CN110423306A - 含杂环六配位双水杨醛亚胺金属催化剂及制备方法和应用 - Google Patents
含杂环六配位双水杨醛亚胺金属催化剂及制备方法和应用 Download PDFInfo
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- CN110423306A CN110423306A CN201910596830.8A CN201910596830A CN110423306A CN 110423306 A CN110423306 A CN 110423306A CN 201910596830 A CN201910596830 A CN 201910596830A CN 110423306 A CN110423306 A CN 110423306A
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- catalyst
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- containing heterocycle
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 125000000623 heterocyclic group Chemical group 0.000 title claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 22
- BPELEZSCHIEMAE-UHFFFAOYSA-N salicylaldehyde imine Chemical compound OC1=CC=CC=C1C=N BPELEZSCHIEMAE-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000002184 metal Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 76
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 38
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims abstract description 32
- 239000003446 ligand Substances 0.000 claims abstract description 20
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical class OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004711 α-olefin Substances 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 41
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 26
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 25
- -1 methoxyl group Chemical group 0.000 claims description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 239000012086 standard solution Substances 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003426 co-catalyst Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000012312 sodium hydride Substances 0.000 claims description 6
- 159000000000 sodium salts Chemical class 0.000 claims description 6
- 150000004818 1,2-dichlorobenzenes Chemical class 0.000 claims description 5
