CN101235106B - Method for preparing metallocene catalyst and application thereof in ethylene propylene rubber production - Google Patents
Method for preparing metallocene catalyst and application thereof in ethylene propylene rubber production Download PDFInfo
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- CN101235106B CN101235106B CN2008100491898A CN200810049189A CN101235106B CN 101235106 B CN101235106 B CN 101235106B CN 2008100491898 A CN2008100491898 A CN 2008100491898A CN 200810049189 A CN200810049189 A CN 200810049189A CN 101235106 B CN101235106 B CN 101235106B
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- propylene rubber
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Abstract
The invention discloses a preparation method of metallocene catalyst and an application in the production of ethylen-propylene rubber, wherein the preparation method comprises at 0-30 DEG C, under nitrogen gas protection, reacting tetramethyl cyclopentadienyl lithium with MCI4 at a mol ratio of 1/2 to prepare (C9H13) MCI3, at 0 to 30 DEG C, under nitrogen gas protection, reacting substituted undenyl ligand and (C9H13) MCI3 at a mol ratio of 1/1, to obtain [(C9H6R)(C9H13)]MCI2. The catalyst synthesis method has simple process, high yield, strong operability and benefit for industrial production. In the presence of a metallocene compound catalyst and a catalyst promoter as methylaluminoxane, ethane and propone can be used as main materials to be polymerized for 1-5h in toluene solution at 30 to 70 DEG C and under 1-10kg/cm2 pressure to prepare ethylen-propylene rubber, with simple polymerization process, low catalyst consumption and low production cost. Compared with the prior art, the invention reduces the pollution of vanadium catalyst, protects environment and develops a new route for ethylen-propylene rubber production.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts and application thereof, relate in particular to a kind of preparation and application in preparation ethylene-propylene rubber(EPR) thereof of metallocene catalyst.
Background technology
Ethylene-propylene rubber(EPR) (EPR) is that come out after invention, polyethylene and the polyacrylic appearance continue Ziegler-Natta catalyst a kind of is the copolymer rubber of basic monomer with ethene and propylene, is divided into ethylene propylene rubber (EPM) and terpolymer EP rubber (EPDM) two big classes.The former is the multipolymer of ethene and propylene; The latter is the multipolymer of ethene, propylene and a small amount of non-conjugated diene hydrocarbon, and two non-conjugated diene hydrocarbon commonly used are ethylidene norbornene (ENB) and dicyclopentadiene (DCPD).Ethylene-propylene rubber(EPR) has excellent anti-ozone, fire-resistant, weather-proof, anti ageing property, monomer is cheap and easy to get in addition, of many uses, be with fastest developing speed a kind of in the external seven big synthetic rubber kinds since the eighties, its output, throughput and consumption all occupy the 3rd in developed country, be only second to styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber.
Ethylene-propylene rubber(EPR) is mainly used in fields such as trolley part, tire, waterproof roll, electric wire, oil product properties-correcting agent, polyolefin modifiers, part of washing machine, solar energy collector.Ethylene-propylene rubber(EPR) production both at home and abroad at present is many to be catalyzer with the vanadium sub-group compound, there are problems such as poisonous and harmful contaminate environment in vanadium series catalyst in preparation and use, therefore preparation and use efficiently, eco-friendly new catalyst becomes new the pursuing one's goal of ethylene-propylene rubber(EPR) production, in recent years, metallocene catalyst and olefinic polymerization development thereof are very fast, that metallocene catalyst has is active high, the active centre is single, polymer architecture, molecular weight and the controllable molecular weight distribution of catalyzed polymerization and good advantages such as copolymerization ability, thereby receives much concern.But the deficiency that synthetic ubiquity yield is low, purity is low of present metallocene catalyst, for this reason, inquire into the synthetic method of metallocene catalyst, improve its yield and purity and be applied to ethylene-propylene rubber(EPR) production, to improving present ethylene-propylene rubber(EPR) production technology deficiency, promote the technical renovation of ethylene-propylene rubber(EPR) production to have great importance.
Summary of the invention
The object of the invention is to provide a kind of yield height, metallocene catalyst new synthetic method that purity is high, and is applied in the production technique of ethylene-propylene rubber(EPR), impels ethylene-propylene rubber(EPR) to realize suitability for industrialized production.
