CN102153681B - Supported metallocene catalyst and application thereof - Google Patents
Supported metallocene catalyst and application thereof Download PDFInfo
- Publication number
- CN102153681B CN102153681B CN2010106125746A CN201010612574A CN102153681B CN 102153681 B CN102153681 B CN 102153681B CN 2010106125746 A CN2010106125746 A CN 2010106125746A CN 201010612574 A CN201010612574 A CN 201010612574A CN 102153681 B CN102153681 B CN 102153681B
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- zrcl
- metallocene catalyst
- promotor
- carrier
- primary catalysts
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Abstract
The invention relates to a novel supported metallocene catalyst and application thereof. The supported metallocene catalyst is prepared by using titanium dioxide nano tubes as carriers and used for catalyzing olefin polymerization. The supported catalyst can be used for preparing polyolefin of different forms under different polymerization conditions.
Description
Technical field
The present invention relates to a kind of carried metallocene catalyst that is used for olefinic polymerization.
Background technology
Carried metallocene catalyst is meant that metallocene compound and promotor are carried on the carrier and exists with heterogeneous.Report that at present the inorganic carrier of selecting for use mainly contains: silicon-dioxide, aluminum oxide, polynite etc.There is a subject matter in the carried metallocene catalyst of various preparing carriers more than using: when being used for olefinic polymerization, polymer morphology is difficult to control.The processing of the direct impact polymer of polymer morphology and thermomechanical property.
Be the carried metallocene catalyst that obtains can effectively controlling polymer morphology, this effective cooperation of 3 of carrier, Primary Catalysts and promotor and selecting for use in the catalyzer is still an important research project of this area.
Summary of the invention
The objective of the invention is to be intended to overcome the problem that exists in the above prior art; And a kind of novel supported metallocene catalyst and application are provided; This catalyst cupport is stable, and charge capacity is high, and this supported catalyst keeps higher ethylene polymerization activity height; Polymericular weight and fusing point are significantly improved, can realize effectively that particularly polymer morphology is controlled.
A kind of carried metallocene catalyst of the present invention is made up of Primary Catalysts, promotor and carrier; Described Primary Catalysts is Cp
2ZrCl
2, (CH
3)
2C [Ind]
2ZrCl
2, (CH
3)
2C [Cp, Ind] ZrCl
2, rac-Et-(Ind)
2ZrCl
2Or CpSi (Me)
2N (t-Bu) ZrCl
2
Described promotor is alkylaluminoxane or boride;
Described carrier is a titania nanotube.
Described alkylaluminoxane preferably includes MAO, ethyl aikyiaiurnirsoxan beta or butyl aikyiaiurnirsoxan beta.
Described boride preferably includes B (C
6F
5)
3, [Ph
3C] B (C
6F
5)
4Or HNR
3B (C
6F
5)
4
The preferred carried metallocene catalyst of the present invention is that Primary Catalysts is Cp
2ZrCl
2Or (CH
3)
2C [Cp, Ind] ZrCl
2, promotor is a MAO, carrier is a titania nanotube.
Another preferred carried metallocene catalyst of the present invention is that Primary Catalysts is Cp
2ZrCl
2, promotor is B (C
6F
5)
3, carrier is a titania nanotube.
Above-mentioned carried metallocene catalyst is used the catalyzer as ethylene homo or ethene and alpha-olefin copolymer.