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical group FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 125000002370 organoaluminium group Chemical group 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances 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
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 2
- JQQSUOJIMKJQHS-UHFFFAOYSA-N pentaphenyl group Chemical group C1=CC=CC2=CC3=CC=C4C=C5C=CC=CC5=CC4=C3C=C12 JQQSUOJIMKJQHS-UHFFFAOYSA-N 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
- 238000010898 silica gel chromatography Methods 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 2
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical class ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims 1
- 229940092714 benzenesulfonic acid Drugs 0.000 claims 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 15
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 9
- 238000003780 insertion Methods 0.000 abstract description 6
- 230000037431 insertion Effects 0.000 abstract description 6
- 238000012644 addition polymerization Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 2
- 238000006482 condensation reaction Methods 0.000 abstract 1
- 230000005595 deprotonation Effects 0.000 abstract 1
- 238000010537 deprotonation reaction Methods 0.000 abstract 1
- 150000002736 metal compounds Chemical class 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 31
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 27
- 238000006555 catalytic reaction Methods 0.000 description 9
- SXZIXHOMFPUIRK-UHFFFAOYSA-N diphenylmethanimine Chemical compound C=1C=CC=CC=1C(=N)C1=CC=CC=C1 SXZIXHOMFPUIRK-UHFFFAOYSA-N 0.000 description 9
- MGHPNCMVUAKAIE-UHFFFAOYSA-N diphenylmethanamine Chemical compound C=1C=CC=CC=1C(N)C1=CC=CC=C1 MGHPNCMVUAKAIE-UHFFFAOYSA-N 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 5
