CN1303115C - Catalysis system of nitrogen-accessory ingredient of oxygen and nickel in use for polymerizaton of norborene and ramification, preparation method and application - Google Patents
Catalysis system of nitrogen-accessory ingredient of oxygen and nickel in use for polymerizaton of norborene and ramification, preparation method and application Download PDFInfo
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- CN1303115C CN1303115C CNB2004100212181A CN200410021218A CN1303115C CN 1303115 C CN1303115 C CN 1303115C CN B2004100212181 A CNB2004100212181 A CN B2004100212181A CN 200410021218 A CN200410021218 A CN 200410021218A CN 1303115 C CN1303115 C CN 1303115C
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- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 15
- 238000006555 catalytic reaction Methods 0.000 title description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title 1
- 239000004615 ingredient Substances 0.000 title 1
- 229910052760 oxygen Inorganic materials 0.000 title 1
- 239000001301 oxygen Substances 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 115
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 62
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims abstract description 47
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims abstract description 43
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical group O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- 239000003446 ligand Substances 0.000 claims abstract description 12
- WARCRYXKINZHGQ-UHFFFAOYSA-N benzohydrazide Chemical class NNC(=O)C1=CC=CC=C1 WARCRYXKINZHGQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- WEDOZAVIBQNLER-UHFFFAOYSA-N [Ni].[O].[N] Chemical compound [Ni].[O].[N] WEDOZAVIBQNLER-UHFFFAOYSA-N 0.000 claims abstract description 9
- AIBQNUOBCRIENU-UHFFFAOYSA-N nickel;dihydrate Chemical compound O.O.[Ni] AIBQNUOBCRIENU-UHFFFAOYSA-N 0.000 claims abstract 4
- VHSVJTYBTJCDFL-UHFFFAOYSA-L 1,2-dimethoxyethane;nickel(2+);dibromide Chemical compound Br[Ni]Br.COCCOC VHSVJTYBTJCDFL-UHFFFAOYSA-L 0.000 claims abstract 2
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims abstract 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 145
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 76
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 76
- 238000003756 stirring Methods 0.000 claims description 62
- 238000006243 chemical reaction Methods 0.000 claims description 51
- 229920000642 polymer Polymers 0.000 claims description 47
- 229910052757 nitrogen Inorganic materials 0.000 claims description 38
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 238000010992 reflux Methods 0.000 claims description 26
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 21
- 239000002244 precipitate Substances 0.000 claims description 16
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 9
- 239000000047 product Substances 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
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- -1 methoxy, ethoxy, isopropoxy Chemical group 0.000 claims description 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000000460 chlorine Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000011630 iodine Chemical group 0.000 claims description 2
- 229910052740 iodine Chemical group 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 2
- 150000002848 norbornenes Chemical class 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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- PFMTUGNLBQSHQC-UHFFFAOYSA-N 4,5-diazafluoren-9-one Chemical group C1=CC=C2C(=O)C3=CC=CN=C3C2=N1 PFMTUGNLBQSHQC-UHFFFAOYSA-N 0.000 claims 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 3
- 239000003426 co-catalyst Substances 0.000 claims 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 2
- JFNLZVQOOSMTJK-UHFFFAOYSA-N norbornene Chemical compound C1C2CCC1C=C2 JFNLZVQOOSMTJK-UHFFFAOYSA-N 0.000 claims 2
- LUMNWCHHXDUKFI-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enylmethanol Chemical compound C1C2C(CO)CC1C=C2 LUMNWCHHXDUKFI-UHFFFAOYSA-N 0.000 claims 1
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 claims 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 1
- 150000001555 benzenes Chemical class 0.000 claims 1
- CPPKAGUPTKIMNP-UHFFFAOYSA-N cyanogen fluoride Chemical group FC#N CPPKAGUPTKIMNP-UHFFFAOYSA-N 0.000 claims 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 claims 1
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 claims 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 3
- HIMJRGGBHZDDQZ-UHFFFAOYSA-N C(=O)NN.C1=CC=CC=C1 Chemical class C(=O)NN.C1=CC=CC=C1 HIMJRGGBHZDDQZ-UHFFFAOYSA-N 0.000 abstract 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 125000005574 norbornylene group Chemical group 0.000 description 31
- 239000000126 substance Substances 0.000 description 25
- 230000000694 effects Effects 0.000 description 20
- 239000000178 monomer Substances 0.000 description 20
- 230000002378 acidificating effect Effects 0.000 description 19
- 230000009466 transformation Effects 0.000 description 19
- 150000001298 alcohols Chemical class 0.000 description 18
- 238000006073 displacement reaction Methods 0.000 description 18
- 238000001914 filtration Methods 0.000 description 18
- 238000001291 vacuum drying Methods 0.000 description 18
- 229960000935 dehydrated alcohol Drugs 0.000 description 17
- 229960004756 ethanol Drugs 0.000 description 14
- 238000001953 recrystallisation Methods 0.000 description 13
- 239000002262 Schiff base Substances 0.000 description 12
- 150000004753 Schiff bases Chemical class 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 7
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N methyl alcohol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- 125000003236 benzoyl group Chemical class [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 125000004494 ethyl ester group Chemical group 0.000 description 4
- OTTZHAVKAVGASB-UHFFFAOYSA-N hept-2-ene Chemical compound CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910000474 mercury oxide Inorganic materials 0.000 description 4
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 4
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 4
- 238000012644 addition polymerization Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- SCZGZDLUGUYLRV-UHFFFAOYSA-N (2-methylphenyl)hydrazine Chemical class CC1=CC=CC=C1NN SCZGZDLUGUYLRV-UHFFFAOYSA-N 0.000 description 2
- XAMBIJWZVIZZOG-UHFFFAOYSA-N (4-methylphenyl)hydrazine Chemical class CC1=CC=C(NN)C=C1 XAMBIJWZVIZZOG-UHFFFAOYSA-N 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- ZLWLTDZLUVBSRJ-UHFFFAOYSA-K chembl2360149 Chemical compound [Na+].[Na+].[Na+].O=C1C(N=NC=2C=CC(=CC=2)S([O-])(=O)=O)=C(C(=O)[O-])NN1C1=CC=C(S([O-])(=O)=O)C=C1 ZLWLTDZLUVBSRJ-UHFFFAOYSA-K 0.000 description 2
- 150000002220 fluorenes Chemical class 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
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GPTOGZLZMLJZCV-UHFFFAOYSA-N (3-methylphenyl)hydrazine Chemical class CC1=CC=CC(NN)=C1 GPTOGZLZMLJZCV-UHFFFAOYSA-N 0.000 description 1
