CN1300786A - Metallocene catalyst for polymerizing olefine - Google Patents
Metallocene catalyst for polymerizing olefine Download PDFInfo
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- CN1300786A CN1300786A CN 00132847 CN00132847A CN1300786A CN 1300786 A CN1300786 A CN 1300786A CN 00132847 CN00132847 CN 00132847 CN 00132847 A CN00132847 A CN 00132847A CN 1300786 A CN1300786 A CN 1300786A
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- metallocene
- tetrahydrofuran
- toluene
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Abstract
A metallocene catalyst for polymerizing olefine features that the reaction resultants of the indene, fluorene or its substituted derivative, cyclopentadiene or substituted cyclopentadiene with zironium, titanium, or hafnium tertra-chloride are used as its active components to catalyze ethylene or copolymerize ethlene with alpha-olefine. The obtained resin has wide distribution peak of molecular weights (0.3-300 for Mw/Mn) and better processing performance.
Description
The present invention relates to a kind of metallocene catalyst.Be specifically related to a kind of metallocene catalyst for olefine polymerization.
The metallocene compound kind that is used for olefinic polymerization is a lot, can be summarized as three kinds of metallocene compound, the monocyclopentadienyl metallocene compounds of non-bridged combined metal compound, bridge crosslinking structure substantially.In the above-mentioned all kinds of metallocene compound, most complex structures, synthesis flow is long, and the target product synthesis yield is low, causes the cost height of the finished product; Only have a few simple in structure, synthetic route is short, and product cost is lower, and as described in WO9634895, EP692499, WO9515216, CN1051363A, when they were used for olefinic polymerization, gained molecular resin amount distributed narrow, the poor processability of resin own.US5539076, US5529965, US6001766 have proposed the technology with traditional Ziegler one Natta catalyst and the composite use acquisition of various metallocene catalyst wide molecular weight distribution resin.CN1032343A discloses a kind of at least two kinds of different chiralitys and the inflexible general formula is R " (C
5(R ')
4)
2MQ
pThe system that forms of metallocene catalyst, in the formula: (C
5(R ')
4) be the cyclopentadiene of cyclopentadiene or replacement, also optional from the indenyl atomic group group that contains indenyl atomic group and hydration; R " be methylene radical; Q is hydrocarbon radical or halogen; 0＜P＜3, this system contains at least a zirconium metallocene catalyst and at least a hafnium metallocene catalyst, is used for the polyolefine of propylene polymerization production wide molecular weight distribution.
The purpose of this invention is to provide a kind of metallocene catalyst for olefine polymerization.
Catalyzer of the present invention is that the reactant by (1) indenes, fluorenes or its substitutive derivative, cyclopentadiene or substituted-cyclopentadienyl and zirconium tetrachloride or titanium, hafnium is the metallocene active ingredient; (2) promotor methylaluminoxane; (3 carriers are formed, and adopt conventional preparation method to obtain.
The selection of carrier can be silica gel, aluminium sesquioxide, magnesium chloride etc.
The raw material of preparation active ingredient can be wherein one or more of various reactants, and preferred feedstock is cyclopentadiene, zirconium tetrachloride and indenes.
Active ingredient can be made by different methods.Because of length is limit, the present invention only lists two kinds of representational preparation methods, but and non exhaustive.
Method one is that (1) adds indenes in the tetrahydrofuran (THF), stirs to add butyl lithium solution simultaneously, and reaction mixture A preserves stand-by; (2) in addition with adding tetrahydrofuran (THF) in the zirconium tetrachloride, make complex compound, add reaction solution A under the room temperature again, stir, get reaction solution B in 45 ℃ of constant temperature; (3) cyclopentadiene is joined in tetrahydrofuran (THF) or the toluene, add butyllithium or sodium sand and stirring again, get reaction liquid C; (4) reaction liquid C is joined among the reaction solution B, stir in 45 ℃ of constant temperature, question response stops, and solvent is removed, and remaining solid carries out recrystallization with toluene, obtains the metallocene active ingredient.
To be (1) join indenes/fluorenes or its substitutive derivative and cyclopentadiene or substituted-cyclopentadienyl in tetrahydrofuran (THF) or the toluene by 0.001 ~ 1000 mol ratio method two, with butyllithium or sodium sand effect, obtains mixed liquor A after the stirring again; (2) zirconium tetrachloride or titanium, hafnium are joined and make complex compound B in the tetrahydrofuran (THF); (3) make solvent with tetrahydrofuran (THF) or toluene, under-20 ~ 100 ℃ of temperature, A mixed with B solution and be stirred to reaction and finish.The reactant crude product is carried out recrystallization, the metallocene active ingredient that promptly gets with the mixed solvent of toluene or toluene and hexane.