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000006384 oligomerization reaction Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 150000002466 imines Chemical class 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- FABVMBDCVAJXMB-UHFFFAOYSA-N 3,5-dichloro-2-hydroxybenzaldehyde Chemical compound OC1=C(Cl)C=C(Cl)C=C1C=O FABVMBDCVAJXMB-UHFFFAOYSA-N 0.000 description 3
- STBGLXMINLWCNL-UHFFFAOYSA-N 3-bromo-2-hydroxybenzaldehyde Chemical compound OC1=C(Br)C=CC=C1C=O STBGLXMINLWCNL-UHFFFAOYSA-N 0.000 description 3
- WHSXTWFYRGOBGO-UHFFFAOYSA-N 3-methylsalicylic acid Chemical compound CC1=CC=CC(C(O)=O)=C1O WHSXTWFYRGOBGO-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- JHZOXYGFQMROFJ-UHFFFAOYSA-N 3,5-dibromo-2-hydroxybenzaldehyde Chemical compound OC1=C(Br)C=C(Br)C=C1C=O JHZOXYGFQMROFJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- KUKRLSJNTMLPPK-UHFFFAOYSA-N 4,7,7-trimethylbicyclo[2.2.1]hept-2-ene Chemical group C1CC2(C)C=CC1C2(C)C KUKRLSJNTMLPPK-UHFFFAOYSA-N 0.000 description 1
- GLVKGYRREXOCIB-UHFFFAOYSA-N Bornylene Natural products CC1CCC(C(C)(C)C)C=C1 GLVKGYRREXOCIB-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical group C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Inorganic materials Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WDWDWGRYHDPSDS-UHFFFAOYSA-N methanimine Chemical compound N=C WDWDWGRYHDPSDS-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/14—Monomers containing five or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/70—Iron group metals, platinum group metals or compounds thereof
- C08F4/7001—Iron group metals, platinum group metals or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
- C08F4/7003—Bidentate ligand
- C08F4/7032—Dianionic ligand
- C08F4/7036—NO
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/70—Iron group metals, platinum group metals or compounds thereof