- KPPNLSKVTKSSTG-UHFFFAOYSA-N 2-chlorobenzohydrazide Chemical class NNC(=O)C1=CC=CC=C1Cl KPPNLSKVTKSSTG-UHFFFAOYSA-N 0.000 description 1
- YJCCKQQVXNNAAR-UHFFFAOYSA-N 2-fluorobenzohydrazide Chemical class NNC(=O)C1=CC=CC=C1F YJCCKQQVXNNAAR-UHFFFAOYSA-N 0.000 description 1
- VMZSDAQEWPNOIB-UHFFFAOYSA-N 3-methoxybenzohydrazide Chemical class COC1=CC=CC(C(=O)NN)=C1 VMZSDAQEWPNOIB-UHFFFAOYSA-N 0.000 description 1
- UIVXXFYJRYVRKJ-UHFFFAOYSA-N 4-fluorobenzohydrazide Chemical class NNC(=O)C1=CC=C(F)C=C1 UIVXXFYJRYVRKJ-UHFFFAOYSA-N 0.000 description 1
- REKQLYUAUXYJSZ-UHFFFAOYSA-N 4-methoxybenzohydrazide Chemical class COC1=CC=C(C(=O)NN)C=C1 REKQLYUAUXYJSZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- HEGVYZJCELUPOJ-UHFFFAOYSA-N [N].[O].[Ti] Chemical compound [N].[O].[Ti] HEGVYZJCELUPOJ-UHFFFAOYSA-N 0.000 description 1
- ANMIZSGJINIIAN-UHFFFAOYSA-N [N].[O].[Zr] Chemical compound [N].[O].[Zr] ANMIZSGJINIIAN-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000011243 crosslinked material Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical class [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000710 polymer precipitation Methods 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention provides a nitrogen-oxygen nickel coordination compound catalytic system used for polymerizing norbornene and derivates thereof, and a preparation method and the application thereof. The catalytic system used for polymerization is composed of a main catalyst of a nitrogen-oxygen nickel coordination compound of bi(4, 5-diazafluorene-9-ketone substituted benzoyl hydrazone)II nickel dihydrate (A)or bromized bi(2-pyridylaldehyde substituted benzoyl hydrazone)II nickel (B) and methylaluminoxane as a catalyst promoter. In the preparation method of the nitrogen-oxygen nickel coordination compound as the main catalyst, firstly, substituted benzene formyl hydrazine and 4, 5-diazafluorene-9-ketone or 2-pyridylaldehyde are prepared into N-O bidentate ligands; then, the ligands react with nickelous acetate tetrahydrate or 1, 2-dimethoxyethane nickel bromide for respectively preparing the main catalyst (A) or (B). The present invention has the advantages of simple technology, easy raw material obtainment, little using quantity of methylaluminoxane, low aluminum nickel ratio, low cost and high catalytic activity (1*10<4> to 1.41*10<6>g PNB/mol Ni. h); the yield of polynorbornene and derivates thereof can reach 20 to 100%, and the molecular weight and the molecular weight distribution can be adjusted within a very large range.
Description
Technical field
The present invention relates to a kind of norbornylene and derivative polymeric nitrogen-oxygen nickel complex catalytic system thereof and its production and application of being used in the high molecular polymer.
Background technology
Dicyclo [2,2,1] hept-2-ene" is commonly called as and is norbornylene.Norbornylene and derivative thereof can illustrate three kinds of modes by figure below and carry out polymerization
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 contain two keys in the resulting polymers chain, therefore can be by hydrogenation or the crosslinked material that is applicable to different purposes that is processed into, be the maximum a kind of norbornene polymerization mode of research, industrial polynorbornene Norsorex technology is exactly the application of ROMP in actual production.Second kind of polymerization methods about norbornylene is positively charged ion or radical polymerization mode (cationic or radical), and it is few that people understand, and products obtained therefrom also only is that 2,7 of norbornylene connects oligopolymer.In the third polymerization methods, still the twin nuclei that has kept norbornylene in the product, only be to have opened the two keys of π-π, be similar to traditional olefinic polymerization mode, therefore be called as vinyl polymerization (Vinylpolymerization), sometimes the vinyl polymerization of this cycloolefin is also referred to as " addition polymerization " (additionpolymerization) (US Patent 5468819,5569730,1995) (Japanese Patent, JP 07 18,021[9518,021]).
Different with first kind of ROMP polymerization methods and second kind of positively charged ion or radical polymerization mode (cationic or radical) products obtained therefrom, vinyl polymerization mode resulting polymers no longer contains two keys, and can obtain the polymkeric substance of higher molecular weight.The homogeneous phase vinyl polymerization can obtain the polymer materials of function uniqueness, and many solvents are presented inertia.Resulting polymers not only has excellent machining property, metal had advantages of good caking property, and has high glass transition, has the optical clarity that good thermotolerance is become reconciled, has very strong anti-ultraviolet radiation ability (can be used as protective material), high tension fracture value and low-tension (preparing high transparent film); The low-k of polynorbornene makes it can be used 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 is 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 Nipon Zeon of the Ticona company and the Japan of Germany, Mitsui Chemical, JSR company, annual production is approximately 20,000,000 pounds.
Every year is produced a large amount of norbornylene byproducts in petrochemical industry, still, because China does not have catalyzer well to convert it into norbornene polymer, and most norbornylene resource is wasted.Simultaneously, China needs the norbornene polymers such as sealer of high price import liquid-crystal display.In order to develop the catalysis technique of norbornene polymerization with China's independent intellectual property rights, we have carried out number of research projects (Chinese patent application number: 02126318.3,02126507.0,02126509.7, granted patent number: ZL 02 126508.9), have great importance for the norbornene polymerization industry of development China.Relevant phenol hydrazone class early transition metal title complex is used for the patented material (application number: 03158058.0) that vinyl polymerization catalysis has formed " a kind of nitrogen-oxygen titanium or nitrogen-oxygen zirconium complex catalyst system "; For acylhydrazone class nickel complex, discover to have good norbornene polymerization catalyst activity, be necessary to carry out patent protection.
Summary of the invention
The invention provides a kind of preparation method and application that is used for norbornylene and derivative polymeric nitrogen-oxygen nickel complex catalytic system and nitrogen-oxygen nickel complex.
Catalyst system provided by the invention, comprise Primary Catalysts and promotor, described Primary Catalysts is nitrogen-oxygen nickel complex-two [4,5-diaza fluorenes-9-ketone-substituted benzoyl acylhydrazone] II nickel two water (A) or two (2-pyridylaldehyde substituted benzoyl acylhydrazone) the II nickel (B) of bromination, described promotor is methylaluminoxane (MAO), Primary Catalysts (A) or (B) and the mol ratio of promotor be 1: 50-5000; Primary Catalysts has following structure:
Wherein, R is 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.
