CN1160380C - Method for synthesizing supported metallocene catalyst - Google Patents
Method for synthesizing supported metallocene catalyst Download PDFInfo
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- CN1160380C CN1160380C CNB011311363A CN01131136A CN1160380C CN 1160380 C CN1160380 C CN 1160380C CN B011311363 A CNB011311363 A CN B011311363A CN 01131136 A CN01131136 A CN 01131136A CN 1160380 C CN1160380 C CN 1160380C
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- 239000012968 metallocene catalyst Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 title abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- 150000003624 transition metals Chemical class 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000741 silica gel Substances 0.000 claims description 12
- 229910002027 silica gel Inorganic materials 0.000 claims description 12
- 238000010189 synthetic method Methods 0.000 claims description 9
- -1 cyclopentadienyl indenyl Chemical group 0.000 claims description 8
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 8
- 125000003454 indenyl group Chemical class C1(C=CC2=CC=CC=C12)* 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical group [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 claims description 5
- 239000000284 extract Substances 0.000 claims description 5
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 2
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical compound C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 10
- 238000006116 polymerization reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 2
- 150000001336 alkenes Chemical class 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 150000002500 ions Chemical class 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
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 19
- 229910007926 ZrCl Inorganic materials 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- FTFYDDRPCCMKBT-UHFFFAOYSA-N 1-butylcyclopenta-1,3-diene Chemical compound CCCCC1=CC=CC1 FTFYDDRPCCMKBT-UHFFFAOYSA-N 0.000 description 2
- 208000035126 Facies Diseases 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- VRNCRGHDRGGBLW-UHFFFAOYSA-N cyclopenta-1,2-diene Chemical compound C1CC=C=C1 VRNCRGHDRGGBLW-UHFFFAOYSA-N 0.000 description 2
- SSLYIXHGTXGSJZ-UHFFFAOYSA-L cyclopentane;dichlorozirconium;indene Chemical compound Cl[Zr]Cl.[CH]1[CH][CH][CH][CH]1.C1=CC=C[C]2[CH][CH][CH][C]21 SSLYIXHGTXGSJZ-UHFFFAOYSA-L 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- JMYQTVXVDLDIFI-UHFFFAOYSA-L [Cl-].[Cl-].C(CCC)[Zr+2](C1C=CC=C1)CCCC Chemical compound [Cl-].[Cl-].C(CCC)[Zr+2](C1C=CC=C1)CCCC JMYQTVXVDLDIFI-UHFFFAOYSA-L 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PSOUOKYUENGTOA-UHFFFAOYSA-N ethene;dihydrochloride Chemical group Cl.Cl.C=C PSOUOKYUENGTOA-UHFFFAOYSA-N 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical group 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 1
- QMBQEXOLIRBNPN-UHFFFAOYSA-L zirconocene dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 QMBQEXOLIRBNPN-UHFFFAOYSA-L 0.000 description 1
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
A process for synthesizing supported metallocene catalyst includes such steps as mixing carrier with IVB group transition metal halide in solvent under normal pressure, and directly reacting with ligand negative ions. The synthesis and the loading of the metallocene catalyst are completed in one step, the process steps are simple, the metallocene catalyst is matched with a cocatalyst for olefin polymerization, and the activity of the catalyst meets the use requirement.
Description
Technical field
The present invention relates to the synthetic method of metallocene catalyst, be specifically related to a kind of synthetic method of for olefines polymerization carried metallocene catalyst.
Background technology
Polymerization mainly is divided into equal facies pattern and loading type two big classes with metallocene catalysis system.All there is the poor morphology of polymkeric substance in the facies pattern metallocene catalysis system on industrial applications, problems such as the consumption height of promotor, so the loaded metallocene catalyst system becomes the main direction of research.Present modal preparation method makes metallocene catalyst earlier, makes metallocene catalysis system with promoter aluminium alkyl oxygen alkane, the common reaction of silica gel again.Wherein as part, with transition metal halide reaction and purify and make, its relevant patent has WO 9,632 423, DE4426 122, US5006 to metallocene catalyst behind negative ionization by at least one cyclopentadiene or derivatives thereof, and 500, EP727,443 etc.But because part and halid reaction are liquid-solid reactions, transition metal halide can only with a small amount of complexing of solvent, productive rate is not high during polymerization catalyst, in addition the purification processes complexity of reactant.The preparation method of another kind of promising metallocene catalyst is that transition metal contacts with carrier earlier, and the lithium salts with part reacts again, typically zirconium tetrachloride (the ZrCl that makes gasification earlier that describes as patent EP708116
4) under 160 ℃～450 ℃ temperature, contact and load again that load is good ZrCl with carrier
4With the method for the lithium salts of part reaction, cooperate with promotor to be used for polymerization.The problem of its existence is that load process requires high temperature, and high vacuum is not suitable for industrial production.
