CN109575066A - Beta-diimine zinc catalyst and its ligand, preparation method and purposes - Google Patents
Beta-diimine zinc catalyst and its ligand, preparation method and purposes Download PDFInfo
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- CN109575066A CN109575066A CN201910036944.7A CN201910036944A CN109575066A CN 109575066 A CN109575066 A CN 109575066A CN 201910036944 A CN201910036944 A CN 201910036944A CN 109575066 A CN109575066 A CN 109575066A
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- diisopropyl
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- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 239000003446 ligand Substances 0.000 title claims abstract description 27
- 239000011701 zinc Substances 0.000 title claims description 55
- 229910052725 zinc Inorganic materials 0.000 title claims description 29
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 21
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 229910000071 diazene Inorganic materials 0.000 title description 7
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 55
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 38
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002841 Lewis acid Substances 0.000 claims abstract description 29
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 29
- 230000000694 effects Effects 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 54
- -1 (2,6- diisopropyl phenyl) imino Chemical group 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002879 Lewis base Substances 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 17
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 17
- 150000007527 lewis bases Chemical class 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 15
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical class CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910015845 BBr3 Inorganic materials 0.000 claims description 3
- 229910015844 BCl3 Inorganic materials 0.000 claims description 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 3
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Substances BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 3
- 150000002431 hydrogen Chemical group 0.000 claims 2
- 229910052710 silicon Inorganic materials 0.000 claims 2
- 239000010703 silicon Substances 0.000 claims 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 39
- 239000000178 monomer Substances 0.000 description 28
- 238000006116 polymerization reaction Methods 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 20
- 230000003197 catalytic effect Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 11
- 238000010586 diagram Methods 0.000 description 10
- 150000002596 lactones Chemical group 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000002184 metal Substances 0.000 description 9
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 8
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 8
- 229910015900 BF3 Inorganic materials 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 230000000379 polymerizing effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- ZMQBBPRAZLACCW-UHFFFAOYSA-N acetic acid;dichloromethane Chemical compound ClCCl.CC(O)=O ZMQBBPRAZLACCW-UHFFFAOYSA-N 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920000747 poly(lactic acid) Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 150000003752 zinc compounds Chemical class 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229950005499 carbon tetrachloride Drugs 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 239000004626 polylactic acid Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- JONIMGVUGJVFQD-UHFFFAOYSA-N (4-methylphenyl)sulfonylformonitrile Chemical compound CC1=CC=C(S(=O)(=O)C#N)C=C1 JONIMGVUGJVFQD-UHFFFAOYSA-N 0.000 description 1
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001669 calcium Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical group N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical group [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RDRCCJPEJDWSRJ-UHFFFAOYSA-N pyridine;1h-pyrrole Chemical compound C=1C=CNC=1.C1=CC=NC=C1 RDRCCJPEJDWSRJ-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C251/10—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
- C07C251/12—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton being acyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/61—Carboxylic acid nitriles containing cyano groups and nitrogen atoms being part of imino groups bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to the Zn complex of formula (I) and its ligand, preparation method and application, R therein1~R6And X is as defined herein.The Zn complex of formula (I) of the invention can be used as catalyst in the ring-opening polymerization of catalysis lactide and caprolactone, and the activity of the catalyst can carry out the regulation of " off/on " formula by lewis acid and/or alkali.
Description
Technical field
The present invention relates to high molecular materials and catalyst field, and in particular to beta-diimine zinc catalyst and its ligand, system
Preparation Method and purposes.
Background technique
In recent years, change catalyst catalytic performance under outside stimulus, to control polymerizate structure, become one fastly
The research field of speed development.Similar research was reported in existing document, including electrochemical regulating and controlling free radical acrylate
Polymerization；The anionic polymerisation of the ferrocene aromatic monomer of photochemistry control；The ring opening metathesis polymerization of mechanochemistry control；Oxidation
Restore the caprolactone and lactide open loop (co) polymerization of control；And the olefinic polymerization etc. of redox control.
The redox regulatory ring-opening polymerisation (ROP) of cyclic ester be widely studied [Chen CL.ACS Catal, 2018,8:
5506-5514].In such system, the variation of the redox state at ligand or catalytically-active metals center can be effective
Ground adjust catalysis behavior, thus come adjust polymer composition and property.Chen in 2015 etc. successfully expands to this strategy
Olefinic polymerization [Chen M, Yang BP, Chen CL.Angew Chem Int Ed, 2015,54:15520-15524].Some
In palladium catalyst, the ferrocene units that can be reversibly aoxidized and be restored are connected in advance, it is possible thereby to cause catalyst in second
There are different catalytic performances in polyamino alkenyl and polymerization process.In addition, Long seminar [Kaiser JM, Long BK.Coord
Chem Rev, 2018,372:141-152] and Diaconescu and Chen et al. using different olefin polymerization catalysis into
The application for the redox regulatory strategy that one step demonstrates.
