CN1167720C - A kind of norbornene polymerization catalytic system and preparation method - Google Patents
A kind of norbornene polymerization catalytic system and preparation method Download PDFInfo
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- CN1167720C CN1167720C CNB021263183A CN02126318A CN1167720C CN 1167720 C CN1167720 C CN 1167720C CN B021263183 A CNB021263183 A CN B021263183A CN 02126318 A CN02126318 A CN 02126318A CN 1167720 C CN1167720 C CN 1167720C
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- hydroxy benzaldehyde
- hydroxy
- benzaldehyde
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 59
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims description 49
- 230000003197 catalytic effect Effects 0.000 title abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 106
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims abstract description 46
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 11
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims abstract description 5
- WEDOZAVIBQNLER-UHFFFAOYSA-N [Ni].[O].[N] Chemical compound [Ni].[O].[N] WEDOZAVIBQNLER-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000003756 stirring Methods 0.000 claims description 64
- 125000005574 norbornylene group Chemical group 0.000 claims description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- 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 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- DOHOPUBZLWVZMZ-UHFFFAOYSA-N 3-chloro-2-hydroxybenzaldehyde Chemical class OC1=C(Cl)C=CC=C1C=O DOHOPUBZLWVZMZ-UHFFFAOYSA-N 0.000 claims description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 6
- 239000005695 Ammonium acetate Substances 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 229940043376 ammonium acetate Drugs 0.000 claims description 6
- 235000019257 ammonium acetate Nutrition 0.000 claims description 6
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims description 6
- 238000009792 diffusion process Methods 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- -1 isobutyl- Chemical group 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000012312 sodium hydride Substances 0.000 claims description 6
- HWJJTWWMMHEEAK-UHFFFAOYSA-N 2-hydroxy-3-iodobenzaldehyde Chemical class OC1=C(I)C=CC=C1C=O HWJJTWWMMHEEAK-UHFFFAOYSA-N 0.000 claims description 5
- IYIFOKIWVIENPU-UHFFFAOYSA-N 2-hydroxy-3-naphthalen-1-ylbenzaldehyde Chemical compound OC1=C(C=O)C=CC=C1C1=CC=CC2=CC=CC=C12 IYIFOKIWVIENPU-UHFFFAOYSA-N 0.000 claims description 5
- ROILLNJICXGZQQ-UHFFFAOYSA-N 3-tert-butyl-2-hydroxybenzaldehyde Chemical compound CC(C)(C)C1=CC=CC(C=O)=C1O ROILLNJICXGZQQ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001299 aldehydes Chemical class 0.000 claims description 5
- OEGXBDVJNNPUCE-UHFFFAOYSA-N 2-hydroxy-3,5-bis(2-methylpropyl)benzaldehyde Chemical compound CC(C)CC1=CC(C=O)=C(O)C(CC(C)C)=C1 OEGXBDVJNNPUCE-UHFFFAOYSA-N 0.000 claims description 4
- QFVWZKZXZUKIQH-UHFFFAOYSA-N 2-hydroxy-3,5-di(propan-2-yl)benzaldehyde Chemical compound CC(C)C1=CC(C=O)=C(O)C(C(C)C)=C1 QFVWZKZXZUKIQH-UHFFFAOYSA-N 0.000 claims description 4
- PFPKICDQZCJLSR-UHFFFAOYSA-N 2-hydroxy-3-(2-methylpropyl)benzaldehyde Chemical compound CC(C)CC1=CC=CC(C=O)=C1O PFPKICDQZCJLSR-UHFFFAOYSA-N 0.000 claims description 4
- HHDPXULKSZZACU-UHFFFAOYSA-N 2-hydroxy-4-nitrobenzaldehyde Chemical compound OC1=CC([N+]([O-])=O)=CC=C1C=O HHDPXULKSZZACU-UHFFFAOYSA-N 0.000 claims description 4
- RRIQVLZDOZPJTH-UHFFFAOYSA-N 3,5-di-tert-butyl-2-hydroxybenzaldehyde Chemical compound CC(C)(C)C1=CC(C=O)=C(O)C(C(C)(C)C)=C1 RRIQVLZDOZPJTH-UHFFFAOYSA-N 0.000 claims description 4
- OARBTVZDTRPROC-UHFFFAOYSA-N 3,5-diethyl-2-hydroxybenzaldehyde Chemical compound CCC1=CC(CC)=C(O)C(C=O)=C1 OARBTVZDTRPROC-UHFFFAOYSA-N 0.000 claims description 4
- MSORTWTUEMKQRL-UHFFFAOYSA-N 3-anthracen-1-yl-2-hydroxybenzaldehyde Chemical compound OC1=C(C=O)C=CC=C1C1=CC=CC2=CC3=CC=CC=C3C=C12 MSORTWTUEMKQRL-UHFFFAOYSA-N 0.000 claims description 4
- STBGLXMINLWCNL-UHFFFAOYSA-N 3-bromo-2-hydroxybenzaldehyde Chemical class OC1=C(Br)C=CC=C1C=O STBGLXMINLWCNL-UHFFFAOYSA-N 0.000 claims description 4
- KJDPLFMXUGEZSU-UHFFFAOYSA-N 3-butyl-2-hydroxybenzaldehyde Chemical compound CCCCC1=CC=CC(C=O)=C1O KJDPLFMXUGEZSU-UHFFFAOYSA-N 0.000 claims description 4
- NWDHTEIVMDYWQJ-UHFFFAOYSA-N 3-fluoro-2-hydroxybenzaldehyde Chemical compound OC1=C(F)C=CC=C1C=O NWDHTEIVMDYWQJ-UHFFFAOYSA-N 0.000 claims description 4
- ZRUOTKQBVMWMDK-UHFFFAOYSA-N 6-Oxy-2-methyl-benzaldehyd Natural products CC1=CC=CC(O)=C1C=O ZRUOTKQBVMWMDK-UHFFFAOYSA-N 0.000 claims description 4
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 4
- GEAPDYBQINBSRA-UHFFFAOYSA-N 3-ethyl-2-hydroxybenzaldehyde Chemical compound CCC1=CC=CC(C=O)=C1O GEAPDYBQINBSRA-UHFFFAOYSA-N 0.000 claims description 3
- JODRRPJMQDFCBJ-UHFFFAOYSA-N 2-Hydroxy-4-methylbenzaldehyde Chemical compound CC1=CC=C(C=O)C(O)=C1 JODRRPJMQDFCBJ-UHFFFAOYSA-N 0.000 claims description 2
- FZIBGCDUHZBOLA-UHFFFAOYSA-N 2-fluoro-6-hydroxybenzaldehyde Chemical compound OC1=CC=CC(F)=C1C=O FZIBGCDUHZBOLA-UHFFFAOYSA-N 0.000 claims description 2
- DSXKMMAQDSAZAC-UHFFFAOYSA-N 2-hydroxy-3,5-dimethylbenzaldehyde Chemical compound CC1=CC(C)=C(O)C(C=O)=C1 DSXKMMAQDSAZAC-UHFFFAOYSA-N 0.000 claims description 2
- UPUMRAVJDXWXMP-UHFFFAOYSA-N 2-hydroxy-4-iodobenzaldehyde Chemical compound OC1=CC(I)=CC=C1C=O UPUMRAVJDXWXMP-UHFFFAOYSA-N 0.000 claims description 2
- PDFVIWFKGYODKD-UHFFFAOYSA-N 2-hydroxy-5-iodobenzaldehyde Chemical compound OC1=CC=C(I)C=C1C=O PDFVIWFKGYODKD-UHFFFAOYSA-N 0.000 claims description 2
