (II):
Substituent R wherein
1And R
2, identical or inequality, be hydrogen atom, C
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
2-C
20Alkenyl, C
6-C
20Aryl, C
7-C
20Alkaryl or C
7-C
20Aralkyl, the substituent R of optional two vicinities
1And R
2Can form a ring that contains 5-8 carbon atom, in addition, substituent R
1And R
2Can contain silicon or germanium atom;
Z is NR
3Or O, R
3The same substituent R of definition
1And R
2
X and Y, identical or inequality, be to be selected from (CR
4 2)
r, BR
4 2, PR
4, SiR
4 2Or GeR
4 2Substituent R
4, identical or inequality, be hydrogen atom, C
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
2-C
20Alkenyl, C
6-C
20Aryl, C
7-C
20Alkaryl or C
7-C
20Aralkyl; In addition, substituent R
4Also heteroatoms such as nitrogen, phosphorus, oxygen, silicon or germanium atom can be contained, carbon atom can not be simultaneously but prerequisite is X and Y;
A is selected from replacement or unsubstituted cyclopentadienyl, this cyclopentadienyl can have one or more condensed rings ,=NR
5,-O-,-S-and=PR
5Group, R
5The same substituent R of definition
1And R
2, and corresponding to the group of formula (II);
M is those transition metal that are selected from 3,4,5 or 6 families in the periodic table of elements (new IUPAC version) or group of the lanthanides or actinium series;
Substituting group L, identical or inequality, be selected from hydrogen, halogen ,-SR
6, R
6,-OR
6,-NR
6 2, OCOR
6, OSO
2CF
3And PR
6 2The univalent anion ligand, substituent R wherein
6, identical or inequality, be linearity or branching, saturated or undersaturated C
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
2-C
20Alkenyl, C
6-C
20Aryl, C
7-C
20Alkaryl or C
7-C
20Aralkyl, optional silicon or the germanium atom of containing;
P is the integer of 0-3, and the oxidation state that p equals metal M subtracts 2;
N is the integer of 0-4; With
R is the integer of 1-4.
According to a further aspect in the invention, provide a class new ligand suc as formula (III)
R
n(Cp)(A)
q
Wherein R, n, Cp, A are identical with above-mentioned implication, and when n was 0, q was 0, and q is 1 when n is 1-4, and this ligand is particularly useful as the intermediate product when the metallocene compound of preparation formula (I).
Another aspect of the present invention is the ligand R of preparation formula (III)
n(Cp) (A)
qMethod, R wherein
n, Cp, A be identical with above-mentioned implication with q.
The present invention still also has the method that the aspect is the metallocene compound of preparation formula (I), and this method comprises formula (III) R
n(Cp) (A)
qLigand and molecular formula ML
P+2, wherein the definition of M, L and p is the same, contact in the presence of the compound of the dianion compound that can form corresponding formula (III) ligand.
Another aspect of the present invention is to contain the catalyzer of olefinic polymerization of described heterocyclic metallocene and the application in olefinic polymerization thereof.
Detailed Description Of The Invention
Substituent label on the cyclopentadienyl of formula (II) is as follows in the present invention:
In the metallocene compound of the above-mentioned type, the cyclopentadienyl of formula (II) can be by containing the divalent group of one or more carbon atoms, as CH
2Base, or the divalent group of the atom beyond the carbon atoms, as the dimethyl silyl base, be connected to an identical cyclopentadienyl, be connected to cyclopentadienyl derivative, or be connected to and contain heteroatomic group, on amino, described divalent group is connected to cyclopentadienyl identical cyclopentadienyl, cyclopentadienyl derivative or contains on the heteroatomic group 4 of above-mentioned member ring systems.
One class favourable according to the present invention corresponding to the heterocyclic metallocene of formula (I), wherein A is selected from group replacement or unsubstituted cyclopentadienyl, this group can have fused rings one or more aromatics or non-aromatics, as indenyl, fluorenyl, benzo indenyl, hydrogenation or partially hydrogenated ring, n is not 0, that is to say that two cyclopentadienyls are connected with each other by the abutment of a divalence.Preferably, the group (QR of this divalence
7 m)
nBe to be selected from CR
7 2, SiR
7 2, GeR
7 2, NR
7, PR
7(CR
7 2)
2, R
7Group, identical or inequality, randomly be linearity or branching, saturated or undersaturated C
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
2-C
20Alkenyl, C
6-C
20Aryl, C
7-C
20Alkaryl or or C
7-C
20Aralkyl, when Q is C, Si or Ge, two substituent R
7Can form a ring that contains 3-8 atom.More preferably, described divalent group is Si (CH
3)
2, SiPh
2, CH
2, (CH
2)
2Or C (CH
3)
2
M is 1 or 2, is 1 when Q is N or P, is 2 when Q is C, Si or Ge; The scope of n be 0-6 and, when n＞1, atom Q can be identical or inequality, as, for example, abutment-CH
2-Si (CH
3)
2-,-CH
2-NR
2-and CH
2-PR
2-.
Transition metal is preferably titanium, zirconium and hafnium, is more preferably zirconium.
Substituent R
1And R
2Be preferably hydrogen atom.
Substituting group L is preferably halogen atom or R
6Group, R
6Definition the same.More preferably they are chlorine atom or methyl.
One class more favourable according to the present invention corresponding to the heterocyclic metallocene of formula (I), wherein A is for above-mentioned formula (II) representative, that is to say, two cyclopentadienyl groups of metallocene compound of the present invention are identical.
The nonrestrictive example of described metallocene is:
Two { 2-(methyl)-1,1,3,3-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes (azadisilole) between the azepine of [c] [1,2,5] also } zirconiums of dichloride or dimethyl isopropylidene;
Two { 2-(ethyl)-1,1,3,3-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also } zirconiums of dichloride or dimethyl isopropylidene;
Two { 2-(sec.-propyl)-1,1,3,3-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also } zirconiums of dichloride or dimethyl isopropylidene;
Two { 2-(tertiary butyl)-1,1,3,3,5-pentamethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also } zirconiums of dichloride or dimethyl isopropylidene;
Two { 2-(ethyl)-1,1,3,3,5-pentamethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also } zirconiums of dichloride or dimethyl isopropylidene;
Two { 2-(sec.-propyl)-1,1,3,3,5-pentamethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also } zirconiums of dichloride or dimethyl isopropylidene;
Dichloride or dimethyl isopropylidene two { 2-(tertiary butyl)-1,1,3-trimethylammonium-1,2,3,3a-tetrahydro cyclopentyl diene be the assorted sila cyclopentenes (azaborasilole) of [c] [1,2,5] azepine boron also } zirconium;
Two { 3a-tetrahydro cyclopentyl diene is [c] [1,2,5] azepine phospha sila cyclopentenes (azaphosphasilole) also for 2-(tertiary butyl)-1,1,3-trimethylammonium-1,2, the 3 } zirconiums of dichloride or dimethyl isopropylidene;
Two { 2-(tertiary butyl)-1,3-dimethyl-1,2,3,3a-tetrahydro cyclopentyl diene be two boron heterocyclic pentenes (azadiborole) between the azepine of [c] [1,2,5] also } zirconiums of dichloride or dimethyl isopropylidene;
Two { 2-(tertiary butyl)-1,3-dimethyl-1,2,3,3a-tetrahydro cyclopentyl diene be two phosphorus heterocycle amylenes (azadiphosphole) between the azepine of [c] [1,2,5] also } zirconiums of dichloride or dimethyl isopropylidene;
Dichloride or dimethyl isopropylidene two { 2-(tertiary butyl)-1,1,3,5-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be the assorted sila cyclopentenes of [c] [1,2,5] azepine boron also } zirconium;
Two { 2-(tertiary butyl)-1,1,3,5-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be [c] [1,2,5] the azepine phospha sila cyclopentenes also } zirconiums of dichloride or dimethyl isopropylidene;
Two { 2-(tertiary butyl)-1,3,5-trimethylammonium-1,2,3,3a-tetrahydro cyclopentyl diene be two boron heterocyclic pentenes between the azepine of [c] [1,2,5] also } zirconiums of dichloride or dimethyl isopropylidene;
Two { 2-(tertiary butyl)-1,3,5-trimethylammonium-1,2,3,3a-tetrahydro cyclopentyl diene be two phosphorus heterocycle amylenes between the azepine of [c] [1,2,5] also } zirconiums of dichloride or dimethyl isopropylidene;
Dichloride or dimethylformamide dimethyl base silicomethane two bases two { 2-(tertiary butyl)-1,1,3 ,-trimethylammonium-1,2,3,3a-tetrahydro cyclopentyl diene be the assorted sila cyclopentenes of [c] [1,2,5] azepine boron also } zirconium;
Dichloride or two { 2-(tertiary butyl)-1,1,3,5-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene also [c] [1,2,5] the azepine phospha silicon cough up } zirconiums of dimethylformamide dimethyl base silicomethane two bases;
Dichloride or two { 2-(tertiary butyl)-1,3-dimethyl-1,2,3,3a-tetrahydro cyclopentyl diene be two boron heterocyclic pentenes between the azepine of [c] [1,2,5] also } zirconiums of dimethylformamide dimethyl base silicomethane two bases;
Dichloride or two { 2-(tertiary butyl)-1,3-dimethyl-1,2,3,3a-tetrahydro cyclopentyl diene be two phosphorus heterocycle amylenes between the azepine of [c] [1,2,5] also } zirconiums of dimethylformamide dimethyl base silicomethane two bases;
Dichloride or two { 2-(tertiary butyl)-1,3,5-trimethylammonium-1,2,3,3a-tetrahydro cyclopentyl diene be two boron heterocyclic pentenes between the azepine of [c] [1,2,5] also } zirconiums of dimethylformamide dimethyl base silicomethane two bases;
Dichloride or two { 2-(tertiary butyl)-1,3,5-trimethylammonium-1,2,3,3a-tetrahydro cyclopentyl diene be two phosphorus heterocycle amylenes between the azepine of [c] [1,2,5] also } zirconiums of dimethylformamide dimethyl base silicomethane two bases;
Dichloride or dimethyl isopropylidene { 2-(tertiary butyl)-1,1-dimethyl-2,3,4,7a-tetrahydrochysene-1H-cyclopenta [c] [1,2] aza-silicon quinoline (azasiline) } zirconium;
Dichloride or two { 2-(tertiary butyl)-1,1-dimethyl-2,3,4,7a-tetrahydrochysene-1H-cyclopenta [c] [1, the 2] aza-silicon quinoline } zirconiums of dimethylformamide dimethyl base silicomethane two bases;
Another kind of interesting according to the present invention corresponding to the heterocyclic metallocene of formula (I), wherein A that is to say that corresponding to formula (II) and n=0 two identical cyclopentadienyls do not interconnect by the abutment of divalence each other.