For realizing the object of the invention, technical solution of the present invention is as follows: synthetic as follows metallocene catalyst:
1, catalyst A is synthetic:
R ' in the formula=H, the alkyl of C1-10 etc., M=Zr, Ti
(1) 0-30 ℃, under the nitrogen protection, tetramethyl-ring pentadienyl lithium and MCl
4With mol ratio 1/2 prepared in reaction (C
9H
13) MCl
3
(2) 0-30 ℃, under the nitrogen protection, substituted indenyl lithium and (C
9H
13) MCl
3Make [(C with mol ratio 1/1 reaction
9H
6R ') (C
9H
13)] MCl
2
2, catalyst B is synthetic:
R=C1-10 alkyl, phenyl etc. in the formula, R '=H, C1-10 alkyl etc., X=Si, C, M=Zr, Ti.
(1) 0-30 ℃, under the nitrogen protection, tetramethyl-ring pentadienyl lithium and R
2XCl
2With mol ratio 1/1-1/3 prepared in reaction (C
9H
13) R
2XCl;
(2) 0-30 ℃, under the nitrogen protection, substituted indenyl lithium and (C
9H
13) R
2XCl makes [(C with mol ratio 1/1-1/1.5 reaction
9H
6R ') (C
9H
13)] R
2X;
(3) 0-30 ℃, under the nitrogen protection, [(C
9H
6R ') (C
9H
13)] R
2X and n-Butyl Lithium react in diethyl ether solution with mol ratio 1/1-1/1.5 and make lithium salts, then with MCl
4Make [(C with mol ratio 1/1-1/1.5 reaction
9H
5R ') (C
9H
12)] R
2XMCl
2
Above reaction yield is about 90%, total reaction yield about 70%.
3, ethylene-propylene rubber(EPR) preparation: adopt a kind of in the above-mentioned metallocene compound for catalyzer, methylaluminoxane (MAO) are promotor, in 30～70 ℃, 1-10Kg/cm
2Under the pressure in toluene solution the ethene of catalysis different ratios, propylene mixed gas, polyreaction 1～5 hour obtains the ethylene-propylene rubber(EPR) of different molecular weight.Catalyzer metallocene compound consumption is that 1～10ppm, promotor methylaluminoxane (MAO) consumption are 1000～3000 times of metallocene compound consumption.
Advantage of the present invention: 1) the catalyzer synthesis technique is simple, the yield height, and per step reaction yield is about 90%, and the purity height is workable, helps suitability for industrialized production; 2) adopt efficient metallocene catalyst to produce ethylene-propylene rubber(EPR), catalyst levels is few, and production cost is low, and polymerization technology is simple, and the polymerization efficiency height can reach 1 * 10
5-10 * 10
5G/gZr; 3) polymer architecture, molecular weight and controllable molecular weight distribution, proportioning raw materials is unrestricted, can obtain the ethylene-propylene rubber(EPR) of different model.Compared with prior art, reduced the pollution that vanadium series catalyst brings, helped environment protection,, be fit to suitability for industrialized production for a new operational path has been developed in the production of ethylene-propylene rubber(EPR).
Embodiment
For the present invention is described in detail better, it is as follows to give an actual example:
Embodiment 1 compound [(C
9H
7) (C
9H
13)] ZrCl
2Synthetic
The anhydrous ether solution that under 0 ℃ of nitrogen protection 100mL is contained 12.8g tetramethyl-ring pentadienyl lithium splashes in the 120mL ether that contains the 50g zirconium tetrachloride; dropwise; stirred two hours; drip 100mL again and contain the anhydrous ether solution of 12.3g indenyl lithium; dropwise, stirred two hours, reaction mixture filters with anhydrous sodium sulphate; that filtrate steams is freezing behind most of solvent, crystallization obtains clear crystal 37g, yield 92%.
Embodiment 2 compound [(C
9H
6) (C
9H
13)] Me
2SiTiCl
2Synthetic
1, compound (C
9H
13) Me
2SiCl's is synthetic
The anhydrous ether solution that under 10 ℃ of nitrogen protections 100mL is contained 12.8g tetramethyl-ring pentadienyl lithium splashes in the 120mL diethyl ether solution that contains the 26g dimethyldichlorosilane(DMCS); dropwise; stirred two hours; reaction mixture filters with anhydrous sodium sulphate; that filtrate steams is freezing behind most of solvent, crystallization obtains clear crystal 23g; crystal is used the anhydrous diethyl ether recrystallization once again, gets clear crystal 20g, yield 91%.
