CN1151993A - Novel metallocene catalyst for ethylene polymerization and polymerization method - Google Patents
Novel metallocene catalyst for ethylene polymerization and polymerization method Download PDFInfo
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- CN1151993A CN1151993A CN 95117839 CN95117839A CN1151993A CN 1151993 A CN1151993 A CN 1151993A CN 95117839 CN95117839 CN 95117839 CN 95117839 A CN95117839 A CN 95117839A CN 1151993 A CN1151993 A CN 1151993A
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Abstract
The invention provides a novel metallocene catalyst for ethylene polymerization and a polymerization method, and simultaneously relates to a preparation method of the catalyst, belonging to the field of olefin polymerization. The present invention changes the ligand of metallocene atom and reduces the dependence of metallocene atom on cocatalyst aluminoxane to reduce the dosage of aluminoxane and even replace aluminoxane with other general alkylaluminums. The catalyst is expressed by (formula I), (formula II) is pyrrole ring, R is aliphatic alkyl or aryl of 1-10 carbon atoms, M is metal of IVB group of periodic table, X is alkyl or halogen of 1-10 carbon atoms, L is more than or equal to 1 and less than or equal to 4.
Description
The present invention relates to be used for the novel metallocene catalyst of vinyl polymerization and by the formed polymerization system of this catalyzer. the present invention further comprises by the poly method of above-mentioned Preparation of Catalyst.Comprise method for preparing catalyst simultaneously.
The new LDPE (film grade) of producing with high-pressure process and think early that with the method for the low-pressure high-density polyethylene of ziegler produced common people are known.
In recent years, Kaminsky metallocene/methylaluminoxane catalyst system has been opened up frontier to olefinic polymerization, and it has unique advantage.Reach 107-108 gram polymkeric substance/mole metallocene as super-active.Normal atmosphere. the time. narrow molecular weight distribution Mw/Mn is 2-3, has unique three-dimensional arrangement chiral catalyst and can also obtain the high polymkeric substance of legislate, and can obtain with unavailable syndiotactic polymer of other catalyst system such as syndiotactic polypropylene, syndiotactic polystyrene etc.
The big shortcoming of another of this catalyst system is that promotor methylaluminoxane consumption is big, and the mol ratio of aluminium/metallocene is up to 10
3About.And methylaluminoxane is to be obtained by the quite high aluminium trimethide of price, and transformation efficiency is only about 30%, and this shortcoming has restricted the speed of its industrialization development.
In order to overcome the big weakness of methylaluminoxane consumption, people attempt with other compound substituent methyl aikyiaiurnirsoxan beta as promotor, perhaps use methylaluminoxane less, as using boron compound substituent methyl aikyiaiurnirsoxan beta (Am.Chem.Soc., 1989,111,2728),, in EP0422703, narrate with tin compound substituent methyl aikyiaiurnirsoxan beta, along with being substituted of aikyiaiurnirsoxan beta, metallocene polymerization activity all certain degree ground reduces.
The present invention sets about from the metallocene molecular structure, change the part of metallocene atom, reduce the dependency of metallocene atom pairs promotor aikyiaiurnirsoxan beta, thereby reduce the consumption of aikyiaiurnirsoxan beta even replace aikyiaiurnirsoxan beta and reach the purpose of improving the Kaminsky metallocene catalysis system with other general aluminum alkyls. be noted that this catalyzer is used for vinyl polymerization for using first.
The present invention is a kind of metallocene catalyst that is used for vinyl polymerization, and described catalyzer is explained by following formula:
In the above-mentioned catalyzer
Be preferably
Or
M is preferably titanium in the above-mentioned catalyzer, zirconium or hafnium.
X is preferably the chlorine atom in the above-mentioned catalyzer.
The used promotor of above-mentioned catalyzer comprises and is selected from aikyiaiurnirsoxan beta, aluminum alkyls, and composition thereof aluminum compound, preferably use sesquialter aluminium triethyl Al
2(C
2H
5)
3Cl
3
The present invention comprises that also the catalyst system of forming with above-mentioned catalyzer and aluminum compound is used for the method for vinyl polymerization.
Described method comprises that (a) selects the metalloscene catalyst that is expressed from the next
Wherein
Be pyrrole ring, R is the aliphatic alkyl or the aryl of 1-10 carbon atom, and M is the metal in the IVB family in the periodictable, and X is the alkyl or the halogen of 1-10 carbon atom, 1≤L≤4.
In the above-mentioned catalyzer
Be preferably
With
M is preferably titanium in the above-mentioned catalyzer, zirconium, hafnium.