- ILEIUTCVWLYZOM-UHFFFAOYSA-N 2-hydroxy-5-methylbenzaldehyde Chemical compound CC1=CC=C(O)C(C=O)=C1 ILEIUTCVWLYZOM-UHFFFAOYSA-N 0.000 claims description 2
- IHFRMUGEILMHNU-UHFFFAOYSA-N 2-hydroxy-5-nitrobenzaldehyde Chemical compound OC1=CC=C([N+]([O-])=O)C=C1C=O IHFRMUGEILMHNU-UHFFFAOYSA-N 0.000 claims description 2
- RYWYLFSBHZEAJD-UHFFFAOYSA-N 2-hydroxy-6-nitrobenzaldehyde Chemical compound OC1=CC=CC([N+]([O-])=O)=C1C=O RYWYLFSBHZEAJD-UHFFFAOYSA-N 0.000 claims description 2
- IPPQNXSAJZOTJZ-UHFFFAOYSA-N 3-methylsalicylaldehyde Chemical compound CC1=CC=CC(C=O)=C1O IPPQNXSAJZOTJZ-UHFFFAOYSA-N 0.000 claims description 2
- HXTWKHXDFATMSP-UHFFFAOYSA-N 4-bromo-2-hydroxybenzaldehyde Chemical compound OC1=CC(Br)=CC=C1C=O HXTWKHXDFATMSP-UHFFFAOYSA-N 0.000 claims description 2
- LIEUCMPDXHTPIQ-UHFFFAOYSA-N 4-butyl-2-hydroxybenzaldehyde Chemical compound CCCCC1=CC=C(C=O)C(O)=C1 LIEUCMPDXHTPIQ-UHFFFAOYSA-N 0.000 claims description 2
- QNZWAJZEJAOVPN-UHFFFAOYSA-N 4-chloro-2-hydroxybenzaldehyde Chemical compound OC1=CC(Cl)=CC=C1C=O QNZWAJZEJAOVPN-UHFFFAOYSA-N 0.000 claims description 2
- GBJJCODOZGPTBC-UHFFFAOYSA-N 4-fluoro-2-hydroxybenzaldehyde Chemical compound OC1=CC(F)=CC=C1C=O GBJJCODOZGPTBC-UHFFFAOYSA-N 0.000 claims description 2
- UYRSLWPKZKASRB-UHFFFAOYSA-N 4-tert-butyl-2-hydroxybenzaldehyde Chemical compound CC(C)(C)C1=CC=C(C=O)C(O)=C1 UYRSLWPKZKASRB-UHFFFAOYSA-N 0.000 claims description 2
- RMXFTNYYIDMHAB-UHFFFAOYSA-N 5-butyl-2-hydroxybenzaldehyde Chemical compound CCCCC1=CC=C(O)C(C=O)=C1 RMXFTNYYIDMHAB-UHFFFAOYSA-N 0.000 claims description 2
- FUGKCSRLAQKUHG-UHFFFAOYSA-N 5-chloro-2-hydroxybenzaldehyde Chemical compound OC1=CC=C(Cl)C=C1C=O FUGKCSRLAQKUHG-UHFFFAOYSA-N 0.000 claims description 2
- FDUBQNUDZOGOFE-UHFFFAOYSA-N 5-fluoro-2-hydroxybenzaldehyde Chemical compound OC1=CC=C(F)C=C1C=O FDUBQNUDZOGOFE-UHFFFAOYSA-N 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052740 iodine Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000002685 polymerization catalyst Substances 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
- 238000009826 distribution Methods 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 21
- 229920000636 poly(norbornene) polymer Polymers 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 82
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 50
- 239000000126 substance Substances 0.000 description 46
- 229910052757 nitrogen Inorganic materials 0.000 description 41
- 229920000642 polymer Polymers 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 230000002378 acidificating effect Effects 0.000 description 21
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 21
- 238000006073 displacement reaction Methods 0.000 description 20
- 238000001914 filtration Methods 0.000 description 20
- 239000000178 monomer Substances 0.000 description 20
- 230000009466 transformation Effects 0.000 description 20
- 238000001291 vacuum drying Methods 0.000 description 20
- 239000000047 product Substances 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- NLIZASSFYAXKIH-UHFFFAOYSA-N [Ni].C1(=CC=CC2=CC=CC=C12)C1=C(C=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [Ni].C1(=CC=CC2=CC=CC=C12)C1=C(C=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 NLIZASSFYAXKIH-UHFFFAOYSA-N 0.000 description 8
- OTTZHAVKAVGASB-UHFFFAOYSA-N hept-2-ene Chemical compound CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 6
- UYLRKRLDQUXYKB-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UYLRKRLDQUXYKB-UHFFFAOYSA-N 0.000 description 6
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- 238000012644 addition polymerization Methods 0.000 description 3
- 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 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N methyl alcohol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LUMNWCHHXDUKFI-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enylmethanol Chemical compound C1C2C(CO)CC1C=C2 LUMNWCHHXDUKFI-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000008422 chlorobenzenes Chemical class 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000005516 engineering process 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
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent 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
- 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
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- WREHYJHRNFMNPS-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enylmethyl decanoate Chemical compound C1C2C(COC(=O)CCCCCCCCC)CC1C=C2 WREHYJHRNFMNPS-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- GSXAHMHUZBSEMO-UHFFFAOYSA-N [Ni+2].C1(=CC=CC2=CC=CC=C12)C1=C(C=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [Ni+2].C1(=CC=CC2=CC=CC=C12)C1=C(C=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 GSXAHMHUZBSEMO-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XQMWEVWTNXPXAI-UHFFFAOYSA-N bis(2-methylpropyl) bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate Chemical compound C1C2C=CC1C(C(=O)OCC(C)C)C2C(=O)OCC(C)C XQMWEVWTNXPXAI-UHFFFAOYSA-N 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
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- JFFRIBIWDZTESQ-UHFFFAOYSA-N dibutyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate Chemical compound C1C2C=CC1C(C(=O)OCCCC)C2C(=O)OCCCC JFFRIBIWDZTESQ-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
- 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
- 230000009477 glass transition Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 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
