CN101092459A - supported polymerization catalytic system and preparation method and application thereof - Google Patents
supported polymerization catalytic system and preparation method and application thereof Download PDFInfo
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- CN101092459A CN101092459A CN 200610090009 CN200610090009A CN101092459A CN 101092459 A CN101092459 A CN 101092459A CN 200610090009 CN200610090009 CN 200610090009 CN 200610090009 A CN200610090009 A CN 200610090009A CN 101092459 A CN101092459 A CN 101092459A
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 160
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 128
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 64
- OTTZHAVKAVGASB-UHFFFAOYSA-N hept-2-ene Chemical compound CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 claims abstract description 53
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 10
- 239000000741 silica gel Substances 0.000 claims abstract description 10
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 10
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims abstract description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 281
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 246
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 196
- 229910052757 nitrogen Inorganic materials 0.000 claims description 104
- 238000003756 stirring Methods 0.000 claims description 98
- 238000006243 chemical reaction Methods 0.000 claims description 79
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 47
- 238000000967 suction filtration Methods 0.000 claims description 43
- 230000002378 acidificating effect Effects 0.000 claims description 38
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 24
- 239000000706 filtrate Substances 0.000 claims description 21
- -1 substituted-phenyl Chemical group 0.000 claims description 18
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 8
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 8
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 claims description 6
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- INKDAKMSOSCDGL-UHFFFAOYSA-N [O].OC1=CC=CC=C1 Chemical compound [O].OC1=CC=CC=C1 INKDAKMSOSCDGL-UHFFFAOYSA-N 0.000 claims description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N methyl alcohol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- 150000002466 imines Chemical class 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 125000004076 pyridyl group Chemical group 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- WEDOZAVIBQNLER-UHFFFAOYSA-N [Ni].[O].[N] Chemical compound [Ni].[O].[N] WEDOZAVIBQNLER-UHFFFAOYSA-N 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 125000004494 ethyl ester group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 2
- 125000000018 nitroso group Chemical group N(=O)* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000000710 polymer precipitation Methods 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 70
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 60
- 239000000126 substance Substances 0.000 description 55
- 125000005574 norbornylene group Chemical group 0.000 description 40
- 230000000694 effects Effects 0.000 description 38
- 239000000178 monomer Substances 0.000 description 37
- 230000009466 transformation Effects 0.000 description 37
- 238000006073 displacement reaction Methods 0.000 description 36
- 238000001914 filtration Methods 0.000 description 36
- 238000001291 vacuum drying Methods 0.000 description 36
- 239000007789 gas Substances 0.000 description 22
- 238000011049 filling Methods 0.000 description 18
- 239000000843 powder Substances 0.000 description 18
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- LUMNWCHHXDUKFI-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enylmethanol Chemical compound C1C2C(CO)CC1C=C2 LUMNWCHHXDUKFI-UHFFFAOYSA-N 0.000 description 3
- 238000012644 addition polymerization Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- FYGUSUBEMUKACF-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carboxylic acid Chemical compound C1C2C(C(=O)O)CC1C=C2 FYGUSUBEMUKACF-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000000460 chlorine Chemical group 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- KUKRLSJNTMLPPK-UHFFFAOYSA-N 4,7,7-trimethylbicyclo[2.2.1]hept-2-ene Chemical group C1CC2(C)C=CC1C2(C)C KUKRLSJNTMLPPK-UHFFFAOYSA-N 0.000 description 1
- YRIYXMAKROEVBQ-UHFFFAOYSA-N 5,5-dimethylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C)(C)CC1C=C2 YRIYXMAKROEVBQ-UHFFFAOYSA-N 0.000 description 1
- UVFFMASFIIKUOD-UHFFFAOYSA-N 5-(chloromethyl)bicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCl)CC1C=C2 UVFFMASFIIKUOD-UHFFFAOYSA-N 0.000 description 1
- WEOXTJYELQBBEK-UHFFFAOYSA-N 5-(isocyanatomethyl)bicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CN=C=O)CC1C=C2 WEOXTJYELQBBEK-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- WTQBISBWKRKLIJ-UHFFFAOYSA-N 5-methylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C)CC1C=C2 WTQBISBWKRKLIJ-UHFFFAOYSA-N 0.000 description 1
- GLVKGYRREXOCIB-UHFFFAOYSA-N Bornylene Natural products CC1CCC(C(C)(C)C)C=C1 GLVKGYRREXOCIB-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000005640 Methyl decanoate Substances 0.000 description 1
- IGHHPVIMEQGKNE-UHFFFAOYSA-N [3-(hydroxymethyl)-2-bicyclo[2.2.1]hept-5-enyl]methanol Chemical compound C1C2C=CC1C(CO)C2CO IGHHPVIMEQGKNE-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- BMAXQTDMWYDIJX-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carbonitrile Chemical compound C1C2C(C#N)CC1C=C2 BMAXQTDMWYDIJX-UHFFFAOYSA-N 0.000 description 1
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- VFHHEWHSMUDLNQ-UHFFFAOYSA-N butyl 2-methylhept-5-enoate Chemical compound CC(CCC=CC)C(=O)OCCCC VFHHEWHSMUDLNQ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- BLQVQLFURKNSON-UHFFFAOYSA-N dibutyl 2-but-2-enyl-3-methylbutanedioate Chemical compound C(CCC)OC(=O)C(C)C(CC=CC)C(=O)OCCCC BLQVQLFURKNSON-UHFFFAOYSA-N 0.000 description 1
- UXRMRBNLTQHPEU-UHFFFAOYSA-N diethyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate Chemical compound C1C2C=CC1C(C(=O)OCC)C2C(=O)OCC UXRMRBNLTQHPEU-UHFFFAOYSA-N 0.000 description 1
- VGQLNJWOULYVFV-UHFFFAOYSA-N dimethyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate Chemical compound C1C2C=CC1C(C(=O)OC)C2C(=O)OC VGQLNJWOULYVFV-UHFFFAOYSA-N 0.000 description 1
- FCCGTJAGEHZPBF-UHFFFAOYSA-N ethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OCC)CC1C=C2 FCCGTJAGEHZPBF-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Chemical group 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011630 iodine Chemical group 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- RMAZRAQKPTXZNL-UHFFFAOYSA-N methyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OC)CC1C=C2 RMAZRAQKPTXZNL-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- VHDXYZOZULHRIL-UHFFFAOYSA-N n,n-dimethylbicyclo[2.2.1]hept-2-ene-5-carboxamide Chemical compound C1C2C(C(=O)N(C)C)CC1C=C2 VHDXYZOZULHRIL-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention relates to a novel compound for bicyclo [2.2.1 ]]A catalytic system for catalyzing polymerization of hept-2-ene and derivatives thereof, a preparation method and application thereof. The catalytic system comprises a carrier, a main catalyst and a cocatalyst, wherein the carrier is a magnesium chloride alcoholate (MgCl)2xROH, x ═ 1-3, ROH is C3－C8Alcohol) or silica gel, the cocatalyst is methylaluminoxane, the main catalyst is a nickel oxynitride complex, and the catalytic system can adopt spherical MgCl2The preparation process of the invention is simple, the raw materials are easy to obtain, the catalytic activity is high,
Description
Technical field
The present invention relates to a kind of supported catalyst system and its production and application, especially a kind of dicyclo [2.2.1] hept-2-ene" and derivatives catalysis polymeric catalyst system thereof and its production and application of being used for.
