CN1306014A - Polynuclear pyridine biimine iron (or cobalt) catalyst for polymerization of olefine - Google Patents

Polynuclear pyridine biimine iron (or cobalt) catalyst for polymerization of olefine Download PDF

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CN1306014A
CN1306014A CN 00136191 CN00136191A CN1306014A CN 1306014 A CN1306014 A CN 1306014A CN 00136191 CN00136191 CN 00136191 CN 00136191 A CN00136191 A CN 00136191A CN 1306014 A CN1306014 A CN 1306014A
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methyl
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pyridine diimine
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李悦生
刘靖宇
戴可
郑毅
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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Abstract

A polynuclear pyridine biimine iron (or cobalt) catalyst for polymerizing olefin is disclosed, which can be used to prepare high-molecular polyethylene by catalytic polymerization of ethylene.

Description

Polynuclear pyridine diimine iron, cobalt olefin polymerization catalysis
The present invention relates to a kind of olefin polymerization catalysis, its preparation method and the application in catalysis in olefine polymerization.
Polyolefine is the important macromolecular material of a class, accounts for 50% of plastics, is widely used in industry, agricultural, national defence, communications and transportation and the daily life.Alkene is under the effect of catalyzer, and polymerization reaction take place generates macromolecular compound, i.e. polyolefine.Catalyzer is the core of polyolefin industry development, is the key of control polyolefin structure and performance.
On the basis of traditional Ziegler-Natta catalyst, it is found that metallocene calalyst for polymerization of olefine with single catalytic active center, this catalyzer has very high catalytic activity, but the polyolefinic narrow molecular weight distribution of gained is unfavorable for processing.Du Pont company in 1998 discloses a class, and (WO98/27124, WO98/30612), BP chemical company disclosed the similar olefin polymerization catalysis of a class formation (WO99/12981) in 1999 with pyridine diimine Fe (II), Co (II) olefin polymerization catalysis.Under the effect of methylaluminoxane (MAO) or modified methylaluminoxane neutral Lewis acid such as (MMAO), this class catalyst vinyl polymerization secures satisfactory grades, and son is measured, the polyethylene of wide molecular weight distribution.
The purpose of this invention is to provide a kind of polynuclear pyridine diimine Fe (II), Co (II) olefin polymerization catalysis, the precursor of this catalyzer is polynuclear pyridine diimine Fe (II), Co (II) title complex, under the activation of neutral Lewis acid such as MAO, MMAO, this class polynuclear coordination compound can obtain high molecular polyolefine by catalyzed ethylene polymerization.
Polynuclear pyridine diimine Fe disclosed by the invention (II), Co (II) olefin polymerization catalysis precursor have following structure:
Figure A0013619100051
Wherein M represents Fe or Co, preferred Fe; X is Cl or Br, preferred Cl; M and n are respectively the integer of 0-20 and 1-20, and preferred m is the integer of 0-10, and n is the integer of 1-10, and more preferably m is the integer of 0-5, and n is the integer of 1-5; R is H or methyl, preferable methyl; R 1, R 2, R 3With R 4Can be identical or different, be respectively H, Cl, methyl, ethyl, sec.-propyl or the tertiary butyl; R 5, R 6And R 7Can be identical or different, be respectively H, Cl, methyl, ethyl, sec.-propyl or the tertiary butyl; Y 1Be CR 8R 9, R wherein 8With R 9Can be identical or different, be respectively H, methyl, ethyl, propyl group, butyl or phenyl, preferred H or methyl, perhaps R 8And R 9Form a cycloalkyl, preferred cyclohexyl; Y 2Be CR 10R 11, R wherein 10With R 11Can be identical or different, be respectively H, methyl, ethyl, propyl group, butyl or phenyl, preferred H or methyl, perhaps R 10And R 11Form a cycloalkyl respectively, preferred cyclohexyl.