This preparation method adopts the disposable multiple metallocene catalysis active ingredient that synthesizes.Shorten the synthetic technical process, simplified postprocessing working procedures.Load metallization processes when also making final formation olefin polymerization catalysis is greatly simplified, and has saved a series of charging process and relevant program and equipment.
Without special instruction, the reagent in all tests of the present invention is commercially available industrial goods.
When catalyzer of the present invention was used for olefinic polymerization, especially when it was used for catalyzed ethylene polymerization or ethene and alpha-olefin copolymer, its catalytic activity can reach 7.4 * 10
6GPE/molM.hr (M is transition metals Ti, zirconium or hafnium).The ratio of adjusting between component is formed and operating procedure, can make the polyolefin resin of gained have the molecular weight distribution (molecular weight distribution mw/mn is between 0.3-300) of broad peak, and good processing properties.
Further strengthen the understanding of the present invention below in conjunction with embodiment.
Embodiment 1
6.6 gram cyclopentadiene and 11.6 gram indenes are added one successively and are equipped with in the there-necked flask of 100ml tetrahydrofuran (THF), and fully stirring mixes it, and Dropwise 5 7.1ml concentration is the butyl lithium solution of 3.5mol/1 while stirring.Dropwise, continue to stir 0.5 hour, reaction mixture is preserved stand-by.
Other gets a there-necked flask, to wherein adding 23.3 gram zirconium tetrachlorides, adds tetrahydrofuran (THF), makes it make complex compound.Under the room temperature, drip homemade reaction mixture in the aforementioned there-necked flask while stirring, dropwise, continue to stir after two hours, reaction mixture was stirred 4 hours stopped reaction in 45 ℃ of constant temperature.
Except that desolvating, remaining solid carries out recrystallization with toluene with reaction mixture, gets 20.5 gram solids.Get this solid 0.04 gram and load on the 2.4 gram silica gel,, under the 0.8Mpa, made vinyl polymerization 1 hour, get 743 gram polyethylene at 60 ℃ with 1.7 gram methylaluminoxane.After testing, this poly molecular weight distribution is Mw/Mn=6.7, and melting index MI=4.3 has the favorable mechanical processing characteristics.Embodiment 2
(1) 11.6 gram indenes addings is equipped with in the there-necked flask of 100ml tetrahydrofuran (THF), fully stirs, it is mixed, drip the butyl lithium solution that 13ml concentration is 3.5mol/l while stirring.Dropwise, continue to stir 0.5 hour, reaction mixture is preserved stand-by.
(2) get a there-necked flask in addition,, add tetrahydrofuran (THF), make it make complex compound to wherein adding 23.3 gram zirconium tetrachlorides.Under the room temperature, drip homemade reaction solution in the step (1) while stirring, dropwise, continue to stir after two hours, reaction mixture was stirred 4 hours in 45 ℃ of constant temperature.
(3) get a there-necked flask in addition,, drip the butyl lithium solution that 13ml concentration is 3.5mol/l while stirring to wherein adding 6.6 gram cyclopentadiene and 50ml tetrahydrofuran (THF)s.Dropwise, continue to stir 0.5 hour.
This reaction solution is dropped to the reaction solution of step (2) while stirring, dropwise, continue to stir after two hours, reaction mixture was stirred 4 hours stopped reaction in 45 ℃ of constant temperature.
Except that desolvating, remaining solid carries out recrystallization with toluene with reaction mixture, gets 19.97 gram solids.Get 0.04 gram solid and load on the 2.4 gram silica gel,, under the 0.8Mpa, made vinyl polymerization 1 hour at 60 ℃ with 1.7 gram methylaluminoxane, 735 restrain polyethylene.After testing, this poly molecular weight distribution is Mw/Mn=3.6, melting index MI=3.8, and its machining property is better.
Embodiment 3
13.2 gram cyclopentadiene and 0.33 gram fluorenes are added one successively and be equipped with in the there-necked flask of 100ml tetrahydrofuran (THF), and fully stirring mixes it, and Dropwise 5 7.7ml concentration is the butyl lithium solution of 3.5mol/l while stirring.Dropwise, continue to stir 0.5 hour, reaction mixture is preserved stand-by.
Other gets a there-necked flask, to wherein adding 19.2 gram titanium tetrachlorides, adds 100ml toluene and makes reaction solvent.Under the room temperature, drip homemade reaction mixture in the aforementioned there-necked flask while stirring, dropwise, continue to stir after two hours, reaction mixture was stirred 4 hours stopped reaction in 45 ℃ of constant temperature.