(I) N, the preparation of O bitooth ligand:
By every 1mmol 4,5-diaza fluorenes-9-ketone or 2-pyridylaldehyde are dissolved in the ratio in the 2-10 milliliter dehydrated alcohol, and with 4,5-diaza fluorenes-9-ketone or 2-pyridylaldehyde are dissolved in the dehydrated alcohol, and add the p-methyl benzenesulfonic acid of catalytic amount, reflux and stirred 5-30 minute down; The substituted benzoyl hydrazides was joined in 1: 1 in molar ratio in the ethanol solution of diaza fluorenes-9-ketone or 2-pyridylaldehyde; Stir down at 40-100 ℃, reacted 4-10 hour; Concentrated solution is to original 1/3, filter yellow mercury oxide or white precipitate.Yellow mercury oxide or white precipitate recrystallization in dehydrated alcohol gets yellow crystal or white crystals, productive rate 70-100%.
(II) preparation of two [4,5-diaza fluorenes-9-ketone-substituted benzoyl acylhydrazone] II nickel two water (A) of Primary Catalysts;
With the yellow crystal N of step (I) preparation, the O bitooth ligand is dissolved in the 10-50 milliliter dehydrated alcohol by every 1mmol, stirs and makes solution 1 in 5-60 minute; Four hydration nickel acetates are dissolved in ratio in the 5-20 milliliter dehydrated alcohol in every 1mmol, make solution 2;
Stir down, press N, the mol ratio 2 of O bitooth ligand and nickel acetate: 0.8-1 splashes into solution 2 in the solution 1, reacts 1-12 hour, filters, and obtains product.
(III) preparation of two (2-pyridylaldehyde substituted benzoyl acylhydrazone) the II nickel (B) of Primary Catalysts bromination:
With the white crystals N of step (I) preparation, the O bitooth ligand is dissolved in the 10-50 milliliter methylene dichloride by every 1mmol, stirs and makes solution 1; With 1,2-glycol dimethyl ether nickelous bromide is dissolved in ratio in the 5-20 milliliter methylene dichloride in every 1mmol, makes solution 2;
Stir down, press N, O bitooth ligand and 1, the mol ratio 2 of 2-glycol dimethyl ether nickelous bromide: 0.8-1.0 splashes into solution 2 in the solution 1, reacts 1-12 hour, filters, and obtains product.
Catalyst body provided by the invention ties up to the application in the polymerization of norbornylene or derivatives thereof, under nitrogen environment, be dissolved in the organic solvent with Primary Catalysts (A) or (B), its ratio is 1 μ mol: the 2-20 milliliter, add the norbornylene or derivatives thereof again, norbornylene or derivatives thereof and Primary Catalysts (A) or mol ratio 500-100000 (B): 1,-30-180 ℃ of reaction, preferably-30-150 ℃, add the promotor methylaluminoxane, promotor/Primary Catalysts mol ratio is 50-5000: 1, after reacting 5 seconds to 72 hour, add 2-15 milliliter isopropylcarbinol and stop polyreaction, add 5 ‰ acidic alcohol of 20-500 milliliter again, make Primary Catalysts (A) or (B) and methylaluminoxane decompose, and make polymer precipitation complete.
Described norbornene derivative is dicyclo [2,2,1] hept-2-ene", 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, the 3-dimethyl dicarboxylate.
Described organic solvent is selected from methylene dichloride, toluene, chlorobenzene, 1,2-dichlorobenzene, normal heptane, Nitromethane 99Min., 1,2-ethylene dichloride or 1,2,4-trichlorobenzene.
Catalyst system of the present invention has following feature:
1, catalyst system therefor preparation of the present invention is simple, and raw material is easy to get.
2, catalyst system of the present invention has been realized the vinyl polymerization (addition polymerization) to norbornylene and derivative thereof, resulting polymkeric substance 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 by changing temperature of reaction or solvent to reach molecular weight and the molecular weight distribution of adjusting polymkeric substance, the purpose of telomerized polymer form and performance, thus be met the norbornylene of different demands and purposes and the polymkeric substance of derivative thereof.
3, catalyst system catalytic activity height of the present invention, active in 1 * 10
4-1.41 * 10
6GPNB/ (molNih).
Embodiment
Embodiment 1
1.N the preparation of O part: with 3 mmoles (mmol) 4,5-diaza fluorenes-9-ketone is dissolved in 30 milliliters of (ml) dehydrated alcohols, and adds the p-methyl benzenesulfonic acid of catalytic amount, refluxes and stirs 10 minutes; 3 mmole benzoyl hydrazines are joined 4, in the ethanol solution of 5-diaza fluorenes-9-ketone; Backflow stirring reaction 5 hours, concentrated solution be to original 1/3, filter the yellow-white precipitation.Yellow-white is deposited in recrystallization in the dehydrated alcohol, gets the yellow-white crystallization.Yield: 90 (13.7%), 154 (7.9%), 139 (3.6%), 122 (10.1%), 105 (100%), 94 (5.6%), 77 (33.7%).
2. Preparation of catalysts: reflux down, the above-mentioned yellow schiff bases of 1 mmole is dissolved in 15 milliliters of dehydrated alcohols, drip 10 milliliters of ethanol solutions that are dissolved with 0.5 mmole, four water acetic acid nickel thereafter, react after 5 hours, filter, get yellow powder.Use hot absolute ethanol washing, yield: 78.7%, ultimate analysis (C
18H
11N
4O) Ni (H
2O)
2Theoretical value: C, 62.36; H, 3,78; N, 16.16%; Measured value: C, 62.56; H, 3.50; N, 16.09%.
3. norbornene polymerization: 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 the described Primary Catalysts of 8 μ mol steps 2,19.13 milliliter methylene dichloride, add 5.44 milliliters of the dichloromethane solutions (norbornene monomer and catalyst molar ratio are 5000) that contain 3.766 gram norbornylenes again, in the time of 25 ℃, stir after 5 minutes, add 0.43 milliliter of promotor MAO (MAO/ Primary Catalysts mol ratio is 75), reaction is after 30 minutes in the time of 25 ℃, add 15 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 80 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 2.84 grams, transformation efficiency 75.5%, catalyst activity are 7.10 * 10
5GPNB/ (mol Nih).Polymer property viscosity [η]=1.86 (deciliter/gram).