- C08F4/7095—Cobalt, nickel or compounds thereof
- C08F4/7098—Nickel or compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种含杂环六配位双水杨醛亚胺金属催化剂及制备方法和应用。在对甲苯磺酸催化条件下,水杨醛或水杨醛衍生物与芳香胺在甲苯溶液中进行缩合反应,得到配体。无水无氧的条件下,在四氢呋喃溶液中将配体脱质子后与金属预配盐和杂环化合物一起配位,得到含杂环六配位双水杨醛亚胺金属催化剂,该催化剂制备方法简单,催化活性高,热稳定性好;在不同的反应条件下能催化降冰片烯与α‑烯烃加成聚合,所得聚合物热学性能和加工性能优异且α‑烯烃单体的插入率可控。
Description
技术领域
本发明属于催化剂技术领域,涉及到催化剂、制备方法及应用。
背景技术
高分子材料是现代科学技术和社会发展的支柱,是生活中不可缺少的重要材料。聚环烯烃材料具有诸多的优点和优异的性能更是研究的重点,降冰片烯是一种典型的环烯烃材料,其聚合方式有三种:开环易位聚合,自由基或阳离子聚合,乙烯基加成型聚合,其中加成型聚合方式保留了降冰片烯的二元环结构(US Patent 5468819,5569730),有诸多优点而广泛应用在包装材料,光学材料,医药装置,打印机色带,电器材料等方面。不同催化剂对聚合物的结构和性能也有很大的影响。因此,对配体进行有效的分子结构设计,提高催化剂性能在催化剂研发领域中占有核心地位。目前,催化降冰片烯加成聚合的催化剂主要有Ziegler-Natta催化剂,茂金属催化剂和后过渡金属催化剂,但是Ziegler-Natta催化剂具有多个活性中心,耐极性基团能力差,限制了降冰片烯与α-烯烃共聚的应用,茂金属催化剂虽然是单活性中心,但是合成较为繁琐,对官能团具有较强的亲氧性,对杂原子敏感,易于极性基团形成稳定的络合物,从而降低了活性,且助催化剂甲基铝氧烷(MAO)用量过大。后过渡金属催化剂中以镍和钯为金属中心合成催化降冰片烯与α-烯烃共聚的催化剂,解决了Ziegler-Natta催化剂和茂金属催化剂的这些缺点。α-烯烃与环烯烃共聚合已有报道(CN1280140A,CN 101180327A),日本特开平10-287713号公报中,还实现了α-烯烃、环烯烃以及芳香族乙烯基三元共聚合,这些专利所述的共聚物具有高透光性等优点而用于光学材料,但所得聚合物的热学性能和加工性能并不令人满意。
发明内容
本发明的目的之一是提供一种含杂环六配位双水杨醛亚胺金属催化剂及制备方法。
本发明的目的之二是提供上述含杂环六配位双水杨醛亚胺金属催化剂在催化降冰片烯与α-烯烃共聚合中的应用。
本发明是通过以下技术方案实现的。
本发明所述的一种含杂环六配位双水杨醛亚胺金属催化剂,其结构式如下所示:
Mt为:镍,钯,钴,铁,铜金属原子。
R1和R2分别为氢、氟、氯、溴、碘,甲基、三氟甲基、甲氧基、三氟甲氧基、硝基、氰基、乙基、乙氧基、异丙基、叔丁基或苯基中的一种或者同种。
R3为杂环化合物:
Ar为芳香环:
本发明所述的含杂环六配位双水杨醛亚胺金属催化剂的制备方法,包括以下步骤:
(1)水杨醛亚胺配体制备:在氮气氛围下,将水杨醛衍生物0.01-0.1mol,芳香胺0.01-0.1mol和催化量的对甲苯磺酸(p-TsOH)依次加入装有磁力搅拌子的250mL反应烧瓶中,然后再加入50-150mL甲苯,在80-130℃下回流反应8-12小时,该反应产生的水用分水器除去。将所得粗产品采用硅胶层析柱提纯,并从正己烷和乙酸乙酯的混合物中挥发结晶,得到水杨醛亚胺配体。
(2)主催化剂含杂环和[N^O]六配位立构型双水杨醛亚胺金属配合物制备:在氮气氛围下,向100mL带支口的圆底烧瓶中加入水杨醛亚胺配体0.002-0.01mol,接着加20-50mL的四氢呋喃(THF)溶液,然后在真空线上向反应瓶中加入适量氢化钠(NaH),常温下搅拌6-12h,当烧瓶中的溶液变成橙色时,用冷肼除去反应瓶中的溶液,随后在氮气氛围下将0.001-0.005mol乙二醇二甲醚溴化镍(DME)NiBr2和0.002-0.01mol THF加入反应瓶中,最后加入20-50mL干燥的二氯甲烷(DCM)溶液,在室温下搅拌6-12h。当瓶中溶液由橙色变成浅绿色时,在氮气氛围下用砂芯滤球除去产生的钠盐,得到澄清溶液,然后自然挥发结晶,即可得到含四氢呋喃杂环和[N^O]六配位立构型双水杨醛亚胺金属催化剂的晶体。
