CN1062275C - Metallocene catalyst system for ethylene polymerization and application thereof - Google Patents
Metallocene catalyst system for ethylene polymerization and application thereof Download PDFInfo
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- CN1062275C CN1062275C CN95117839A CN95117839A CN1062275C CN 1062275 C CN1062275 C CN 1062275C CN 95117839 A CN95117839 A CN 95117839A CN 95117839 A CN95117839 A CN 95117839A CN 1062275 C CN1062275 C CN 1062275C
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- Prior art keywords
- polymerization
- catalyst system
- catalyst
- metallocene
- pyrrole ring
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 20
- 239000012968 metallocene catalyst Substances 0.000 title claims abstract description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title abstract description 6
- 239000005977 Ethylene Substances 0.000 title abstract 2
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 10
- 125000000168 pyrrolyl group Chemical group 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 32
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000012725 vapour phase polymerization Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 6
- 125000004429 atom Chemical group 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229910052736 halogen Chemical group 0.000 abstract description 2
- 150000002367 halogens Chemical group 0.000 abstract description 2
- 230000000737 periodic effect Effects 0.000 abstract description 2
- 150000001336 alkenes Chemical class 0.000 abstract 1
- 125000005234 alkyl aluminium group Chemical group 0.000 abstract 1
- 239000003446 ligand Substances 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- -1 polypropylene Polymers 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 150000003233 pyrroles Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 5
- 230000037048 polymerization activity Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 102000040350 B family Human genes 0.000 description 1
- 108091072128 B family Proteins 0.000 description 1
- OEOUWMSQXZQDIP-UHFFFAOYSA-N CC[Al](CC)CC.CC1=CC=CC=C1 Chemical compound CC[Al](CC)CC.CC1=CC=CC=C1 OEOUWMSQXZQDIP-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920001576 syndiotactic polymer Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
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 described by the formula
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, comprises 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 10 as super-active
7-10
8During gram polymkeric substance/mole metallocene normal atmosphere, narrow molecular weight distribution Mw/Mn is 2-3, have unique three-dimensional arrangement chiral catalyst 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%, 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, thereby the dependency that reduces metallocene atom pairs promotor aikyiaiurnirsoxan beta reduces the consumption of aikyiaiurnirsoxan beta even replaces the purpose that aikyiaiurnirsoxan beta reaches improvement 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, described catalysis
It is characterized in that
Be pyrrole ring, R is the aliphatic alkyl or the aryl of 1-10 carbon atom, and M is an IV B family metal in the periodic table of elements; X is the alkyl of 1-10 carbon atom or is
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
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, hexanaphthene 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 ℃ feeds 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/Mn 1.47.
Embodiment 2～3 sees Table 1 with embodiment 1.The result of table 1. embodiment 2-3
Embodiment 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.Get 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, and 150 milliliters of toluene feed ethene 0.04MPa, and 50 ℃ of bath temperatures stir adding 8 milliliters of triethyl aluminum toluene solutions (0.00187mol/ml) down, polymerization 4 hours, and ethanol stops.Get 1.26 gram polyethylene.Polymerization activity is 1.69*10
4GPE/molZr.
Claims (4)
1. a metallocene catalyst systems that is used for vinyl polymerization is characterized in that, described catalyst system comprises following component: (A) Primary Catalysts;
Wherein, described Primary Catalysts is prepared by following preparation method: in reactor, add MCl
4Toluene solution, under less than 0 ℃ temperature, agitation and dropping contains the compound of pyrrole ring, wherein MCl
4With the mol ratio of the compound that contains pyrrole ring be 0.3-2, more after filtration, the washing, drying obtains described Primary Catalysts;
Wherein M is a titanium, a kind of in zirconium or the hafnium; (B) promotor;
Described promotor comprises aikyiaiurnirsoxan beta, aluminum alkyls, or its mixture.
2. catalyst system as claimed in claim 1 is characterized in that described promotor adopts the sesquialter aluminium triethyl.
3. catalyst system as claimed in claim 1 is characterized in that the described pyrrole ring that contains
4. the application of the described catalyst system of claim 1 in vinyl polymerization is characterized in that, polymerization methods is solvent polymeric or vapour phase polymerization.
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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1151993A CN1151993A (en) | 1997-06-18 |
| CN1062275C true CN1062275C (en) | 2001-02-21 |
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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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| Country | Link |
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| CN (1) | CN1062275C (en) |
Families Citing this family (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 |
| CN101245084B (en) | 2007-02-14 | 2013-02-20 | 中国石油天然气股份有限公司 | Phosphine-substituted vinyl-containing metallocene catalyst, and preparation method and application thereof |
| KR102577009B1 (en) * | 2015-05-29 | 2023-09-12 | 다우 글로벌 테크놀로지스 엘엘씨 | Method for producing polyolefin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0401166A2 (en) * | 1989-06-01 | 1990-12-05 | Ciba-Geigy Ag | Nitrogen-containing titanocenes and their use |
| WO1995018158A1 (en) * | 1993-12-28 | 1995-07-06 | Idemitsu Kosan Co., Ltd. | Process for producing olefin polymer and ethylene polymer |
-
1995
- 1995-12-15 CN CN95117839A patent/CN1062275C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0401166A2 (en) * | 1989-06-01 | 1990-12-05 | Ciba-Geigy Ag | Nitrogen-containing titanocenes and their use |
| WO1995018158A1 (en) * | 1993-12-28 | 1995-07-06 | Idemitsu Kosan Co., Ltd. | Process for producing olefin polymer and ethylene polymer |
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| Publication number | Publication date |
|---|---|
| CN1151993A (en) | 1997-06-18 |
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Granted publication date: 20010221 Termination date: 20101215 |