The nonrestrictive example of described this class is:
Dichloride or dimethyl { 2-(tertiary butyl)-1,1,3,3-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also } zirconium;
Dichloride or dimethyl { 2-(tertiary butyl)-1,1,3,3,5-pentamethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also } zirconium;
Dichloride or dimethyl { 2-(methyl)-1,1,3,3-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also } zirconium;
Dichloride or dimethyl { 2-(methyl)-1,1,3,3,5-pentamethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also } zirconium;
Dichloride or dimethyl { 2-(ethyl)-1,1,3,3-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also } zirconium;
Dichloride or dimethyl { 2-(ethyl)-1,1,3,3,5-pentamethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also } zirconium;
Dichloride or dimethyl { 2-(sec.-propyl)-1,1,3,3-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also } zirconium;
Dichloride or dimethyl { 2-(sec.-propyl)-1,1,3,3,5-pentamethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also } zirconium;
Dichloride or dimethyl { 2-(tertiary butyl)-1,1,3-trimethylammonium-1,2,3,3a-tetrahydro cyclopentyl diene be the assorted sila cyclopentenes of [c] [1,2,5] azepine boron also } zirconium;
Dichloride or dimethyl { 2-(tertiary butyl)-1,1,3-trimethylammonium-1,2,3,3a-tetrahydro cyclopentyl diene be [c] [1,2,5] azepine phospha sila cyclopentenes also } zirconium;
Dichloride or dimethyl { 2-(tertiary butyl)-1,3-dimethyl-1,2,3,3a-tetrahydro cyclopentyl diene be two boron heterocyclic pentenes (azadiborol) between the azepine of [c] [1,2,5] also } zirconium;
Dichloride or dimethyl { 2-(tertiary butyl)-1,3-dimethyl-1,2,3,3a-tetrahydro cyclopentyl diene be two phosphorus heterocycle amylenes between the azepine of [c] [1,2,5] also } zirconium;
Dichloride or dimethyl { 2-(tertiary butyl)-1,1,3,5-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be the assorted sila cyclopentenes of [c] [1,2,5] azepine boron also } zirconium;
Dichloride or dimethyl { 2-(tertiary butyl)-1,1,3,5-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be [c] [1,2,5] azepine phospha sila cyclopentenes also } zirconium;
Dichloride or dimethyl { 2-(tertiary butyl)-1,3,5-trimethylammonium-1,2,3,3a-tetrahydro cyclopentyl diene be two boron heterocyclic pentenes between the azepine of [c] [1,2,5] also } zirconium;
Dichloride or dimethyl { 2-(tertiary butyl)-1,3,5-trimethylammonium-1,2,3,3a-tetrahydro cyclopentyl diene be two phosphorus heterocycle amylenes between the azepine of [c] [1,2,5] also } zirconium;
Dichloride or dimethyl { 2-(tertiary butyl)-1,1-dimethyl-2,3,4,7a-tetrahydrochysene-1H-cyclopenta [c] [1,2] aza-silicon quinoline } zirconium;
Dichloride or dimethyl { 2-(tertiary butyl)-1,1-dimethyl-2,3,4,7a-tetrahydrochysene-1H-cyclopenta [c] [1,2] aza-silicon quinoline zirconium;
The coordination body of formula (III) is provided according to a further aspect in the invention:
R
n(Cp)(A)
q????(II])
R wherein
nIt is structure bridge;
Cp is the heterocyclic ring pentadienyl of formula (IV):
Wherein R, R
1, R
2, X, Y and Z, n and q implication the same, A is selected from group replacement or unsubstituted cyclopentadienyl, this group can have one or more fused rings ,=NR
5,-O-,-S-and=PR
5Group, R
5Definition such as substituent R
1And R
2With corresponding to the group of formula (IV).
Two two keys of the cyclopentadienyl rings of formula (IV) ligand can be on the position of any permission.
The compound of above-mentioned formula (IV) is useful especially as the intermediate product ligand of the heterocyclic metallocene compounds of preparation formula (I).
One class favourable according to the present invention corresponding to the heterocycle ligand of formula (III), wherein A is selected from group replacement or unsubstituted cyclopentadienyl, this group can have fused rings one or more aromatics or non-aromatics, as indenyl, fluorenyl, benzo indenyl, hydrogenation or partially hydrogenated ring, n is not 0, that is to say that two cyclopentadienyls are connected with each other by the abutment of a divalence.As for divalent group R
nCan be referring to the above.
One class more favourable according to the present invention corresponding to the heterocycle ligand of formula (III), wherein n be not 0 and A corresponding to formula (IV).