Embodiment 2-7
The N of embodiment 2-embodiment 7, the O part is identical with enforcement 1 with Preparation of catalysts, the condition of norbornene polymerization and the results are shown in Table 1:
Table 1 embodiment 2-7 norbornylene is in different catalysts ratio and polymerization temperature, the experimental data of time
| Embodiment | Norbornylene (monomer) (g) | Primary Catalysts (μ mol) | Methylene dichloride (ml) | Monomer/Primary Catalysts (mol) | Promotor (ml) | Help/lead (mol) | Polymerization temperature (℃) | Polymerization time (branch) | Polymer output (g) | Transformation efficiency (%) | Catalyst activity (gPNB/mol Nih) | Polymer property viscosities il (deciliter/gram) |
| 2 | 3.766 | 8 | 24.57 | 5000 | 0.43 | 75 | 25 | 120 | 3.62 | 96.2 | 4.53×10 5 | 1.48 |
| 3 | 3.766 | 8 | 24.43 | 5000 | 0.57 | 75 | 25 | 30 | 3.76 | 100.0 | 9.42×10 5 | 1.48 |
| 4 | 3.766 | 8 | 24.57 | 5000 | 0.43 | 75 | -5 | 30 | 1.41 | 37.6 | 3.54×10 5 | 1.58 |
| 5 | 3.766 | 8 | 24.57 | 5000 | 0.43 | 75 | 35 | 30 | 2.38 | 63.3 | 5.76×10 5 | 1.15 |
| 6 | 1.883 | 8 | 24.57 | 2500 | 0.43 | 75 | 25 | 30 | 0.87 | 46.6 | 2.19×10 5 | 0.79 |
| 7 | 7.532 | 8 | 24.57 | 10000 | 0.43 | 75 | 25 | 30 | 3.26 | 43.3 | 8.15×10 5 | 2.58 |
Embodiment 8
1, Preparation of catalysts: the preparation method is with embodiment one.
2, norbornene polymerization: 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 the described catalyzer of 5 μ mol steps 2,19.32 milliliter toluene, add 3.89 milliliters of the toluene solutions (norbornene monomer and catalyst molar ratio are 5000) that contain 2.3538 gram norbornylenes again, stir after 5 minutes in the time of 25 ℃, add 1.79 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 500), reaction is after 240 minutes in the time of 25 ℃, add 15 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 80 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 1.54 grams, transformation efficiency 65.6%, catalyst activity are 7.72 * 10
4GPNB/ (mol Nih).Polymer property viscosity [η]=1.49 (deciliter/gram).
Embodiment 9
1, Preparation of catalysts: the preparation method is with embodiment one.
2, norbornene polymerization: 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 the described catalyzer of 5 μ mol steps 2,16.03 milliliter heptane, add 3.61 milliliters of the n-heptane solutions (norbornene monomer and catalyst molar ratio are 5000) that contain 2.3538 gram norbornylenes again, stir after 5 minutes in the time of 25 ℃, add 5.36 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 1500), reaction is after 120 minutes in the time of 25 ℃, add 15 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 80 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 1.69 grams, transformation efficiency 71.8%, catalyst activity are 1.69 * 10
5GPNB/ (mol Nih).Polymer property viscosity [η]=1.48 (deciliter/gram).
Embodiment 10
1, N, the preparation of O part: with 3 mmoles (mmol) 4,5-diaza fluorenes-9-ketone is dissolved in 30 milliliters of (ml) dehydrated alcohols, and adds catalytic amount to this sulfonic acid of methyl, refluxes and stirs 10 minutes; 3 mmole 2-fluorobenzoyl hydrazines are joined 4, in the ethanol solution of 5-diaza fluorenes-9-ketone; Backflow stirring reaction 5 hours, concentrated solution be to original 1/3, filter yellow mercury oxide.Yellow mercury oxide is recrystallization in dehydrated alcohol, gets yellow crystal.Yield: 74.2%,
1H-NMR (d-DMSO, 300MHz): δ 7.40-7.58 (m, 3H), 7.60-7.72 (m, 3H), 7.88 (s, IH), 8.60 (s, 1H), 8.74-8.79 (m, 2H), 12.18 (NH).
2, Preparation of catalysts: reflux down, in 15 milliliters of dehydrated alcohols of the above-mentioned yellow schiff bases dissolving of 1 mmole, drip 10 milliliters of ethanol solutions that are dissolved with 0.5 mmole, four water acetic acid nickel thereafter, react after 5 hours, filter, get orange-yellow powder.Use hot absolute ethanol washing, yield: 78.2%, ultimate analysis (C
18H
11N
4O) Ni (H
2O)
20.5C
2H
5OH theoretical value: C, 59.07; H, 3.62; N, 14.89%; Measured value: C, 59.18; H3.31; N, 14.57%.
3, norbornene polymerization: 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 the described catalyzer of 8 μ mol steps 2,19.13 milliliter methylene dichloride, add 5.44 milliliters of the dichloromethane solutions (norbornene monomer and catalyst molar ratio are 5000) that contain 3.766 gram norbornylenes again, in the time of 25 ℃, stir after 5 minutes, add 0.43 milliliter of promotor MAO (the MAO/ catalyst molar ratio is 75), reaction is after 30 minutes in the time of 25 ℃, add 15 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 80 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 1.48 grams, transformation efficiency 39.3%, catalyst activity are 3.70 * 10
5GPNB/ (mol Nih).Polymer property viscosity [η]=1.53 (deciliter/gram).
Embodiment 11
1, N, the preparation of O part: with 3 mmoles (mmol) 4,5-diaza fluorenes-9-ketone is dissolved in 30 milliliters of (ml) dehydrated alcohols, and adds the catalytic amount p-methyl benzenesulfonic acid, refluxes and stirs 10 minutes; 3 mmole 4-fluorobenzoyl hydrazines are joined 4, in the ethanol solution of 5-diaza fluorenes 9-ketone; Backflow stirring reaction 5 hours, concentrated solution be to original 1/3, filter the yellow-white precipitation.Yellow-white is deposited in recrystallization in the dehydrated alcohol, gets the yellow-white crystallization.Yield: 78.4%,
1H-NMR (d-DMSO, 300MHz): δ 7.47 (s, 1H), 7.49-7.60 (m, 3H), 7.85-7.88 (d, 2H), 8.35-8.35 (d, 1H), 8.66-8.90 (m, 3H), 9.64 (NH).
2, Preparation of catalysts: reflux down, in 15 milliliters of dehydrated alcohols of the above-mentioned yellow schiff bases dissolving of 1 mmole, drip 10 milliliters of ethanol solutions that are dissolved with 0.5 mmole, four water acetic acid nickel thereafter, react after 5 hours, filter, get orange-yellow powder.Hot absolute ethanol washing, yield: 78.7%, ultimate analysis (C
18H
11N
4O) Ni (H
2O)
20.5C
2H
5OH theoretical value: C, 59.07; H, 3.62; N, 14.89%; Measured value: C, 59.46; H, 3.33; N, 14.23%.