2, compound [(C
9H
7) (C
9H
13)] Me
2Si's is synthetic
The anhydrous ether solution that under 25 ℃ of nitrogen protections 100mL is contained 12.3g indenyl lithium splashes into and contains 22g (C
9H
13) Me
2In the 120mL diethyl ether solution of SiCl, dropwise, restir two hours, reaction mixture filters with anhydrous sodium sulphate, and filtrate steams the back freezing and crystallizing and obtains white solid 27g, purity 97.1%, yield 91%.
3, compound [(C
9H
6) (C
9H
13)] Me
2SiTiCl
2Synthetic
N-Butyl Lithium hexane solution with 10mL2.4M under 30 ℃ of nitrogen protections adds 2.94g[(C
9H
7) (C
9H
13)] Me
2In the 100mL anhydrous ether solution of Si, stir adding 2.0g titanium tetrachloride after 3 hours, restir 2 hours, steaming desolventizes, and solid normal hexane washed twice adds the 100mL methylene dichloride, leave standstill, filter with anhydrous sodium sulphate, filtrate steams solvent, adds normal hexane, freezing, filter, obtain safran solid 3.6g, yield 87%.
Embodiment 3 compound [(MeC
9H
6) (C
9H
13)] Ph
2SiZrCl
2Synthetic
1, compound (C
9H
13) Ph
2SiCl's is synthetic
The anhydrous ether solution that under 10 ℃ of nitrogen protections 100mL is contained 12.8g tetramethyl-ring pentadienyl lithium splashes in the 120mL diethyl ether solution that contains the 25g diphenyl dichlorosilane; dropwise; stirred two hours; reaction mixture filters with anhydrous sodium sulphate; that filtrate steams is freezing behind most of solvent, crystallization obtains clear crystal 33g; crystal is used the anhydrous diethyl ether recrystallization once again, gets clear crystal 30g, yield 89%.
2, compound [(MeC
9H
6) (C
9H
13)] Ph
2Si's is synthetic
The anhydrous ether solution that under 25 ℃ of nitrogen protections 100mL is contained 15.1g (methyl) fluorenyl lithium splashes into and contains 34g (C
9H
13) Ph
2In the 120mL diethyl ether solution of SiCl, dropwise, restir two hours, reaction mixture filters with anhydrous sodium sulphate, and filtrate steams the back freezing and crystallizing and obtains white solid 38g, purity 97%, yield 86%.
3, compound [(MeC
9H
6) (C
9H
13)] Ph
2SiZrCl
2Synthetic
N-Butyl Lithium hexane solution with 10mL2.4M under 30 ℃ of nitrogen protections adds 4.47g[(MeC
9H
6) (C
9H
13)] Ph
2In the 100mL anhydrous ether solution of Si, stir adding 2.5g zirconium tetrachloride after 3 hours, restir 2 hours, steaming desolventizes, and solid normal hexane washed twice adds the 100mL methylene dichloride, leave standstill, filter with anhydrous sodium sulphate, filtrate steams solvent, adds normal hexane, freezing, filter, obtain orange solid 5g, yield 85%.
The production of embodiment 4 ethylene-propylene rubber(EPR)
Adding 3L polymerization-grade toluene solvant in 5L stainless steel polymeric kettle, is 40 ℃ by chuck recirculated water controlled polymerization still temperature, and begins to stir.In polymeric kettle, add 10g ethylidene norbornene (ENB), 5mg catalyzer [(C
9H
6) (C
9H
13)] Me
2SiZrCl
2And the MAO toluene solution of 50mL10%, feed and consist of ethylene content 35mol%, the ethene of propylene content 65mol%, propylene gas mixture; By pressurized circulation pump control reactor total pressure is 4Kg/cm
2, and keep gas composition constant, polymerization is after 4 hours, and reactor emptying is to normal pressure, and polymers soln is emitted at the bottom of by still, steams toluene and obtains ethylene-propylene-ENB terpolymer EP rubber (EPDM), and catalytic efficiency is 7.0 * 10
5G/gZr.
Polymkeric substance is by analysis: propylene content is 21%, and iodine number is 8.11, is solvent with the perhydronaphthalene, and 135 ℃ are measured intrinsic viscosities down is 1.29dl/g.