After successfully the strategy of the ring-opening polymerisation of redox regulatory is applied in olefinic polymerization, ring-opening polymerisation starts
New strategy is found from olefinic polymerization regulation method.Exist between the ring-opening polymerisation of metal catalytic and the olefinic polymerization of metal catalytic
Many similarities, so that determine that a kind of strategy that can be potentially suitable for two kinds of catalytic polymerization systems becomes simply,
Redox regulatory strategy as escribed above.Nearest Chen et al. is pointed out, in some Raney nickels, lewis acid and sulfonic acid portion
The coordination of position can reduce thus catalytic performance [Chen M, Zou that the electron density at nickel center adjusts them to vinyl polymerization
WP,Cai ZG,Chen CL.Poly Chem,2015,6:2669-2676].The effect of lewis acid coordination and above-mentioned oxidation are also
The effect that ferrocenyl aoxidizes in former control system is closely similar: applying the smallest disturbance on ligand to keep catalytic activity golden
Belonging to supercentral electron density reduces.
Had been reported that beta-diimine zinc catalyst have in the ring-opening polymerisation of lactide preferable activity [Cheng M,
Attygalle AB, Lobkovsky EB, Coates GW, J Am Chem Soc, 1999,121:11583-11584], but should
The mainly alkoxy grp of substituent group involved in document, and by the different designs of intermediate linker and benzene ring substituents, it can
To realize better catalytic activity；Moreover, Lewis Acids and Bases binding site is not present in the catalyst in the document, it can not be to it
Catalytic activity is regulated and controled.Lewis Acids and Bases are as outside stimulus by being implemented in combination with catalyst to lactone ring opening polymerization mistake
The regulation of journey rarely has research；In addition, only the disengaging catalyst backbone of the lewis acid after coordination just can be able to achieve " switchable
The polymerization of switching ".
Therefore, new catalyst of this field there is still a need for exploitation for the ring-opening polymerization of efficient catalytic lactone, together
When a possibility that there is still a need for the ring-opening polymerizations of further research Lewis Acids and Bases regulation lactone.
Summary of the invention
In view of above-mentioned, the object of the present invention is to provide a kind of new catalysts, can be in no initiator using the catalyst
In the case where efficient catalytic lactone ring-opening polymerization, and can be realized by lewis acid and/or alkali to the catalysis
The activity of agent carries out the regulation of " off/on " formula.
For this purpose, in one aspect, the present invention provides the Zn complex of formula (I) a kind of,
Wherein
R1、R2、R3、R4、R5And R6It is hydrogen, halogen, C independently of one another1-C4Alkyl, halogenated C1-C4Alkyl or C1-C4Alcoxyl
Base；
X is cyano, propiono, tertiary bytyry or benzoyl.
In preferred embodiments, R1、R3、R4And R6It is C independently of one another1-C4Alkyl or C1-C4Alkoxy, and R2With
R5It is hydrogen, halogen or C independently of one another1-C4Alkyl.
In preferred embodiments, X is cyano, propiono or tertiary bytyry.
In preferred embodiments, the Zn complex is 2- ((2,6- diisopropyl) amino) -3- cyano -4- ((2,6-
Diisopropyl phenyl) imino group) -2- amylene closes bis- (trimethyl silicon substrate) amido zinc or 2- ((2,6- diisopropyl) amino) -3-
Tertiary bytyry -4- ((2,6- diisopropyl phenyl) imino group) -2- amylene closes bis- (trimethyl silicon substrate) amido zinc.
On the other hand, the present invention provides the ligand compound of formula (II) a kind of,
Wherein R1、R2、R3、R4、R5、R6It is as defined above with X.
In preferred embodiments, the ligand compound be 2- ((2,6- diisopropyl) amino) -3- cyano -4- ((2,
6- diisopropyl phenyl) imino group) ((2,6- bis- is different by -3- tertiary bytyry -4- by -2- amylene or 2- ((2,6- diisopropyl) amino)
Propyl phenyl) imino group) -2- amylene.
On the other hand, the present invention provides a kind of method for preparing above-mentioned formula (I) Zn complex, the method packets
It includes；
In organic solvent, at 70-90 DEG C, keep above-mentioned formula (II) ligand compound and bis- (double trimethyl silicon substrates) amine zinc anti-
It answers.