Background technology
At present, dicyclo [2.2.1] hept-2-ene" is commonly called as norbornylene.Dicyclo [2.2.1] hept-2-ene" and derivative thereof can carry out polymerization by three kinds of modes as shown below:
Different polymerization methodses obtain the polymkeric substance of different structure and character.First kind of polymerization methods is called ring-opening metathesis polymerization (ROMP), still contains two keys in the resulting polymers chain, can be the maximum a kind of norbornene polymerization modes of research by hydrogenation or crosslinked processing to be used for different purposes therefore.Holy second kind of polymerization methods is positively charged ion or radical polymerization mode (cationic or radical), and people understand seldom, and products obtained therefrom also only is that 2,7 of norbornylene connects oligopolymer.In the product of the third polymerization methods, still remain with the twin nuclei of norbornylene, only be to have opened the two keys of π-π, be similar to traditional olefinic polymerization mode, therefore be called as vinyl polymerization (Vinyl polymerization), the vinyl polymerization of this cycloolefin is also referred to as " addition polymerization " (addition polymerization) (US Patent 5468819,5569730 sometimes, 1995) (Japanese Patent, JP 07 18, and 021,[95 18,021]).
Different with the product of first kind of ROMP polymerization methods and second kind of positively charged ion or radical polymerization mode (cationic or radical) gained, vinyl polymerization mode resulting polymers does not contain two keys, and the molecular weight of polymkeric substance is higher.The homogeneous phase vinyl polymerization can obtain the polymer materials of function uniqueness, and many solvents are presented inertia, the characteristics such as optical clarity, very strong anti-ultraviolet radiation ability, high tension fracture value and low-tension that resulting polymers has excellent machining property, has advantages of good caking property, high glass transition, good thermotolerance to become reconciled with metal.The low-k of polynorbornene makes it can be as the interface dielectric medium in the microelectronic device, thereby realizes efficient mutually connection the between the interface; In addition, such polynorbornene material has good viscosity, can be bonded at securely on various films and the substrate.In a word, norbornene polymer can be widely used in top coat or the protective layer of making electrical condenser (comdenser) or thermal insulator (insulator) and liquid-crystal display.At present, four tame well-known Production in Chemical Plant polynorbornene products have been arranged in the world, be respectively the Ticona company of Germany and Nipon Zeon, Mitsui Chemical, three major companies of JSR company of Japan, annual production is approximately 20,000,000 pounds.
Produce a large amount of norbornylene byproducts though petroleum industry is annual,, thereby caused the waste of part bornylene resource because the catalyzer that China does not have to be fit to converts it into norbornene polymer; On the other hand, China's norbornene polymer products such as high price import liquid crystal display surface protective layer of still needing.In order to develop the norbornene polymerization catalyst technology with independent intellectual property right, we have carried out number of research projects (Chinese patent application number: 02126318,02126507,02126508,02126509,200410021218).What above-mentioned technology related to mainly is the rear transition metal nickel catalyzator that reaction has greater activity to norbornene polymerization, can be used in the polymerization in homogeneous phase, but this type of homogeneous catalyst can't directly apply on existing industrial what slurry and the gas phase polymerization apparatus.For making it be applied to industrial production, we have carried out rear transition metal nickel catalyzator load research, and effectively control the particle form of polynorbornene by loadization.
Summary of the invention
The object of the present invention is to provide a kind of dicyclo [2.2.1] hept-2-ene" and derivatives catalysis polymeric load nitrogen-oxygen nickel complex catalytic system thereof; Another object of the present invention is to provide the method for the above-mentioned catalyst system of preparation; Another purpose of the present invention is to provide a kind of application of above-mentioned catalyst system.
Catalyst system provided by the invention comprises carrier, Primary Catalysts and promotor.Described carrier is magnesium chloride alcohol adduct (MgCl
2XROH, x=1～3, ROH is C
3～C
8Pure) or silica gel; Described promotor is that methylaluminoxane (is called for short: MAO); Described Primary Catalysts for two [N-(substituent methyl) salicylic alidehyde imine] nickel (II) [also can be described as two-the 2-[[(substituent methyl) amido] methyl] phenol oxygen base-O, N} nickel (II)], two [the 1-[[(substituted-phenyl) imido grpup] methyl]-2-naphthalene oxygen-nitrogen, oxygen] nickel (II), two [the 1-[[(substituted pyridinyl) imido grpup] methyl]-2-naphthalene oxygen-nitrogen, oxygen] nickel (II), [2-methyl-8-(diphenyl phosphine) quinoline] nickelous chloride, one of { (1-naphthyl) (triphen phosphino-) [2-(4,5 phenylbenzene-3-imidazoles-2-yl)-6-tertiary butyl] phenol oxygen base } nickel (II) or (1-naphthyl) (triphen phosphino-) N-[1-(substituted-phenyl)]-(substituted salicylic aldehydes imido grpup) } nickel (II); Primary Catalysts has following structure:
Two [N-(substituent methyl) salicylic alidehyde imine] nickel (II)
Two [1-[[(substituted-phenyl) imido grpup] methyl]-2-naphthalene oxygen-nitrogen, oxygen] nickel (II) two [1-[[(substituted pyridinyl) imido grpup] methyl]-2-naphthalene oxygen-nitrogen, oxygen] nickel (II)
[2-methyl-8-(diphenyl phosphine) quinoline] nickelous chloride
{ (1-naphthyl) (triphen phosphino-) [2-(4,5 phenylbenzene-3-imidazoles-2-yl)-6-tertiary butyl] phenol oxygen base } nickel (II)
(1-naphthyl) (triphen phosphino-) N-[1-(substituted-phenyl)]-(substituted salicylic aldehydes imido grpup) } nickel (II)
Wherein, R1, R2, R3, R4 are hydrogen, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the tertiary butyl, isobutyl-, phenyl, methoxyl group, oxyethyl group, isopropoxy, nitroso-group, nitro, cyano group, fluorine, chlorine, bromine, iodine etc.