3, norbornene polymerization: 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 the described catalyzer of 8 μ mol steps 2,19.13 milliliter methylene dichloride, add 5.44 milliliters of the dichloromethane solutions (norbornene monomer and catalyst molar ratio are 5000) that contain 3.766 gram norbornylenes again, in the time of 25 ℃, stir after 5 minutes, add 0.43 milliliter of promotor MAO (the MAO/ catalyst molar ratio is 75), reaction is after 30 minutes in the time of 25 ℃, add 15 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 80 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 1.03 grams, transformation efficiency 27.5%, catalyst activity are 2.59 * 10
5GPNB/ (mol Nih).Polymer property viscosity [η]=1.63 (deciliter/gram).
Embodiment 12
1, N, the preparation of O part: with 3 mmoles (mmol) 4,5-diaza fluorenes-9-ketone is dissolved in 30 milliliters of (ml) dehydrated alcohols, and adds the catalytic amount p-methyl benzenesulfonic acid, refluxes and stirs 10 minutes; 3 mmole 2-toluyl hydrazines are joined 4, in the ethanol solution of 5-diaza fluorenes 9-ketone; Backflow stirring reaction 5 hours, concentrated solution be to original 1/3, filter the yellow-white precipitation.Yellow-white is deposited in recrystallization in the dehydrated alcohol, gets the yellow-white crystallization.Yield: 79.2%,
1H-NMR (d-DMSO, 300MHZ): δ 2.55 (s, 3H), 7.29-7.58 (m, 6H), 8.20 (s, 2H), 8.74 (d, 1H), 8.81 (d, 1H), 9.90 (NH).
2, Preparation of catalysts: reflux down, in 15 milliliters of dehydrated alcohols of the above-mentioned yellow schiff bases dissolving of 1 mmole, drip 10 milliliters of ethanol solutions that are dissolved with 0.5 mmole, four water acetic acid nickel thereafter, react after 5 hours, filter, get orange-yellow powder.Hot absolute ethanol washing, yield: 79.2%, ultimate analysis (C
19H
13N
4O) Ni (H
2O)
20.5C
2H
5OH theoretical value: C, 62.92; H, 4.47; N, 15.05%; Measured value: C, 62.95; H, 3.88; N, 14.68%.
3, norbornene polymerization: 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 the described catalyzer of 8 μ mol steps 2,19.13 milliliter methylene dichloride, add 5.44 milliliters of the dichloromethane solutions (norbornene monomer and catalyst molar ratio are 5000) that contain 3.766 gram norbornylenes again, in the time of 25 ℃, stir after 5 minutes, add 0.43 milliliter of promotor MAO (the MAO/ catalyst molar ratio is 75), reaction is after 30 minutes in the time of 25 ℃, add 15 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 80 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 0.56 gram, transformation efficiency 15.1%, catalyst activity are 1.42 * 10
5GPNB/ (mol Nih).Polymer property viscosity [η]=1.30 (deciliter/gram).
Embodiment 13
1, N, the preparation of O part: with 3 mmoles (mmol) 4,5-diaza fluorenes-9-ketone is dissolved in 30 milliliters of (ml) dehydrated alcohols, and adds the catalytic amount p-methyl benzenesulfonic acid, refluxes and stirs 10 minutes; 3 mmole 3-toluyl hydrazines are joined 4, in the ethanol solution of 5-diaza fluorenes-9-ketone; Backflow stirring reaction 5 hours, concentrated solution be to original 1/3, filter the yellow-white precipitation.Yellow-white is deposited in recrystallization in the dehydrated alcohol, gets the yellow-white crystallization.Yield: 82.1%,
1H-NMR (d-DMSO 300MHZ): δ 2.48 (s, 3H), 7.21-7.46 (m, 4H), 7.75 (s, 1H), 7.82 (s, 1H), 8.17-8.23 (t, 2H), 8.74-876 (d, IH), 8.80-8.82 (d, 1H), 10.03 (NH).
2, Preparation of catalysts: reflux down, in 15 milliliters of dehydrated alcohols of the above-mentioned yellow schiff bases dissolving of 1 mmole, drip 10 milliliters of ethanol solutions that are dissolved with 0.5 mmole, four water acetic acid nickel thereafter, react after 5 hours, filter, get orange-yellow powder.Hot absolute ethanol washing, yield: 78.7%, ultimate analysis (C
19H
13N
4O) Ni (H
2O)
2C
2H
5OH theoretical value: C, 62.60; H, 4.73; N, 14.60%; Measured value: C, 62.57; H, 4.28; N, 14.14%.
3, norbornene polymerization: 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 the described catalyzer of 8 μ mol steps 2,19.13 milliliter methylene dichloride, add 5.44 milliliters of the dichloromethane solutions (norbornene monomer and catalyst molar ratio are 5000) that contain 3.766 gram norbornylenes again, in the time of 25 ℃, stir after 5 minutes, add 0.43 milliliter of promotor MAO (the MAO/ catalyst molar ratio is 75), reaction is after 30 minutes in the time of 25 ℃, add 15 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 80 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 1.08 grams, transformation efficiency 28.8%, catalyst activity are 2.71 * 10
5GPNB/ (mol Nih).Polymer property viscosity [η]=1.77 (deciliter/gram).
Embodiment 14
1, N, the preparation of O part: with 3 mmoles (mmol) 4,5-diaza fluorenes-9-ketone is dissolved in 30 milliliters of (ml) dehydrated alcohols, and adds the catalytic amount p-methyl benzenesulfonic acid, refluxes and stirs 10 minutes; 3 mmole 4-toluyl hydrazines are joined 4, in the ethanol solution of 5-diaza fluorenes-9-ketone; Backflow stirring reaction 5 hours, concentrated solution be to original 1/3, filter the yellow-white precipitation.Yellow-white is deposited in recrystallization in the dehydrated alcohol, gets the yellow-white crystallization.Yield: 90.3%,
1H-NMR (d-DMSO, 300MHz): δ 2.48 (s, 3H), 7.27-7.44 (m, 4H), 7.89-7.91 (d, 2H), 8.18-8.21 (d, 2H) 8.74-8.76 (d, 1H), 8.80-8.82 (d, 1H), 10.00 (NH).
2, Preparation of catalysts: reflux down, in 15 milliliters of dehydrated alcohols of the above-mentioned yellow schiff bases dissolving of 1 mmole, drip 10 milliliters of ethanol solutions that are dissolved with 0.5 mmole, four water acetic acid nickel thereafter, react after 5 hours, filter, get orange powder.Hot absolute ethanol washing, yield: 79.3%, ultimate analysis (C
19H
13N
4O) NiH
2OC
2H
5OH theoretical value: C, 64.10; H, 4.57; N, 14.95%; Measured value: C, 64.56; H, 4.51; N, 14.27%.