According to the present invention, the non-limitative example of this class ligand is:
Isopropylidene two { 2-(tertiary butyl)-1,1,3,3-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also };
Isopropylidene two { 2-(methyl)-1,1,3,3-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also };
Isopropylidene two { 2-(ethyl)-1,1,3,3-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also };
Isopropylidene two { 2-(sec.-propyl)-1,1,3,3-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also };
Isopropylidene two { 2-(tertiary butyl)-1,1,3,3,5-pentamethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also };
Isopropylidene two { 2-(ethyl)-1,1,3,3,5-pentamethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also };
Isopropylidene two { 2-(sec.-propyl)-1,1,3,3,5-pentamethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also };
Isopropylidene two { 2-(tertiary butyl)-1,1,3-trimethylammonium-1,2,3,3a-tetrahydro cyclopentyl diene be the assorted sila cyclopentenes of [c] [1,2,5] azepine boron also };
Isopropylidene two { 2-(tertiary butyl)-1,1,3-trimethylammonium-1,2,3,3a-tetrahydro cyclopentyl diene be [c] [1,2,5] azepine phospha sila cyclopentenes also };
Isopropylidene two { 2-(tertiary butyl)-1,3-dimethyl-1,2,3,3a-tetrahydro cyclopentyl diene be two boron heterocyclic pentenes between the azepine of [c] [1,2,5] also };
Isopropylidene two { 2-(tertiary butyl)-1,3-dimethyl-1,2,3,3a-tetrahydro cyclopentyl diene be two phosphorus heterocycle amylenes between the azepine of [c] [1,2,5] also };
Isopropylidene two { 2-(tertiary butyl)-1,1,3,5-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be the assorted sila cyclopentenes of [c] [1,2,5] azepine boron also };
Isopropylidene two { 2-(tertiary butyl)-1,1,3,5-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be [c] [1,2,5] azepine phospha sila cyclopentenes also };
Isopropylidene two { 2-(tertiary butyl)-1,3,5-trimethylammonium-1,2,3,3a-tetrahydro cyclopentyl diene be two boron heterocyclic pentenes between the azepine of [c] [1,2,5] also };
Isopropylidene two { 2-(tertiary butyl)-1,3,5-trimethylammonium-1,2,3,3a-tetrahydro cyclopentyl diene be two phosphorus heterocycle amylenes between the azepine of [c] [1,2,5] also };
Dimethyl silyl base two { 2-(tertiary butyl)-1,1,3-trimethylammonium-1,2,3,3a-tetrahydro cyclopentyl diene be the assorted sila cyclopentenes of [c] [1,2,5] azepine boron also };
Dimethyl silyl base two { 2-(tertiary butyl)-1,1,3-trimethylammonium-1,2,3,3a-tetrahydro cyclopentyl diene be [c] [1,2,5] azepine phospha sila cyclopentenes also };
Dimethyl silyl base two { 2-(tertiary butyl)-1,3-dimethyl-1,2,3,3a-tetrahydro cyclopentyl diene be two boron heterocyclic pentenes between the azepine of [c] [1,2,5] also };
Dimethyl silyl base two { 2-(tertiary butyl)-1,3-dimethyl-1,2,3,3a-tetrahydro cyclopentyl diene be two phosphorus heterocycle amylenes between the azepine of [c] [1,2,5] also };
Dimethyl silyl base two { 2-(tertiary butyl)-1,1,3,5-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be the assorted sila cyclopentenes of [c] [1,2,5] azepine boron also };
Dimethyl silyl base two { 2-(tertiary butyl)-1,1,3,5-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be [c] [1,2,5] azepine phospha sila cyclopentenes also };
Dimethyl silyl base two { 2-(tertiary butyl)-1,3,5-trimethylammonium-1,2,3,3a-tetrahydro cyclopentyl diene be two boron heterocyclic pentenes between the azepine of [c] [1,2,5] also };
Dimethyl silyl base two { 2-(tertiary butyl)-1,3,5-trimethylammonium-1,2,3,3a-tetrahydro cyclopentyl diene be two phosphorus heterocycle amylenes between the azepine of [c] [1,2,5] also };
Isopropylidene two { 2-(tertiary butyl)-1,1-dimethyl-2,3,4,7a-tetrahydrochysene-1H-cyclopenta [c] [1,2] aza-silicon quinoline (azasiline) };
Dimethyl silyl base two { 2-(tertiary butyl)-1,1-dimethyl-2,3,4,7a-tetrahydrochysene-1H-cyclopenta [c] [1,2] aza-silicon quinoline };
Another kind of interesting according to the present invention corresponding to the ligand of formula (III), wherein A that is to say that corresponding to formula (IV) and n=0 two identical cyclopentadienyls do not interconnect by the abutment of divalence each other.
The nonrestrictive example of described ligand is:
Two { 2-(tertiary butyl)-1,1,3,3-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also };
Two { 2-(tertiary butyl)-1,1,3,3,5-pentamethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also };
Two { 2-(methyl)-1,1,3,3-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also };
Two { 2-(methyl)-1,1,3,3,5-pentamethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also };
Two { 2-(ethyl)-1,1,3,3-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also };
Two { 2-(ethyl)-1,1,3,3,5-pentamethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also };
Two { 2-(sec.-propyl)-1,1,3,3-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also };
Two { 2-(sec.-propyl)-1,1,3,3,5-pentamethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also };
Two { 2-(tertiary butyl)-1,1,3-trimethylammonium-1,2,3,3a-tetrahydro cyclopentyl diene be the assorted sila cyclopentenes of [c] [1,2,5] azepine boron also };
Two { 2-(tertiary butyl)-1,1,3-trimethylammonium-1,2,3,3a-tetrahydro cyclopentyl diene be [c] [1,2,5] azepine phospha sila cyclopentenes also };
Two { 2-(tertiary butyl)-1,3-dimethyl-1,2,3,3a-tetrahydro cyclopentyl diene be two boron heterocyclic pentenes between the azepine of [c] [1,2,5] also };
Two { 2-(tertiary butyl)-1,3-dimethyl-1,2,3,3a-tetrahydro cyclopentyl diene be two phosphorus heterocycle amylenes between the azepine of [c] [1,2,5] also };
Two { 2-(tertiary butyl)-1,1,3,5-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be the assorted sila cyclopentenes of [c] [1,2,5] azepine boron also };
Two { 2-(tertiary butyl)-1,1,3,5-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be [c] [1,2,5] azepine phospha sila cyclopentenes also };
Two { 2-(tertiary butyl)-1,3,5-trimethylammonium-1,2,3,3a-tetrahydro cyclopentyl diene be two boron heterocyclic pentenes between the azepine of [c] [1,2,5] also };
Two { 2-(tertiary butyl)-1,3,5-trimethylammonium-1,2,3,3a-tetrahydro cyclopentyl diene be two phosphorus heterocycle amylenes between the azepine of [c] [1,2,5] also };
According to a further aspect in the invention, provide formula (III) R
n(Cp) (A)
qThe preparation method of ligand, wherein R such as above-mentioned implication, Cp is corresponding to formula (IV), and the same and n of the implication of A and q are 0, and this method is included under the existence of alkali, makes the compound of formula V:
With its double bond isomer, wherein X, R
1And R
2Definition the same: Z is a nitrogen, with general formula YZ '
2Compound contact, wherein the definition of Y is the same, Z ' is a halogen atom, forms formula (VI) compound
Step with its double bond isomer.
The cyclopentadienyl derivative of above-mentioned formula V can be by the preparation of known method, as in those methods described in International Patent Application PCT/US92/08730.
The R of formula (IIIa) is provided according to a further aspect in the invention,
n(Cp) (A ')
qThe preparation method of ligand, wherein R such as above-mentioned implication, n is that integer and the q of 1-4 is 1, that is to say that two groups of Cp and A ' link to each other by the abutment of divalence, A ' is selected from group replacement or unsubstituted cyclopentadienyl, this group can have one or more fused rings ,=NR
5,-O-,-S-and=PR
5Group, R
5Definition such as substituent R
1And R
2, Cp is a halogen atom corresponding to formula (IV) and Z ', this method comprises the steps:
(a) in the presence of alkali, make the compound of formula V
With its double bond isomer, wherein X, R
1And R
2Definition the same, Z is a nitrogen, with general formula YZ '
2Compound contact, wherein the definition of Y and Z ' is the same, forms formula (VI) compound
With its double bond isomer and
(b) contact with the anionic compound that can form formula (VII),
Thereafter the compound with general formula (VIII) contacts,
R
nZ '
2(VIII) mol ratio (VII)/(VIII) is equal to or greater than 2, or contacts with the compound of general formula (IX),
Z ' R
nA ' HR
5(IX) mol ratio (VII)/(IX) is equal to or greater than 1.
As for the structure bridge R in the above-mentioned ligand
nCan be referring to the above.
The non-limitative example that forms all alkali of above-mentioned formula (VI) compound is oxyhydroxide and hydride, sodium Metal 99.5 or potassium and the organo-metallic lithium compound of basic metal or alkaline-earth metal.Preferred lithium methide or the n-Butyl Lithium of using.
The non-limitative example that can form the anionic compound of formula (VII) is oxyhydroxide and hydride, sodium Metal 99.5 or potassium and the organo-metallic lithium compound of basic metal or alkaline-earth metal.Preferred lithium methide or the n-Butyl Lithium of using.
General formula R
nZ '
2The non-limitative example of compound (VIII) is dimethyldichlorosilane(DMCS), diphenyl dichlorosilane, dimethyl anium dichloride, 2,2-propylene dichloride and glycol dibromide.
The synthetic of the ligand of above-mentioned bridging preferably undertaken by the method that the solution of organolithium compound in non-polar solvent is added in the solution of compound (VI) in non-proton polar solvent.The solution that contains the compound (VII) with anionic form that obtains like this is added to formula R then
nZ '
2In the solution in non-proton polar solvent.The ligand of bridging adopts common known method to separate at last then.