The method of the above-mentioned catalyst system of preparation provided by the invention, a kind of is ball-type MgCl
2Nickel-loaded title complex technology, a kind of is silica gel load nickel complex technology.
1, ball-type MgCl
2Alcohol adduct nickel-loaded title complex processing step is:
By per 1 gram ball-type magnesium chloride alcohol adduct (MgCl
2XROH, x=1～3, ROH=C
3～C
8Alcohol)/and the ratio of 10-100 milliliter hexane, ball-type magnesium chloride alcohol adduct is suspended in the hexane, in-60 ℃～30 ℃ temperature ranges, add the toluene solution of methylaluminoxane, under this temperature, stir suction filtration then, hexane wash, drying; 10～100 milliliters of the toluene solutions of adding 0.01～1 gram Primary Catalysts stir in-60 ℃～100 ℃ temperature ranges; Get final product through aftertreatment.
Last handling process comprises that suction filtration, hexane are washed till that filtrate is colourless substantially, drying etc.Productive rate is about 70～100%.
2, silica gel load nickel complex processing step is:
Be dissolved in 10～100 milliliters of ratios in the hexane in per 1 gram silica gel, silica gel is suspended in the hexane, in-60 ℃～30 ℃ temperature ranges, add the toluene solution of methylaluminoxane, under this temperature, stir, suction filtration then, hexane wash, drying; 10～100 milliliters of the toluene solutions of adding 0.01～1 gram Primary Catalysts stir in-60 ℃～100 ℃ temperature ranges; Get final product through aftertreatment.
Last handling process comprises that suction filtration, hexane are washed till that filtrate is colourless substantially, drying etc.Productive rate is about 70～100%.
The application of catalyst system provided by the invention in the polymerization of dicyclo [2.2.1] hept-2-ene" or derivatives thereof.Under anhydrous, oxygen free condition, Primary Catalysts is suspended in the organic solvent, its ratio is 1 μ mol Primary Catalysts: 2～30ml organic solvent; Add dicyclo [2.2.1] hept-2-ene" or derivatives thereof, the mol ratio 500～100000 of dicyclo [2.2.1] hept-2-ene" or derivatives thereof and Primary Catalysts;-30～180 ℃ of reactions, preferred-30～150 ℃; Add promotor, promotor/Primary Catalysts mol ratio is 50～5000; Add the isopropylcarbinol termination reaction after reacting 5 second～72 hour; Adding acidic alcohol again makes catalyzer and methylaluminoxane decomposition and makes polymer precipitation complete.
Described dicyclo [2.2.1] hept-2-ene" derivative is dicyclo [2.2.1] hept-2-ene" (norbomene), dicyclo [2.2.1] hept-2-ene"-5-nitrile (bicyclo[2,2,1] hept-2-ene-5-carbonitrile), 5-(chloromethyl)-dicyclo [2.2.1] hept-2-ene" (5-(chloromethyl)-bicyclo[2,2,1] hept-2-ene), 5-(methylol)-dicyclo [2.2.1] hept-2-ene" (5-(hydroxymethyl)-bicyclo[2,2,1] hept-2-ene), 5,6-two (methylol)-dicyclo [2.2.1] hept-2-ene" (5,6-bis (hydroxymethyl)-bicyclo[2,2,1] hept-2-ene), two (5-methylol)-dicyclo [2.2.1] hept-2-ene" (bis (5-hydroxymethyl)-bicyclo[2,2,1] hept-2-ene), 5-isocyanatomethyl-dicyclo [2.2.1] hept-2-ene" (5-isocyanatomethylbicyclo[2,2,1] hept-2-ene), N, N-dimethyl dicyclo [2.2.1] hept-2-ene"-5-methane amide (N, N-dimethylbicyclo[2,2,1] hept-2-ene-5-carboxamide), 5,5-dimethyl dicyclo [2.2.1] hept-2-ene" (5,5-dimethylbicyclo[2,2,1] hept-2-ene), 1,1-dioxy tetramethylene sulfide-3-base dicyclo [2.2.1] hept-2-ene"-5-methyl ether (1,1-dioxotetrahydrothien-3-y1bicyclo[2,2,1] hept-2-ene-5-methyl ether), acetic acid (dicyclo [2.2.1] heptan-5-alkene-2-first) ester (bicyclo[2,2,1] hept-5-ene-2-methyl acetate), capric acid (dicyclo [2.2.1] heptan-5-alkene-2-first) ester (bicyclo[2,2,1] hept-5-ene-2-methyl decanoate), dicyclo [2.2.1] heptan-5-alkene-2-carboxylate methyl ester (bicyclo[2,2,1] hept-5-ene-2-carboxylic acid methyl ester), dicyclo [2.2.1] heptan-5-alkene-2-methyl alcohol (bicyclo[2,2,1] hept-5-ene-2-methanol), dicyclo [2.2.1] heptan-5-alkene-2-carboxylic acid, ethyl ester (bicyclo[2,2,1] hept-5-ene-2-carboxylic acid ethyl ester), dicyclo [2.2.1] heptan-positive butyl ester (bicyclo[2 of 5-alkene-2-carboxylic acid, 2,1] hept-5-ene-2-carboxylic acid n-butyl ester), dicyclo [2.2.1] heptan-5-alkene-2-carboxylic acid isobutyl ester (bicyclo[2,2,1] hept-5-ene-2-carboxylic acidiso-butyl ester), dicyclo [2.2.1] heptan-5-alkene-2-carboxylic acid (bicyclo[2,2,1] hept-5-ene-2-carboxylic acid), 5-methylene radical-dicyclo [2.2.1] hept-2-ene" (5-methylene-bicyclo[2,2,1] hept-2-ene), 5-ethylidene-dicyclo [2.2.1] hept-2-ene" (5-vinylbicyclo[2,2,1] hept-2-ene), dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxylic anhydride (carbic anhydride), dicyclo [2.2.1] heptan-5-alkene-2,3-dimethyl dicarboxylate (bicyclo[2,2,1] hept-5-ene-2,3-dicarboxylic acid dimethyl ester), dicyclo [2.2.1] heptan-5-alkene-2,3-diethyl dicarboxylate (bicyclo[2,2,1] hept-5-ene-2,3-dicarboxylic acid diethyl ester), dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxylic acid di-n-butyl (bicyclo[2, hept-5-ene-2,3-dicarboxylic acid di-n-butyl ester) or dicyclo [2.2.1] heptan-5-alkene-2 2,1], 3-diisobutyl dicarboxylate (bicyclo[2,2,1] hept-5-ene-2,3-dicarboxylic aciddi-isobutyl ester).