3, norbornene polymerization: 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 the described catalyzer of 8 μ mool steps 2,19.13 milliliter methylene dichloride, add 5.44 milliliters of the dichloromethane solutions (norbornene monomer and catalyst molar ratio are 5000) that contain 3.766 gram norbornylenes again, in the time of 25 ℃, stir after 5 minutes, add 0.43 milliliter of promotor MAO (the MAO/ catalyst molar ratio is 75), reaction is after 30 minutes in the time of 25 ℃, add 15 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 80 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 1.01 grams, transformation efficiency 26.9%, catalyst activity are 2.53 * 10
5GPNB/ (mol Nih).Polymer property viscosity [η]=1.55 (deciliter/gram).
Embodiment 15
1, N, the preparation of O part: 3 mmoles (mmol) 2-pyridylaldehyde is dissolved in 30 milliliters of (ml) dehydrated alcohols, and adds the catalytic amount p-methyl benzenesulfonic acid, reflux and stirred 10 minutes; 3 mmole benzoyl hydrazines are joined in the ethanol solution of 2-pyridylaldehyde: backflow stirring reaction 5 hours, concentrated solution be to original 1/3, filter white precipitate.White precipitate is recrystallization in dehydrated alcohol, gets white crystals.Yield: 91.8%,
1H-NMR (d-CDCl
3, 300MHz): δ 7.39-7.41 (m, 1H), 7.51-7.59 (m, 5H), 7.90-7.94 (m, 1H), 8.01-8.03 (d, J=7.5Hz, 2H), 8.74-8.75 (d, J=4.5Hz, 1H), 15.47 (s, 1H).
2, Preparation of catalysts: reflux down, in 15 milliliters of methylene dichloride of the above-mentioned white schiff bases dissolving of 1 mmole, drip 10 milliliters thereafter and be dissolved with 0.5 mmole 1, the dichloromethane solution of 2-glycol dimethyl ether nickelous bromide, react after 5 hours, filter, get green powder.Washed with dichloromethane, yield: 82.0%, ultimate analysis C
26H
22N
6O
2NiBr
2Theoretical value: C, 46.68; H, 3.31; N, 12.56%; Measured value: C, 46.37; H, 3.40; N, 12.37%.
3, norbornene polymerization: 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 the described catalyzer of 8 μ mol steps 2,19.13 milliliter methylene dichloride, add 5.44 milliliters of the dichloromethane solutions (norbornene monomer and catalyst molar ratio are 5000) that contain 3.766 gram norbornylenes again, stir after 5 minutes in the time of 25 ℃, add 0.43 milliliter of promotor MAO (the MAO/ catalyst molar ratio is 75), reaction is after 30 minutes in the time of 25 ℃, add 15 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 80 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 2.94 grams, transformation efficiency 78%, catalyst activity are 7.34 * 10
5GPNB/ (mol Nih).Polymer property viscosity [η]=1.85 (deciliter/gram).
Embodiment 16
1, N, the preparation of O part: 3 mmoles (mmol) 2-pyridylaldehyde is dissolved in 30 milliliters of (ml) dehydrated alcohols, and adds the catalytic amount p-methyl benzenesulfonic acid, reflux and stirred 10 minutes; 3 mmole 2-toluyl hydrazines are joined in the anhydrous acetic acid solution of 2-pyridylaldehyde: backflow stirring reaction 5 hours, concentrated solution be to original 1/3, filter white precipitate.White precipitate is recrystallization in dehydrated alcohol, gets white crystals.Yield: 87.1%,
1H-NMR (d-CDCl
3, 300MHz): δ 2.57 (s, 3H), 7.13-7.59 (m, 7H), 7.86 (s, 1H), 8.55 (s, 1H), 14.92 (s, NH).
2, Preparation of catalysts: reflux down, in 15 milliliters of methylene dichloride of the above-mentioned white schiff bases dissolving of 1 mmole, drip 10 milliliters thereafter and be dissolved with 0.5 mmole 1, the dichloromethane solution of 2-glycol dimethyl ether nickelous bromide, react after 5 hours, filter, get green powder.Washed with dichloromethane, yield: 83.2%, ultimate analysis C
28H
26N
6O
2NiBr
2H
2O.Theoretical value: C, 46.68; H, 3.31; N, 12.56%; Measured value: C, 46.37; H, 3.40; N, 12.37%.
3, norbornene polymerization: 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 the described catalyzer of 8 μ mol steps 2,19.13 milliliter methylene dichloride, add 5.44 milliliters of the dichloromethane solutions (norbornene monomer and catalyst molar ratio are 5000) that contain 3.766 gram norbornylenes again, stir after 5 minutes in the time of 25 ℃, add 0.43 milliliter of promotor MAO (the MAO/ catalyst molar ratio is 75), reaction is after 30 minutes in the time of 25 ℃, add 15 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 80 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 2.79 grams, transformation efficiency 74%, catalyst activity are 6.97 * 10
5GPNB/ (mol Nih).Polymer property viscosity [η]=1.90 (deciliter/gram).
Embodiment 17
1, N, the preparation of O part: 3 mmoles (mmol) 2-pyridylaldehyde is dissolved in 30 milliliters of (ml) dehydrated alcohols, and adds the catalytic amount p-methyl benzenesulfonic acid, reflux and stirred 10 minutes; 3 mmole 4-toluyl hydrazines are joined in the anhydrous acetic acid solution of 2-pyridylaldehyde: backflow stirring reaction 5 hours, concentrated solution be to original 1/3, filter white precipitate.White precipitate is recrystallization in dehydrated alcohol, gets white crystals.Yield: 95.2%,
1H-NMR (d-CDCl
3, 300MHz): δ 2.40 (s, 3H), 7.30-7.39 (m, 3H), 7.48-7.51 (d, J=9Hz, 2H), 7.89 (s, 3H), 8.71 (s, 1H), 15.47 (s, NH).
2, Preparation of catalysts: reflux down, in 15 milliliters of methylene dichloride of the above-mentioned white schiff bases dissolving of 1 mmole, drip 10 milliliters thereafter and be dissolved with 0.5 mmole 1, the dichloromethane solution of 2-glycol dimethyl ether nickelous bromide, react after 5 hours, filter, get green powder.Washed with dichloromethane, yield: 82.0%, ultimate analysis C
28H
26N
6O
2NiBr
20.5H
2O theoretical value: C, 47.46; H, 3.76; N, 11.76%; Measured value: C, 47.63; H, 3.85; N, 11.90%.