本发明所述的含杂环六配位双水杨醛亚胺金属催化剂作为主催化剂,在降冰片烯与α-烯烃共聚合中的应用,其聚合反应式如下:
所述的助催化剂为有机硼或有机铝,例如:三氟化硼乙醚络合物、三五氟苯硼、三甲基铝、三乙基铝、三丙基铝、二甲基氯化铝、二乙基氯化铝或二异丙基氯化铝等。
所述的溶剂可以为单一组分的甲苯、氯苯、1,2-二氯苯、1,2,4-三氯苯,正己烷、正庚烷或三氯甲烷。也可以是双组分的甲苯和正己烷、氯苯和正己烷、1,2-二氯苯与正己烷、甲苯与三氯甲烷、氯苯与三氯甲烷或1,2-二氯苯与三氯甲烷等。
具体的聚合方法如下:
在氮气条件下,先将适量的助催化剂标准溶液和2-10mL的有机溶剂加入到100mL带支口的圆底烧瓶中,然后将配制好的降冰片烯(NB)标准溶液和α-烯烃依次加入,接着将溶于有机溶剂的含杂环和[N^O]六配位立构型双水杨醛亚胺金属主催化剂加入其中。降冰片烯和α-烯烃与主催化剂的摩尔比在500-5000:1,有机铝/主催化剂摩尔比100-3000:1,有机硼/主催化剂摩尔比的摩尔比为1-50:1,在0-120℃恒温条件下反应5min-48h,最后加入盐酸和甲醇的混合溶液终止反应,过滤,用甲醇洗涤2-3次,在真空干燥箱中干燥至恒重得环烯烃共聚物。
本发明提供的含杂环和[N^O]六配位立构型双水杨醛亚胺金属催化剂制备方法简单,催化活性高,热稳定性好,能实现降冰片烯与α-烯烃加成聚合,所得聚合物热学性能和加工性能优异且α-烯烃单体的插入率可控。此外,通过调整主催化剂与助催化剂的比例,反应时间,反应温度及单体投料比可调节聚合物形态与性能。
附图说明
图1为本发明含四氢呋喃杂环和[N^O]六配位立构型双-(3-溴水杨醛二苯甲基亚胺)镍(II)(Ni1)单晶结构图。
图2为本发明含四氢呋喃杂环和[N^O]六配位立构型双-(3,5-二溴水杨醛二苯甲基亚胺)镍(II)(Ni2)单晶结构图。
图3为本发明含四氢呋喃杂环和[N^O]六配位立构型双-(3,5-二氯水杨醛二苯甲基亚胺)镍(II)(Ni3)单晶结构图。
图4为本发明含二苯甲胺杂环和[N^O]六配位立构型双-(3,5-二氯水杨醛二苯甲基亚胺)镍(II)(Ni4)单晶结构图。
图5为本发明含四氢呋喃杂环和[N^O]六配位立构型双水杨醛亚胺镍(II)(Ni1-Ni3)催化剂催化降冰片烯与1-己烯聚合的GPC谱图。
图6为本发明含四氢呋喃杂环和[N^O]六配位立构型双水杨醛亚胺镍(II)(Ni1-Ni3)催化剂催化降冰片烯与1-己烯聚合的1H NMR谱图。
图7为本发明含四氢呋喃杂环和[N^O]六配位立构型双水杨醛亚胺镍(II)(Ni1-Ni3)催化剂催化降冰片烯与1-己烯聚合的TGA曲线。
图8为本发明含四氢呋喃杂环和[N^O]六配位立构型双水杨醛亚胺镍(II)(Ni1-Ni3)催化剂催化降冰片烯与1-己烯聚合的DSC曲线。
图9为本发明含四氢呋喃杂环和[N^O]六配位立构型双水杨醛亚胺镍(II)(Ni1-Ni3)催化剂催化降冰片烯与1-己烯聚合的UV-vis谱图。
具体实施方式
本发明将通过以下实施例作进一步说明。
实施例1。
(I).3-溴水杨醛二苯甲基亚胺配体的制备。
在氮气氛围下,将3-溴水杨醛0.01mol(2.01g),二苯甲胺0.01mol(1.83g)和催化量的对甲苯磺酸(p-TsOH)依次加入装有磁力搅拌子的250mL反应烧瓶中,然后再加入150mL甲苯,120℃下回流反应12小时,该反应产生的水用分水器除去。将所得粗产品采用硅胶层析柱(V正己烷/V乙酸乙酯=50:1)提纯,并从正己烷和乙酸乙酯的混合物中挥发结晶,得到3-溴水杨醛二苯甲基亚胺配体,产率82%。元素分析(%),理论值:C,65.59;H,4.40;N,3.82;实验值:C,65.61;H,4.41;N,3.80。
(II).主催化剂(Ni1)含四氢呋喃杂环和[N^O]六配位立构型双-(3-溴水杨醛二苯甲基亚胺)镍(II)的制备。