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000710 polymer precipitation Methods 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
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
一种氮-氧镍配合物降冰片烯聚合催化体系，该催化体系由主催化剂[2-(2’-取代-羟基苯基)-4，5-二苯基咪唑]-(1-萘基)-(三苯基膦)镍(II)配合物和助催化剂甲基铝氧烷(MAO)组成。本发明工艺简单，原料易得，成本低，催化活性最高达1.62×109克聚降冰片烯每摩尔催化剂每小时每大气压(1.62×109gPNB/(molNi·h·atm))，且通过改变反应条件，催化剂的活性(1×104-1.62×109gPNB/(molNi·h·atm))以及所得聚降冰片烯产率(20%-100%)，分子量(1×105-3.5×106)和分子量分布(1.5-20)在很大范围内可调。A nitrogen-oxygen nickel complex norbornene polymerization catalytic system, the catalytic system is composed of the main catalyst [2-(2'-substituted-hydroxyl phenyl)-4,5-diphenylimidazole]-(1-naphthyl )-(triphenylphosphine)nickel(II) complex and cocatalyst methylaluminoxane (MAO). The process of the present invention is simple, the raw materials are easily obtained, the cost is low, and the catalytic activity is up to 1.62×10 9 grams of polynorbornene per mole of catalyst per hour per atmospheric pressure (1.62×10 9 gPNB/(molNi·h·atm)). Changing the reaction conditions, catalyst activity (1×10 4 -1.62×10 9 gPNB/(molNi·h·atm)) and yield of polynorbornene (20%-100%), molecular weight (1×10 5 - 3.5×10 6 ) and molecular weight distribution (1.5-20) are adjustable in a wide range.
Description
Technical field
The present invention relates to a kind of norbornylene and derivative polymeric catalyst system thereof of being used for, relate in particular to a kind of norbornylene and derivative polymeric [2-(2 '-substituted 4-hydroxy phenyl)-4,5-diphenyl-imidazole]-complex-catalyzed system of (1-naphthyl)-(triphenylphosphine) nickel (II) thereof of being used for.
The invention still further relates to the preparation method of above-mentioned catalyst system.
The invention still further relates to the purposes of above-mentioned catalyst system in norbornylene and derivative polymerization thereof.
Background technology
Dicyclo [2.2.1] hept-2-ene" is commonly called as and is norbornylene.Norbornylene and derivative thereof can carry out polymerization by three kinds of modes showing down:
Different polymerization methodses obtain the polymkeric substance of different structure and character.First kind of polymerization methods is called ring-opening metathesis polymerization (ROMP), is the maximum a kind of norbornene polymerization mode of research, and 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), the vinyl polymerization of this cycloolefin is also referred to as " addition polymerization " (additionpolymerization) sometimes.
Different with first kind of ROMP polymerization methods and second kind of positively charged ion or radical polymerization mode (cationicor 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, 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.
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.
Summary of the invention
The object of the present invention is to provide a kind of [2-(2 '-substituted 4-hydroxy phenyl)-4,5-diphenyl-imidazole]-complex-catalyzed system of (1-naphthyl)-(triphenylphosphine) nickel (II);
Another object of the present invention is to provide a kind of method for preparing above-mentioned catalyst system;
Another purpose of the present invention is to provide the application of a kind of above-mentioned catalyst system in norbornylene and derivative polymerization thereof.
For achieving the above object, catalyst system provided by the invention comprises Primary Catalysts and promotor, and described Primary Catalysts is [2-(2 '-substituted 4-hydroxy phenyl)-4, the 5-diphenyl-imidazole]-(1-naphthyl)-(triphenylphosphine) nickel (II) title complex, be shown below:
Wherein, R
1Be methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the tertiary butyl, isobutyl-, methoxyl group, oxyethyl group, chlorine atom, bromine atoms or iodine atom.
Described promotor is methylaluminoxane (MAO).
The method of the above-mentioned catalyst system of preparation provided by the invention, its key step comprises:
(A) N, the preparation of O bitooth ligand:
In 3 milliliters of Glacial acetic acid, add respectively: substituted salicylic aldehydes 0.8-1.2 mmole, benzil 0.8-1.5 mmole, ammonium acetate 6.4-7.5 mmole, place flask, after stirring and refluxing 4-15 hour, this mixing solutions is cooled to room temperature, stirs then in the following impouring 500-2500 milliliter saturated sodium bicarbonate solution, obtain white solid, filter, this white solid is dissolved in the 20-300 milliliter methylene dichloride, use Skellysolve A to wherein diffusion, separate out white products, productive rate 85-96%;
Substituted salicylic aldehydes of the present invention is a salicylic aldehyde, the 3-tertiary butyl-2-hydroxy benzaldehyde, the 4-tertiary butyl-2-hydroxy benzaldehyde, 3,5-di-t-butyl-2-hydroxy benzaldehyde, 3-isobutyl--2-hydroxy benzaldehyde, 3-naphthyl-2-hydroxy benzaldehyde, 3-anthryl-2-hydroxy benzaldehyde, 3,5-diisobutyl-2-hydroxy benzaldehyde, 3-normal-butyl-2-hydroxy benzaldehyde, 4-normal-butyl-2-hydroxy benzaldehyde, 5-normal-butyl-2-hydroxy benzaldehyde, 4-nitro-2-hydroxy benzaldehyde, 4-nitroso-group-2-hydroxy benzaldehyde, 5-nitro-2-hydroxy benzaldehyde, 5-nitroso-group-2-hydroxy benzaldehyde, 6-nitro-2-hydroxy benzaldehyde, 6-nitroso-group-2-hydroxy benzaldehyde, 3-methoxyl group-2-hydroxy benzaldehyde, 4-methoxyl group-2-hydroxy benzaldehyde, 5-methoxyl group-2-hydroxy benzaldehyde, 6-methoxyl group-2-hydroxy benzaldehyde, 3,5-two iodo-2-hydroxy benzaldehydes, 4-iodo-2-hydroxy benzaldehyde, 5-iodo-2-hydroxy benzaldehyde, 3,5-two chloro-2-hydroxy benzaldehydes, 3-chloro-2-hydroxy benzaldehyde, 5-chloro-2-hydroxy benzaldehyde, 4-chloro-2-hydroxy benzaldehyde, 3,5-two bromo-2-hydroxy benzaldehydes, 4-fluoro-2-hydroxy benzaldehyde, 5-fluoro-2-hydroxy benzaldehyde, 3-fluoro-2-hydroxy benzaldehyde, 6-fluoro-2-hydroxy benzaldehyde, 3,5-two fluoro-2-hydroxy benzaldehydes, 4-bromo-2-hydroxy benzaldehyde, 3-methyl-2-hydroxy benzaldehyde, 4-methyl-2-hydroxy benzaldehyde, 5-methyl-2-hydroxy benzaldehyde, 6-methyl-2-hydroxy benzaldehyde, 3,5-dimethyl-2-hydroxy benzaldehyde, 3-sec.