Described organic solvent is methylene dichloride, toluene, chlorobenzene, 1,2-dichlorobenzene, normal hexane, normal heptane, Nitromethane 99Min., 1,2-ethylene dichloride or 1,2,4-trichlorobenzene.
Effect of the present invention is mainly reflected in the following aspects:
1, catalyst system preparation technology of the present invention is simple, and raw material is easy to get.
2, catalyst system of the present invention can be applicable to the vinyl polymerization (addition polymerization) of dicyclo [2.2.1] hept-2-ene" and derivative thereof, and prepared ball-type carried catalyst sphere is regular, good fluidity, and specific surface area is 0.183m
2/ g～218.6m
2/ g, narrow diameter distribution can be produced spherical polymer preferably simultaneously.Under same polymerizing condition: 1. before the title complex load, monomer almost completely transforms in several minutes, and rate of polymerization is very fast, emits big calorimetric simultaneously, and the polynorbornene that obtains is the bulk polymkeric substance, makes the post-processed step numerous tired; 2. title complex is after load, catalytic polymerization is more steady, transformation efficiency and time are linear, imperceptible tangible heat release takes place, rate of polymerization is controlled, and the polymkeric substance that generates is good spherical polymer, and its form has obtained tangible improvement, make the post-processed work simplification, be easy to industrialization.
3, can be by adjusting the different ratios of MAO/ catalyzer, or the volume by changing reaction solvent (promptly changing the concentration of catalyzer and MAO in the polymerization system), or the method by changing temperature of reaction or solvent is to reach molecular weight and the molecular weight distribution of adjusting polymkeric substance, regulate the form of institute's synthetic polymkeric substance and the purpose of performance, thereby be met dicyclo [2.2.1] hept-2-ene" of different demands and purposes and the polymkeric substance of derivative thereof.
4, the catalytic activity height of catalyst system of the present invention, active in 1 * 10
4～1.02 * 10
6G PNB/ (molNih).
Embodiment
Now in conjunction with the embodiments the present invention is described in detail.
Embodiment 1:
1 supported catalyst preparation process
Vacuum nitrogen filling gas in the reactor repeatedly several times, adds 4.54 gram MgCl
2.2.97C
2H
5OH, and add about 100 ml n-hexanes drips 10% 29.3 milliliters of MAO toluene solutions (greatly in 0.5～1.0 hour) down at-30 ℃, and-30 ℃ were stirred 4 hours down, suction filtration then, and hexane washes twice, drying.
50 milliliters of toluene solutions that add the title complex of 0.1388 gram nickel as shown below, stirring at room 4 hours.It is colourless substantially that suction filtration, hexane are washed till filtrate, dry then, obtains buff powder.
The analytical results of 2 catalyzer
3 norbornene polymerizations:
Polymerisation medium toluene: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.1630 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter toluene, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, in the time of 25 ℃, stir after 5 minutes, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, acidic alcohol (the volume ratio: 5 parts of concentrated hydrochloric acids that adds 100 milliliter 5 ‰ again, 995 parts of ethanol), under room temperature, stirred 10 hours, leave standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 1.4030 grams, transformation efficiency 59.6%, catalyst activity are 2.81 * 10
5GPNB/ (molNi.h).Polymkeric substance weight-average molecular weight (Mw) is 1.61 * 10
6, Mw/Mn is 4.91.
Polymerisation medium hexane: will have the 100 milliliters of Sch of exsiccant that stir magneton] the enk bottle, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.1630 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter hexane, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, in the time of 25 ℃, stir after 5 minutes, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction added 5 milliliters of isopropylcarbinols and stops polymerization after 1 hour in the time of 25 ℃, added 100 milliliter 5 ‰ acidic alcohol (volume ratio) again, under room temperature, stirred 10 hours, leave standstill 2 hours after-filtration then, resulting polymers gets polymkeric substance 1.1900 grams in 80 ℃ of vacuum-dryings 48 hours, transformation efficiency 50.6%, catalyst activity are 2.38 * 10
5GPNB/ (molNi.h).Polymkeric substance weight-average molecular weight (Mw) is 1.87 * 10
6, Mw/Mn is 3.85.
Embodiment 2:
1 supported catalyst preparation process
Vacuum nitrogen filling gas in the reactor repeatedly several times, adds 5.48 gram MgCl
22.97C
2H
5OH, and add about 100 ml n-hexanes drips 10% 35.4 milliliters of MAO toluene solutions (greatly in 0.5～1.0 hour) down at 0 ℃, and 0 ℃ was stirred 4 hours down, suction filtration then, and hexane washes twice, drying.
50 milliliters of toluene solutions that add the title complex of following 0.1675 gram nickel, stirring at room 4 hours.It is colourless substantially that suction filtration, hexane are washed till filtrate, dry then, obtains buff powder.
The analytical results of 2 catalyzer
3 norbornene polymerizations:
Polymerisation medium toluene: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.1048 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter toluene, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 1.0036 grams, transformation efficiency 42.7%, catalyst activity are 2.01 * 10
5GPNB/ (molNih).Polymkeric substance weight-average molecular weight (Mw) is 1.39 * 10
6, Mw/Mn is 5.55.
Polymerisation medium hexane: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.1048 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter hexane, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 0.4613 gram, transformation efficiency 19.6%, catalyst activity are 0.92 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=1.15 (deciliter/gram).
Embodiment 3:
1 supported catalyst preparation process
Vacuum nitrogen filling gas in the reactor repeatedly several times, adds 3.42 gram MgCl
22.97C
2H
5OH, and add about 100 ml n-hexanes drips 10% 33.9 milliliters of MAO toluene solutions (greatly in 0.5～1.0 hour) down at-30 ℃, and-30 ℃ were stirred 4 hours down, suction filtration then, and hexane washes twice, drying.
50 milliliters of toluene solutions that add the title complex of 0.4182 gram nickel as shown below, stirring at room 4 hours.It is colourless substantially that suction filtration, hexane are washed till filtrate, dry then, obtains buff powder.
The analytical results of 2 catalyzer
3 norbornene polymerizations:
Polymerisation medium toluene: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.0381 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter toluene, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 0.9910 gram, transformation efficiency 42.1%, catalyst activity are 1.98 * 10
5GPNB/ (molNih).Polymkeric substance weight-average molecular weight (Mw) is 2.17 * 10
6, Mw/Mn is 6.42.
Polymerisation medium hexane: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.0381 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter hexane, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 0.4943 gram, transformation efficiency 21.0%, catalyst activity are 0.99 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=1.36 (deciliter/gram).