3, norbornene polymerization: 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 the described catalyzer of 8 μ mol steps 2,19.13 milliliter methylene dichloride, add 5.44 milliliters of the dichloromethane solutions (norbornene monomer and catalyst molar ratio are 5000) that contain 3.766 gram norbornylenes again, stir after 5 minutes in the time of 25 ℃, add 0.43 milliliter of promotor MAO (the MAO/ catalyst molar ratio is 75), reaction is after 30 minutes in the time of 25 ℃, add 15 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 80 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 2.45 grams, transformation efficiency 65%, catalyst activity are 6.12 * 10
5GPNB/ (mol Nih).Polymer property viscosity [η]=1.53 (deciliter/gram).
Embodiment 18
1, N, the preparation of O part: 3 mmoles (mmol) 2-pyridylaldehyde is dissolved in 30 milliliters of (ml) dehydrated alcohols, and adds the catalytic amount p-methyl benzenesulfonic acid, reflux and stirred 10 minutes; 3 mmole 2-chlorobenzoyl hydrazines are joined in the anhydrous acetic acid solution of 2-pyridylaldehyde: backflow stirring reaction 5 hours, concentrated solution be to original 1/3, filter white precipitate.White precipitate is recrystallization in dehydrated alcohol, gets white crystals.Yield: 92.3%,
1H-NMR (d-CDCl
3, 300MHz): δ 7.39-7.59 (m, 5H), 7.69-7.76 (m, 2H), 8.03-8.05 (d, J=7Hz, 1H), 8.79-8.80 (d, J=4Hz, 1H), 14.62 (s, NH).
2, Preparation of catalysts: reflux down, in 15 milliliters of methylene dichloride of the above-mentioned white schiff bases dissolving of 1 mmole, drip 10 milliliters thereafter and be dissolved with 0.5 mmole 1, the dichloromethane solution of 2-glycol dimethyl ether nickelous bromide, react after 5 hours, filter, get green powder.Washed with dichloromethane, yield: 82.0%, ultimate analysis C
26H
20N
6O
2NiBr
2Cl
2H
2O theoretical value: C, 41.31; H, 2.93; N, 11.12%; Measured value: C, 41.27; H, 2.68; N, 11.07%.
3, norbornene polymerization: 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 the described catalyzer of 8 μ mol steps 2,19.13 milliliter methylene dichloride, add 5.44 milliliters of the dichloromethane solutions (norbornene monomer and catalyst molar ratio are 5000) that contain 3.766 gram norbornylenes again, stir after 5 minutes in the time of 25 ℃, add 0.43 milliliter of promotor MAO (the MAO/ catalyst molar ratio is 75), reaction is after 30 minutes in the time of 25 ℃, add 15 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 80 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 2.71 grams, transformation efficiency 72%, catalyst activity are 6.78 * 10
5GPNB/ (mol Nih).Polymer property viscosity [η]=1.95 (deciliter/gram).
Embodiment 19
1, N, the preparation of O part: 3 mmoles (mmol) 2-pyridylaldehyde is dissolved in 30 milliliters of (ml) dehydrated alcohols, and adds the catalytic amount p-methyl benzenesulfonic acid, reflux and stirred 10 minutes; 3 mmole 4-methoxybenzoyl hydrazines are joined in the anhydrous acetic acid solution of 2-pyridylaldehyde: backflow stirring reaction 5 hours, concentrated solution be to original 1/3, filter white precipitate.White precipitate is recrystallization in dehydrated alcohol, gets white crystals.Yield: 83.8%,
1H-NMR (d-CDCl
3, 300MHz): δ 3.84 (s, 3H), 6.95-6.98 (d, J=7Hz, 2H), 7.36 (t, J=5Hz, 1H), 7.45-7.48 (d, J=8Hz, 2H), 7.85-7.96 (m, 3H), 8.72 (s, 1H), 15.38 (s, NH).
2, Preparation of catalysts: reflux down, in 15 milliliters of methylene dichloride of the above-mentioned white schiff bases dissolving of 1 mmole, drip 10 milliliters thereafter and be dissolved with 0.5 mmole 1, the dichloromethane solution of 2-glycol dimethyl ether nickelous bromide, react after 5 hours, filter, get green powder.Washed with dichloromethane, yield: 82.0%, ultimate analysis C
28H
26N
6O
4NiBr
2H
2O theoretical value: C, 45.02; H, 3.78; N, 11.25%; Measured value: C, 45.10; H, 3.47; N, 11.02%.
3, norbornene polymerization: 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 the described catalyzer of 8 μ mol steps 2,19.13 milliliter methylene dichloride, add 5.44 milliliters of the dichloromethane solutions (norbornene monomer and catalyst molar ratio are 5000) that contain 3.766 gram norbornylenes again, stir after 5 minutes in the time of 25 ℃, add 0.43 milliliter of promotor MAO (the MAO/ catalyst molar ratio is 75), reaction is after 30 minutes in the time of 25 ℃, add 15 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 80 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 2.45 grams, transformation efficiency 65%, catalyst activity are 6.12 * 10
5GPNB/ (mol Nih).Polymer property viscosity [η]=1.53 (deciliter/gram).
Embodiment 20
1, N, the preparation of O part: 3 mmoles (mmol) 2-pyridylaldehyde is dissolved in 30 milliliters of (ml) dehydrated alcohols, and adds the catalytic amount p-methyl benzenesulfonic acid, reflux and stirred 10 minutes; 3 mmole 3-methoxybenzoyl hydrazines are joined in the anhydrous acetic acid solution of 2-pyridylaldehyde: backflow stirring reaction 5 hours, concentrated solution be to original 1/3, filter white precipitate.White precipitate is recrystallization in dehydrated alcohol, gets white crystals.Yield: 87.6%,
1H-NMR (d-CDCl
3, 300MHz): δ 3.85 (s, 3H), 7.07-7.09 (d, J=8Hz, 1H), 7.37-7.44 (m, 2H), 7.51-7.54 (d, J=8Hz, 4H), 7.90 (t, J=8Hz, 1H), 8.69-8.70 (d, J=4Hz, 1H), 15.51 (s, NH).
2, Preparation of catalysts: reflux down, in 15 milliliters of methylene dichloride of the above-mentioned white schiff bases dissolving of 1 mmole, drip 10 milliliters thereafter and be dissolved with 0.5 mmole 1, the dichloromethane solution of 2-glycol dimethyl ether nickelous bromide, react after 5 hours, filter, get green powder.Washed with dichloromethane, yield: 82.0%, ultimate analysis C
28H
26N
6O
4NiBr
2H
2O theoretical value: C, 45.02; H, 3.78; N, 11.25%; Measured value: C, 44.82; H, 3.53; N, 11.02%.