Polynuclear pyridine diimine Fe disclosed by the invention (II), Co (II) olefin polymerization catalysis precursor prepare according to the following procedure:
HCOOH, CF 3Under the catalysis such as COOH or HCl, in alcohol, aromatic hydrocarbons, alcohol-ether mixture or alcohol-Halocarbon blends, carry out 2,6-acyl pyridine and the condensation reaction that replaces aryl diamine, substituted aromatic amines, the pyridine diimine oligopolymer that obtains replacing.Under the condition of anhydrous and oxygen-free, carry out pyridine diimine oligopolymer and MX 2Coordination reaction, obtain polynuclear pyridine diimine Fe (II), Co (II) title complex, its chemical equation is as follows: Wherein M represents Fe or Co; X is Cl or Br; M and n are respectively the integer of 0-20 and 1-20; R is H or methyl; R 1, R 2, R 3With R 4Can be identical or different, be respectively H, Cl, methyl, ethyl, sec.-propyl or the tertiary butyl; R 5, R 6And R 7Can be identical or different, be respectively H, Cl, methyl, ethyl, sec.-propyl or the tertiary butyl; Y 1Be CR 8R 9, R wherein 8With R 9Can be identical or different with, be respectively H, methyl, ethyl, propyl group, butyl or phenyl, perhaps R 8And R 9Form a cycloalkyl; Y 2Be CR 10R 11, R wherein 10With R 11Can be identical or different, be respectively H, methyl, ethyl, propyl group, butyl or phenyl, perhaps R 10And R 11Form a cycloalkyl respectively.
Polynuclear pyridine diimine Fe disclosed by the invention (II), Co (II) title complex are under neutral Lewis acid such as MAO or MMAO effect, and catalyzed ethylene polymerization obtains ultra high molecular weight polyethylene.
Embodiment provided by the invention is as follows:
Embodiment 1
In the 150ml reaction flask, add 2,3 of 6-diacetyl pyridine 0.816g (5.0mmol), two (4-amino-3-tert.-butylbenzene) methane 0.776g (2.5mmol), methyl alcohol 50ml, hydrochloric acid, heating reflux reaction 3 days.Cooling adds 2,4-two chloro-6-tertiary butyl aniline 1.635g (7.5mmol), and heating reflux reaction 7 days, steaming desolventizes.Column chromatography gets pyridine diimine dipolymer 1.59g, yield 63%.
Embodiment 2
In the 150ml reaction flask, add 2,6-diacetyl pyridine 0.816g (5.0mmol), 2,3 of 2-two (4-amino-3-chloro-5-isopropyl benzene) propane 0.948g (2.5mmol), toluene 50ml, formic acid acid, heating reflux reaction 5 days.Cooling adds 2,6-diisopropyl aniline 0.975g (5.5mmol), and heating reflux reaction 7 days, cooling is filtered, filter cake cold methanol washed twice, 60 ℃ of vacuum-drying 48h get pyridine diimine dipolymer 1.98g, yield 80%.
Embodiment 3
In the 150ml reaction flask, add 2,3 of 6-diacetyl pyridine 0.734g (4.5mmol), two (4-amino-3-methyl-5-isopropyl benzene) methane 0.931g (3.0mmol), 30ml ethanol, formic acid, heating reflux reaction 3 days.Cooling adds 2-methyl-6-isopropyl aniline 0.492g (3.3mmol), trichloromethane 30ml, heating reflux reaction 7 days.Below operation gets pyridine diimine trimer 1.76g, yield 92% with embodiment 2.
Embodiment 4
Use 2 respectively, 2-two (4-amino-3,5-di-isopropyl hexichol) propane 1.184g (3.0mmol), 2,4, in 6-triisopropyl aniline 0.724g (3.3mmol) alternate embodiment 3 two (4-amino-3-methyl-5-isopropyl benzene) methane, 2-methyl-6-isopropyl aniline, operating process gets pyridine diimine trimer 1.91g, yield 79% with embodiment 3.
Embodiment 5
In the 150ml reaction flask, add 2,6-pyridine dicarbaldehyde 0.540g (4.0mmol), 1,3 of 1-two (4-amino-3,5-diisopropyl benzene) phenylethane 1.370g (3.0mmol), 30ml methyl alcohol, formic acid, heating reflux reaction 3 days.Cooling adds 2 0.298g (2.2mmol), tetrahydrofuran (THF) 30ml, heating reflux reaction 5 days.Below operation gets pyridine diimine oligopolymer 1.79g, yield 81% with embodiment 2.