Embodiment 4:
1 supported catalyst preparation process
Handle MgCl with gas fluidized bed
22.97C
2H
5OH, 30 milliliters of per seconds of nitrogen flow rate, 120 ℃ of temperature, obtain MgCl at 2 hours time
20.38C
2H
5OH.
Vacuum nitrogen filling gas in the reactor repeatedly several times, adds 3.90 gram MgCl
20.38C
2H
5OH, and add about 100 ml n-hexanes drips 10% 31.0 milliliters of MAO toluene solutions (greatly in 0.5～1.0 hour) down at-30 ℃, and-30 ℃ were stirred 4 hours down, suction filtration then, and hexane washes twice, drying.
50 milliliters of toluene solutions that add the title complex of following 0.2424 gram nickel, stirring at room 4 hours.It is colourless substantially that suction filtration, hexane are washed till filtrate, dry then, obtains buff powder.
The analytical results of 2 catalyzer
3 norbornene polymerizations:
Polymerisation medium toluene: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.1129 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter toluene, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 1.2146 grams, transformation efficiency 51.6%, catalyst activity are 2.43 * 10
5GPNB/ (molNih).Polymkeric substance weight-average molecular weight (Mw) is 1.50 * 10
6, Mw/Mn is 5.76.
Polymerisation medium hexane: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.1129 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter hexane, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 0.9580 gram, transformation efficiency 40.7%, catalyst activity are 1.92 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=1.02 (deciliter/gram).
Embodiment 5:
1 supported catalyst preparation process
Handle MgCl with gas fluidized bed
22.97C
2H
5OH, 30 milliliters of per seconds of nitrogen flow rate, 100 ℃ of temperature, obtain MgCl at 2 hours time
21.30C
2H
5OH.
Vacuum nitrogen filling gas in the reactor repeatedly several times, adds 4.14 gram MgCl
21.30C
2H
5OH, and add about 100 ml n-hexanes drips 35.0 milliliters of 10% MAO toluene solutions down at-30 ℃, and-30 ℃ were stirred 4 hours down, suction filtration then, and hexane is washed, drying.
50 milliliters of toluene solutions that add the title complex of following 0.1756 gram nickel, stirring at room 4 hours.It is colourless substantially that suction filtration, hexane are washed till filtrate, dry then, obtains buff powder.
The analytical results of 2 catalyzer
3 norbornene polymerizations:
Polymerisation medium toluene: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.1544 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter toluene, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 1.2672 grams, transformation efficiency 53.8%, catalyst activity are 2.53 * 10
5GPNB/ (molNih).Polymkeric substance weight-average molecular weight (Mw) is 1.52 * 10
6, Mw/Mn is 4.97.
Polymerisation medium hexane: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.1544 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter hexane, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 1.1793 grams, transformation efficiency 50.1%, catalyst activity are 2.36 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=0.98 (deciliter/gram).
Embodiment 6:
1 supported catalyst preparation process
Handle MgCl with gas fluidized bed
22.97C
2H
5OH, 30 milliliters of per seconds of nitrogen flow rate, 80 ℃ of temperature, obtain MgCl at 2 hours time
21.72C
2H
5OH.
Vacuum nitrogen filling gas in the reactor repeatedly several times, adds 3.24 gram MgCl
21.72C
2H
5OH, and add about 100 ml n-hexanes drips 10% 30.0 milliliters of MAO toluene solutions (greatly in 0.5～1.0 hour) down at-30 ℃, and-30 ℃ were stirred 4 hours down, suction filtration then, and hexane washes twice, drying.
50 milliliters of toluene solutions that add the title complex of following 0.1315 gram nickel, stirring at room 4 hours.It is colourless substantially that suction filtration, hexane are washed till filtrate, dry then, obtains buff powder.
The analytical results of 2 catalyzer
3 norbornene polymerizations:
Polymerisation medium toluene: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.1174 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter toluene, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 1.3420 grams, transformation efficiency 57.0%, catalyst activity are 2.68 * 10
5GPNB/ (molNih).Polymkeric substance weight-average molecular weight (Mw) is 1.98 * 10
6, Mw/Mn is 5.70.
Polymerisation medium hexane: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.1174 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter hexane, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 1.2640 grams, transformation efficiency 53.7%, catalyst activity are 2.53 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=1.17 (deciliter/gram).
Embodiment 7:
1 supported catalyst preparation process
Handle MgCl with gas fluidized bed
22.97C
2H
5OH, 30 milliliters of per seconds of nitrogen flow rate, 60 ℃ of temperature, obtain MgCl at 2 hours time
22.44C
2H
5OH.
Vacuum nitrogen filling gas in the reactor repeatedly several times, adds 2.60 gram MgCl
22.44C
2H
5OH, and add about 100 ml n-hexanes drips 10% 20.0 milliliters of MAO toluene solutions (greatly in 0.5-1.0 hour) down at-30 ℃, and-30 ℃ were stirred 4 hours down, suction filtration then, and hexane washes twice, drying.
50 milliliters of toluene solutions that add the title complex of following 0.0888 gram nickel, stirring at room 4 hours.It is colourless substantially that suction filtration, hexane are washed till filtrate, dry then, obtains buff powder.
The analytical results of 2 catalyzer
3 norbornene polymerizations:
Polymerisation medium toluene: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.1087 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter toluene, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 1.2357 grams, transformation efficiency 52.5%, catalyst activity are 2.47 * 10
5GPNB/ (molNih).Polymkeric substance weight-average molecular weight (Mw) is 1.28 * 10
6, Mw/Mn is 5.52.
Polymerisation medium hexane: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.1087 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter hexane, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 1.1816 grams, transformation efficiency 50.2%, catalyst activity are 2.36 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=1.00 (deciliter/gram).
Embodiment 8:
1 supported catalyst preparation process
Vacuum nitrogen filling gas in the reactor repeatedly several times, adds 3.61 gram MgCl
22.97C
2H
5OH, and add about 100 ml n-hexanes drips 10% 24.0 milliliters of MAO toluene solutions (greatly in 0.5-1.0 hour) down at-30 ℃, and-30 ℃ were stirred 4 hours down, suction filtration then, and hexane washes twice, drying.
50 milliliters of toluene solutions that add the title complex of following 0.1026 gram nickel, stirring at room 4 hours.It is colourless substantially that suction filtration, hexane are washed till filtrate, dry then, obtains buff powder.
The analytical results of 2 catalyzer
3 norbornene polymerizations:
Polymerisation medium toluene: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.0587 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter toluene, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 1.1463 grams, transformation efficiency 48.7%, catalyst activity are 2.01 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=0.93 (deciliter/gram).
Polymerisation medium hexane: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.0587 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter hexane, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 0.9392 gram, transformation efficiency 39.9%, catalyst activity are 1.65 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=0.93 (deciliter/gram).