-propyl-2-hydroxy benzaldehyde, 4-sec.-propyl-2-hydroxy benzaldehyde, 3,5-di-isopropyl-2-hydroxy benzaldehyde, 33-ethyl-2-hydroxy benzaldehyde or 3,5-diethyl-2-hydroxy benzaldehyde.Wherein preferred salicylic aldehyde, 4-methoxyl group-2-hydroxy benzaldehyde, 4-nitro-2-hydroxy benzaldehyde, the 3-tertiary butyl-2-hydroxy benzaldehyde, 3-naphthyl-2-hydroxy benzaldehyde, 3,5-di-t-butyl-2-hydroxy benzaldehyde, 3-isobutyl--2-hydroxy benzaldehyde, 3-anthryl-2-hydroxy benzaldehyde, 3,5-diisobutyl-2-hydroxy benzaldehyde, 3-normal-butyl-2-hydroxy benzaldehyde, 3,5-two iodo-2-hydroxy benzaldehydes, 3,5-two bromo-2-hydroxy benzaldehydes, 3,5-two chloro-2-hydroxy benzaldehydes, 3-sec.-propyl-2-hydroxy benzaldehyde, 3,5-di-isopropyl-2-hydroxy benzaldehyde, 3-ethyl-2-hydroxy benzaldehyde or 3,5-diethyl-2-hydroxy benzaldehyde.
(B) preparation of Primary Catalysts:
Trans-[chlorine (1-naphthyl) (two (triphenylphosphine))] nickel (trans-chloro (1-naphthyl) bis (triphenylphosphane) nickel (II)) is dissolved in ratio in the 5-50ml methylene dichloride in every 1mmol, makes solution 1;
A certain amount of step (A) gained white products is dissolved in the 2-50ml anhydrous tetrahydro furan (THF) by 1mmol, stirs the sodium hydride (NaH) of amount of substance such as adding and white products down, reaction was made solution 2 after 30-120 minute under anhydrous condition;
Stir down, press N, the mol ratio 1 of O bitooth ligand and trans-[chlorine (1-naphthyl) (two (triphenylphosphine))] nickel (trans-chloro (1-naphthyl) bis (triphenylphosphane) nickel (II)): 0.8-1 splashes into solution 1 in the solution 2, reacted 5 minutes to 3 days, filter, obtain product.
The application of catalyst system provided by the invention in the polymerization of norbornylene or derivatives thereof, under the nitrogen environment, Primary Catalysts is dissolved in the organic solvent, its ratio is 1 μ mol: 2-30ml, add norbornylene again, the mol ratio 2000-100000 of norbornylene and Primary Catalysts,-30-120 ℃ of reaction, preferably-15-100 ℃, add promotor, promotor/Primary Catalysts mol ratio is 50-5000, adds 2-15mL isopropylcarbinol termination reaction after reacting 5 second-500 minute, and 5 ‰ the acidic alcohol that adds 50-500ml again makes polymer precipitation complete.
Norbornylene of the present invention can also be its derivative, be specially: dicyclo [2.2.1] hept-2-ene" (norbomene), capric acid (dicyclo [2.2.1] heptan-5-alkene-2-first) ester (bicyclo[2,2,1] hept-5-ene-2-ylmethyl 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 ethylester), 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 acid iso-butyl ester), dicyclo [2.2.1] heptan-5-alkene-2-carboxylic acid (bicyclo[2,2,1] hept-5-ene-2-carboxylic acid), 5-ethylidene-dicyclo [2.2.1] hept-2-ene" (bicyclo[2,2,1] hept-2-ene-5-ethylene), 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[2,2,1] hept-5-ene-2,3-dicarboxylic acid di-n-butyl ester) or dicyclo [2.2.1] heptan-5-alkene-2,3-diisobutyl dicarboxylate (bicyclo[2,2,1] hept-5-ene-2,3-dicarboxylic acid di-isobutyl ester).
Described organic solvent is toluene, chlorobenzene, 1,2-dichlorobenzene, normal hexane, 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, and stable performance.
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 by changing the volume of reaction solvent, 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
4-1.62 * 10
9GPNB/ (molNihatm).
Embodiment
Embodiment one:
1.N, the preparation of O bitooth ligand: with 30 milliliters of Glacial acetic acid, 8.8 the ammonium acetate of the 3-tertiary butyl-2-hydroxy benzaldehyde of mmole (mmol) and the benzil of 8.6 mmoles (mmol) and 64 mmoles (mmol) places 250 milliliters of (mL) round-bottomed flasks, after the stirring and refluxing 4 hours, this mixing solutions is cooled to room temperature, in 500 milliliters of saturated sodium bicarbonate solutions of impouring, obtain white solid under stirring then.Filter, this white solid is dissolved in 50 milliliters of methylene dichloride, to wherein diffusion, separate out white crystal, productive rate 85% with Skellysolve A.Ultimate analysis measured value: C, 81.51; H, 6.55; N, 7.56; O, 4.38%; C
25H
24N
2The theoretical value of O: C, 81.49; H, 6.57; N, 7.60; O, 4.34%;
1H NMR (CDCl
3): 1.49 (s, 9H), 5.31 (s, 1H), 6.85-7.83 (m, 13H), 10.02 (s, 1H);
2. Preparation of catalysts:
The above-mentioned gained white products of 2 mmoles is dissolved in the 20ml anhydrous tetrahydro furan (THF), stir the sodium hydride (NaH) that adds 2 mmoles down, reaction is after 60 minutes under anhydrous condition, stir down, be added dropwise to the dichloromethane solution that 40ml is dissolved with trans-[chlorine (1-naphthyl) (two (triphenylphosphine))] nickel (trans-chloro (1-naphthyl) bis (triphenylphosphane) nickel (II)) (2 mmole), react after 8 hours, filter, obtain product.Ultimate analysis measured value: C, 78.03; H, 5.57; N, 3.44; Ni, 7.18; O, 1.97; P, 3.81%; C
53H
45N
2The theoretical value of NiOP: C, 78.05; H, 5.56; N, 3.43; Ni, 7.20; O, 1.96; P, 3.80%.