X is preferably the chlorine atom in the above-mentioned catalyzer.
Above-mentioned Preparation of catalysts method is: in reactor, add MCl
4The toluene solution of (wherein M is a titanium, zirconium, hafnium) at＜0 ℃, under the stirring state, drips the compound (MCl that contains pyrrole ring
4With pyrroles's mol ratio be 0.3～2), after reaction finishes, filter, washing, drying obtains catalyzer.
The all promotors of above-mentioned catalyzer comprise and are selected from aikyiaiurnirsoxan beta that the aluminum compound of aluminum alkyls and composition thereof preferably uses the sesquialter aluminium triethyl.
Import this catalyst body and be tied in the polyreaction zone of containing vinyl monomer, and keep this conversion zone under polymeric reaction condition.
Polymerization process can adopt solution polymerization or vapour phase polymerization.
Solvent for use is a toluene in the solution polymerization, hexane, cyclohexane etc.
Polymerization temperature is 0～80 ℃, is preferably 30～60 ℃.
Polymerization time is 1～10 hour.
System of the present invention obtains the molecular weight ethylene polymer narrowly distributing, Mw/Mn＜1.8, the outstanding suitable low molecular polyethylene of doing.
System of the present invention compared with prior art has following advantage:
1. above-mentioned catalyzer can not use aikyiaiurnirsoxan beta to make promotor as a kind of novel metallocene catalyst.
2. above-mentioned catalyzer is not using aikyiaiurnirsoxan beta to do under the situation of promotor, and the polyethylene of acquisition has narrow molecular weight distribution.
3. above-mentioned catalyzer is not using aikyiaiurnirsoxan beta to do to have quite high polymerization activity under the situation of promotor.
4. above-mentioned catalyzer has the long polymerization activity life-span.
5. above-mentioned method for preparing catalyst is simple, and catalyst compound is stable, and cost is low.
Embodiment 1 catalyzer is synthetic
In three mouthfuls of vials of 500 milliliters, add 5 milliliters of TiCl
4And an amount of toluene, slow Dropwise 5 milliliter pyrroles (being diluted in an amount of toluene) is down stirred in the frozen water cooling, and unreacted TiCl is removed in the heating down of stirring reaction final vacuum half an hour
4And the pyrroles, obtain black solid, use toluene wash, promptly get catalyzer.
Polymerization
1000 milliliters of three mouthfuls of glass reaction bottles of nitrogen replacement, add 400 milliliters of toluene and the above-mentioned catalyzer of 0.0300 gram, warming-in-water to 50 ℃, logical people's ethene 0.04MPa, stir 19 milliliters of (2.52M) sesquialter aluminium triethyl of adding down, keep this temperature and pressure reaction 7 hours.The ethanol termination reaction gets 30.5 gram polyethylene.Polymerization activity 3.4*10
5G/molTi, Mw/Mn1.47.
Embodiment 2～3 sees Table 1 with embodiment 1.The acetonideexample Primary Catalysts promotor polymerization temperature polymerization time polymer active of table 1. embodiment 2-3
Sesquialter/ml ℃ hour gram of gram MAO/ml gPE/molTi2 0.0307-20 60 7 41.2 4.5*10
53 0.0201 15-15 2 0.4 6.7*10
3Embodiment 4
In 5 liters autoclave, add 1.8 liters of toluene, be warming up to 79 ℃, add pyrroles's titanium 0.0415 gram, 0.09 mole of sesquialter aluminium triethyl feeds ethene 1MPa, and polyreaction is 5 hours under stirring.Getting 275 gram polyethylene. catalyst activity is 2.2*10
6GPE/molTi, recording molecular weight is Mw=1881, molecular weight distribution is Mw/Mn=1.4.Embodiment 5 catalyzer are synthetic
Restrain ZrCl with 4.76 under the nitrogen protection
4Be suspended in 120 milliliters of toluene, add 2.8 milliliters of pyrroles, warming-in-water to 70 ℃, induction stirring 6 hours, heating under vacuum is removed toluene and unreacted pyrroles, obtains the yellow pyrroles's Zr catalyst of 6.1 grams.
Polymerization
The nitrogen replacement reaction flask adds above-mentioned catalyzer 0.0324 gram, 150 milliliters of toluene, feed ethene 0.04MPa, 50 ℃ of bath temperatures stir adding 8 milliliters of triethyl aluminum toluene solutions (0.00187mol/ml) down, polymerization 4 hours, ethanol stops. get 1.26 gram polyethylene.Polymerization activity is 1.69*10
4GPE/molZr.