Embodiment 9:
1 supported catalyst preparation process
Vacuum nitrogen filling gas in the reactor repeatedly several times, adds 4.59 gram MgCl
22.97C
2H
5OH, and add about 100 ml n-hexanes drips 10% 32.5 milliliters of MAO toluene solutions (greatly in 0.5-1.0 hour) down at-30 ℃, and-30 ℃ were stirred 4 hours down, suction filtration then, and hexane washes twice, drying.
50 milliliters of toluene solutions that add the title complex of following 0.1745 gram nickel, stirring at room 4 hours.It is colourless substantially that suction filtration, hexane are washed till filtrate, dry then, obtains buff powder.
The analytical results of 2 catalyzer
3 norbornene polymerizations:
Polymerisation medium toluene: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.1048 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter toluene, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 1.0757 grams, transformation efficiency 45.7%, catalyst activity are 1.98 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=1.00 (deciliter/gram).
Polymerisation medium hexane: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.1048 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter hexane, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 0.7650 gram, transformation efficiency 32.5%, catalyst activity are 1.53 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=1.06 (deciliter/gram).
Embodiment 10:
1 supported catalyst preparation process
Vacuum nitrogen filling gas in the reactor repeatedly several times, adds 4.22 gram MgCl
22.97C
2H
5OH, and add about 100 ml n-hexanes drips 10% 27.3 milliliters of MAO toluene solutions (greatly in 0.5-1.0 hour) down at-30 ℃, and-30 ℃ were stirred 4 hours down, suction filtration then, and hexane washes twice, drying.
50 milliliters of toluene solutions that add the title complex of following 0.1385 gram nickel, stirring at room 4 hours.It is colourless substantially that suction filtration, hexane are washed till filtrate, dry then, obtains buff powder.
The analytical results of 2 catalyzer
3 norbornene polymerizations:
Polymerisation medium toluene: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.1222 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter toluene, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 0.1342 gram, transformation efficiency 5.7%, catalyst activity are 0.27 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=1.02 (deciliter/gram).
Polymerisation medium hexane: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.1222 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter hexane, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 0.1036 gram, transformation efficiency 4.4%, catalyst activity are 0.21 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=1.03 (deciliter/gram).
Embodiment 11:
1 supported catalyst preparation process
Vacuum nitrogen filling gas in the reactor repeatedly several times, adds 3.40 gram MgCl
22.97C
2H
5OH, and add about 100 ml n-hexanes drips 10% 21.9 milliliters of MAO toluene solutions (greatly in 0.5-1.0 hour) down at-30 ℃, and-30 ℃ were stirred 4 hours down, suction filtration then, and hexane washes twice, drying.
50 milliliters of toluene solutions that add the title complex of following 0.1046 gram nickel, stirring at room 4 hours.It is colourless substantially that suction filtration, hexane are washed till filtrate, dry then, obtains buff powder.
The analytical results of 2 catalyzer
3 norbornene polymerizations:
Polymerisation medium toluene: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.1334 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter toluene, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 0.3695 gram, transformation efficiency 15.7%, catalyst activity are 0.74 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=0.96 (deciliter/gram).
Polymerisation medium hexane: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.1334 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter hexane, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 0.3319 gram, transformation efficiency 14.1%, catalyst activity are 0.70 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=1.06 (deciliter/gram).
Embodiment 12:
1 supported catalyst preparation process
Vacuum nitrogen filling gas in the reactor repeatedly several times, adds 2.50 gram MgCl
22.97C
2H
5OH, and add about 100 ml n-hexanes drips 10% 16.20 milliliters of MAO toluene solutions (greatly in 0.5-1.0 hour) down at-30 ℃, and-30 ℃ were stirred 4 hours down, suction filtration then, and hexane washes twice, drying.
50 milliliters of toluene solutions that add the title complex of following 0.0927 gram nickel, stirring at room 4 hours, it is colourless substantially that suction filtration, hexane are washed till filtrate, dry then, obtains buff powder.
The analytical results of 2 catalyzer
3 norbornene polymerizations:
Polymerisation medium toluene: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.0863 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter toluene, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 0.2824 gram, transformation efficiency 12.0%, catalyst activity are 0.56 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=1.02 (deciliter/gram).
Polymerisation medium hexane: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.0863 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter hexane, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 0.2165 gram, transformation efficiency 9.2%, catalyst activity are 0.43 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=1.20 (deciliter/gram).
Embodiment 13:
1 supported catalyst preparation process
Vacuum nitrogen filling gas in the reactor repeatedly several times, adds 5.60 gram MgCl
22.97C
2H
5OH, and add about 100 ml n-hexanes drips 10% 36.3 milliliters of MAO toluene solutions (greatly in 0.5-1.0 hour) down at-30 ℃, and-30 ℃ were stirred 4 hours down, suction filtration then, and hexane washes twice, drying.
50 milliliters of toluene solutions that add the title complex of following 0.1238 gram nickel, stirring at room 4 hours.It is colourless substantially that suction filtration, hexane are washed till filtrate, dry then, obtains buff powder.
The analytical results of 2 catalyzer
3 norbornene polymerizations:
Polymerisation medium toluene: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.0918 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter toluene, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 1.0427 grams, transformation efficiency 44.3%, catalyst activity are 2.09 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=1.11 (deciliter/gram).
Polymerisation medium hexane: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.0918 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter hexane, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 0.8992 gram, transformation efficiency 38.2%, catalyst activity are 1.80 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=1.07 (deciliter/gram).
Embodiment 14:
1 supported catalyst preparation process
Vacuum nitrogen filling gas in the reactor repeatedly several times, adds 3.50 gram MgCl
22.97C
2H
5OH, and add about 100 ml n-hexanes drips 10% 22.7 milliliters of MAO toluene solutions (greatly in 0.5-1.0 hour) down at-30 ℃, and-30 ℃ were stirred 4 hours down, suction filtration then, and hexane washes twice, drying.
50 milliliters of toluene solutions that add the title complex of following 0.1382 gram nickel, stirring at room 4 hours.It is colourless substantially that suction filtration, hexane are washed till filtrate, dry then, obtains buff powder.
The analytical results of 2 catalyzer
3 norbornene polymerizations:
Polymerisation medium toluene: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.1727 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter toluene, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 1.2146 grams, transformation efficiency 51.6%, catalyst activity are 2.43 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=1.11 (deciliter/gram).
Polymerisation medium hexane: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.1727 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter hexane, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 1.2381 grams, transformation efficiency 52.6%, catalyst activity are 2.48 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=0.98 (deciliter/gram).