Embodiment 6
In the 150ml flask, add 2,6-diacetyl pyridine 0.734g (4.5mmol), 1,3 of 1-two (4-amino-3,5-diisopropyl benzene) hexanaphthene 1.565g (3.6mmol), ethanol 30ml, trifluoroacetic acids, heating reflux reaction 3 days.Cooling adds 2,6-Diethyl Aniline 0.328g (2.2mmol), tetrahydrofuran (THF) 20ml, heating reflux reaction 7 days.Following process gets pyridine diimine oligopolymer 1.88g, yield 78% with embodiment 2.
Embodiment 7
In the 150ml flask, add 2; 6-diacetyl pyridine 0.685g (4.2mmol), 2; 2-two (4-amino-3; the 5-diethylbenzene) propane 0.203g (0.6mmol), 1; 1-two (4-amino-3; the 5-diisopropyl benzene) cyclohexane 1.304g (3.0mmol), ethanol 50ml, formic acid are 3, heating reflux reaction 3 days.Cooling adds 2,6-diisopropyl aniline 0.249g (1.4mmol), tetrahydrofuran (THF) 20ml, and following process is with embodiment 2.Get pyridine diimine oligopolymer 1.83g, yield 82%.Embodiment 8
With 2 in two (4-amino-3,5-dimethyl benzene) methane 0.153g (0.6mmol) alternate embodiment 7,2-two (4-amino-3,5-diethylbenzene) propane, other is with embodiment 7.Get pyridine diimine oligopolymer 1.83g, yield 83%.
Embodiment 9
In the 150ml flask, add 2; 6-diacetyl pyridine 0.685g (4.2mmol), 2; 2-two (4-amino-3; the 5-diisopropyl benzene) propane 0.710g (1.8mmol), 1; 1-two (4-amino-3; the 5-diisopropyl benzene) phenylethane 0.797g (1.8mmol), methyl alcohol 50ml, formic acid are 3, heating reflux reaction 3 days.Cooling adds 2,6-diisopropyl aniline 0.249g (1.4mmol), tetrahydrofuran (THF) 20ml, heating reflux reaction 7 days.Below operation gets pyridine diimine oligopolymer 1.87g, yield 82% with embodiment 2.
Embodiment 10
Under the argon atmospher, in exsiccant 100ml Schlenk bottle, add FeCl 20.254g (2.0mmol) with anhydrous tetrahydro furan 10ml, stir into mashed prod, add the pyridine diimine dipolymer 1.010g that embodiment 1 obtains, stirring at room reaction 12h, back flow reaction 2 days, cooling, filter, filter cake cold methanol washed twice, 60 ℃ of vacuum-drying 48h get mazarine double-core pyridine diimine Fe (II) title complex 1.04g, yield 82%.
Embodiment 11
The pyridine diimine dipolymer that the pyridine diimine dipolymer 0.990g that obtains with embodiment 2 replaces embodiment 1 to obtain, operation is with embodiment 10.Get mazarine double-core pyridine diimine Fe (II) title complex 1.01g, yield 81%.
Embodiment 12
The pyridine diimine dipolymer that the pyridine diimine trimer 0.870g that obtains with embodiment 3 replaces embodiment 1 to obtain, operation is with embodiment 10.Get mazarine three polypyridine diimine Fe (II) muriate 0.899g, yield 80%.
Embodiment 13
The pyridine diimine dipolymer that the pyridine diimine trimer 1.027g that obtains with embodiment 4 replaces embodiment 1 to obtain, operation is with embodiment 10.Get mazarine three polypyridine diimine Fe (II) muriate 1.046g, yield 80%.
Embodiment 14
Under the argon atmospher, in exsiccant 100ml Schlenk bottle, add CoCl 20.260g (2.00mmol), embodiment 4 the pyridine diimine trimer 1.007g, the butanols 30ml that obtain, stir down heat temperature raising to 80 ℃, reaction 15min is chilled to room temperature.Below operation gets mazarine three polypyridine diimine Co (II) muriate 1.012g, yield 80% with embodiment 10.
Embodiment 15
Under the argon atmospher, in exsiccant 100ml Schlenk bottle, add FeBr 20.431g (2.00mmol), add the pyridine diimine oligopolymer 1.054g that embodiment 5 obtains, butanols 30ml stirs down heat temperature raising to 80 ℃, and reaction 15min is chilled to room temperature.Below operation gets mazarine oligomerisation pyridine diimine Fe (II) bromide 1.18g, yield 81% with embodiment 10.
