CN101045738A - Metallocene Zr-rare earth isodinuclear catalyst and preparation method and application thereof - Google Patents
Metallocene Zr-rare earth isodinuclear catalyst and preparation method and application thereof Download PDFInfo
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- CN101045738A CN101045738A CN 200710013766 CN200710013766A CN101045738A CN 101045738 A CN101045738 A CN 101045738A CN 200710013766 CN200710013766 CN 200710013766 CN 200710013766 A CN200710013766 A CN 200710013766A CN 101045738 A CN101045738 A CN 101045738A
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- 239000003054 catalyst Substances 0.000 title claims description 23
- 229910052761 rare earth metal Inorganic materials 0.000 title claims description 8
- 238000002360 preparation method Methods 0.000 title description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 69
- 238000006243 chemical reaction Methods 0.000 claims description 61
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 34
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 23
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 22
- 238000000605 extraction Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 239000000706 filtrate Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims description 10
- 159000000002 lithium salts Chemical class 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- 150000002910 rare earth metals Chemical class 0.000 claims description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 239000012044 organic layer Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 229960001866 silicon dioxide Drugs 0.000 claims description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 238000010189 synthetic method Methods 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 claims description 3
- 125000006038 hexenyl group Chemical group 0.000 claims description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 3
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- -1 aluminium alkyl oxygen alkane Chemical class 0.000 abstract description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract 1
- 230000003213 activating effect Effects 0.000 abstract 1
- 125000003342 alkenyl group Chemical group 0.000 abstract 1
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- 239000004411 aluminium Substances 0.000 abstract 1
- 125000003710 aryl alkyl group Chemical group 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 238000010992 reflux Methods 0.000 description 22
- 239000012968 metallocene catalyst Substances 0.000 description 20
- 239000013078 crystal Substances 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 230000000630 rising effect Effects 0.000 description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 229910052709 silver Inorganic materials 0.000 description 10
- 239000004332 silver Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 238000006073 displacement reaction Methods 0.000 description 7
- 150000002469 indenes Chemical class 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 7
- 230000005408 paramagnetism Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 230000003595 spectral effect Effects 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- 238000005660 chlorination reaction Methods 0.000 description 5
- 230000037048 polymerization activity Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- MFGOTAHWOBKNNU-XMHGGMMESA-N Isodigeranyl Chemical group CC(C)=CCC\C(C)=C\CC(C)(C=C)CCC=C(C)C MFGOTAHWOBKNNU-XMHGGMMESA-N 0.000 description 3
- MFGOTAHWOBKNNU-FQEVSTJZSA-N Isodigeranyl Natural products CC(=CCCC(=CC[C@](C)(CCC=C(C)C)C=C)C)C MFGOTAHWOBKNNU-FQEVSTJZSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- NBHBNYRLTADHQY-UHFFFAOYSA-N 1-benzyl-1h-indene Chemical class C1=CC2=CC=CC=C2C1CC1=CC=CC=C1 NBHBNYRLTADHQY-UHFFFAOYSA-N 0.000 description 2
- PYSHWNQKDHBAAI-UHFFFAOYSA-N 1-but-3-enyl-1h-indene Chemical class C1=CC=C2C(CCC=C)C=CC2=C1 PYSHWNQKDHBAAI-UHFFFAOYSA-N 0.000 description 2
- OWNWPBRJHNIUFC-UHFFFAOYSA-N 1-pent-4-enyl-1h-indene Chemical class C1=CC=C2C(CCCC=C)C=CC2=C1 OWNWPBRJHNIUFC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
- QINIUZWXFSJAJM-UHFFFAOYSA-N 1-hex-5-enyl-1H-indene Chemical class C1=CC=C2C(CCCCC=C)C=CC2=C1 QINIUZWXFSJAJM-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- KKDBZWZRJNRBGA-UHFFFAOYSA-L Cl[Ti]Cl.[CH]1C=CC=C1 Chemical compound Cl[Ti]Cl.[CH]1C=CC=C1 KKDBZWZRJNRBGA-UHFFFAOYSA-L 0.000 description 1