The non-limitative example of used aprotic polar solvent is tetrahydrofuran (THF), glycol dimethyl ether, ether, toluene and methylene dichloride in the aforesaid method.The non-limitative example that is fit to non-polar solvent in the aforesaid method is pentane, hexane and benzene.In whole process, temperature preferably remains on-180 ℃ to 80 ℃, more preferably-20 ℃ to 40 ℃.
Another aspect of the present invention is the preparation method of the metallocene compound of formula (I), and the method that obtains this metallocene compound is by making the ligand R of above-mentioned formula (III)
n(Cp) (A)
qWith the compound that can form its corresponding dianion compound, then with formula ML
P+2Compound contact, the wherein same above definition of M, L and p.
The compound that can form described dianion is oxyhydroxide and hydride, sodium Metal 99.5 or potassium and the organometallic lithium salts of basic metal or alkaline-earth metal, and preferred described negatively charged ion is a n-Butyl Lithium.
Formula ML
1 P+2The non-limitative example of compound be titanium tetrachloride, zirconium tetrachloride and hafnium tetrachloride.
The metallocene compound of formula (I), when n is not 0 and A when being cyclopentadienyl derivative, the preparation method can be by at first making the bridged ligand of the formula (III) as above-mentioned preparation, and can form the anionic compound reaction of delocalized on cyclopentadienyl rings, thereafter with formula ML
P+2Compound reaction, wherein M and substituting group L are with above definition.Formula ML
P+2The non-limitative example of compound be titanium tetrachloride, zirconium tetrachloride and hafnium tetrachloride.
More particularly, the ligand of described bridging is dissolved in the non-proton polar solvent, the solution that obtains is added in the solution of organolithium compound in non-polar solvent.Separate the negatively charged ion thing that obtains like this, be dissolved in again in the aprotic polar solvent, be added to compound ML thereafter
P+2In the suspension in aprotic polar solvent.When reaction finishes, the solid product that obtains is separated from reaction mixture by the method that this area is commonly used.The non-limitative example that is suitable for polar solvent non-proton in the aforesaid method is tetrahydrofuran (THF), glycol dimethyl ether, ether, toluene and methylene dichloride.The non-limitative example that is fit to non-polar solvent in the aforesaid method is pentane, hexane and benzene.
In whole process, temperature preferably remains on-180 ℃ to 80 ℃, more preferably-20 ℃ to 40 ℃.
The metallocene compound of the formula of bridging (I) not, wherein n=0 and A be corresponding to formula (II), and the negatively charged ion that can be by making formula (VII) and the tetrahalide of transition metal M (that is to say ML
4) reaction prepare, M and L have above same implication, described being reflected in the suitable solvent carried out.
When the L substituting group in the metallocene compound of at least one formula (I) is not halogen, just need be with another is not that the substituting group of halogen replaces at least one the substituting group L in the metallocene obtain at least.This substitution reaction can be undertaken by methods known in the art.For example, when substituting group L was alkyl, metallocene can react with magnesium alkyl halide (Grignard reagent) or alkyl lithium compounds.
In whole process, temperature preferably remains on-180 ℃ to 80 ℃, more preferably-20 ℃ to 40 ℃.
Heterocyclic metallocene compounds of the present invention can be used as the catalyst component of olefinic polymerization easily.
So another aspect still according to the present invention provides a kind of catalyzer of olefinic polymerization, this catalyzer can obtain by following two components contact:
(A) metallocene compound of formula (I) and
(B) aikyiaiurnirsoxan beta and/or can form the compound of alkyl metallocene cation.
Aikyiaiurnirsoxan beta as component (B) can be passed through water and formula Al
2R
8 3Or Al
2R
8 6Organo-aluminium compound reaction obtain at least one R here
8It or not halogen.In this reaction.The mol ratio of Al/ water is 1: 1-100: 1.
The mol ratio of the metal of aluminium and metallocene is about 10: about 20000: 1 of 1-, preferred about 100: about 5000: 1 of 1-.
Used aikyiaiurnirsoxan beta considers it is linearity, branching or the cyclic compound that contains the group of at least a following type in catalyzer of the present invention:
R wherein
9Substituting group, identical or inequality, be hydrogen atom, C
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl or or C
7-C
20Aralkyl, optional silicon or the germanium atom of containing, or-O-(AlR
9)
2Base and, if be fit to, some R
8Substituting group can be a halogen atom.
Particularly, ol cpds in this way, can use formula:
Aikyiaiurnirsoxan beta, wherein n is 0 or integer and the R of 1-40
9Substituent definition is the same, and ring compound in this way can be used formula:
Aikyiaiurnirsoxan beta, wherein n is integer and the R of 2-40
9Substituent definition is the same.
The example that is suitable for aikyiaiurnirsoxan beta of the present invention is methylaluminoxane (MAO), isobutyl aluminium alkoxide (TIBAO) and 2,4,4-trimethylammonium-amyl group aikyiaiurnirsoxan beta (TIOAO).
In the polyolefinic catalyzer of the used preparation of method of the present invention, the heterocyclic metallocene compounds of formula (I) and aikyiaiurnirsoxan beta can be used as and formula Al
2R
3 3Or Al
2R
8 6The form of reaction product of organo-metallic aluminum compound have R wherein
8Substituting group, identical or inequality, be C
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl or or C
7-C
20Aralkyl, optional silicon or the germanium atom of containing.
Formula Al
2R
8 6Or Al
2R
8 6The non-limitative example of aluminum compound be Al (Me)
3, Al (Et)
3, AlH (Et)
2, Al (iBu)
3, Al (iHex)
3, Al (iOct)
3, Al (C
6H
5)
3, Al (CH
2C
6H
5)
3, Al (CH
2CMe
3)
3, Al (CH
2SiMe
3)
3, Al (Me)
2IBu, Al (Me)
3Et, AlMe (Et)
2, AlMe (iBu)
2, Al (Me)
2IBu, Al (Me)
2Cl, Al (Et)
2Cl, AlEtCl
2, Al
2(Et)
3Cl
3, M=methyl wherein, Et=ethyl, iBu=isobutyl-, iHex=isohexyl, iOct=2,4,4-tri-methyl-amyl.
In above-mentioned aluminum compound, trimethyl aluminium (TMA), triisobutyl aluminium (TIBAL) and three (2,4,4-trimethylammonium-amyl group) aluminium are preferred.
The non-limitative example that can form the cationic compound of metallocene alkyl is formula T
+D
-Compound, T wherein
+Be protonic acid, can provide proton and carry out irreversible reaction with the substituting group L of the metallocene of formula (I), and D
-Be compatible negatively charged ion, it is a coordinate not, can stablize from two kinds of compound reactive activity catalyst species, and be easy to remove from olefin substrate.Negatively charged ion D preferably
-Contain one or more boron ions.More preferably, negatively charged ion D
-Be formula BAr
(-) 4Negatively charged ion, wherein substituent A r is mutually the same or inequality, is aryl such as phenyl, pentafluorophenyl group, two (trifluoromethyl) phenyl.Particularly preferably be four-pentafluorophenyl group borate.In addition, formula BAr
3Compound also be suitable for.
The used catalyzer of the inventive method also can be used on the inert support.This can be by with metallocene (A), or the reaction product of itself and component (B), or component (B) and metallocene (A) thereafter, is deposited on the carrier, as for example silicon oxide, aluminum oxide, styrene diethylene benzene copoly mer, polyethylene or polypropylene.
The solid chemical compound that obtains like this, again in conjunction with add former state or with the alkylaluminium cpd of water pre-reaction, be normally used for vapour phase polymerization.
Catalyzer of the present invention can be used for the homopolymerization and the copolyreaction of alkene.
So the present invention still also has the method that purpose is olefinic polymerization, comprises the polyreaction of at least a olefinic monomer in the presence of above-mentioned catalyzer.
Catalyzer of the present invention can be used for the homopolymerization of alkene, and alkene is preferably ethene, with preparation HDPE, or alpha-olefin, as propylene and 1-butylene.When vinyl polymerization, heterocyclic metallocene of the present invention shows good activity, even ought the low-down Al/Zr ratio of employing be also to be like this.
The interesting application of another of catalyzer of the present invention is the copolymerization of ethene and higher alkene.Particularly, catalyzer of the present invention can be used to prepare LLDPE.