3. norbornene polymerization: will have the 250 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 prepared catalyzer of 5 μ mol steps 2,20 milliliters of toluene, add 1.00 gram norbornylenes (norbornene monomer and catalyst molar ratio are 2100) again, stir after 5 minutes in the time of 25 ℃, add 3.6 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 1000), reaction is after 60 minutes in the time of 25 ℃, add the 5ml isopropylcarbinol 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 40 hours, get polymkeric substance 0.5607 gram, transformation efficiency 56.07%, catalyst activity are 1.1 * 10
5GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 8.3 * 10
5, number-average molecular weight (Mn) is 1.9 * 10
5, Mw/Mn is 4.4.
Embodiment two:
1, Preparation of catalysts: the preparation method is with embodiment one.
2, norbornene polymerization: will have the 250 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 prepared catalyzer of 5 μ mol steps 1,20 milliliters of toluene, add 1.00 gram norbornylenes (norbornene monomer and catalyst molar ratio are 2100) again, stir after 5 minutes in the time of 25 ℃, add 5.4 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 1500), reaction is after 60 minutes in the time of 25 ℃, add the 5ml isopropylcarbinol 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 40 hours, get polymkeric substance 0.3480 gram, transformation efficiency 34.8%, catalyst activity are 7.0 * 10
4GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 2.6 * 10
5, number-average molecular weight (Mn) is 1.5 * 10
5, molecular weight distribution is 1.7.
Embodiment three:
1, Preparation of catalysts: the preparation method is with embodiment one.
2, norbornene polymerization: will have the 250 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 prepared catalyzer of 5 micromoles (μ mol) step 1,20 milliliters of toluene, add 1.00 gram norbornylenes (norbornene monomer and catalyst molar ratio are 2100) again, stir after 5 minutes in the time of 25 ℃, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 60 minutes in the time of 25 ℃, add the 5ml isopropylcarbinol 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 40 hours, get polymkeric substance 0.5602 gram, transformation efficiency 56.02%, catalyst activity are 1.1 * 10
5GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 1.2 * 10
6, number-average molecular weight (Mn) is 3.5 * 10
5, molecular weight distribution is 3.4.
Embodiment four:
1, Preparation of catalysts: the preparation method is with embodiment one.
2, norbornene polymerization: will have the 250 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 prepared catalyzer of 5 micromoles (μ mol) step 1,30 milliliters of toluene, add 4.708 gram norbornylenes (norbornene monomer and catalyst molar ratio are 10000) again, stir after 5 minutes in the time of 25 ℃, add 3.6 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 1000), reaction is after 30 minutes in the time of 25 ℃, add the 5ml isopropylcarbinol 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 40 hours, get polymkeric substance 1.8619 grams, transformation efficiency 39.55%, catalyst activity are 7.45 * 10
5GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 5.8 * 10
5, number-average molecular weight (Mn) is 3.2 * 10
5, molecular weight distribution is 1.8.
Embodiment five:
1, Preparation of catalysts: the preparation method is with embodiment one.
2, norbornene polymerization: will have the 250 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 prepared catalyzer of 5 micromoles (μ mol) step 1,30 milliliters of toluene, add 9.415 gram norbornylenes (norbornene monomer and catalyst molar ratio are 20000) again, stir after 5 minutes in the time of 25 ℃, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 1 minute in the time of 25 ℃, add the 5ml isopropylcarbinol 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 40 hours, get polymkeric substance 4.3430 grams, transformation efficiency 46.13%, catalyst activity are 5.21 * 10
7GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 3.9 * 10
5, number-average molecular weight (Mn) is 1.4 * 10
5, molecular weight distribution is 2.8.
Embodiment six:
1, Preparation of catalysts: the preparation method is with embodiment one.
2, norbornene polymerization: will have the 250 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 prepared catalyzer of 5 micromoles (μ mol) step 1,30 milliliters of toluene, add 18.83 gram norbornylenes (norbornene monomer and catalyst molar ratio are 40000) again, in the time of 25 ℃, stir after 5 minutes, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), in the time of 25 ℃, reacted for 20 seconds after, add the 5ml isopropylcarbinol 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 40 hours, get polymkeric substance 5.8178 grams, transformation efficiency 30.90%, catalyst activity are 2.09 * 10
8GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 3.2 * 10
5, number-average molecular weight (Mn) is 2.1 * 10
5, molecular weight distribution is 1.5.
Embodiment seven:
1, Preparation of catalysts: the preparation method is with embodiment one.
2, norbornene polymerization: will have the 250 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 prepared catalyzer of 5 micromoles (μ mol) step 1,30 milliliters of toluene, add 4.708 gram norbornylenes (norbornene monomer and catalyst molar ratio are 10000) again, stir after 5 minutes in the time of 50 ℃, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 30 minutes in the time of 50 ℃, add the 5ml isopropylcarbinol 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 40 hours, get polymkeric substance 2.6355 grams, transformation efficiency 55.95%, catalyst activity are 1.05 * 10
6GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 8.9 * 10
5, number-average molecular weight (Mn) is 2.5 * 10
5, molecular weight distribution is 3.56.
Embodiment eight:
1, Preparation of catalysts: the preparation method is with embodiment one.
2, norbornene polymerization: will have the 250 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 prepared catalyzer of 5 micromoles (μ mol) step 1,30 milliliters of toluene, add 4.708 gram norbornylenes (norbornene monomer and catalyst molar ratio are 10000) again, stir after 5 minutes in the time of 0 ℃, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 30 minutes in the time of 0 ℃, add the 5ml isopropylcarbinol 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 40 hours, get polymkeric substance 2.7135 grams, transformation efficiency 57.64%, catalyst activity are 1.09 * 10
6GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 7.3 * 10
5, number-average molecular weight (Mn) is 3.4 * 10
5, molecular weight distribution is 2.15.
Embodiment nine:
1, Preparation of catalysts: the preparation method is with embodiment one.