- XJONFIGVOQMBIP-UHFFFAOYSA-L Cl[Zr](Cl)C1C=CC=C1 Chemical compound Cl[Zr](Cl)C1C=CC=C1 XJONFIGVOQMBIP-UHFFFAOYSA-L 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- ZMMRKRFMSDTOLV-UHFFFAOYSA-N cyclopenta-1,3-diene zirconium Chemical compound [Zr].C1C=CC=C1.C1C=CC=C1 ZMMRKRFMSDTOLV-UHFFFAOYSA-N 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical group C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000029305 taxis Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
Embodiment number | The catalyzer numbering | Catalyzer add-on (mmol) | MAO add-on (ml) | Al/M | Catalyst activity (10 5gPE/mol Cat h) | Mw | Mw/Mn | Tm (℃) |
12 | A | 0.01 | 6.4 | 500 | 1.88 | 193000 | 3.05 | 135.44 |
13 | B | 0.008 | 4.9 | 500 | 1.05 | 287500 | 2.34 | 135.16 |
14 | C | 0.004 | 12.85 | 1500 | 1.44 | 324100 | 3.16 | 134.95 |
15 | D | 0.0012 | 7.8 | 500 | 1.61 | 432500 | 2.25 | 137.47 |
16 | E | 0.012 | 7.8 | 500 | 1.48 | 254300 | 2.37 | 136.31 |
17 | F | 0.004 | 2.57 | 500 | 8.18 | 145000 | 2.65 | 135.23 |
18 | G | 0.0095 | 6.04 | 500 | 2.85 | 296000 | 2.33 | 134.34 |
19 | H | 0.004 | 5.08 | 1000 | 1.08 | 339000 | 3.27 | 135.18 |
20 | I | 0.002 | 2.85 | 500 | 1.75 | 382000 | 1.98 | 139.92 |
21 | J | 0.002 | 5.08 | 250 | 1.59 | 421000 | 2.26 | 138.36 |
22 | A | 0.0069 | 8.8 | 1000 | 4.38 | 372000 | 2.94 | 131.69 |
23 | B | 0.011 | 7.7 | 500 | 2.47 | 325000 | 2.16 | 133.67 |
24 | C | 0.006 | 3.9 | 500 | 2.53 | 231000 | 2.08 | 137.39 |
25 | D | 0.0069 | 8.8 | 1000 | 4.72 | 342000 | 2.67 | 132.66 |
26 | E | 0.004 | 2.57 | 500 | 8.09 | 201000 | 2.54 | 134.89 |
27 | F | 0.0066 | 4.2 | 500 | 2.03 | 332500 | 2.48 | 134.78 |
28 | G | 0.006 | 3.9 | 500 | 2.49 | 262000 | 2.15 | 136.25 |
29 | H | 0.002 | 5.08 | 500 | 1.74 | 327000 | 1.96 | 139.48 |
30 | I | 0.006 | 3.9 | 500 | 2.89 | 449200 | 2.88 | 136.33 |
31 | K | 0.006 | 3.9 | 500 | 1.79 | 423500 | 2.79 | 137.21 |
Claims (8)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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CNB2007100137663A CN100546995C (en) | 2007-03-08 | 2007-03-08 | Metallocene Zr-rare earth isodinuclear catalyst and preparation method thereof and application |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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CNB2007100137663A CN100546995C (en) | 2007-03-08 | 2007-03-08 | Metallocene Zr-rare earth isodinuclear catalyst and preparation method thereof and application |
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Publication Number | Publication Date |
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CN101045738A true CN101045738A (en) | 2007-10-03 |
CN100546995C CN100546995C (en) | 2009-10-07 |
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CNB2007100137663A Active CN100546995C (en) | 2007-03-08 | 2007-03-08 | Metallocene Zr-rare earth isodinuclear catalyst and preparation method thereof and application |
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CN (1) | CN100546995C (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107903346A (en) * | 2017-11-22 | 2018-04-13 | 宁波大学 | A kind of double-core rare earth catalyst and the polymerization of preparation method and syndiotactic polytyrene |
-
2007
- 2007-03-08 CN CNB2007100137663A patent/CN100546995C/en active Active
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107903346A (en) * | 2017-11-22 | 2018-04-13 | 宁波大学 | A kind of double-core rare earth catalyst and the polymerization of preparation method and syndiotactic polytyrene |
CN107903346B (en) * | 2017-11-22 | 2020-03-03 | 宁波大学 | Binuclear rare earth catalyst, preparation method thereof and polymerization method of syndiotactic polystyrene |
Also Published As
Publication number | Publication date |
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CN100546995C (en) | 2009-10-07 |
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Denomination of invention: Metallocene Zr rare earth heterobinuclear catalyst and its preparation method and Application Effective date of registration: 20220225 Granted publication date: 20091007 Pledgee: Dongying Bank Co.,Ltd. Zibo Linzi sub branch Pledgor: ZIBO XINSU CHEMICAL Co.,Ltd. Registration number: Y2022980001873 |
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