Embodiment 16
The pyridine diimine dipolymer that the pyridine diimine oligopolymer 1.108g that obtains with embodiment 6 replaces embodiment 1 to prepare, operation gets mazarine oligomerisation pyridine diimine Fe (II) muriate 1.09g, yield 80% with embodiment 10.
Embodiment 17
The pyridine diimine dipolymer that the pyridine diimine oligopolymer 1.073g that obtains with embodiment 7 replaces embodiment 1 to prepare, operation gets mazarine oligomerisation pyridine diimine Fe (II) muriate 0.976g, yield 79% with embodiment 10.
Embodiment 18
The pyridine diimine oligopolymer that the pyridine diimine oligopolymer 1.049g that obtains with embodiment 8 replaces embodiment 1 to obtain, operation get mazarine oligomerisation pyridine diimine Fe (II) muriate 0.990g, yield 81% with embodiment 10.
Embodiment 19
The pyridine diimine oligopolymer that the pyridine diimine oligopolymer 1.085g that obtains with embodiment 9 replaces embodiment 1 to obtain, operation get mazarine oligomerisation pyridine diimine Fe (II) muriate 0.87g, yield 80% with embodiment 10.
Embodiment 20
Under the ethene atmosphere, in exsiccant 250ml polymerization, add double-core pyridine diimine Fe (II) title complex 1.6mg (2.5 μ mol Fe), the dry toluene 50ml of embodiment 10 preparations, stirring and dissolving, the MAO3ml of adding 1M, 25 ℃ of polymerization under atmospheric pressure 30min.Reaction solution is poured in the ethanol solution hydrochloride of 200ml1%, filtration, washing with alcohol three times, 80 ℃ of vacuum-dryings get polymkeric substance 3.76g, catalytic efficiency 3.0 * 10 6G PE/mol Feh.
Embodiment 21
Double-core pyridine diimine Fe (II) title complex that double-core pyridine diimine Fe (II) the title complex 1.6mg (2.5 μ mol Fe) for preparing with embodiment 11 replaces embodiment 10 to prepare, operation is with embodiment 20.Get polymkeric substance 4.56g, catalytic efficiency 3.65 * 10 6G PE/mol Feh.
Embodiment 22
Examine double-core pyridine diimine Fe (II) title complex that pyridine diimine Fe (II) title complex 1.3mg (2.3 μ molFe) replace embodiment 10 preparations with three of embodiment 12 preparations, operation is with embodiment 20.Get polymkeric substance 2.64g, catalytic efficiency 2.30 * 10 6G PE/mol Feh.
Embodiment 23
Double-core pyridine diimine Fe (II) title complex that three nuclear pyridine diimine Fe (II) the title complex 1.4mg (2.2 μ molFe) that obtain with embodiment 13 replace embodiment 10 to prepare, operation is with embodiment 20.Get polymkeric substance 4.27g, catalytic efficiency 2.89 * 10 6G PE/mol Feh.
Embodiment 24
Double-core pyridine diimine Fe (II) title complex that three nuclear pyridine diimine Co (II) the title complex 1.6mg (2.5 μ molFe) that obtain with embodiment 14 replace embodiment 10 to prepare, operation is with embodiment 20.Get polymkeric substance 0.86g, catalytic efficiency 6.88 * 10 5G PE/mol Feh.
Embodiment 25
Double-core pyridine diimine Fe (II) title complex that polynuclear pyridine diimine Fe (II) the title complex 1.5mg (2.0 μ molFe) for preparing with embodiment 15 replaces embodiment 10 to prepare, operation is with embodiment 20.Get polymkeric substance 1.08g, catalytic efficiency 1.08 * 10 6G PE/mol Feh.
Embodiment 26
Double-core pyridine diimine Fe (II) title complex that polynuclear pyridine diimine Fe (II) the title complex 1.7mg (2.5 μ molFe) for preparing with embodiment 16 replaces embodiment 10 to prepare, operation is with embodiment 20.Get polymkeric substance 2.96g, catalytic efficiency 2.37 * 10 6G PE/mol Feh.