The present invention is the carried metallocene catalyst of carrier with the titania nanotube, is made up of carrier, Primary Catalysts and promotor.The Primary Catalysts that the present invention selects for use is Cp
2ZrCl
2, (CH
3)
2C [Ind]
2ZrCl
2, (CH
3)
2C [Cp, Ind] ZrCl
2, rac-Et-(Ind)
2ZrCl
2Or CpSi (Me)
2N (t-Bu) ZrCl
2, because these Primary Catalysts central metals are Zr, after load, part is very little to the form influence of polymkeric substance.And bis cyclopentadienyl zirconium dichloride (Cp simple to operate, that cheaply be easy to get
2ZrCl
2) be the most preferred Primary Catalysts of optimum of the present invention.With respect to Primary Catalysts; The promotor that the present invention selects for use can effectively make Primary Catalysts form the compound in metallic cation active site; Like alkylaluminoxane or boride etc.; Wherein suitable alkylaluminoxane comprises MAO, ethyl aikyiaiurnirsoxan beta, butyl aikyiaiurnirsoxan beta and boron cpd etc., is preferably MAO, and suitable boride comprises B (C
6F
5)
3, [Ph
3C] B (C
6F
5)
4Or HNR
3B (C
6F
5)
4Deng.Primary Catalysts on the promotor elder generation activated carrier that when carrying out polyreaction, can add forms active site, catalyzed polymerization then.In addition, confirming of carrier of the present invention is extremely important too, and for obtaining the controlled catalyzer of polymer morphology, we also attempt the Primary Catalysts and the promotor that adopt other carrier loaded the present invention to select for use, like Cp
2ZrCl
2Deng being used for catalyzed ethylene polymerization, all can't obtain the controlled polymkeric substance of form in any case change polymerizing condition, with the resulting polymer morphology of polymerization in homogeneous phase, molecular weight and fusing point difference little (referring to Comparative Examples).Just because of trial and the cooperation of contriver through above Primary Catalysts, promotor and three aspect compositions of carrier; Just be able to obtain the technical scheme that the present invention can implement; And can realize effectively that catalyst cupport is stable, and charge capacity is high, and this supported catalyst keeps higher ethylene polymerization activity height; Polymericular weight and fusing point are significantly improved, the purpose that polymer morphology is controlled.
Catalyzer of the present invention can be used for olefinic polymerization, like vinyl polymerization and ethene and alpha-olefin copolymer etc.After adopting catalyst component of the present invention, the technician only need just can obtain the polyolefin products of different shape through the consumption of regulation and control polymerizing condition, particularly promotor of the present invention.
In the prior art; But though Primary Catalysts that the present invention selects for use and promotor all catalyzed ethylene polymerization and ethene and alpha-olefin copolymer under condition of loading not; But still can't effectively realize effective control of polymer morphology; And after exactly having only Primary Catalysts and promotor and carrier of the present invention effectively to combine, the control of just real effectively realization polymer morphology.
Description of drawings
Fig. 1. embodiment 1 makes three kinds of Vilaterm sem photograph contrasts, and wherein a and b obtain Vilaterm for the supported catalyst catalyzed ethylene polymerization, and the Al/Zr ratio is respectively 1000 and 3000 during polymerization; C is that unsupported catalyst vinyl polymerization obtains Vilaterm.
Fig. 2. embodiment 2 makes two kinds of Vilaterm sem photographs, and the Al/Zr ratio was respectively 1000 and 3000 when wherein a and b were polymerization.
Fig. 3. embodiment 3 makes two kinds of Vilaterm sem photographs, and the Al/Zr ratio was respectively 1000 and 3000 when wherein a and b were polymerization.
Fig. 4. embodiment 4 makes two kinds of Vilaterm sem photographs, and the B/Zr ratio was respectively 1000 and 3000 when wherein a and b were polymerization.
Fig. 5. embodiment 5 makes two kinds of Vilaterm sem photographs, and the B/Zr ratio was respectively 1000 and 3000 when wherein a and b were polymerization.
Fig. 6. Comparative Examples 1 makes two kinds of Vilaterm sem photographs, and the Al/Zr ratio was respectively 1000 and 3000 when wherein a and b were polymerization.
Embodiment
The embodiment of following preparation process and effect is intended to explain the present invention rather than to further qualification of the present invention.
Embodiment 1
Primary Catalysts is: Cp
2ZrCl
2
Carrier is: titania nanotube;
The preparation of supported catalyst: the MAO (20mmol) of 1 gram titania nanotube and 50mL stirred 5 hours at 50 ℃.Filter the back with 25 milliliters of toluene wash, refilter and remove liquid.Add 50 milliliters of toluene and aluminium zirconium then than the Cp that is 50
2ZrCl
2Stirred 5 hours at 50 ℃, filter the back at every turn with 25 milliliters of toluene wash 5 times, refilter and remove liquid, obtain solid supported catalyst, all operations carries out under nitrogen protection.
Vinyl polymerization: vinyl polymerization pressure is 0.13MPa, and polymerization temperature is 60 ℃, and polymer solvent is a 100mL toluene; Supported catalyst concentration is 2.5 μ molZr/L, and promotor is MAO (MAO), at different al/Zr than under the condition; After polymerase 10 .5 hour, with the ethanolic soln termination reaction of 10% hydrochloric acid, petroleum ether precipitation; Filtering and washing, drying is weighed.As a comparison, under same polymerizing condition, adopt the Primary Catalysts catalyzed ethylene polymerization in the present embodiment of unsupportedization.