Summary of the invention
The present invention proposes a kind of method of under normal pressure, synthesizing carried metallocene catalyst
The preparation process of metallocene catalyst is as follows:
A) with carrier and solvent, again at 20-150 ℃, be preferably under 40-120 ℃, add transition metal halide, extract solvent after the stirring, get solid A;
B) choose part and being dissolved in the solvent, under the inert gas protection, add the proton donor, be reflected at-100-50 ℃, be preferably in-carry out under the 78-25 ℃, stirred 4-24 hour, be preferably 8-12 hour, obtain solution B:
C) solid A is joined with 1: 1 the ratio of mole number of part in titanium (or zirconium or hafnium) with B solution mix stirring in the solvent, reacted at normal temperatures 4-20 hour, be preferably 6-12 hour, extract solvent and washing, make metallocene catalyst.
Carrier is selected from wherein one or more such as silica gel, aluminium sesquioxide, magnesium chloride, lithium chloride, clay, silica gel commonly used.The central atom content that the usage quantity of carrier should guarantee to contain metallocene compound in the final title complex is preferably in 0.1%-10% at 0.01%-50%.
The proton donor comprises organometallic compound, and metal hydride or basic metal are generally used lithium alkylide, preferably butyllithium.
Part can be bridging or non-bridging, comprises the indenes of cyclopentadienyl and derivative thereof, indenyl, fluorenyl, replacement or fluorenyl, dimethyl carbon bridged cyclopentadienyl indenyl, dimethyl-silicon bridged cyclopentadienyl indenyl.
One step of synthetic and loadization of metallocene catalyst finishes among the present invention, and preparation process is simple, and the easier realization of processing condition cooperates with promotor to be used for polymerization, and activity of such catalysts has reached service requirements.
Embodiment
Embodiment 1, dichloride sec.-propyl (9-fluorenes) (1-cyclopentadiene) are changed the zirconium loaded catalyst
A), get 113 gram silica gel and in the Schlenk flask, mix with the 200ml tetrahydrofuran (THF), add 5.8 again and restrain zirconium tetrachloride (ZrCl
4), vigorous stirring 4hrs extracts tetrahydrofuran (THF) with vacuum under the normal temperature, gets solid A;
B), under agitation 0.05mol (1.6M) butyllithium is joined 200ml and be dissolved with in the tetrahydrofuran solution of 6.8 gram sec.-propyl (9-fluorenes) (1-cyclopentadiene) parts, solution is stir about 12hrs at room temperature, gets solution B;
C), solid A is added in the B solution vigorous stirring, gained dark red solution restir 12hrs.Obtain 120.6 gram red solid after extracting all solvents under the vacuum, promptly make the catalyzer of this patent, cooperate with promotor methylaluminoxane (MAO) again and be used for polyreaction, the results are shown in Table 2.
Embodiment 2, dichloride sec.-propyl (9-fluorenes) (1-cyclopentadiene) are changed the hafnium loaded catalyst
With hafnium tetrachloride (HfCl
4) replacement ZrCl
4Part, the preparation method is identical with embodiment 1, and the catalyzer result of preparation sees Table 1,2.
Embodiment 3, dibutyl cyclopentadienyl zirconium dichloride loaded catalyst
Replacing sec.-propyl (9-fluorenes) (1-cyclopentadiene) with the butyl cyclopentadiene is part, and the preparation method is identical with embodiment 1, and the catalyzer result of preparation sees Table 1,2.
Example 4, dimethyl-silicon bridging (cyclopentadienyl) (indenyl) zirconium dichloride loaded catalyst
Replacing sec.-propyl (9-fluorenes) (1-cyclopentadiene) with dimethyl-silicon bridging indenyl rings pentadienyl is part, and the preparation method is identical with embodiment 1, and the catalyzer result of preparation sees Table 1,2.
Embodiment 5, bis cyclopentadienyl zirconium dichloride loaded catalyst
Replacing sec.-propyl (9-fluorenes) (1-cyclopentadiene) with cyclopentadiene is part, and the preparation method is identical with embodiment 1, and the catalyzer result of preparation sees Table 1,2.
Embodiment 6, dichloride ethylene two (1-indenes) are changed the zirconium loaded catalyst
Replacing sec.-propyl (9-fluorenes) (1-cyclopentadiene) with 2-ethylenebis (1-indenes) is part, and the preparation method is identical with embodiment 1, and the catalyzer result of preparation sees Table 1,2.
Embodiment 7, cyclopentadienyl indenyl zirconium dichloride loaded catalyst
With the aluminium sesquioxide is carrier, and it is part that cyclopentadiene and indenes replace sec.-propyl (9-fluorenes) (1-cyclopentadiene), and the preparation method is identical with embodiment 1, and the catalyzer result of preparation sees Table 1,2.
Embodiment 8, two (tetramethyl-ring pentadienyl) zirconium dichloride loaded catalyst
Replacing sec.-propyl (9-fluorenes) (1-cyclopentadiene) with the tetramethyl-ring pentadiene is part, and the preparation method is identical with embodiment 1, and the catalyzer result of preparation sees Table 1,2.