The production of embodiment 5 ethylene-propylene rubber(EPR)
Adding 3L polymerization-grade toluene solvant in 5L stainless steel polymeric kettle, is 70 ℃ by chuck recirculated water controlled polymerization still temperature, and begins to stir.In polymeric kettle, add 8g ethylidene norbornene (ENB), 7mg catalyzer [(MeC
9H
5) (C
9H
13)] Ph
2SiZrCl
2And the MAO toluene solution of 150mL10%, feed and consist of ethylene content 45mol%, the ethene of propylene content 55mol%, propylene gas mixture; By pressurized circulation pump control reactor total pressure is 10Kg/cm
2, and keep gas composition constant, and polymerization is after 1 hour, and reactor emptying is to normal pressure.Polymers soln is emitted at the bottom of by still, steams toluene and obtains ethylene-propylene-ENB terpolymer EP rubber (EPDM), and catalytic efficiency is 5.0 * 10
5G/gZr.
Polymkeric substance is by analysis: propylene content is 17%, and iodine number is 12.3, is solvent with the perhydronaphthalene, and 135 ℃ are measured intrinsic viscosities down is 1.29dl/g.
Claims (4)
1. the preparation method of metallocene catalyst is characterized in that, makes as follows:
(1) 0-30 ℃, under the nitrogen protection, tetramethyl-ring pentadienyl lithium and MCl
4Make with mol ratio 1/2 reaction
(2) 0-30 ℃, under the nitrogen protection, the substituted indenyl lithium
The compound that makes with step (1) reacts with mol ratio 1/1
R '=H, the C1-10 alkyl; M=Zr, Ti.
2. the preparation method of metallocene catalyst is characterized in that, makes as follows:
(1) 0-30 ℃, under the nitrogen protection, tetramethyl-ring pentadienyl lithium and R
2XCl
2Make with mol ratio 1/1-1/3 reaction
(2) 0-30 ℃, under the nitrogen protection, the substituted indenyl lithium
The compound that makes with step (1) makes with mol ratio 1/1-1/1.5 reaction
(3) 0-30 ℃, under the nitrogen protection, compound that step (2) makes and n-Butyl Lithium react in diethyl ether solution with mol ratio 1/1-1/1.5 and make lithium salts, then with MCl
4Make with mol ratio 1/1-1/1.5 reaction
The R=C1-10 alkyl or phenyl; R '=H, the C1-10 alkyl; X=Si; M=Zr, Ti.
3. the application of the metallocene catalyst of method preparation in preparation ethylene-propylene rubber(EPR) as claimed in claim 1 or 2 is characterized in that, is main raw material with ethene and propylene gas mixture, with the metallocene compound is catalyzer, methylaluminoxane is a promotor, in 30～70 ℃, and 1-10Kg/cm
2Carry out polyreaction under the pressure in toluene solution, react after 1～5 hour, steaming desolventizes and obtains ethylene-propylene rubber(EPR).
4. the application of metallocene catalyst as claimed in claim 3 in preparation ethylene-propylene rubber(EPR) is characterized in that the metallocene catalyst consumption is 1～10ppm, and promotor methylaluminoxane consumption is 1000～3000 times of metallocene compound consumption.
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|---|---|---|---|
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| CN101235106B true CN101235106B (en) | 2010-09-08 |
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| CN103641863B (en) * | 2013-11-14 | 2016-05-11 | 浙江大学 | A kind of bridged combined metal complex and application thereof |
| CN103641864B (en) * | 2013-11-14 | 2016-06-01 | 浙江大学 | A kind of method preparing ethylene-propylene rubber(EPR) |
| WO2024036052A1 (en) | 2022-08-09 | 2024-02-15 | Exxonmobil Chemical Patents Inc. | Methods for preparing diphenylsilane bridged c1 symmetric catalysts and polymers made therefrom |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5892079A (en) * | 1997-10-17 | 1999-04-06 | Sri International | Metallocene catalysts and associated methods of preparation and use |
| CN1282343A (en) * | 1997-12-22 | 2001-01-31 | 拜尔公司 | Method for producing elastomers |
| CN1478104A (en) * | 2000-11-16 | 2004-02-25 | 尤尼威蒂恩技术有限责任公司 | Catalyst system and its use in olefin polymerization |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5892079A (en) * | 1997-10-17 | 1999-04-06 | Sri International | Metallocene catalysts and associated methods of preparation and use |
| CN1282343A (en) * | 1997-12-22 | 2001-01-31 | 拜尔公司 | Method for producing elastomers |
| CN1478104A (en) * | 2000-11-16 | 2004-02-25 | 尤尼威蒂恩技术有限责任公司 | Catalyst system and its use in olefin polymerization |
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