3, norbornene polymerization: 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 the described catalyzer of 8 μ mol steps 2,19.13 milliliter methylene dichloride, add 5.44 milliliters of the dichloromethane solutions (norbornene monomer and catalyst molar ratio are 5000) that contain 3.766 gram norbornylenes again, stir after 5 minutes in the time of 25 ℃, add 0.43 milliliter of promotor MAO (the MAO/ catalyst molar ratio is 75), reaction is after 30 minutes in the time of 25 ℃, add 15 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 80 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 2.67 grams, transformation efficiency 71%, catalyst activity are 6.68 * 10
5GPNB/ (mol Nih).Polymer property viscosity [η]=1.86 (deciliter/gram).
Embodiment 21
1, Preparation of catalysts: the preparation method is with embodiment one.
2, acetic acid (dicyclo [2,2,1]-and 5-alkene-2-first) polyisocyanate polyaddition: 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 the described catalyzer of 8 μ mol steps 2,14.59 milliliters of methylene dichloride, add again and contain 6.64 gram acetic acid (dicyclos [2,2,1] heptan-5-alkene-2-first) 9.84 milliliters of (acetic acid (dicyclos [2,2 of dichloromethane solution of ester, 1] heptan-5-alkene-2-first) ester monomer and catalyst molar ratio be 5000), stir after 5 minutes in the time of 25 ℃, add 0.57 milliliter of promotor MAO (the MAO/ catalyst molar ratio is 100), reaction is after 30 minutes in the time of 25 ℃, add 15 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 80 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 5.18 grams, transformation efficiency 78%, catalyst activity are 12.95 * 10
5GPNB/ (mol Nih).Polymer property viscosity [η]=1.75 (deciliter/gram).
Embodiment 22
1, Preparation of catalysts: the preparation method is with embodiment one.
2, dicyclo [2,2,1] heptan-5-alkene-2,3-is methanol polymerized: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, and vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add the described catalyzer of 8 μ mol steps 2,16.75 milliliters of methylene dichloride, add again and contain 4.96 gram dicyclos [2,2,1] heptan-5-alkene-2,7.68 milliliters of (dicyclos [2 of the dichloromethane solution of 3-methyl alcohol, 2,1] heptan-5-alkene-2,3-methyl alcohol monomer and catalyst molar ratio are 5000), in the time of 25 ℃, stir after 5 minutes, add 0.57 milliliter of promotor MAO (the MAO/ catalyst molar ratio is 100), reaction added 15 milliliters of isopropylcarbinols and stops polymerization after 30 minutes in the time of 25 ℃, added 80 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 3.72 grams in 80 ℃ of vacuum-dryings 48 hours, transformation efficiency 75%, catalyst activity are 9.30 * 10
5GPNB/ (mol Nih).Polymer property viscosity [η]=1.96 (deciliter/gram).
Embodiment 23
1, Preparation of catalysts: the preparation method is with embodiment one.
2, dicyclo [2,2,1] heptan-5-alkene-2-carboxylic acid, ethyl ester polymerization: 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 the described catalyzer of 8 μ mol steps 2,14.75 milliliters of methylene dichloride, add again and contain 6.64 gram dicyclos [2,2,1] heptan-9.68 milliliters of (dicyclos [2,2 of dichloromethane solution of 5-alkene-2-carboxylic acid, ethyl ester, 1] heptan-5-alkene-2-carboxylic acid, ethyl ester monomer and catalyst molar ratio are 5000), stir after 5 minutes in the time of 25 ℃, add 0.57 milliliter of promotor MAO (the MAO/ catalyst molar ratio is 100), reaction is after 30 minutes in the time of 25 ℃, add 15 milliliters of isopropylcarbinols and stop polymerization, the acidic alcohol (volume ratio) that adds 80 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 5.44 grams, transformation efficiency 82%, catalyst activity are 13.61 * 10
5GPNB/ (molNih).Polymer property viscosity [η]=1.64 (deciliter/gram).
Embodiment 24
1, Preparation of catalysts: the preparation method is with embodiment one.
2, dicyclo [2,2,1] heptan-5-alkene-2,3-dimethyl dicarboxylate polymerization: will have the 100 milliliters of Schlenk bottles of exsiccant that stir magneton, and vacuumize successively, inflated with nitrogen displacement three times, make reaction system in nitrogen environment, add the described catalyzer of 8 μ mol steps 2,12.33 milliliters of methylene dichloride, add again and contain 8.40 gram dicyclos [2,2,1] heptan-5-alkene-2,12.10 milliliters of (dicyclos [2 of 3-dimethyl dicarboxylate's dichloromethane solution, 2,1] heptan-5-alkene-2,3-dimethyl dicarboxylate monomer and catalyst molar ratio are 5000), in the time of 25 ℃, stir after 5 minutes, add 0.57 milliliter of promotor MAO (the MAO/ catalyst molar ratio is 100), reaction added 15 milliliters of isopropylcarbinols and stops polymerization after 30 minutes in the time of 25 ℃, added 80 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 5.63 grams in 80 ℃ of vacuum-dryings 48 hours, transformation efficiency 67%, catalyst activity are 14.07 * 10
5GPNB/ (mol Nih).Polymer property viscosity [η]=1.56 (deciliter/gram).
Claims (5)
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60223806A (en) * | 1984-04-23 | 1985-11-08 | Dai Ichi Kogyo Seiyaku Co Ltd | Production of composite resin |
| JPH0718021A (en) * | 1993-06-30 | 1995-01-20 | Mitsui Toatsu Chem Inc | Polymerization method of cyclic olefin |
| CN1388140A (en) * | 2002-07-19 | 2003-01-01 | 中国科学院化学研究所 | Nickel compound catalyst system for polymerization of norbornene and its prepn |
| CN1394685A (en) * | 2002-07-19 | 2003-02-05 | 中国科学院化学研究所 | Norbornene catalytic system and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS60223806A (en) * | 1984-04-23 | 1985-11-08 | Dai Ichi Kogyo Seiyaku Co Ltd | Production of composite resin |
| JPH0718021A (en) * | 1993-06-30 | 1995-01-20 | Mitsui Toatsu Chem Inc | Polymerization method of cyclic olefin |
| CN1388140A (en) * | 2002-07-19 | 2003-01-01 | 中国科学院化学研究所 | Nickel compound catalyst system for polymerization of norbornene and its prepn |
| CN1394685A (en) * | 2002-07-19 | 2003-02-05 | 中国科学院化学研究所 | Norbornene catalytic system and its preparation method and application |
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