在氮气氛围下,向100mL带支口的圆底烧瓶中加入3-溴水杨醛二苯甲基亚胺配体0.002mol(0.776g),接着加入30mL的四氢呋喃(THF)溶液,然后在真空线上向反应瓶中加入0.06mol 60%氢化钠,常温下搅拌12h,当烧瓶中的溶液由黄色变成橙色时,用冷肼除去反应瓶中的溶液,随后在氮气氛围下将(DME)NiBr2 0.001mol(0.308g)和0.002mol(0.144g)THF加入反应瓶中,最后加入30mL干燥的二氯甲烷(DCM)溶液,在室温下搅拌12h。当瓶中溶液由橙色变成浅绿色时,在氮气氛围下用砂芯滤球除去产生的钠盐,得到澄清溶液,然后自然挥发结晶,得到含四氢呋喃杂环和[N^O]六配位立构型双-(3-溴水杨醛二苯甲基亚胺)镍(II)催化剂(Ni1)的晶体,纯度98%,产率72%。元素分析(%),理论值:C,61.92;H,5.41;N,2.95;实验值:C,61.87;H,5.32;N,3.02。
实施例2。
含四氢呋喃杂环和[N^O]六配位立构型双-(3-溴水杨醛二苯甲基亚胺)镍(II)催化降冰片烯与1-己烯共聚合。
在真空线上对装有磁力搅拌子的100mL带支口圆底烧瓶抽真空,然后使用真空/高纯氮气置换3次,确保聚合瓶为无水无氧的状态。用注射器依次注入降冰片烯标准溶液(0.4g/mol)、1-己烯和5mL新蒸甲苯溶液,然后依次注入B(C6F5)3的标准溶液(5×10-2mol/L)、含四氢呋喃杂环和[N^O]六配位立构型双-(3-溴水杨醛二苯甲基亚胺)镍(II)催化剂标准溶液(5×10-3mol/L),将上述混合溶液放入提前设定好温度(60℃)的恒温油浴锅中,搅拌30min,之后加入盐酸/甲醇(v盐酸/v甲醇=1/9)的混合溶液终止反应,室温下静置24小时以上,抽滤,收集所得聚合物。用三氯甲烷/甲醇反沉淀法纯化所得到的聚合物,最后将产物放入50℃的真空干燥箱干燥至恒重,称量,密封保存。其中聚合物的转化率为60-100%,催化活性在105数量级,1-己烯插入率在8.64-19.82%,所制备的样品分别为a,b,c。
实施例3。
(I).3,5-二溴水杨醛二苯甲基亚胺配体的制备。
在氮气氛围下,将3,5-二溴水杨醛0.01mol(2.80g),二苯甲胺0.01mol(1.83g)和催化量的对甲苯磺酸(p-TsOH)依次加入装有磁力搅拌子的250mL反应烧瓶中,然后再加入150mL甲苯,120℃下回流反应12小时,该反应产生的水用分水器除去。将所得粗产品采用硅胶层析柱(V正己烷/V乙酸乙酯=50:1)提纯,并从正己烷和乙酸乙酯的混合物中挥发结晶,得到3,5-二溴水杨醛二苯甲基亚胺配体,产率80%。元素分析(%),理论值:C,53.96;H,3.40;N,3.15;实验值:C,53.97;H,3.41;N,3.13。
(II).主催化剂(Ni2)含四氢呋喃杂环和[N^O]六配位立构型双-(3,5-二溴水杨醛二苯甲基亚胺)镍(II)的制备。
在氮气氛围下,向100mL带支口的圆底烧瓶中加入3,5-二溴水杨醛二苯甲基亚胺配体0.002mol(0.886g),接着加入30mL的四氢呋喃(THF)溶液,然后在真空线上向反应瓶中加入0.06mol 60%氢化钠,常温下搅拌12h,当烧瓶中的溶液由黄色变成橙黄色时,用冷肼除去反应瓶中的溶液,随后在氮气氛围下将(DME)NiBr2 0.001mol(0.308g)和0.002mol(0.144g)THF加入反应瓶中,最后加入30mL干燥的二氯甲烷(DCM)溶液,在室温下搅拌12h。当瓶中溶液由橙黄色变成浅绿色时,在氮气氛围下用砂芯滤球除去产生的钠盐,得到澄清溶液,然后自然挥发结晶,得到含四氢呋喃杂环和[N^O]六配位立构型双-(3,5-二溴水杨醛二苯甲基亚胺)镍(II)催化剂(Ni2)的晶体,纯度98%,产率69%。元素分析(%),理论值:C,53.10;H,4.46;N,2.53;实验值:C,52.95;H,4.49;N,2.52。
实施例4。
含四氢呋喃杂环和[N^O]六配位立构型双-(3,5-二溴水杨醛二苯甲基亚胺)镍(II)催化降冰片烯与1-己烯共聚合。
在真空线上对装有磁力搅拌子的100mL带支口圆底烧瓶抽真空,然后使用真空/高纯氮气置换3次,确保聚合瓶为无水无氧的状态。用注射器依次注入降冰片烯标准溶液(0.4g/mol)、1-己烯和5mL新蒸甲苯溶液,然后依次注入B(C6F5)3的标准溶液(5×10-2mol/L)、含四氢呋喃杂环和[N^O]六配位立构型双-(3,5-二溴水杨醛二苯甲基亚胺)镍(II)催化剂标准溶液(5×10-3mol/L),将上述混合溶液放入提前设定好温度(60℃)的恒温油浴锅中,搅拌30min,之后加入盐酸/甲醇(v盐酸/v甲醇=1/9)的混合溶液终止反应,室温下静置24小时以上,抽滤,收集所得聚合物。用三氯甲烷/甲醇反沉淀法纯化所得到的聚合物,最后将产物放入50℃的真空干燥箱干燥至恒重,称量,密封保存。其中聚合物的转化率为62-100%,催化活性在105数量级,1-己烯插入率在8.23-16.74%,所制备的样品分别为d,e,f。