2, norbornene polymerization: will have the 250 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 prepared catalyzer of 5 micromoles (μ mol) step 1,30 milliliters of toluene, add 4.708 gram norbornylenes (norbornene monomer and catalyst molar ratio are 10000) again, stir after 5 minutes in the time of 100 ℃, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 30 minutes in the time of 100 ℃, add the 5ml isopropylcarbinol 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 40 hours, get polymkeric substance 1.7685 grams, transformation efficiency 37.56%, catalyst activity are 7.07 * 10
5GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 1.5 * 10
6, number-average molecular weight (Mn) is 1.6 * 10
5, molecular weight distribution is 9.8.
Embodiment ten:
1, Preparation of catalysts: the preparation method is with embodiment one.
2, norbornene polymerization: will have the 250 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 prepared catalyzer of 5 μ mol steps 1,20 milliliter 1, the 2-dichlorobenzene adds 18.832 gram norbornylenes (norbornene monomer and catalyst molar ratio are 40000) again, stirs after 5 minutes in the time of 25 ℃, add 4.3 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 1200), after in the time of 25 ℃, reacting for 6 seconds, add the 5ml isopropylcarbinol and stop polymerization, add 200 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 13.4521 grams in 80 ℃ of vacuum-dryings 40 hours, transformation efficiency 71.43%, catalyst activity are 1.62 * 10
9GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 1.7 * 10
6, number-average molecular weight (Mn) is 6.1 * 10
5, molecular weight distribution is 2.8.
Embodiment 11:
1, N, the preparation of O bitooth ligand: with 30 milliliters of Glacial acetic acid, 8.8 3 of mmole (mmol), the benzil of 5-two iodo-2-hydroxy benzaldehydes and 8.6 mmoles (mmol) and the ammonium acetate of 64 mmoles (mmol) place 250 milliliters of (mL) round-bottomed flasks, after the stirring and refluxing 6 hours, this mixing solutions is cooled to room temperature, in 500 milliliters of saturated sodium bicarbonate solutions of impouring, obtains white solid under stirring then.Filter, in the molten 80 milliliters of methylene dichloride of this white solid, to wherein diffusion, separate out white crystal, productive rate 95% with Skellysolve A.
2, Preparation of catalysts:
The above-mentioned gained white products of 2 mmoles is dissolved in the 20ml anhydrous tetrahydro furan (THF), stir the sodium hydride (NaH) that adds 2 mmoles down, reaction is after 60 minutes under anhydrous condition, stir down, be added dropwise to the dichloromethane solution that 40ml is dissolved with trans-[chlorine (1-naphthyl) (two (triphenylphosphine))] nickel (trans-chloro (1-naphthyl) bis (triphenylphosphane) nickel (II)) (2 mmole), react after 8 hours, filter, obtain product, productive rate 54.62%.
3, norbornene polymerization: will have the 250 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 prepared catalyzer of 5 micromoles (μ mol) step 1,20 milliliter 1, the 2-ethylene dichloride, add again 6.209 the gram dicyclos [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-methyl alcohol monomer and catalyst molar ratio are 10000) stirs after 5 minutes in the time of 25 ℃, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction added the 5ml isopropylcarbinol and stops polymerization after 30 minutes 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 3.7643 in 80 ℃ of vacuum-dryings 40 hours, transformation efficiency 60.63%, catalyst activity are 1.5 * 10
6GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 2.2 * 10
6, number-average molecular weight (Mn) is 3.2 * 10
5, molecular weight distribution is 6.88.
Embodiment 12:
1, Preparation of catalysts: the preparation method is with embodiment 11.
2, norbornene polymerization: will have the 250 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 prepared catalyzer of 5 micromoles (μ mol) step 1,20 milliliters of chlorobenzenes, add 9.416 gram norbornylenes (norbornene monomer and catalyst molar ratio are 20000) again, in the time of 25 ℃, stir after 5 minutes, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), in the time of 25 ℃, reacted for 20 seconds after, add the 5ml isopropylcarbinol 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 40 hours, get polymkeric substance 6.124 grams, transformation efficiency 65.04%, catalyst activity are 2.2 * 10
8GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 3.1 * 10
6, number-average molecular weight (Mn) is 2.2 * 10
5, molecular weight distribution is 14.1.
Embodiment 13:
1.N, the preparation of O bitooth ligand: with 30 milliliters of Glacial acetic acid, 8.8 the ammonium acetate of the 3-methoxyl group-2-hydroxy benzaldehyde of mmole (mmol) and the benzil of 8.6 mmoles (mmol) and 64 mmoles (mmol) places 250 milliliters of (mL) round-bottomed flasks, after the stirring and refluxing 4 hours, this mixing solutions is cooled to room temperature, in 500 milliliters of saturated sodium bicarbonate solutions of impouring, obtain white solid under stirring then.Filter, this white solid is dissolved in 50 milliliters of methylene dichloride, to wherein diffusion, separate out white crystal, productive rate 85% with Skellysolve A.
2. Preparation of catalysts:
The above-mentioned gained white products of 2 mmoles is dissolved in the 20ml anhydrous tetrahydro furan (THF), stir the sodium hydride (NaH) that adds 2 mmoles down, reaction is after 60 minutes under anhydrous condition, stir down, be added dropwise to the dichloromethane solution that 40ml is dissolved with trans-[chlorine (1-naphthyl) (two (triphenylphosphine))] nickel (trans-chloro (1-naphthyl) bis (triphenylphosphane) nickel (II)) (2 mmole), react after 8 hours, filter, obtain product, productive rate 93%.
3, norbornene polymerization: will have the 250 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 prepared catalyzer of 5 micromoles (μ mol) step 1,20 milliliters of toluene, add again 15.219 the gram dicyclos [2.2.1] heptan-5-alkene-2-carboxylate methyl ester (bicyclo[2,2,1] hept-5-ene-2-carboxylic acidmethyl ester) (dicyclo [2.2.1] heptan-5-alkene-2-carboxylate methyl ester monomer and catalyst molar ratio are 20000), stir after 5 minutes in the time of 25 ℃, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 30 minutes in the time of 25 ℃, add the 5ml isopropylcarbinol 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 40 hours, get polymkeric substance 3.326 grams, transformation efficiency 21.85%, catalyst activity are 1.3 * 10
6GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 3.4 * 10
5, number-average molecular weight (Mn) is 2.1 * 10
5, molecular weight distribution is 1.6.
Embodiment 14:
1, Preparation of catalysts: the preparation method is with embodiment 13.