Embodiment 27
Double-core pyridine diimine Fe (II) title complex that polynuclear pyridine diimine Fe (II) the title complex 2.0mg (3.0 μ molFe) for preparing with embodiment 17 replaces embodiment 10 to prepare, operation is with embodiment 20.Get polymkeric substance 4.38g, catalytic efficiency 2.92 * 10 6G PE/mol Feh.
Embodiment 28
Polynuclear pyridine diimine Fe (II) with embodiment 18 preparations cooperates 1.5mg (2.3 μ mol Fe) to replace double-core pyridine diimine Fe (II) title complex of embodiment 10 preparations, and operation is with embodiment 20.Get polymkeric substance 2.98g, catalytic efficiency 2.59 * 10 6G PE/mol Feh.
Embodiment 29
Polynuclear pyridine diimine Fe (II) with embodiment 19 preparations cooperates 1.33mg (2.0 μ mol Fe) to replace double-core pyridine diimine Fe (II) title complex of embodiment 10 preparations, and operation is with embodiment 20.Get polymkeric substance 3.03g, catalytic efficiency 3.03 * 10 6G PE/mol Feh.
Embodiment 30
Under the ethene atmosphere, in 1 liter of polymeric kettle of exsiccant, add embodiment 13 preparation polynuclear pyridine diimine Fe (II) and cooperate 8mg (12.5 μ mol Fe), dry toluene 500ml, stirring and dissolving, the MAO 30ml that adds 1M, polyreaction 1h under 25 ℃ and 1.0MP, the ethanol termination polyreaction with 1%.Filtration, washing with alcohol three times, 60 vacuum-dryings get polymkeric substance 274g, catalytic efficiency 2.19 * 10 7G PE/mol Feh.

Claims (9)

1. a polynuclear pyridine diimine Fe (II), Co (II) olefin polymerization catalysis precursor, it has following structure:
Figure A0013619100021
Wherein M represents Fe or Co; X is Cl or Br; M and n are respectively the integer of 0-20 and 1-20; R is H or methyl; R 1, R 2, R 3With R 4Can be identical or different, be respectively H, Cl, methyl, ethyl, sec.-propyl or the tertiary butyl; R 5, R 6And R 7Can be identical or different, be respectively H, Cl, methyl, ethyl, sec.-propyl or the tertiary butyl; Y 1Be CR 8R 9, R wherein 8With R 9Can be identical or different, be respectively H, methyl, ethyl, propyl group, butyl or phenyl, perhaps R 8And R 9Form a cycloalkyl; Y 2Be CR 10R 11, R wherein 10With R 11Can be identical or different, be respectively H, methyl, ethyl, propyl group, butyl or phenyl, perhaps R 10And R 11Form a cycloalkyl respectively.
2. according to the described polynuclear pyridine diimine of claim 1 Fe (II), Co (II) olefin polymerization catalysis precursor, wherein M is Fe; X is Cl; M is the integer of 0-10, and n is the integer of 1-10; R is a methyl; R 1, R 2, R 3With R 4Can be identical or different, be respectively H, Cl, methyl, ethyl, sec.-propyl or the tertiary butyl; R 5, R 6And R 7Can be identical or different, be respectively H, Cl, methyl or sec.-propyl; R 8With R 9Be all H or methyl, perhaps R 8And R 9Form a cyclohexyl; R 10With R 11Be all H or methyl, perhaps R 10And R 11Form a cyclohexyl.
3. according to the described polynuclear pyridine diimine of claim 1 Fe (II), Co (II) olefin polymerization catalysis precursor, wherein M is Fe; X is Cl; M is the integer of 0-5, and n is the integer of 1-5; R is a methyl; R 1, R 2, R 3With R 4Can be identical or different, be respectively H, Cl, methyl, ethyl, sec.-propyl or the tertiary butyl; R 5, R 6And R 7Can be identical or different, be respectively H, Cl, methyl or sec.-propyl; R 8With R 9Be all H or methyl, perhaps R 8And R 9Form a cyclohexyl; R 10With R 11Be all H or methyl, perhaps R 10And R 11Form a cyclohexyl.