实施例5。
(I).3,5-二氯水杨醛二苯甲基亚胺配体的制备。
在氮气氛围下,将3,5-二氯水杨醛0.01mol(1.91g),二苯甲胺0.01mol(1.83g)和催化量的对甲苯磺酸(p-TsOH)依次加入装有磁力搅拌子的250mL反应烧瓶中,然后再加入150mL甲苯,120℃下回流反应12小时,该反应产生的水用分水器除去。将所得粗产品采用硅胶层析柱(V正己烷/V乙酸乙酯=50:1)提纯,并从正己烷和乙酸乙酯的混合物中挥发结晶,得到3,5-二氯水杨醛二苯甲基亚胺配体,产率87%。元素分析(%),理论值:C,67.43;H,4.24;N,3.93;实验值:C,67.42;H,4.25;N,3.91。
(II).主催化剂(Ni3)含四氢呋喃杂环和[N^O]六配位立构型双-(3,5-二氯水杨醛二苯甲基亚胺)镍(II)的制备。
在氮气氛围下,向100mL带支口的圆底烧瓶中加入3,5-二氯水杨醛二苯甲基亚胺配体0.002mol(0.713g),接着加入30mL的四氢呋喃(THF)溶液,然后在真空线上向反应瓶中加入0.06mol 60%氢化钠,常温下搅拌12h,当烧瓶中的溶液由黄色变成橙黄色时,用冷肼除去反应瓶中的溶液,随后在氮气氛围下将(DME)NiBr2 0.001mol(0.308g)和0.002mol(0.144g)THF加入反应瓶中,最后加入30mL干燥的二氯甲烷(DCM)溶液,在室温下搅拌12h。当瓶中溶液由橙黄色变成浅绿色时,在氮气氛围下用砂芯滤球除去产生的钠盐,得到澄清溶液,然后自然挥发结晶,得到含四氢呋喃杂环和[N^O]六配位立构型双-(3,5-二氯水杨醛二苯甲基亚胺)镍(II)催化剂(Ni3)的晶体,纯度98%,产率76%。元素分析(%),理论值:C,63.25;H,4.46;N,2.53;实验值:C,63.22;H,4.44;N,2.57。
实施例6。
含四氢呋喃杂环和[N^O]六配位立构型双-(3,5-二氯水杨醛二苯甲基亚胺)镍(II)催化降冰片烯与1-己烯共聚合。
在真空线上对装有磁力搅拌子的100mL带支口圆底烧瓶抽真空,然后使用真空/高纯氮气置换3次,确保聚合瓶为无水无氧的状态。用注射器依次注入降冰片烯标准溶液(0.4g/mol)、1-己烯和5mL新蒸甲苯溶液,然后依次注入B(C6F5)3的标准溶液(5×10-2mol/L)、含四氢呋喃和[N^O]六配位立构型双-(3,5-二氯水杨醛二苯甲基亚胺)镍(II)催化剂标准溶液(5×10-3mol/L),将上述混合溶液放入提前设定好温度(60℃)的恒温油浴锅中,搅拌30min,之后加入盐酸/甲醇(v盐酸/v甲醇=1/9)的混合溶液终止反应,室温下静置24小时以上,抽滤,收集所得聚合物。用三氯甲烷/甲醇反沉淀法纯化所得到的聚合物,最后将产物放入50℃的真空干燥箱干燥至恒重,称量,密封保存。其中聚合物的转化率为70-100%,催化活性在105数量级,1-己烯插入率在9.21-26.58%,所制备的样品分别为g,h,i,j。
实施例7。
(I).3-甲基水杨醛二苯甲基亚胺配体的制备。
在氮气氛围下,将3-甲基水杨醛0.01mol(1.36g),二苯甲胺0.01mol(1.83g)和催化量的对甲苯磺酸(p-TsOH)依次加入装有磁力搅拌子的250mL反应烧瓶中,然后再加入150mL甲苯,120℃下回流反应12小时,该反应产生的水用分水器除去。将所得粗产品采用硅胶层析柱(V正己烷/V乙酸乙酯=50:1)提纯,并从正己烷和乙酸乙酯的混合物中挥发结晶,得到3-甲基水杨醛二苯甲基亚胺配体,产率78%。元素分析(%),理论值:C,83.69;H,6.35;N,4.65;实验值:C,83.71;H,6.36;N,4.63。
(II).主催化剂(Ni4)含二苯甲胺和[N^O]六配位立构型双-(3-甲基水杨醛二苯甲基亚胺)镍(II)的制备。