2, norbornene polymerization: will have the 250 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 prepared catalyzer of 5 micromoles (μ mol) step 1,20 milliliters of toluene, add 1.00 gram norbornylenes (norbornene monomer and catalyst molar ratio are 2100) again, stir after 5 minutes in the time of 25 ℃, add 1.8 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 500), reaction is after 30 minutes in the time of 25 ℃, add the 5ml isopropylcarbinol 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 40 hours, get polymkeric substance 0.5653 gram, transformation efficiency 56.53%, catalyst activity are 1.13 * 10
5GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 7.5 * 10
5, number-average molecular weight (Mn) is 3.2 * 10
5, molecular weight distribution is 2.3.
Embodiment 15:
1, Preparation of catalysts: the preparation method is with embodiment 13.
2, norbornene polymerization: will have the 250 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 prepared catalyzer of 5 micromoles (μ mol) step 1,30 milliliters of toluene, add 4.708 gram norbornylenes (norbornene monomer and catalyst molar ratio are 10000) again, stir after 5 minutes in the time of 25 ℃, add 1.8 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 500), reaction is after 30 minutes in the time of 25 ℃, add the 5ml isopropylcarbinol 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 40 hours, get polymkeric substance 1.3580 grams, transformation efficiency 28.84%, catalyst activity are 5.43 * 10
5GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 9.80 * 10
5, number-average molecular weight (Mn) is 2.94 * 10
5, molecular weight distribution is 3.33.
Embodiment 16:
1, N, the preparation of O bitooth ligand: with 30 milliliters of Glacial acetic acid, 8.8 the ammonium acetate of the 3-naphthyl-2-hydroxy benzaldehyde of mmole (mmol) and the benzil of 8.6 mmoles (mmol) and 64 mmoles (mmol) places 250 milliliters of (mL) round-bottomed flasks, after the stirring and refluxing 4 hours, this mixing solutions is cooled to room temperature, in 500 milliliters of saturated sodium bicarbonate solutions of impouring, obtain white solid under stirring then.Filter, this white solid is dissolved in 50 milliliters of methylene dichloride, to wherein diffusion, separate out white crystal, productive rate 85% with Skellysolve A.
2, Preparation of catalysts:
The above-mentioned gained white products of 2 mmoles is dissolved in the 20ml anhydrous tetrahydro furan (THF), stir the sodium hydride (NaH) that adds 2 mmoles down, reaction is after 60 minutes under anhydrous condition, stir down, be added dropwise to the dichloromethane solution that 40ml is dissolved with trans-[chlorine (1-naphthyl) (two (triphenylphosphine))] nickel (trans-chloro (1-naphthyl) bis (triphenylphosphane) nickel (II)) (2 mmole), react after 8 hours, filter, obtain product, productive rate 54%.
3, norbornene polymerization: will have the 250 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 prepared catalyzer of 5 micromoles (μ mol) step 1,30 milliliters of toluene, add 4.708 gram norbornylenes (norbornene monomer and catalyst molar ratio are 10000) again, stir after 5 minutes in the time of 25 ℃, add 10.7 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 3000), reaction is after 30 minutes in the time of 25 ℃, add the 5ml isopropylcarbinol 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 40 hours, get polymkeric substance 1.8645 grams, transformation efficiency 39.60%, catalyst activity are 7.46 * 10
5GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 2.5 * 10
6, number-average molecular weight (Mn) is 3.4 * 10
5, molecular weight distribution is 7.4.
Embodiment 17:
1, Preparation of catalysts: the preparation method is with embodiment 16.
2, norbornene polymerization: will have the 250 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 prepared catalyzer of 5 micromoles (μ mol) step 1,30 milliliters of toluene, add 4.708 gram norbornylenes (norbornene monomer and catalyst molar ratio are 10000) again, stir after 5 minutes in the time of 75 ℃, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 30 minutes in the time of 75 ℃, add the 5ml isopropylcarbinol 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 40 hours, get polymkeric substance 2.1510 grams, transformation efficiency 45.69%, catalyst activity are 8.61 * 10
5GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 1.3 * 10
6, number-average molecular weight (Mn) is 5.1 * 10
5, molecular weight distribution is 2.55.
Embodiment 18:
1, Preparation of catalysts: the preparation method is with embodiment 16.
2, norbornene polymerization: will have the 250 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 prepared catalyzer of 5 micromoles (μ mol) step 1,30 milliliters of toluene, add again 8.31 the gram dicyclos [2.2.1] heptan-5-alkene-2-carboxylic acid, ethyl ester (bicyclo[2,2,1] hept-5-ene-2-carboxylic acidethyl ester) (dicyclo [2.2.1] heptan-5-alkene-2-carboxylic acid, ethyl ester monomer and catalyst molar ratio are 10000), stir after 5 minutes in the time of 75 ℃, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 30 minutes in the time of 75 ℃, add the 5ml isopropylcarbinol 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 40 hours, get polymkeric substance 2.8971 grams, transformation efficiency 34.86%, catalyst activity are 1.16 * 10
6GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 2.3 * 10
6, number-average molecular weight (Mn) is 7.5 * 10
5, molecular weight distribution is 3.07.
Embodiment 19:
1, Preparation of catalysts: the preparation method is with embodiment 16.
2, norbornene polymerization: will have the 250 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 prepared catalyzer of 5 micromoles (μ mol) step 1,30 milliliters of toluene, add again 5.2558 the gram dicyclos [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-dimethyl dicarboxylate monomer and catalyst molar ratio are 5000), in the time of 75 ℃, stir after 5 minutes, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 30 minutes in the time of 75 ℃, add the 5ml isopropylcarbinol and stop polymerization, the acidic alcohol (volume ratio) that adds 100 milliliter 5 ‰ again, under room temperature, stirred 10 hours, leave standstill 2 hours after-filtration then, resulting polymers gets polymkeric substance 1.354 grams in 80 ℃ of vacuum-dryings 40 hours, transformation efficiency 25.76%, catalyst activity are 5.4 * 10
5GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 3.4 * 10
5, number-average molecular weight (Mn) is 1.6 * 10
5, molecular weight distribution is 2.2.
Embodiment 20:
1, Preparation of catalysts: the preparation method is with embodiment 16.