Can comprise formula CH as the alkene that is fit to of comonomer
2=CHR
10Alpha-olefin, R wherein
10Be the alkyl of 1-10 carbon atom, and cycloolefin.The example of these alkene is propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-laurylene, 1-tetradecylene, 1-esadecene, 1-octadecylene, 1-icosa alkene, allyl group tetrahydrobenzene, cyclopentenes, norbornylene and 4,6-dimethyl-1-heptene.
Multipolymer also can contain the unit of small part from polyene hydrocarbon, particularly straight chain or cyclic, conjugation or unconjugated diolefine, as 1, and 4-hexadiene, isoprene, 1,3-butadiene, 1,5-hexadiene and 1,6-heptadiene.
From formula CH
2=CHR
10Alpha-olefin, be preferably 1-20% (mole) from cycloolefin and/or from the amount of unit in multipolymer of polyene hydrocarbon.
Saturated elastomer copolymer can contain the unit of ethylene unit and alpha-olefin and/or non-conjugated diene hydrocarbon that can ring-opening polymerization.Undersaturated elastomer copolymer can contain, and with the polymeric unit that comes from ethene and alpha-olefin, also is the unsaturated unit that small part comes from one or more polyene hydrocarbon copolymerizations.The content of unsaturated unit is preferably 0-5% (weight).
The non-limitative example of the alpha-olefin that is fit to comprises propylene, 1-butylene and 4-methyl-1-pentene.Be fit to can copolymerization the non-conjugated diene hydrocarbon comprise 1,5-hexadiene, 1,6-heptadiene and 2-methyl isophthalic acid, 5-hexadiene.
The nonrestrictive example of the polyene hydrocarbon that is fit to is:
(i) can provide the polyene hydrocarbon of unsaturated unit, as:
-linear, unconjugated diolefine, as anti-1,4-hexadiene, along 1,4-hexadiene, 6-methyl isophthalic acid, 5-heptadiene, 3,7-dimethyl-1,6-octadiene and 11-methyl isophthalic acid, 10-12 carbon diene;
-bicyclodiolefin, as 4,5,8,9-tetrahydroindene and 6 and 7-methyl-4,5,8,9-tetrahydroindene;
-alkenyl or alkylidene group norbornylene are as 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornylene and outer-5-isopropenyl-2-nirbornene;
-many cyclodiene are as dicyclopentadiene, three ring-[6.2.1.0
2.7] 4,9-11 carbon diene and its 4-methyl-derivatives;
Non-conjugated diene hydrocarbon that (ii) can ring-opening polymerization, as 1,5-hexadiene, 1,6-heptadiene and 2-methyl isophthalic acid, 5-hexadiene;
(iii) conjugated diene is as divinyl and isoprene.
Another object of the present invention is the method for carrying out propylene polymerization in the presence of above-mentioned catalyzer.
It is the preparation of cyclic olefin polymer that catalyzer of the present invention also has an interesting application.Monocyclic and polycyclic olefinic monomer both all polymerization also can carry out copolymerization with the olefinic monomer of linearity.
Polymerization process of the present invention can carry out under gas phase or liquid phase, and optional have the inert hydrocarbon solvent, no matter is (as the toluene) of aromatics, and still (propane, hexane, heptane, Trimethylmethane and the hexanaphthene) of aliphatic series exists.
Polymerization temperature is preferably about 0 ℃-Yue 250 ℃.Particularly, in the technology of preparation HDPE and LLDPE, be preferably 20-150 ℃, more preferably 40-90 ℃, and during the preparation elastomer copolymer, be preferably 0-200 ℃ and, more preferably 20-100 ℃.
Polymerization pressure is preferably 0.5-100 crust, is preferably 2-50 crust and 4-30 crust more preferably.
As long as the change of the molecular weight of polymkeric substance also can be by changing polymerization temperature, the type of catalyst component and concentration, or adopt molecular weight regulator as, for example, hydrogen is realized.
The change of molecular weight distribution can be by adopting the mixture of different metallocenes, or carry out multistep polymerization and realize under the concentration of different polymerization temperatures and/or different molecular weight regulator.
Polymerization yield rate depends on the purity of catalyzer metallocenes.So in order to increase polymerization yield rate, metallocene uses after purification process usually.
Each component of catalyzer can contact in the past in polymerization.For metallocenes (A), the concentration of pre-contact is generally 1-10
-8Mol/l, and component (B) is generally 10-10
-8Mol/l.Pre-contact usually hydrocarbon solvent and, if be fit to, carry out under the existence of small amounts of monomer.Be generally 1 minute to 24 hours pre-duration of contact.
The following examples are explanation of the invention rather than restriction.
The feature of general method
All operations all are by using conventional Schlenk line technology to carry out under nitrogen.Solvent is at the Na-of blue look diphenylmethanone ketyl (Et
2O), CaH
2(CH
2Cl
2) or 6AliBu
3There is distillation down in (hydro carbons), and is stored under the nitrogen.BuLi (Aldrich company) directly uses.
Metallocene
1H-NMR analyzes and carry out (CD on AC200 Bruker spectrograph
2Cl
2, the residual CHDCl of reference
2Middle crest at the triplet of 5.35ppm).All NMR solvents are at P
2O
5Last dry, and use preceding distillation.The preparation of sample adopts the inert atmosphere technology of standard to carry out under nitrogen.
Polymkeric substance
1H-NMR and
13C-NMR analyzes and carries out on Bruker 400 MHZ instruments.Sample is to analyze at 130 ℃ for the solution of ethane with tetrachloro two deuteriums.Limiting viscosity [η] is to measure down in 135 ℃ in tetraline (dl/g).
The fusing point Tm of polymkeric substance (℃) and AH (J/g) measure on Mettler equipment by differential scanning calorimeter (DSC), its method is as follows: the sample that will about 10mg obtains from polymerization is heated to 180 ℃ with the sweep velocity that equals 20 ℃/minute; Sample kept 5 minutes and cooled off with the sweep velocity that equals 20 ℃/minute thereafter at 180 ℃.Carry out scanning second time according to same form for the first time then.The value of report is the data that obtain in scanning for the second time.
Density (g/ml) has in the pillar of density gradient by extruding the immersion of multipolymer sample, measures according to the method for ASTM D-1505.
In multipolymer of the present invention, the product r of specific activity
1r
2, r wherein
1Be relative reactivity and the r of α-comonomer to ethene
2Be the relative reactivity of ethene to α-comonomer.
The preparation of ligand
As Nickias, P.N., Devore, International Patent Application PCT/US92/08730 of D.D. described method preparation (N-tertiary butyl amino) (dimethyl) (cyclopentadienyl) silane and (N-tertiary butyl amino) (dimethyl) (methyl cyclopentadienyl) silane.
Molybdenyl dichloride (1,3-trimethyl silyl cyclopentadienyl) zirconium is available from the Boulder scientific company, Mead company, USA.Molybdenyl dichloride (cyclopentadienyl) zirconium is available from Strem chemical company, Newburyport, MA, USA.
Embodiment 1
1,1,3, the also preparation of two sila cyclopentenes between the azepine of [c] [1,2,5] of 3-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene
(0.071mol 13.9g) is dissolved in THF (100ml) and handle with BuLi (the 2.5M hexane solution of 144mmol) at 0 ℃ with (N-tertiary butyl amino) (dimethyl) (cyclopentadienyl) silane.After at room temperature stirring 16 hours ,-10 ℃ and stir under, the THF solution (75ml) of dianion solution and dichlorodimethylsilane (0.071mol) is added drop-wise in the flask that contains 25ml THF simultaneously.Mixture is heated to room temperature and stirring is spent the night.Remove under vacuum and desolvate, residue extracts with pentane.After filtering and evaporating pentane, distillation extraction liquid obtains the 1.2g colourless liquid, is accredited as 1,1,3, and 3-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes and isomer between the azepine of [c] [1,2,5] also.
1H-NMR δ (CDCl
3) (main isomer): 6.7 (m, 3H), 5.7 (broad peak s, 2H), 1.3 (s, 9H), 0.2 (s, 12H).Mass spectrum (m/e) (relative density): 251 ([PM], 12), 236 (100), 179 (4), 114 (4), 73 (7).