在氮气氛围下,向100mL带支口的圆底烧瓶中加入3-甲基水杨醛二苯甲基亚胺配体0.002mol(0.602g),接着加入30mL的四氢呋喃(THF)溶液,然后在真空线上向反应瓶中加入0.06mol 60%氢化钠,常温下搅拌12h,当烧瓶中的溶液由黄色变成橙黄色时,用冷肼除去反应瓶中的溶液,随后在氮气氛围下将(DME)NiBr2 0.001mol(0.308g)和0.002mol(0.366g)二苯甲胺加入反应瓶中,最后加入30mL干燥的二氯甲烷(DCM)溶液,在室温下搅拌12h。当瓶中溶液由橙黄色变成棕绿色时,在氮气氛围下用砂芯滤球除去产生的钠盐,得到澄清溶液,然后自然挥发结晶,得到含二苯甲胺和[N^O]六配位立构型双-(3-甲基水杨醛二苯甲基亚胺)镍(II)催化剂(Ni4)的晶体,纯度98%,产率51%。元素分析(%),理论值:C,81.98;H,6.28;N,2.77;实验值:C,81.97;H,6.29;N,2.75。
降冰片烯与1-己烯共聚合实验数据如下表:
Ni1-Ni3/B(C6F5)3催化体系催化降冰片烯与1-己烯共聚合a
a反应条件:n[催化剂]=5.0×10-6mol;n[降冰片烯]+n[1-己烯]=0.01mol;溶剂:甲苯;反应时间:30min;反应温度:60℃;n[助催化剂]/n[催化剂]=10/1。
b通过核磁氢普测定。
从表中可以看出,本发明制得的新型催化剂具高活性,能够催化剂降冰片烯与1-己烯加成聚合,分子量达105数量级,所得聚合物玻璃转化温度在208.67-237.42℃之间,从而使降冰片烯与1-己烯共聚物的热学性能和加工性能得到很大改善。此外,所制得新型催化剂能实现降冰片烯与1-己烯的可控聚合,随着1-己烯插入率的增加其玻璃转化温度会有所下降。
Claims (5)
1.一种含杂环六配位双水杨醛亚胺金属催化剂,其特征是结构式如下所示:
Mt为:镍,钯,钴,铁,铜金属原子;
R1和R2分别为氢、氟、氯、溴、碘,甲基、三氟甲基、甲氧基、三氟甲氧基、硝基、氰基、乙基、乙氧基、异丙基、叔丁基或苯基中的一种或者同种;
R3为杂环化合物:
Ar为芳香环:
2.权利要求1所述的含杂环六配位双水杨醛亚胺金属催化剂的制备方法,其特征是包括以下步骤:
(1)在氮气氛围下,将水杨醛衍生物0.01-0.1mol,芳香胺0.01-0.1mol和催化量的对甲苯磺酸依次加入装有磁力搅拌子的250mL反应烧瓶中,然后再加入50-150mL甲苯,在80-130℃下回流反应8-12小时,该反应产生的水用分水器除去;将所得粗产品采用硅胶层析柱提纯,并从正己烷和乙酸乙酯的混合物中挥发结晶,得到水杨醛亚胺配体;
(2)在氮气氛围下,向100mL带支口的圆底烧瓶中加入水杨醛亚胺配体0.002-0.01mol,接着加20-50mL的四氢呋喃溶液,然后在真空线上向反应瓶中加入适量氢化钠,常温下搅拌6-12h,当烧瓶中的溶液变成橙色时,用冷肼除去反应瓶中的溶液,随后在氮气氛围下将0.001-0.005mol乙二醇二甲醚溴化镍和0.002-0.01mol四氢呋喃加入反应瓶中,最后加入20-50mL干燥的二氯甲烷溶液,在室温下搅拌6-12h;当瓶中溶液由橙色变成浅绿色时,在氮气氛围下用砂芯滤球除去产生的钠盐,得到澄清溶液,然后自然挥发结晶。
3.权利要求1所述的含杂环六配位双水杨醛亚胺金属催化剂在降冰片烯与α-烯烃共聚合中的应用,其特征是聚合反应式如下:
所述的主催化剂为含杂环六配位双水杨醛亚胺金属催化剂;助催化剂为有机硼或有机铝;
所述的溶剂为单一组分的甲苯、氯苯、1,2-二氯苯、1,2,4-三氯苯、正己烷、正庚烷或三氯甲烷;或者为双组分的甲苯和正己烷、氯苯和正己烷、1,2-二氯苯与正己烷、甲苯与三氯甲烷、氯苯与三氯甲烷或1,2-二氯苯与三氯甲烷。
4.根据权利要求1所述的含杂环六配位双水杨醛亚胺金属催化剂在降冰片烯与α-烯烃共聚合中的应用,其特征是所述的助催化剂为三氟化硼乙醚络合物、三五氟苯硼、三甲基铝、三乙基铝、三丙基铝、二甲基氯化铝、二乙基氯化铝或二异丙基氯化铝。
5.根据权利要求1所述的含杂环六配位双水杨醛亚胺金属催化剂在降冰片烯与α-烯烃共聚合中的应用,其特征是所述的聚合反应按如下步骤:
在氮气条件下,先将适量的助催化剂标准溶液和2-10mL的有机溶剂加入到100mL带支口的圆底烧瓶中,然后将配制好的降冰片烯标准溶液和α-烯烃依次加入,接着将溶于有机溶剂的主催化剂加入其中;降冰片烯和α-烯烃与主催化剂的摩尔比在500-5000:1,有机铝/主催化剂摩尔比100-3000:1,有机硼/主催化剂摩尔比的摩尔比为1-50:1,在0-120℃恒温条件下反应5min-48h,最后加入盐酸和甲醇的混合溶液终止反应,过滤,用甲醇洗涤2-3次,在真空干燥箱中干燥至恒重得环烯烃共聚物。
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