2, norbornene polymerization: will have the 250 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 prepared catalyzer of 5 micromoles (μ mol) step 1,30 milliliters of chlorobenzenes, add 5.3085 gram 5-ethylidene-dicyclo [2.2.1] hept-2-ene" (bicyclo[2 again, 2,1] alkene (norbornene monomer and catalyst molar ratio are 10000) hept-2-ene-5-ethylene), stir after 5 minutes in the time of 75 ℃, add 7.2 milliliters of promotor MAO (the MAO/ catalyst molar ratio is 2000), reaction is after 30 minutes in the time of 75 ℃, add the 5ml isopropylcarbinol 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 40 hours, get polymkeric substance 3.214 grams, transformation efficiency 60.54%, catalyst activity are 1.29 * 10
6GPNB/ (molNihatm).Polymkeric substance weight-average molecular weight (Mw) is 3.1 * 10
6, number-average molecular weight (Mn) is 7.6 * 10
5, molecular weight distribution is 4.08.
Claims (5)
1, a kind of nitrogen-oxygen nickel complex norbornene polymerization catalyst system, comprise Primary Catalysts and promotor, it is characterized in that, described Primary Catalysts is [2-(2 '-substituted 4-hydroxy phenyl)-4, the 5-diphenyl-imidazole]-(1-naphthyl)-(triphenylphosphine) nickel (II) title complex, its structure is shown below:
Wherein, R
1Be methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the tertiary butyl, isobutyl-, methoxyl group, oxyethyl group, chlorine atom, bromine atoms or iodine atom.
Described promotor is a methylaluminoxane.
2, a kind of method for preparing the described catalyst system of claim 1, its key step comprises:
(A) N, the preparation of O bitooth ligand:
In 3 milliliters of Glacial acetic acid, add respectively: substituted salicylic aldehydes 0.8-1.2 mmole, benzil 0.8-1.5 mmole, ammonium acetate 6.4-7.5 mmole, place flask, after stirring and refluxing 4-15 hour, this mixing solutions is cooled to room temperature, in the impouring 500-2500 milliliter saturated sodium bicarbonate solution, obtains white solid under stirring then, filter, this white solid is dissolved in the 20-300 milliliter methylene dichloride, to wherein diffusion, separates out white products with Skellysolve A;
(B) preparation of Primary Catalysts:
Trans-[chlorine (1-naphthyl) (two (triphenylphosphine))] nickel (II) is dissolved in ratio in the 5-50ml methylene dichloride in every 1mmol, makes solution 1;
Step (A) gained white products is dissolved in the 2-50ml anhydrous tetrahydro furan by 1mmol, stirs the sodium hydride that adds down with white products equivalent, reaction was made solution 2 after 30-120 minute under anhydrous condition;
Stir down, press N, the mol ratio 1 of O bitooth ligand and trans-[chlorine (1-naphthyl) (two (triphenylphosphine))] nickel (II): 0.8-1 splashes into solution 1 in the solution 2, reacts 5 minutes-3 days, filters, and obtains product.
3, method as claimed in claim 2, it is characterized in that, substituted salicylic aldehydes described in the steps A is a salicylic aldehyde, the 3-tertiary butyl-2-hydroxy benzaldehyde, the 4-tertiary butyl-2-hydroxy benzaldehyde, 3,5-di-t-butyl-2-hydroxy benzaldehyde, 3-isobutyl--2-hydroxy benzaldehyde, 3-naphthyl-2-hydroxy benzaldehyde, 3-anthryl-2-hydroxy benzaldehyde, 3,5-diisobutyl-2-hydroxy benzaldehyde, 3-normal-butyl-2-hydroxy benzaldehyde, 4-normal-butyl-2-hydroxy benzaldehyde, 5-normal-butyl-2-hydroxy benzaldehyde, 4-nitro-2-hydroxy benzaldehyde, 4-nitroso-group-2-hydroxy benzaldehyde, 5-nitro-2-hydroxy benzaldehyde, 5-nitroso-group-2-hydroxy benzaldehyde, 6-nitro-2-hydroxy benzaldehyde, 6-nitroso-group-2-hydroxy benzaldehyde, 3-methoxyl group-2-hydroxy benzaldehyde, 4-methoxyl group-2-hydroxy benzaldehyde, 5-methoxyl group-2-hydroxy benzaldehyde, 6-methoxyl group-2-hydroxy benzaldehyde, 3,5-two iodo-2-hydroxy benzaldehydes, 4-iodo-2-hydroxy benzaldehyde, 5-iodo-2-hydroxy benzaldehyde, 3,5-two chloro-2-hydroxy benzaldehydes, 3-chloro-2-hydroxy benzaldehyde, 5-chloro-2-hydroxy benzaldehyde, 4-chloro-2-hydroxy benzaldehyde, 3,5-two bromo-2-hydroxy benzaldehydes, 4-fluoro-2-hydroxy benzaldehyde, 5-fluoro-2-hydroxy benzaldehyde, 3-fluoro-2-hydroxy benzaldehyde, 6-fluoro-2-hydroxy benzaldehyde, 3,5-two fluoro-2-hydroxy benzaldehydes, 4-bromo-2-hydroxy benzaldehyde, 3-methyl-2-hydroxy benzaldehyde, 4-methyl-2-hydroxy benzaldehyde, 5-methyl-2-hydroxy benzaldehyde, 6-methyl-2-hydroxy benzaldehyde, 3,5-dimethyl-2-hydroxy benzaldehyde, 3-sec.-propyl-2-hydroxy benzaldehyde, 4-sec.-propyl-2-hydroxy benzaldehyde, 3,5-di-isopropyl-2-hydroxy benzaldehyde, 3-ethyl-2-hydroxy benzaldehyde or 3,5-diethyl-2-hydroxy benzaldehyde.
4, claim 2 or 3 described methods, it is characterized in that, substituted salicylic aldehydes described in the steps A is a salicylic aldehyde, 4-methoxyl group-2-hydroxy benzaldehyde, 4-nitro-2-hydroxy benzaldehyde, the 3-tertiary butyl-2-hydroxy benzaldehyde, 3-naphthyl-2-hydroxy benzaldehyde, 3,5-di-t-butyl-2-hydroxy benzaldehyde, 3-isobutyl--2-hydroxy benzaldehyde, 3-anthryl-2-hydroxy benzaldehyde, 3,5-diisobutyl-2-hydroxy benzaldehyde, 3-normal-butyl-2-hydroxy benzaldehyde, 3,5-two iodo-2-hydroxy benzaldehydes, 3,5-two bromo-2-hydroxy benzaldehydes, 3,5-two chloro-2-hydroxy benzaldehydes, 3-sec.-propyl-2-hydroxy benzaldehyde, 3,5-di-isopropyl-2-hydroxy benzaldehyde, 3-ethyl-2-hydroxy benzaldehyde or 3,5-diethyl-2-hydroxy benzaldehyde.
5, a kind of as the application of catalyst system in norbornylene and derivative polymerization thereof as described in above-mentioned each claim.
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