Embodiment 2
1,1,3,3, the also preparation of two sila cyclopentenes between the azepine of [c] [1,2,5] of 5-pentamethyl--1,2,3,3a-tetrahydro cyclopentyl diene
(0.070mol 14.7g) is dissolved in THF (199ml) and handle with butyllithium (the 2.5M hexane solution of 0.14mol) at-78 ℃ with (N-tertiary butyl amino) (dimethyl) (methyl cyclopentadienyl) silane.After at room temperature stirring 16 hours, under-78 ℃, the dianion drips of solution is added to dichlorodimethylsilane, and (0.070mol is in the THF solution (100ml) 9.03g).Mixture slowly is heated to room temperature and stirring is spent the night.After solvent evaporated, residue extracts with pentane, obtains oily matter after filtration and the evaporation.Distillation oily matter obtains the 5.0g colourless liquid, is accredited as 1,1,3,3, and 5-pentamethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes and isomer between the azepine of [c] [1,2,5] also.
1H-NMR δ (CDCl
3) (main isomer): (6.3 (m, 1H), 5.8 (broad peak s, 1H), 4.9 (broad peak s, 1H), 2.1 (s, 3H), 1.3 (s, 9H), 0.3 (broad peak s, 6H), 0.15 (broad peak s, 6H).Mass spectrum (m/e) (relative density): 265 ([PM], 14), 250 (100), 193 (3), 135 (4), 73 (16).
Embodiment 3
1,1,5-trimethylammonium-3-phenyl-1,2,3,3a-tetrahydro cyclopentyl diene be the preparation of the assorted sila cyclopentenes of [c] [1,2,5] azepine boron also
(95.7mmol 20g) is dissolved in THF (120ml) and-78 ℃ of coolings with handle with butyllithium (2.1 equivalents, the 2.5M hexane solution of 201mmol) with (N-tertiary butyl amino) (dimethyl) (methyl cyclopentadienyl) silane.After this solution at room temperature stirs 4 hours, under-78 ℃, be added dropwise to 95.1mmol (15.7g) PhBCl
2Solution in the 20ml pentane.Mixture slowly is heated to room temperature and stirring is spent the night.Behind filtration and evaporating solvent, obtain orange.Distillation oily matter obtains the 7.0g colourless liquid, is accredited as title compound.Mass spectrum (m/e) (relative density): 295 ([PM], 80), 280 (70), 239 (30), 224 (70), 160 (100).
Embodiment 4
1,1,5-trimethylammonium-3-phenyl-1,2,3,3a-tetrahydro cyclopentyl diene be the preparation of [c] [1,2,5] azepine phospha sila cyclopentenes also
(20mmol 4.17g) is dissolved in THF (25ml) and-78 ℃ of coolings with handle with butyllithium (40mmol, the 2.5M hexane solution of 16ml) with (N-tertiary butyl amino) (dimethyl) (methyl cyclopentadienyl) silane.After reaction is finished, at room temperature stirred 1.5 hours.In separatory 250ml flask, add the dichlorophenyl phosphine of 2.7ml (20mmol) and the THF of 25ml.Under-78 ℃, be added dropwise to above-mentioned dianion, be heated to room temperature and stirred 2 hours.Behind filtration and evaporating solvent, obtain the 6.61g orange.After with hexane wash, obtain the soluble oily matter of 3.68g pentane, be accredited as title compound.Mass spectrum (m/e) (relative density): 315 ([PM], 100), 300 (40), 244 (50), 135 (30), 57 (60).
The preparation of metallocene
Embodiment 5
Two (1,1,3,3-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also) ZrCl
2Preparation
Under-78 ℃, butyllithium (the 2.5M hexane solution of 4.0mmol) slowly is added to 1,1,3,3-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene also between the azepine of [c] [1,2,5] two sila cyclopentenes (3.8mmol is in ether 0.95g) (30ml) solution.Reaction mixture was heated to room temperature and restir 3 hours.Under vacuum, remove and desolvate, residue in glove box (glovebox) with ZrCl
4(1.9mmol 0.443g) mixes.Mixture is slurryization in pentane (40ml)/ether (1ml), and stirs 16 hours.After the solvent evaporated, residue also filters with dichloromethane extraction.Evaporated filtrate obtains two (1,1,3,3-tetramethyl--1,2,3,3a-tetrahydro cyclopentyl diene be two sila cyclopentenes between the azepine of [c] [1,2,5] also) ZrCl of 1.0g chocolate brown powder form
2, (1,2 (tBuN=(SiMe
2)
2Cp)
2ZrCl
2 1H-NMRδ(CD
2Cl
2)：6.85(s，2H)，6.5(t，1H)，1.4(s，9H)，0.6(s，6H)，0.3(s，6H)。
The polymerization of ethene
Methylaluminoxane (MAO)
What use is the commercial commercially available product of Schering, is the toluene solution of 10% (weight).
Embodiment 6-9
The exsiccant 200ml glass autoclave that will be equipped with magnetic stirring apparatus, temperature probe and ethylene feed pipeline uses ethene at 35 ℃ of purgings.At room temperature introduce the 90ml hexane.Catalyst system prepares in the 10ml hexane independently, and method is that order is introduced methylaluminoxane, or three iso-octyl aluminium/water (Al/H
2O=2.1) mixture stirred after 5 minutes, introduced metallocene compound (1, the 2 (tBuN=(SiMe that is dissolved in the small amount of toluene
2)
2Cp)
2ZrCl
2Stir after 5 minutes, this solution is introduced autoclave in ethylene stream, the off-response device, temperature rises to 80 ℃, is pressurized to 4.6 crust (gauge pressure) with ethene.Total pressure keeps constant on request with reinforced ethene.Polyreaction stops by cooling, reactor exhaust and adding 1ml methyl alcohol.The polymkeric substance that obtains acidic methanol, methanol wash, and dry in 60 ℃ vacuum drying oven.The results are shown in table 1.Polymerizing condition is as shown in table 1.
Embodiment 10-11 (comparative example)
These embodiment repeat the described program of embodiment 6-9, but replace two (1,1 with molybdenyl dichloride [1, two (trimethyl silyl) cyclopentadienyls of 3-] zirconium, 3,3-tetramethyl--1,2, two sila cyclopentenes between 3-three hydrogen cyclopenta [c] [1,2,5] azepines) ZrCl
2Polymerizing condition is as shown in table 1.
Embodiment 12-13 (comparative example)
These embodiment repeat the described program of embodiment 6-9, but replace two (1,1,3,3-tetramethyl--1,2, two sila cyclopentenes between 3-three hydrogen cyclopenta [c] [1,2,5] azepines) ZrCl with molybdenyl dichloride (cyclopentadienyl) zirconium
2Polymerizing condition is as shown in table 1.
The result of table 1. vinyl polymerization
N.d.=does not measure
| Embodiment metallocene promotor Al/Zr time aggregation thing activity [η], mg (μ mol) is mol.ratio min g Kg/gZr/h dL/g (mmol) |
| 6??1.00(1.51)???MAO(1.51)??1000??????10????2.43??105.83????n.d. 7??0.50(0.76)???MAO(0.76)??1000??????10????2.65??230.83????1.48 *8 0.16 (0.24) MAO (0.25) 1,026 10 0.84 228.65 1.26 9 0.50 (0 76) TIOA-H2O, 1,013 8 0.42 45.73 3.58 (0.765) 10 0.13 (0.22) MAO (0.23) 1,028 15 1.34 262.68 2.05 comparative example, 11 0.13 (0.22) TIOA-H2O 1,073 20 0.20 29.40 n.d. comparative examples, (0.24) 12 0.10, (0.34) MAO, (0.35) 1,023 10 1.07 205.76 2.99 comparative example 13 0.30, (1.03) TIOA-H 2O 997 20 weight comparative examples (1.02) |
The copolymerization of ethene and 1-hexene
Embodiment 14
The exsiccant 200ml glass autoclave that will be equipped with magnetic stirring apparatus, temperature inserting tube and ethylene feed pipeline uses ethene at 35 ℃ of purgings.At room temperature introduce heptane (80ml) and 1-hexene (10ml).Catalyst system separately prepares in the 10ml heptane, and method is that order is introduced methylaluminoxane (0.33mmol) and is dissolved in metallocene (0.2mg) in the 3ml toluene.Stir after 5 minutes, this solution is introduced autoclave in ethylene stream, the off-response device, temperature rises to 70 ℃, is pressurized to 4.5 crust (gauge pressure) with ethene.Total pressure keeps constant on request with reinforced ethene.After 10 minutes, polyreaction stops by cooling, reactor exhaust and adding 1ml methyl alcohol.The polymkeric substance that obtains acidic methanol, methanol wash, and dry in 60 ℃ vacuum drying oven.[η] value that reclaims 1.2g polymkeric substance (active 261Kg/g-Zr/h) and obtain is 1.0dL/g, and 7.7% (weight) 1-hexene is introduced into.