Claims (16)
1. a metalloscene catalyst that is used for vinyl polymerization is characterized in that, described catalyzer is expressed from the next:
The promotor that uses jointly with above-mentioned catalyzer is aikyiaiurnirsoxan beta, aluminum alkyls, or its mixture.
2. catalyzer as claimed in claim 1 is characterized in that in the formula
For
Or
3. catalyzer as claimed in claim 1 is characterized in that M is titanium, zirconium or hafnium in the formula.
4. catalyzer as claimed in claim 1 is characterized in that the X in the formula is the Cl atom.
5. catalyzer as claimed in claim 1 is characterized in that further comprising being selected from aikyiaiurnirsoxan beta, the aluminum compound of aluminum alkyls and composition thereof.
6. a polymerizing ethylene monomer forms the method for polymkeric substance, and described method feature comprises a, select the metalloscene catalyst that is expressed from the next
Wherein
Be pyrrole ring, R is the aliphatic alkyl or the aryl of 1-10 carbon atom, and M is the metal in the IVB family in the periodictable, and X is the alkyl halide of 1-10 carbon atom, 1≤L≤4; B, import this catalyzer in the polyreaction zone of containing olefinic monomer and keep this conversion zone under polymeric reaction condition.
7. polymerization process as claimed in claim 6 is characterized in that
For
8. polymerization process as claimed in claim 6 is characterized in that the M in the formula is titanium, zirconium or hafnium.
9. polymerization process as claimed in claim 6 is characterized in that the X in the formula is the chlorine atom.
10. the polymerization process described in claim 6 is characterized in that promotor adopts aikyiaiurnirsoxan beta, the aluminum compound of aluminum alkyls and composition thereof.
11. the polymerization process described in claim 6 is characterized in that promotor adopts the sesquialter aluminium triethyl.
12. the polymerization process described in claim 6 is characterized in that adopting solvent polymeric and vapour phase polymerization.
13. the polymerization process described in claim 12, the polymer solvent of solvent polymeric are toluene, hexane, cyclohexane.
14. the polymerization process described in claim 6, polymerization temperature are 0-80 ℃.
15. the polymerization process described in claim 6, polymerization temperature are 30-60 ℃.
16. the polymerization process described in claim 6, polymerization time are 1-10 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95117839A CN1062275C (en) | 1995-12-15 | 1995-12-15 | Metallocene catalyst system for ethylene polymerization and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95117839A CN1062275C (en) | 1995-12-15 | 1995-12-15 | Metallocene catalyst system for ethylene polymerization and application thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1151993A true CN1151993A (en) | 1997-06-18 |
| CN1062275C CN1062275C (en) | 2001-02-21 |
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ID=5081386
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95117839A Expired - Fee Related CN1062275C (en) | 1995-12-15 | 1995-12-15 | Metallocene catalyst system for ethylene polymerization and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1958969A1 (en) | 2007-02-14 | 2008-08-20 | Petrochina Company Limited | A phosphine-substituted vinyl containing metallocene catalyst, preparation process and the application of the same |
| CN100460422C (en) * | 1997-07-09 | 2009-02-11 | 丸善石油化学株式会社 | Catalyst component for olefin polymerization, polymerization catalyst and method for polymerizing olefins using same |
| CN107709383A (en) * | 2015-05-29 | 2018-02-16 | 陶氏环球技术有限责任公司 | A kind of method for manufacturing polyolefin |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5068371A (en) * | 1989-06-01 | 1991-11-26 | Ciba-Geigy Corporation | Novel nitrogen-containing titanocenes, and the use thereof |
| US5739225A (en) * | 1993-12-28 | 1998-04-14 | Idemitsu Kosan Co., Ltd. | Process for preparing olefin polymer, and ethylenic polymer |
-
1995
- 1995-12-15 CN CN95117839A patent/CN1062275C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460422C (en) * | 1997-07-09 | 2009-02-11 | 丸善石油化学株式会社 | Catalyst component for olefin polymerization, polymerization catalyst and method for polymerizing olefins using same |
| EP1958969A1 (en) | 2007-02-14 | 2008-08-20 | Petrochina Company Limited | A phosphine-substituted vinyl containing metallocene catalyst, preparation process and the application of the same |
| CN107709383A (en) * | 2015-05-29 | 2018-02-16 | 陶氏环球技术有限责任公司 | A kind of method for manufacturing polyolefin |
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| Publication number | Publication date |
|---|---|
| CN1062275C (en) | 2001-02-21 |
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