Except that desolvating, remaining solid carries out recrystallization with toluene with reaction mixture, gets 15.43 gram solids.Get this solid 0.031 gram and load on the 2.4 gram aluminium sesquioxides,, under the 0.8Mpa, make ethene and butene-1 copolymer-1 hour at 60 ℃ with 1.7 gram methylaluminoxane, 482 gram resins.After testing, this poly molecular weight distribution is Mw/Mn=0.5, melting index MI=18.
Embodiment 4
0.045 gram tetramethyl-ring pentadiene and 16.6 gram fluorenes are added one successively and are equipped with in the there-necked flask of 100ml tetrahydrofuran (THF), and fully stirring mixes it, drips the butyl lithium solution that 28.7ml concentration is 3.5mol/l while stirring.Dropwise, continue to stir 0.5 hour, reaction mixture is preserved stand-by.
Other gets a there-necked flask, to wherein adding 16.1 gram hafnium tetrachlorides, adds the 100ml tetrahydrofuran (THF) and makes reaction solvent.Under the room temperature, drip homemade reaction mixture in the aforementioned there-necked flask while stirring, dropwise, continue to stir after two hours, reaction mixture was stirred 4 hours stopped reaction in 45 ℃ of constant temperature.
Except that desolvating, remaining solid carries out recrystallization with toluene with reaction mixture, gets 14.8 gram solids.Get this solid 0.11 gram and load on the 2.4 gram magnesium chlorides,, under the 0.8Mpa, make ethene and hexene-1 copolymer-1 hour at 60 ℃ with 1.7 gram methylaluminoxane, 934 gram resins.After testing, this poly molecular weight distribution is Mw/Mn=2.8, melting index MI=1.4.Comparative Examples 1
13.2 gram cyclopentadiene and 5 gram sodium Metal 99.5s addings are equipped with in the there-necked flask of 100ml tetrahydrofuran (THF), fully react no longer produce bubble to the sodium Metal 99.5 surface till, the sodium Metal 99.5 of elimination surplus is stored in the nitrogenous hood filtrate stand-by.Other gets a there-necked flask, to wherein adding 23.3 gram zirconium tetrachlorides, adds tetrahydrofuran (THF), makes it make complex compound.Under the room temperature, drip homemade reaction solution in the aforementioned there-necked flask while stirring, dropwise, continue to stir after two hours, reaction mixture was stirred 4 hours stopped reaction in 45 ℃ of constant temperature.
Except that desolvating, remaining solid carries out recrystallization with toluene with reaction mixture, gets 16.6 gram solids.Get this solid 0.034 gram and load on the 2.4 gram silica gel,, under the 0.8Mpa, made vinyl polymerization 1 hour, get 685 gram polyethylene at 60 ℃ with 1.7 gram methylaluminoxane.After testing, this poly molecular weight distribution is Mw/Mn=1.2: 1, and melting index MI=0.85, its machining property is relatively poor.Comparative Examples 2
23.2 gram indenes addings are equipped with in the there-necked flask of 100ml tetrahydrofuran (THF), fully stir, it is mixed, drip the butyl lithium solution that 25.8ml concentration is 3.5mol/l while stirring.Dropwise, continue to stir 0.5 hour, reaction mixture is preserved stand-by.
Other gets a there-necked flask, to wherein adding 23.3 gram zirconium tetrachlorides, adds tetrahydrofuran (THF), makes it make complex compound.Under the room temperature, drip homemade reaction solution in the aforementioned there-necked flask while stirring, dropwise, continue to stir after two hours, reaction mixture was stirred 4 hours stopped reaction in 45 ℃ of constant temperature.
Except that desolvating, remaining solid carries out recrystallization with toluene with reaction mixture, gets 19.2 gram solids.Get this yellow solid 0.046 gram and load on the 2.4 gram silica gel,, under the 0.8Mpa, made vinyl polymerization 1 hour, get 718 gram polyethylene at 60 ℃ with 1.7 gram methylaluminoxane.After testing, this poly molecular weight distribution is Mw/Mn=1.4: 1, and melting index MI=0.49, its machining property is relatively poor.
Embodiment 5
Get the reaction product of 0.017 gram Comparative Examples 1 and the reaction product and the 1.7 gram methylaluminoxane of 0.023 gram Comparative Examples 2 and load to together on the 2.4 gram silica gel, carry out polymerization, get 712 gram polyethylene by the method for embodiment 1.After testing, this poly molecular weight distribution is Mw/Mn=4.8: 1, and melting index MI=4.0, its machining property is better.