Tm=114 ℃ of dsc analysis (2 ° of melts) (2 ° of melt); Δ H=142J/g.
13It is 2.72mol% that C-NMR analyzes the amount that shows the 1-hexene, n
E(average ethylene sequence length) is 37 and r
1=62.1, r
2=0.034, and r
1* r
2=2.11.
Claims (34)
1. the metallocene compound of a formula (I):
R
n(Cp) (A) ML
pR wherein
nIt is structure bridge; Cp is the heterocyclic ring pentadienyl of formula (II):
Substituent R wherein
1And R
2, identical or inequality, be hydrogen atom, C
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
2-C
20Alkenyl, C
6-C
20Aryl, C
7-C
20Alkaryl or C
7-C
20Aralkyl, the substituent R of optional two vicinities
1And R
2Can form a ring that contains 5-8 carbon atom, in addition, substituent R
1And R
2Can contain silicon or germanium atom;
Z is NR
3Or O, R
3The same substituent R of definition
1And R
2
X and Y, identical or inequality, be to be selected from (CR
4 2)
r, BR
4 2, PR
4, SiR
4 2Or GeR
4 2Substituent R
4, identical or inequality, be hydrogen atom, C
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
2-C
20Alkenyl, C
6-C
20Aryl, C
7-C
20Alkaryl or C
7-C
20Aralkyl; Substituent R
4Also heteroatoms such as nitrogen, phosphorus, oxygen, silicon or germanium atom can be contained, carbon atom can not be simultaneously but prerequisite is X and Y;
A is selected from replacement or unsubstituted cyclopentadienyl, this cyclopentadienyl can have one or more condensed rings ,=NR
5,-O-,-S-and=PR
5Group, R
5The same substituent R of definition
1And R
2, and corresponding to the group of formula (II);
M is selected from those transition metal that belong to 3,4,5 or 6 families or group of the lanthanides or actinium series in the periodic table of elements (new IUPAC version);
Substituting group L, identical or inequality, be selected from hydrogen, halogen ,-SR
6, R
6,-OR
6,-NR
6 2, OCOR
6, OSO
2CF
3And PR
6 2The univalent anion ligand, substituent R wherein
6, identical or inequality, be linearity or branching, saturated or undersaturated C
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
2-C
20Alkenyl, C
6-C
20Aryl, C
7-C
20Alkaryl or C
7-C
20Aralkyl, optional silicon or the germanium atom of containing;
P is the integer of 0-3, and the oxidation state that p equals metal M subtracts 2;
N is the integer of 0-4; With
R is the integer of 1-4.
2. according to the metallocene compound of claim 1, it is characterized in that R is QR
7 m, Q is C, Si, Ge, N and P, R
7Group, identical or inequality, be randomly linearity or branching, saturated or undersaturated C
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
2-C
20Alkenyl, C
6-C
20Aryl, C
7-C
20Alkaryl or C
7-C
20Aralkyl, when Q is C, Si or Ge, two substituent R
7Can form a ring that contains 3-8 atom; M is 1 or 2, is 1 when Q is N or P, is 2 when Q is C, Si or Ge.
3. according to the metallocene compound of claim 2, it is characterized in that (QR
7 m)
nBe to be selected from CR
7, SiR
7 2, GeR
7 2, NR
7, PR
7(CR
7 2)
2R
7The definition such as the claim 2 of group.
4. according to the metallocene compound of claim 3, it is characterized in that (QR
7 m)
nBe to be selected from Si (CH
3)
2, SiPh
2, CH
2, (CH
2)
2And C (CH
3)
2
5. according to the metallocene compound of claim 1, wherein transition metal is to be selected from titanium, zirconium and hafnium.
6. according to the metallocene compound of claim 1, wherein substituting group L is halogen or substituent R
6
7. according to the metallocene compound of claim 1, substituent R wherein
1And R
2It is hydrogen atom.
8. according to the metallocene compound of claim 1, wherein A is corresponding to formula (II), and it defines as claim 1.
9. the ligand of a formula (III)
R
n(Cp)(A)
q????(III)
R wherein
nIt is structure bridge;
Cp is the heterocyclic ring pentadienyl of formula (IV):
With its double bond isomer, wherein substituent R
1And R
2, identical or inequality, be hydrogen atom, C
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
2-C
20Alkenyl, C
6-C
20Aryl, C
7-C
20Alkaryl or C
7-C
20Aralkyl, the substituent R of optional two vicinities
1And R
2Can form a ring that contains 5-8 carbon atom, in addition, substituent R
1And R
2Can contain silicon or germanium atom;
Z is NR
3Or O, R
3The same substituent R of definition
1And R
2
X and Y, identical or inequality, be to be selected from (CR
4 2)
r, BR
4 2, PR
4, SiR
4 2Or GeR
4 2Substituent R
4, identical or inequality, be hydrogen atom, C
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
2-C
20Alkenyl, C
6-C
20Aryl, C
7-C
20Alkaryl or C
7-C
20Aralkyl; Substituent R
4Also heteroatoms such as nitrogen, phosphorus, oxygen, silicon or germanium atom can be contained, carbon atom can not be simultaneously but prerequisite is X and Y;
A is selected from replacement or unsubstituted cyclopentadienyl, this cyclopentadienyl can have one or more condensed rings ,=NR
5,-O-,-S-and=PR
5Group, R
5The same substituent R of definition
1And R
2, and corresponding to the group of formula (IV);
N is the integer of 0-4;
Q is the integer of 0-1; With
R is the integer of 1-4.
10. according to the ligand of claim 9, wherein R is QR
7 m, Q is C, Si, Ge, N or P, R
7Group, identical or inequality, be linearity or branching, saturated or undersaturated C
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
2-C
20Alkenyl, C
6-C
20Aryl, C
7-C
20Alkaryl or C
7-C
20Aralkyl, when Q is C, Si or Ge, two substituent R
7Can form a ring that contains 3-8 atom; M is 1 or 2, is 1 when Q is N or P, is 2 when Q is C, Si or Ge.
11. the ligand according to claim 10 is characterized in that, (QR
7 m)
nBe to be selected from CR
7 2, SiR
7 2, GeR
7 2, NR
7, PR
7(CR
7 2)
2, R
7The definition such as the claim 1 of group.
12. the ligand according to claim 11 is characterized in that, (QR
7 m)
nBe to be selected from Si (CH
3)
2, SiPh
2, CH
2, (CH
2)
2And C (CH
3)
2
13. according to the ligand of claim 9, wherein substituent R
1And R
2It is hydrogen atom.
14. according to the ligand of claim 9, wherein A is corresponding to formula (IV), it defines as claim 9.
A 15. preparation formula (III) R
n(Cp) (A)
qThe method of ligand, definition such as the claim 9 of Cp and A, n and q are 0, this method is included under the existence of alkali, makes the compound of formula V:
With its double bond isomer, wherein X, R
1And R
2Definition with claim 9, Z is a nitrogen, with general formula YZ '
2Compound contact, wherein the definition of Y is with claim 9, Z ' is a halogen atom, forms formula (VI) compound
Step with its double bond isomer.
16. the R of a preparation formula (IIIa)
n(Cp) (A ')
qThe method of ligand, wherein R is QR
7 m, among its implication such as the claim 10-12 any one, n is that integer and the q of 1-4 is 1, A ' is selected from group replacement or unsubstituted cyclopentadienyl, this group can have one or more fused rings ,=NR
5,-O-,-S-and=PR
5Group, R
5Definition such as substituent R
1And R
2, Cp is corresponding to formula (IV), and Z ' is a halogen atom, and this method comprises the steps:
(a) in the presence of alkali, make the compound of formula V
With its double bond isomer, wherein X, R
1And R
2Definition be nitrogen with claim 9 and Z, with general formula YZ '
2Compound contact, wherein the definition of Y is with claim 9, Z ' is a halogen atom, forms formula (VI) compound
With its double bond isomer and
(b) contact with the anionic compound that can form formula (VII)
Thereafter with the compound R of general formula (VIII)
nZ '
2Contact, its mol ratio (VII)/(VIII) is equal to or greater than 2, or with the compound Z ' R of general formula (IX)
nA ' HR
5Contact, its mol ratio (VII)/(IX) is equal to or greater than 1.