Embodiment 15:
1 supported catalyst preparation process
Vacuum nitrogen filling gas in the reactor repeatedly several times, adds 3.06 gram MgCl
22.97C
2H
5OH, and add about 100 ml n-hexanes drips 10% 19.8 milliliters of MAO toluene solutions (greatly in 0.5-1.0 hour) down at-30 ℃, and-30 ℃ were stirred 4 hours down, suction filtration then, and hexane washes twice, drying.
50 milliliters of toluene solutions that add the title complex of following 0.1461 gram nickel, stirring at room 4 hours.It is colourless substantially that suction filtration, hexane are washed till filtrate, dry then, obtains buff powder.
The analytical results of 2 catalyzer
3 norbornene polymerizations:
Polymerisation medium toluene: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.1398 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter toluene, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 0.9462 gram, transformation efficiency 40.2%, catalyst activity are 1.89 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=1.09 (deciliter/gram).
Polymerisation medium hexane: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.1398 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter hexane, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 0.8262 gram, transformation efficiency 35.1%, catalyst activity are 1.65 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=1.00 (deciliter/gram).
Embodiment 16:
1 supported catalyst preparation process
Vacuum nitrogen filling gas in the reactor repeatedly several times, adds 2.64 gram silica gel-955, and add about 100 ml n-hexanes, and under-30 ℃, drip 10% 30.0 milliliters of MAO toluene solutions (greatly in 0.5-1.0 hour) ,-30 ℃ were stirred 4 hours down, suction filtration then, hexane washes twice, drying.
50 milliliters of toluene solutions that add the title complex of following 0.4445 gram nickel, stirring at room 4 hours.It is colourless substantially that suction filtration, hexane are washed till filtrate, dry then, obtains buff powder.
The analytical results of 2 catalyzer
3 norbornene polymerizations:
Polymerisation medium toluene: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.0367 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter toluene, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 1.3111 grams, transformation efficiency 55.7%, catalyst activity are 2.62 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=1.07 (deciliter/gram).
Polymerisation medium hexane: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.0367 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter hexane, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 1.2193 grams, transformation efficiency 51.8%, catalyst activity are 2.44 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=1.10 (deciliter/gram).
Embodiment 17:
1 supported catalyst preparation process
Vacuum nitrogen filling gas in the reactor repeatedly several times, adds 3.17 gram silica gel-955, and add about 100 ml n-hexanes, and under-30 ℃, drip 10% 15.0 milliliters of MAO toluene solutions (greatly in 0.5-1.0 hour) ,-30 ℃ were stirred 4 hours down, suction filtration then, hexane washes twice, drying.
50 milliliters of toluene solutions that add the title complex of following 0.4872 gram nickel, stirring at room 4 hours.It is colourless substantially that suction filtration, hexane are washed till filtrate, dry then, obtains buff powder.
The analytical results of 2 catalyzer
3 norbornene polymerizations:
Polymerisation medium toluene: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.0358 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter toluene, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 1.3017 grams, transformation efficiency 55.3%, catalyst activity are 2.60 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=1.06 (deciliter/gram).
Polymerisation medium hexane: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.0358 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter hexane, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 0.9509 gram, transformation efficiency 40.4%, catalyst activity are 1.90 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=1.11 (deciliter/gram).
Embodiment 18:
1 supported catalyst preparation process
Vacuum nitrogen filling gas in the reactor repeatedly several times, adds 3.54 gram MgCl
2.0.94i-PrOH, and add about 100 ml n-hexanes, drip down 10% 29.3 milliliters of MAO toluene solutions (greatly in 0.5～1.0 hour) at-30 ℃ ,-30 ℃ were stirred 4 hours down, suction filtration then, and hexane washes twice, drying.
50 milliliters of toluene solutions that add the title complex of following 0.1656 gram nickel, stirring at room 4 hours.It is colourless substantially that suction filtration, hexane are washed till filtrate, dry then, obtains buff powder.
The analytical results of 2 catalyzer
3 norbornene polymerizations:
Polymerisation medium toluene: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.1223 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter toluene, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 1.3793 grams, transformation efficiency 58.6%, catalyst activity are 2.76 * 10
5GPNB/ (molNih).Polymkeric substance weight-average molecular weight (Mw) is 1.71 * 106, and Mw/Mn is 5.91.
Polymerisation medium hexane: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add described catalyzer 0.1223 gram of the step 1 that contains 5 μ mol nickel, 14.08 milliliter hexane, add 2.3538 gram norbornylenes (norbornene monomer and catalyst molar ratio are 5000) again, stir after 5 minutes in the time of 25 ℃, add 7.14 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 hour in the time of 25 ℃, add 5 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again stirred 10 hours under room temperature, left standstill 2 hours after-filtration then, resulting polymers was in 80 ℃ of vacuum-dryings 48 hours, get polymkeric substance 1.2146 grams, transformation efficiency 51.6%, catalyst activity are 2.43 * 10
5GPNB/ (molNih).Polymkeric substance weight-average molecular weight (Mw) is 1.77 * 10
6, Mw/Mn is 4.15.
The electron scanning micrograph of carrier, catalyzer and polynorbornene is seen accompanying drawing 1.Among the figure:
(a) ball-type magnesium chloride (MgCl
22.97EtOH) (600 *) photo;
(b) embodiment 6 gained catalyzer (600 *) photos;
(c) embodiment 6 gained ball-type polynorbornene particle (40 *) photos;
(d) embodiment 6 gained ball-type polynorbornene particle (100 *) photos;
(e) scanning electron microscope energy dispersive spectroscopy (EDX) spectrogram of elemental nickel, magnesium, aluminium and the chlorine of embodiment 6 gained catalyzer;
(f) silica gel-955 (450 *) photo;
(g) embodiment 17 gained catalyzer (600 *) photos.