Embodiment 6
Get 0.011 the gram Comparative Examples 1 reaction product, 0.015 the gram Comparative Examples 2 reaction product, 0.013 the gram embodiment 2 reaction product and 1.7 the gram methylaluminoxane load to together 2.4 the gram silica gel on, carry out polymerization by the method for embodiment 1,736 the gram polyethylene.After testing, this poly molecular weight distribution is Mw/Mn=5.8, melting index MI=5.1, and its machining property is better.
Claims (5)
1. metallocene catalyst for olefine polymerization, form by metallocene active ingredient, methylaluminoxane, carrier, it is characterized in that the metallocene active ingredient is the reaction product of indenes, fluorenes or its substitutive derivative, cyclopentadiene or substituted-cyclopentadienyl and zirconium tetrachloride or titanium, hafnium.
2. metallocene catalyst according to claim 1, its carrier can be silica gel, aluminium sesquioxide, magnesium chloride.
3. metallocene catalyst according to claim 1, the raw material of preparation metallocene active ingredient is cyclopentadiene, indenes and zirconium tetrachloride.
4. metallocene catalyst according to claim 3, its metallocene active ingredient can be obtained by following method: (1) joins indenes and cyclopentadiene in tetrahydrofuran (THF) or the toluene by 0.001～1000 mol ratio, with butyllithium or sodium sand effect, obtain mixed liquor A after the stirring again; (2) zirconium tetrachloride is joined make complex compound B in the tetrahydrofuran (THF); (3) make solvent with tetrahydrofuran (THF) or toluene, under-20～100 ℃ of temperature, A mixed with B solution and be stirred to reaction and finish.The reactant crude product is carried out recrystallization, the metallocene active ingredient that promptly gets with the mixed solvent of toluene or toluene and hexane.
5. metallocene catalyst according to claim 3, its metallocene active ingredient also can be prepared by following method: (1) adds indenes in the tetrahydrofuran (THF), stirs to add butyl lithium solution simultaneously, and reaction mixture A preserves stand-by; (2) in addition with adding tetrahydrofuran (THF) in the zirconium tetrachloride, make complex compound, add reaction solution A under the room temperature again, stir, get reaction solution B in 45 ℃ of constant temperature; (3) cyclopentadiene is joined in tetrahydrofuran (THF) or the toluene, add butyllithium or sodium sand and stirring again, get reaction liquid C; (4) reaction liquid C is joined among the reaction solution B, stir in 45 ℃ of constant temperature, question response stops, and solvent is removed, and remaining solid carries out recrystallization with toluene, obtains the metallocene active ingredient.
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|---|---|---|---|
| CNB001328476A CN1176114C (en) | 2000-11-08 | 2000-11-08 | Metallocene catalyst for polymerizing olefine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001328476A CN1176114C (en) | 2000-11-08 | 2000-11-08 | Metallocene catalyst for polymerizing olefine |
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| CN1300786A true CN1300786A (en) | 2001-06-27 |
| CN1176114C CN1176114C (en) | 2004-11-17 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100343290C (en) * | 2002-10-18 | 2007-10-17 | 中国石油化工股份有限公司 | Metallocene catalyst for production of polyolefine with broad peak or double peaks molecular weight distribution in monoreactor and its preparation |
| CN1930193B (en) * | 2003-06-05 | 2011-03-23 | 尤尼威蒂恩技术有限责任公司 | Class of metallocenes and method of producing polyethylene |
| CN101817892B (en) * | 2009-02-27 | 2011-11-30 | 中国石油化工股份有限公司 | Method for preparing magnesium chloride loaded metallocene catalyst |
| CN113527547A (en) * | 2021-07-22 | 2021-10-22 | 中国科学院山西煤炭化学研究所 | Polymerization catalyst based on coal tar derivative ligand and preparation method and application thereof |
-
2000
- 2000-11-08 CN CNB001328476A patent/CN1176114C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100343290C (en) * | 2002-10-18 | 2007-10-17 | 中国石油化工股份有限公司 | Metallocene catalyst for production of polyolefine with broad peak or double peaks molecular weight distribution in monoreactor and its preparation |
| CN1930193B (en) * | 2003-06-05 | 2011-03-23 | 尤尼威蒂恩技术有限责任公司 | Class of metallocenes and method of producing polyethylene |
| CN101817892B (en) * | 2009-02-27 | 2011-11-30 | 中国石油化工股份有限公司 | Method for preparing magnesium chloride loaded metallocene catalyst |
| CN113527547A (en) * | 2021-07-22 | 2021-10-22 | 中国科学院山西煤炭化学研究所 | Polymerization catalyst based on coal tar derivative ligand and preparation method and application thereof |
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| CN1176114C (en) | 2004-11-17 |
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