Ethylene polymerization activity and polymkeric substance rerum natura such as following table: the Vilaterm form that makes in the table is referring to Fig. 1
Embodiment 2
With Primary Catalysts Cp among the embodiment 1
2ZrCl
2Change (CH into
3)
2C [Cp, Ind] ZrCl
2, all the other are with embodiment 1.
Ethylene polymerization activity and polymkeric substance rerum natura such as following table: the Vilaterm form is referring to Fig. 2
Embodiment 3
Change ethene among the embodiment 1 into ethene and octene-1 copolymerization, wherein octene content 15%, and all the other are with embodiment 1.
Ethylene polymerization activity and polymkeric substance rerum natura such as following table: the Vilaterm form is referring to Fig. 3
Embodiment 4
With promotor among the embodiment 1 is that MAO (MAO) changes B (C into
6F
5)
3, all the other are with embodiment 1.
Ethylene polymerization activity and polymkeric substance rerum natura such as following table: the Vilaterm form is referring to Fig. 4
Embodiment 5
With promotor among the embodiment 2 is that MAO (MAO) changes B (C into
6F
5)
3, all the other are with embodiment 2.
Ethylene polymerization activity and polymkeric substance rerum natura such as following table: the Vilaterm form is referring to Fig. 5
Comparative Examples 1
As a comparison, we select SiO
2Replace titania nanotube, all the other are with embodiment 1.
Ethylene polymerization activity and polymkeric substance rerum natura such as following table: the Vilaterm form is referring to Fig. 6
Claims (6)
1. a carried metallocene catalyst is made up of Primary Catalysts, promotor and carrier; Described Primary Catalysts is Cp
2ZrCl
2, (CH
3)
2C [Ind]
2ZrCl
2, (CH
3)
2C [Cp, Ind] ZrCl
2, rac-Et-(Ind)
2ZrCl
2Or CpSi (Me)
2N (t-Bu) ZrCl
2
Described promotor is alkylaluminoxane or boride;
Described carrier is a titania nanotube.
2. a kind of carried metallocene catalyst according to claim 1, described alkylaluminoxane comprise MAO, ethyl aikyiaiurnirsoxan beta or butyl aikyiaiurnirsoxan beta.
3. a kind of carried metallocene catalyst according to claim 1, described boride comprises B (C
6F
5)
3, [Ph
3C] B (C
6F
5)
4
4. a kind of carried metallocene catalyst according to claim 1, Primary Catalysts are Cp
2ZrCl
2Or (CH
3)
2C [Cp, Ind] ZrCl
2, promotor is a MAO, carrier is a titania nanotube.
5. a kind of carried metallocene catalyst according to claim 1, Primary Catalysts are Cp
2ZrCl
2, promotor is B (C
6F
5)
3, carrier is a titania nanotube.
6. each described a kind of carried metallocene catalyst of claim 1-5 is used the catalyzer as ethylene homo or ethene and alpha-olefin copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106125746A CN102153681B (en) | 2010-12-30 | 2010-12-30 | Supported metallocene catalyst and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106125746A CN102153681B (en) | 2010-12-30 | 2010-12-30 | Supported metallocene catalyst and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102153681A CN102153681A (en) | 2011-08-17 |
| CN102153681B true CN102153681B (en) | 2012-07-18 |
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ID=44435385
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|---|---|---|---|
| CN2010106125746A Expired - Fee Related CN102153681B (en) | 2010-12-30 | 2010-12-30 | Supported metallocene catalyst and application thereof |
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| CN107089912B (en) * | 2017-05-16 | 2020-10-30 | 湖南大学 | Method for selectively catalyzing and synthesizing mandelate compound by metallocene complex |
| CN116023539A (en) * | 2021-10-26 | 2023-04-28 | 中国石油化工股份有限公司 | Supported metallocene catalyst suitable for solution polymerization and preparation method and application thereof |
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|---|---|---|---|---|
| DK0685494T3 (en) * | 1994-06-03 | 1999-02-15 | Pcd Polymere Ag | Catalyst supports, supported metallocene catalysts and their use in the production of polyolefins |
| US6555495B2 (en) * | 2000-12-06 | 2003-04-29 | Univation Technologies, Llc | Catalyst support method and polymerization with supported catalysts |
| CN1137909C (en) * | 2001-10-26 | 2004-02-11 | 中国科学院长春应用化学研究所 | Intercalated loaded metallocene catalyst and its catalysis in olefine polymerization |
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Granted publication date: 20120718 Termination date: 20121230 |