CN102153681A - Supported metallocene catalyst and application thereof - Google Patents
Supported metallocene catalyst and application thereof Download PDFInfo
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- CN102153681A CN102153681A CN 201010612574 CN201010612574A CN102153681A CN 102153681 A CN102153681 A CN 102153681A CN 201010612574 CN201010612574 CN 201010612574 CN 201010612574 A CN201010612574 A CN 201010612574A CN 102153681 A CN102153681 A CN 102153681A
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- zrcl
- metallocene catalyst
- promotor
- carrier
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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 carried metallocene catalyst with above various preparing carriers: 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 above problems of the prior art, and provide a kind of novel supported metallocene catalyst and application, this catalyst cupport is stable, the charge capacity height, 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 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 methylaluminoxane, 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 methylaluminoxane, 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.
With the catalyzer of above-mentioned carried metallocene catalyst application 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 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 centre, as alkylaluminoxane or boride etc., wherein Shi Yi alkylaluminoxane comprises methylaluminoxane, ethyl aikyiaiurnirsoxan beta, butyl aikyiaiurnirsoxan beta and boron compound etc., be preferably methylaluminoxane, 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 can add when carrying out polyreaction forms active centre, catalyzed polymerization then.In addition, determining of carrier of the present invention is extremely important too, and for obtaining the controlled catalyzer of polymer morphology, we also attempt adopting selected Primary Catalysts of other carrier loaded the present invention and promotor, as 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 by above Primary Catalysts, promotor and three aspect compositions of carrier, just obtained the technical scheme that the present invention can implement, and can realize effectively that catalyst cupport is stable, the charge capacity height, 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, as 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 by the consumption of regulation and control polymerizing condition, particularly promotor of the present invention.
In the prior art, but though selected Primary Catalysts of the present invention 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 the effective combination of Primary Catalysts and promotor and carrier of the present invention, the just real polymer morphology of effectively realizing is controlled.
Description of drawings
Fig. 1. embodiment 1 makes three kinds of polyethylene sem photograph contrasts, and wherein a and b obtain polyethylene 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 polyethylene.
Fig. 2. embodiment 2 makes two kinds of polyethylene 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 polyethylene 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 polyethylene 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 polyethylene 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 polyethylene 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 illustrate the present invention rather than limitation of the invention further.
Embodiment 1
Primary Catalysts is: Cp
2ZrCl
2
Carrier is: titania nanotube;
The preparation of supported catalyst: the methylaluminoxane (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, polymerization temperature is 60 ℃, polymer solvent is a 100mL toluene, and supported catalyst concentration is 2.5 μ molZr/L, and promotor is methylaluminoxane (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 polyethylene 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 polyethylene 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 polyethylene form is referring to Fig. 3
Embodiment 4
With promotor among the embodiment 1 is that methylaluminoxane (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 polyethylene form is referring to Fig. 4
Embodiment 5
With promotor among the embodiment 2 is that methylaluminoxane (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 polyethylene 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 polyethylene form is referring to Fig. 6
Claims (6)
1. a carried metallocene catalyst is made 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 methylaluminoxane, 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)
4Or HNR
3B (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 methylaluminoxane, 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.
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CN2010106125746A CN102153681B (en) | 2010-12-30 | 2010-12-30 | Supported metallocene catalyst and application thereof |
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CN102153681A true CN102153681A (en) | 2011-08-17 |
CN102153681B CN102153681B (en) | 2012-07-18 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107089912A (en) * | 2017-05-16 | 2017-08-25 | 湖南大学 | A kind of method that metallocene complex selective catalysis synthesizes mandelic acid ester type compound |
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 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0685494A1 (en) * | 1994-06-03 | 1995-12-06 | PCD-Polymere Gesellschaft m.b.H. | Catalyst carrier, supported metallocene catalysts and their use in the preparation of polyolefins |
CN1344749A (en) * | 2001-10-26 | 2002-04-17 | 中国科学院长春应用化学研究所 | Intercalated loaded metallocene catalyst and its catalysis in olefine polymerization |
US20020107137A1 (en) * | 2000-12-06 | 2002-08-08 | Peterson Thomas Henry | Catalyst support method and polymerization with supported catalysts |
-
2010
- 2010-12-30 CN CN2010106125746A patent/CN102153681B/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0685494A1 (en) * | 1994-06-03 | 1995-12-06 | PCD-Polymere Gesellschaft m.b.H. | Catalyst carrier, supported metallocene catalysts and their use in the preparation of polyolefins |
US20020107137A1 (en) * | 2000-12-06 | 2002-08-08 | Peterson Thomas Henry | Catalyst support method and polymerization with supported catalysts |
CN1344749A (en) * | 2001-10-26 | 2002-04-17 | 中国科学院长春应用化学研究所 | Intercalated loaded metallocene catalyst and its catalysis in olefine polymerization |
Non-Patent Citations (1)
Title |
---|
《Catalysis communications》 20060525 Kazutada Ikenage etal Ethylene polymerization over zirconocenes supproted on alumina- and titania-based acidic oxides 36-38 1-6 第8卷, 第1期 2 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107089912A (en) * | 2017-05-16 | 2017-08-25 | 湖南大学 | A kind of method that metallocene complex selective catalysis synthesizes mandelic acid ester type compound |
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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