The preparation of table 1 metallocene catalyst
| Catalyzer | Carrier | Metal halide | Part | The content % of Zr in the catalyzer (Hf) |
| 1 | Silica gel | ZrCl 4 | Sec.-propyl (9-fluorenes) (1-cyclopentadiene) | 1.87 |
| 2 | Silica gel | HfCl 4 | Sec.-propyl (9-fluorenes) (1-cyclopentadiene) | 1.3 |
| 3 | Silica gel | ZrCl 4 | The butyl cyclopentadiene | 1.85 |
| 4 | Silica gel | ZrCl 4 | Dimethyl-silicon bridging indenyl rings pentadienyl | 1.85 |
| 5 | Silica gel | ZrCl 4 | Cyclopentadiene | 1.81 |
| 6 | Silica gel | ZrCl 4 | 2-ethylenebis (1-indenes) | 1.78 |
| 7 | Aluminium sesquioxide | ZrCl 4 | Cyclopentadiene and indenes | 1.10 |
| 8 | Silica gel | ZrCl 4 | The tetramethyl-ring pentadiene | 1.82 |
Table 2 aggregation test result
| Catalyzer | Polymerizing condition | Polymerization activity | |||||
| Monomer | Polymerization methods | Temperature ℃ | Pressure KPa | Time hr | Al/Zr(Hf | ×10 7g/(mol·h) | |
| 1 | Propylene | Body | 80 | 0.8 | 4 | 50 | 1.10 |
| 2 | Propylene | Body | 80 | 0.8 | 4 | 50 | 0.5 |
| 3 | Propylene | Body | 80 | 0.8 | 4 | 0.99 | |
| 4 | Propylene | Body | 30 | 0.8 | 4 | 150 | 1.87 |
| 5 * | Ethene | Slurry | 60 | 0.6 | 4 | 100 | 2.71 |
| 6 | Ethene, 15% hexene | Slurry | 60 | 0.6 | 4 | 100 | 3.11 |
| 7 | Ethene | Slurry | 60 | 0.8 | 4 | 200 | 1.10 |
| 8 | Ethene | Slurry | 70 | 0.7 | 4 | 200 | 1.20 |
*Except that promotor among the embodiment 5 is [Ph
3C] B (C
6F
5)
4In addition, metallocene catalyst all cooperates when polymerization and adds the promotor methylaluminoxane.
Claims (8)
1. the method for a synthetic carried metallocene catalyst, carry out according to the following steps:
A) carrier is dissolved in the solvent, adds transition metal halide down at 20-150 ℃, extracts solvent after the stirring, gets solid A;
B) use the dissolution with solvents part, under inert gas protection, add the proton donor, be reflected at-100-50 ℃ carries out, stirs and obtained solution B in 4-24 hour;
C) solid A is joined with 1: 1 the ratio of mole number of part in transition metal with solution B mix stirring in the solvent, reacted at normal temperatures 4-20 hour, extract solvent, make metallocene catalyst after the washing.
2. the synthetic method of catalyzer according to claim 1 is characterized in that the usage quantity of carrier should guarantee to contain in the final title complex central atom content of metallocene compound at 0.01%-50%.
3. the synthetic method of catalyzer according to claim 1 is characterized in that the usage quantity of carrier should guarantee to contain in the final title complex central atom content of metallocene compound at 0.1%-10%.
4. the synthetic method of catalyzer according to claim 1 is characterized in that carrier is a silica gel.
5. the synthetic method of catalyzer according to claim 1 is characterized in that transition metal is selected from titanium, zirconium or hafnium.
6. the synthetic method of catalyzer according to claim 1 is characterized in that part is bridging type or non-bridging type.
7. the synthetic method of catalyzer according to claim 1 is characterized in that part is the indenes of cyclopentadienyl and derivative thereof, indenyl, fluorenyl, replacement or fluorenyl, dimethyl carbon bridged cyclopentadienyl indenyl, dimethyl-silicon bridged cyclopentadienyl indenyl.
8. the synthetic method of catalyzer according to claim 1 is characterized in that the proton donor is a butyllithium.
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| CNB011311363A CN1160380C (en) | 2001-09-03 | 2001-09-03 | Method for synthesizing supported metallocene catalyst |
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| CNB011311363A CN1160380C (en) | 2001-09-03 | 2001-09-03 | Method for synthesizing supported metallocene catalyst |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2202246B1 (en) | 2007-10-16 | 2016-06-15 | Sinopec Yangzi Petrochemical Company Ltd. | Non-metallocene catalyst supported on magnesium compound and its preparation method |
| WO2011057469A1 (en) | 2009-11-13 | 2011-05-19 | 中国石油化工股份有限公司 | Supported non-metallocene catalyst and preparation method and uses thereof |
| WO2011057468A1 (en) | 2009-11-13 | 2011-05-19 | 中国石油化工股份有限公司 | Supported non-metallocene catalyst, preparation method and application thereof |
| CN102190749B (en) * | 2010-03-05 | 2013-02-20 | 中国石油天然气股份有限公司 | Ethylene/alpha-olefin copolymerization method |
| CN102286114A (en) * | 2010-06-21 | 2011-12-21 | 中国石油天然气股份有限公司 | Method for loading metallocene catalyst |
| CN102464732B (en) * | 2010-11-16 | 2013-06-05 | 中国石油化工股份有限公司 | Olefin polymerization method and olefin polymer prepared with same |
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