4. according to the described polynuclear pyridine diimine of claim 1 Fe (II), Co (II) olefin polymerization catalysis precursor, wherein M is Fe; X is Cl; M is the integer of 0-5, and n is the integer of 1-5; R is a methyl; R 1, R 2, R 3With R 4Can be identical or different, be respectively H, Cl, methyl, sec.-propyl or the tertiary butyl; R 5, R 6And R 7Can be identical or different, be respectively methyl or sec.-propyl; R 8With R 9Be all H; R 10And R 11Form a cyclohexyl.
5. according to the described polynuclear pyridine diimine of claim 1 Fe (II), Co (II) olefin polymerization catalysis precursor, wherein M is Fe; X is Cl; M is the integer of 0-5, and n is the integer of 1-5; R is a methyl; R 1, R 2, R 3With R 4Can be identical or different, be respectively H, Cl, methyl, sec.-propyl or the tertiary butyl; R 5, R 6And R 7Can be identical or different, be respectively methyl or sec.-propyl; R 8With R 9Be all methyl; R 10And R 11Form a cyclohexyl.
6. according to the described polynuclear pyridine diimine of claim 1 Fe (II), Co (II) olefin polymerization catalysis precursor, wherein M is Fe; X is Cl; M is the integer of 0-5, and n is the integer of 1-5; R is a methyl; R 1, R 2, R 3With R 4Can be identical or different, be respectively H, Cl, methyl, sec.-propyl or the tertiary butyl; R 5, R 6And R 7Can be identical or different, be respectively methyl or sec.-propyl; R 8With R 9Be all H; R 10And R 11Be all methyl.
7. one kind prepares the described polynuclear pyridine diimine of claim 1 Fe (II), Co (II) olefin polymerization catalysis precursor, comprising:
At HCOOH, CF 3Under the catalysis of COOH or HCl, in alcohol, aromatic hydrocarbons, alcohol-ether mixture or alcohol-Halocarbon blends, carry out 2 shown in the following formula, the 6-diacylpyridines With the substituted aroma diamine mixture shown in the following formula
Figure A0013619100032
With the condensation reaction of the substituted aromatic amines shown in the following formula, Obtain the pyridine diimine oligopolymer of the replacement shown in the following formula
Figure A0013619100041
Under the condition of anhydrous and oxygen-free, carry out above-mentioned pyridine diimine oligopolymer MX 2Coordination reaction, wherein M is Fe or Co, X is Cl or Br, obtains polynuclear pyridine diimine Fe (II), Co (II) title complex of following formula,
Figure A0013619100042
Wherein M represents Fe or Co; X is Cl or Br; M and n are respectively the integer of 0-20 and 1-20; R is H or methyl; R 1, R 2, R 3With R 4Can be identical or different, be respectively H, Cl, methyl, ethyl, sec.-propyl or the tertiary butyl; R 5, R 6And R 7Can be identical or different, be respectively H, Cl, methyl, ethyl, sec.-propyl or the tertiary butyl; Y 1Be CR 8R 9, R wherein 8With R 9Can be identical or different, be respectively H, methyl, ethyl, propyl group, butyl or phenyl, perhaps R 8And R 9Form a cycloalkyl; Y 2Be CR 10R 11, R wherein 10With R 11Can be identical or different, be respectively H, methyl, ethyl, propyl group, butyl or phenyl, perhaps R 10And R 11Form a cycloalkyl respectively.
8. press the described method of claim 7, wherein, 2, the condensation reaction solvent for use of 6-diacylpyridines and substituted aromatic amines, replacement aryl diamine mixture is methyl alcohol-tetrahydrofuran compound, ethanol-tetrahydrofuran compound.
9. produce poly method for one kind, comprising the step of using claim 1 described polynuclear pyridine diimine Fe (II), Co (II) olefin polymerization catalysis precursor.
CN 00136191 2000-12-27 2000-12-27 Polynuclear pyridine biimine iron (or cobalt) catalyst for polymerization of olefine Pending CN1306014A (en)

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US7728160B2 (en) 2005-07-21 2010-06-01 Chevron Phillips Chemical Company Lp Diimine metal complexes, methods of synthesis, and methods of using in oligomerization and polymerization
US7129304B1 (en) 2005-07-21 2006-10-31 Chevron Phillips Chemical Company Lp Dimine metal complexes, methods of synthesis, and methods of using in oligomerization and polymerization
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