Claims (8)
1. nitrogen-oxygen nickel complex catalytic system comprises carrier, Primary Catalysts and promotor, it is characterized in that: described carrier is magnesium chloride alcohol adduct or silica gel, and the molecular formula of magnesium chloride alcohol adduct is MgCl
2XROH, wherein: x=1-3, ROH=C
3-C
8Alcohol; Promotor is a methylaluminoxane; Primary Catalysts is two [N-(substituent methyl) salicylic alidehyde imine] nickel (II), two [the 1-[[(substituted-phenyl) imido grpup] methyl]-2-naphthalene oxygen-nitrogen, oxygen] nickel (II), two [the 1-[[(substituted pyridinyl) imido grpup] methyl]-2-naphthalene oxygen-nitrogen, oxygen] nickel (II), [2-methyl-8-(diphenyl phosphine) quinoline] nickelous chloride, { [2-(4 for (1-naphthyl) (triphen phosphino-), 5 phenylbenzene-3-imidazoles-2-yl)-and the 6-tertiary butyl] phenol oxygen base } nickel (II), one of or (1-naphthyl) (triphen phosphino-) N-[1-(substituted-phenyl)]-(substituted salicylic aldehydes imido grpup) } nickel (II), its structural formula is expressed as follows:
Two [N-(substituent methyl) salicylic alidehyde imine] nickel (II)
Two [1-[[(substituted-phenyl) imido grpup] methyl]-2-naphthalene oxygen-nitrogen, oxygen] nickel (II) two [1-[[(substituted pyridinyl) imido grpup] methyl]-2-naphthalene oxygen-nitrogen, oxygen] nickel (II)
[2-methyl-8-(diphenyl phosphine) quinoline] nickelous chloride
{ (1-naphthyl) (triphen phosphino-) [2-(4,5 phenylbenzene-3-imidazoles-2-yl)-6-tertiary butyl] phenol oxygen base } nickel (II)
(1-naphthyl) (triphen phosphino-) N-[1-(substituted-phenyl)]-(substituted salicylic aldehydes imido grpup) } nickel (II)
In the Primary Catalysts structural formula: R, R
1, R
2, R
3, R
4Be hydrogen atom, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the tertiary butyl, isobutyl-, phenyl, methoxyl group, oxyethyl group, isopropoxy, nitroso-group, nitro, cyano group, fluorine atom, chlorine atom, bromine atoms, iodine atom.
2,, it is characterized in that its preparation method is to adopt ball-type MgCl according to the described catalyst system of claim 1
2Alcohol adduct nickel-loaded title complex technology the steps include: by per 1 gram ball-type magnesium chloride alcohol adduct (MgCl
2XROH, x=1～3, ROH=C
3～C
8Alcohol)/and the ratio of 10-100 milliliter hexane, ball-type magnesium chloride alcohol adduct is suspended in the hexane, in-60 ℃～30 ℃ temperature ranges, add the toluene solution of methylaluminoxane, under this temperature, stir suction filtration then, hexane wash, drying; 10～100 milliliters of the toluene solutions of adding 0.01～1 gram Primary Catalysts stir in-60 ℃～100 ℃ temperature ranges; Get final product through aftertreatment.
3, according to the described catalyst system of claim 1, it is characterized in that its preparation method is to adopt silica gel load nickel complex technology, the steps include: to be dissolved in 10～100 milliliters of ratios in the hexane in per 1 gram silica gel, silica gel is suspended in the hexane, in-60 ℃～30 ℃ temperature ranges, add the toluene solution of methylaluminoxane, under this temperature, stir, then suction filtration, hexane wash, drying; 10～100 milliliters of the toluene solutions of adding 0.01～1 gram Primary Catalysts stir in-60 ℃～100 ℃ temperature ranges; Get final product through aftertreatment.
4, according to claim 2 or 3 described preparation methods, it is colourless substantially, dry to it is characterized in that wherein last handling process is a suction filtration, hexane is washed till filtrate.
5, the application of the described catalyst system of claim 1 in the polymerization of dicyclo [2.2.1] hept-2-ene" or derivatives thereof, it is characterized in that: under anhydrous, oxygen free condition, Primary Catalysts is suspended in the organic solvent, and its ratio is 1 μ mol Primary Catalysts: 2～30ml organic solvent; Add dicyclo [2.2.1] hept-2-ene" or derivatives thereof, the mol ratio 500～100000 of dicyclo [2.2.1] hept-2-ene" or derivatives thereof and Primary Catalysts;-30～180 ℃ of reactions; Add promotor, promotor/Primary Catalysts mol ratio is 50～5000; Add the isopropylcarbinol termination reaction after reacting 5 second～72 hour; Adding acidic alcohol again makes catalyzer and methylaluminoxane decomposition and makes polymer precipitation complete.
6, application according to claim 5 is characterized in that organic solvent wherein is methylene dichloride, toluene, chlorobenzene, 1,2-dichlorobenzene, normal hexane, normal heptane, Nitromethane 99Min., 1,2-ethylene dichloride or 1,2,4-trichlorobenzene.
7, application according to claim 5 is characterized in that temperature of reaction wherein is-30～150 ℃.
8, application according to claim 5, the derivative that it is characterized in that dicyclo [2.2.1] hept-2-ene" wherein be acetic acid (dicyclo [2.2.1] heptan-5-alkene-2-first) ester, dicyclo [2.2.1] heptan-5-alkene-2-methyl alcohol, dicyclo [2.2.1] heptan-5-alkene-2-carboxylic acid, ethyl ester, dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxylic anhydride, dicyclo [2.2.1] heptan-5-alkene-2, the 3-dimethyl dicarboxylate.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864010A (en) * | 2010-06-21 | 2010-10-20 | 北京大学 | Bimetallic catalyst precursor and application thereof to olefin polymerization or copolymerization |
| JP2011506313A (en) * | 2007-12-05 | 2011-03-03 | エルジー・ケム・リミテッド | Nonmetallocene olefin polymerization catalyst containing tetrazole group and olefin polymerization method using the same |
| CN101633707B (en) * | 2008-07-24 | 2011-06-22 | 中国石油天然气股份有限公司 | Method for copolymerizing ethylene and methyl methacrylate |
| CN114789067A (en) * | 2022-04-26 | 2022-07-26 | 中化泉州石化有限公司 | Ethylene selective oligomerization catalyst composition and preparation method thereof |
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2006
- 2006-06-23 CN CN 200610090009 patent/CN101092459A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011506313A (en) * | 2007-12-05 | 2011-03-03 | エルジー・ケム・リミテッド | Nonmetallocene olefin polymerization catalyst containing tetrazole group and olefin polymerization method using the same |
| US8431660B2 (en) | 2007-12-05 | 2013-04-30 | Lg Chem, Ltd. | Non-metallocene catalysts having tetrazol group for olefin polymerization and polymerizing method of olefin using the same |
| CN101633707B (en) * | 2008-07-24 | 2011-06-22 | 中国石油天然气股份有限公司 | Method for copolymerizing ethylene and methyl methacrylate |
| CN101864010A (en) * | 2010-06-21 | 2010-10-20 | 北京大学 | Bimetallic catalyst precursor and application thereof to olefin polymerization or copolymerization |
| CN114789067A (en) * | 2022-04-26 | 2022-07-26 | 中化泉州石化有限公司 | Ethylene selective oligomerization catalyst composition and preparation method thereof |
| CN114789067B (en) * | 2022-04-26 | 2023-10-27 | 中化泉州石化有限公司 | Ethylene selective oligomerization catalyst composition and preparation method thereof |
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