17. method according to claim 15 or 16, the wherein said alkali that forms formula (VI) compound is oxyhydroxide and hydride, sodium Metal 99.5 and the potassium that is selected from basic metal and alkaline-earth metal with the anionic compound that can form described formula (VII), and organometallic lithium salts.
18. according to the method for claim 17, the wherein said alkali that forms formula (VI) compound is n-Butyl Lithium with the anionic compound that can form described formula (VII).
19. according to the method for claim 16, its formula of (VIII) and halogen atom Z ' (IX) are the chlorine atoms.
20. the ligand R of the formula (III) that a method for preparing according to the metallocene compound of claim 1, this metallocene compound can be by making claim 9
n(Cp) (A)
qWith the compound that can form its corresponding dianion compound, then with formula ML
P+2Compound contact, wherein the definition of M, L and p is with claim 1.
21. a method for preparing according to the metallocene compound of claim 20, wherein A is corresponding to formula (II).
22. according to the method for claim 20, the compound that wherein can form corresponding dianion compound is oxyhydroxide and hydride, sodium Metal 99.5 and the potassium that is selected from basic metal and alkaline-earth metal, and organometallic lithium salts.
23. according to the method for claim 22, the compound that wherein can form described dianion compound is a n-Butyl Lithium.
24. according to the method for claim 20, its Chinese style ML
P+2Compound be to be selected from titanium tetrachloride, zirconium tetrachloride and hafnium tetrachloride.
25. the catalyzer of an olefinic polymerization can obtain by following contact:
26. (Q) according to the metallocene compound of any one formula (I) of claim 1-8 and
27. (R) aikyiaiurnirsoxan beta and/or can form the compound of alkyl metallocene cation.
28. the catalyzer according to claim 25 is characterized in that, described aikyiaiurnirsoxan beta is by with water and formula AlR
8 3Or Al
2R
8 3Organo-aluminium compound reaction obtain at least one R here
8It or not halogen.
29. according to the catalyzer of claim 26, wherein the mol ratio of aluminium and water is 1: 1-100: 1.
30. the catalyzer according to claim 25 is characterized in that, described aikyiaiurnirsoxan beta is that to be selected from MAO, TIBAO and TIOAO and described organo-aluminium compound be TIOA, TMA and/or TIBA.
31. the catalyzer according to claim 25 is characterized in that, can form the cationic compound of metallocene alkyl is formula T
+D
-Compound, T wherein
+Be protonic acid, can provide proton and carry out irreversible reaction, D with the substituting group L of the metallocene of formula (I)
-Be compatible negatively charged ion, it is a coordinate not, can stablize from described two kinds of compound reactive activity catalyst species, and be highly susceptible to removing from olefin substrate.
32. the catalyzer according to claim 29 is characterized in that, negatively charged ion D contains one or more boron atoms.
33. the method for an olefinic polymerization, described method comprise the polyreaction of one or more olefinic monomers in the presence of each desired catalyzer of claim 25-30.
34. according to the method for claim 31, wherein olefinic monomer is ethene and/or propylene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP98201501 | 1998-05-08 | ||
| EP98201501.8 | 1998-05-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1268951A true CN1268951A (en) | 2000-10-04 |
Family
ID=8233694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99800705A Pending CN1268951A (en) | 1998-05-08 | 1999-05-07 | Metallocene, ligands and olefin polymerization |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0994886A1 (en) |
| JP (1) | JP2002513428A (en) |
| KR (1) | KR20010021604A (en) |
| CN (1) | CN1268951A (en) |
| AU (1) | AU4141999A (en) |
| CA (1) | CA2294608A1 (en) |
| WO (1) | WO1999058539A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558058A (en) * | 2013-10-12 | 2015-04-29 | 中国科学院长春应用化学研究所 | Metallocene complex, preparation method thereof and catalyst composition |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003524013A (en) | 2000-02-24 | 2003-08-12 | バセル テクノロジー カンパニー ビー．ブイ． | Organometallic compounds useful as cocatalysts for olefin polymerization |
| WO2002051877A2 (en) | 2000-12-22 | 2002-07-04 | Basell Polyolefine Gmbh | Catalyst components for the polymerization of olefins |
| EP1355958A2 (en) | 2000-12-22 | 2003-10-29 | Basell Poliolefine Italia S.p.A. | Process for the preparation of porous polymers and polymers obtainable thereof |
| KR100422940B1 (en) * | 2000-12-23 | 2004-03-12 | 주식회사 엘지화학 | Half metallocene catalyst and method for preparing stereoregular vinyl aromatic polymer using the same |
| EP1392705B1 (en) | 2001-05-21 | 2005-01-05 | Basell Polyolefine GmbH | Catalyst system for the polymerization of olefins |
| US7022793B2 (en) | 2001-11-27 | 2006-04-04 | Basell Polyolefine Gmbh | Process for the treatment of polymer compositions |
| KR100497172B1 (en) * | 2002-11-11 | 2005-06-28 | 주식회사 엘지화학 | Multinuclear half metallocene catalyst having sandwitch type metallocene derivatives as ligands for styrene polymerization and polymerization process using the metallocene catalyst |
| RU2335338C2 (en) | 2003-04-17 | 2008-10-10 | Базелль Полиолефин Италия С.Р.Л. | Method of gas-cycle polymerisation of olefins |
| KR101167877B1 (en) | 2003-07-04 | 2012-07-23 | 바젤 폴리올레핀 게엠베하 | Olefin polymerization process |
| US7799722B2 (en) | 2004-03-12 | 2010-09-21 | Basell Polyolefine Gmbh | Catalyst system for the polymerization of olefin |
| EP1723184A1 (en) | 2004-03-12 | 2006-11-22 | Basell Polyolefine GmbH | Process for polymerizing 1-hexene or higher alpha-olefins |
| US7977444B2 (en) | 2004-03-12 | 2011-07-12 | Basell Polyolefine Gmbh | Process for polymerizaing 1-hexene or higher alpha-olefins |
| EP1655314A1 (en) | 2004-11-09 | 2006-05-10 | Basell Polyolefine GmbH | Process for the preparation of 1-butene/propylene copolymers |
| CN101061142B (en) | 2004-11-22 | 2012-04-18 | 巴塞尔聚烯烃股份有限公司 | Propylene based terpolymers |
| ATE519788T1 (en) | 2007-12-18 | 2011-08-15 | Basell Polyolefine Gmbh | GAS PHASE PROCESS FOR THE POLYMERIZATION OF ALPHA-OLEFINS |
| US11518824B2 (en) | 2017-10-11 | 2022-12-06 | Basell Polyolefine Gmbh | Supported catalyst system |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0590486A3 (en) * | 1992-09-24 | 1994-08-24 | Idemitsu Kosan Co | Polymerization catalysts and process for producing polymers |
-
1999
- 1999-05-07 CN CN99800705A patent/CN1268951A/en active Pending
- 1999-05-07 JP JP55623599A patent/JP2002513428A/en active Pending
- 1999-05-07 KR KR1020007000162A patent/KR20010021604A/en not_active Application Discontinuation
- 1999-05-07 AU AU41419/99A patent/AU4141999A/en not_active Abandoned
- 1999-05-07 EP EP99924944A patent/EP0994886A1/en not_active Withdrawn
- 1999-05-07 CA CA002294608A patent/CA2294608A1/en not_active Abandoned
- 1999-05-07 WO PCT/EP1999/003247 patent/WO1999058539A1/en not_active Application Discontinuation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558058A (en) * | 2013-10-12 | 2015-04-29 | 中国科学院长春应用化学研究所 | Metallocene complex, preparation method thereof and catalyst composition |
| CN104558058B (en) * | 2013-10-12 | 2017-08-08 | 中国科学院长春应用化学研究所 | Metallocene complex and preparation method thereof, carbon monoxide-olefin polymeric |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20010021604A (en) | 2001-03-15 |
| WO1999058539A1 (en) | 1999-11-18 |
| JP2002513428A (en) | 2002-05-08 |
| CA2294608A1 (en) | 1999-11-18 |
| AU4141999A (en) | 1999-11-29 |
| EP0994886A1 (en) | 2000-04-26 |
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