In preferred embodiments, the ligand compound of the formula (II) used and bis- (double trimethyl silicon substrates) amine zinc
Molar ratio is 1:1.1-2.
In preferred embodiments, the time of the reaction is 12-96 hours.
In preferred embodiments, the organic solvent be selected from tetrahydrofuran, n-hexane, toluene, benzene, carbon tetrachloride,
One of ether, 1,4- dioxane and 1,2- dichloroethanes are a variety of.
On the other hand, the present invention provides the Zn complexes of above-mentioned formula (I) to be used to be catalyzed lactide or caprolactone
The purposes of ring-opening polymerization, wherein the Zn complex is used as the catalyst of the ring-opening polymerization.
In preferred embodiments, the catalyst institute is adjusted by addition lewis acid and/or lewis base
State the activity of ring-opening polymerization；It is highly preferred that the lewis acid is BF3、BCl3、BBr3Or (C6F5)3, this described alkali is pyrrole
Pyridine, imidazoles or 2,6- lutidines.
The present invention is obtained by with acetylacetone,2,4-pentanedione and two substituted aniline molecule condensations containing β-via Molecular Design
The ligand compound of diimine structure, then it is compound with zinc metal precursor compound, so that the new zinc metal for providing formula (I) is matched
Close object, and thus provide can in the case where no initiator the ring-opening polymerization of efficient catalytic lactone new catalytic
Agent.
In addition, the catalyst has very high activity to the ring-opening polymerization of catalyzing lactone, it is at the same time, affiliated to urge
Agent can be added by the program of lewis acid and/or alkali during ring-opening polymerization of lactone by catalysis and carry out polymerization reaction
The regulation of " off/on " formula.
In addition, being opened using new catalyst of the invention by regulating and controlling lactide using Lewis Acids and Bases
During cyclopolymerization, there can be better regulation to the stereoselective of polylactic acid simultaneously, this makes it possible to
Lactide ring-opening polymerisation, which obtains high tacticity or steric regularity, has the new polymers of block property.
Detailed description of the invention
Fig. 1 shows the X-ray diffraction mono-crystalline structures schematic diagram for the catalyst 2 that according to the present invention prepared by synthesis example 4.
Fig. 2 shows the X-ray diffraction mono-crystalline structures schematic diagrames for the catalyst 3 that according to the present invention prepared by control synthesis example 5.
Fig. 3 shows the mass spectrogram of the resulting polymer of application examples 1 according to the present invention, and according to peak computational, polymerization is drawn
Sending out group is bis- (trimethyl silicon substrate) amidos.
Fig. 4-6 respectively illustrates the power of the catalyst lactide ring-opening polymerisation of application examples 1,2 and 5 according to the present invention
It learns curve graph (relation curve i.e. between the logarithm and monomer conversion of monomer concentration ratio), slope (i.e. K) therein is respectively
It indicates the rate constant of ring-opening polymerization, is used to indicate the speed of ring-opening polymerisation speed；Polymerizing condition therein are as follows: 10 is micro-
Mol catalyst；Catalyst concn: monomer concentration=1:100；5 milliliters of methylene chloride；30 DEG C of reaction temperature.
It is resulting that Fig. 7 shows the catalyst lactide of application examples and caprolactone ring-opening polymerisation according to the present invention
Graph of relation between the molecular weight (■) and molecular weight distribution (▲) and monomer conversion of polymer, wherein polymerizing condition
Are as follows: 10 micromole's catalyst；Catalyst concn: monomer concentration=1:100；5 milliliters of methylene chloride；30 DEG C of reaction temperature.
It is resulting that Fig. 8 shows the catalyst lactide of application examples and caprolactone ring-opening polymerisation according to the present invention
Graph of relation between the molecular weight (■) and molecular weight distribution (▲) and monomer conversion of polymer, wherein polymerizing condition
Are as follows: 10 micromole's catalyst；Catalyst concn: monomer concentration=1:100；5 milliliters of methylene chloride；30 DEG C of reaction temperature.
It is resulting that Fig. 9 shows the catalyst lactide of application examples and caprolactone ring-opening polymerisation according to the present invention
Graph of relation between the molecular weight (■) and molecular weight distribution (▲) and monomer conversion of polymer, wherein polymerizing condition
Are as follows: 10 micromole's catalyst；Catalyst concn: monomer concentration=1:100；5 milliliters of methylene chloride；30 DEG C of reaction temperature.
Figure 10-13 show application examples 10-13 according to the present invention by adding lewis acid (B (C5F6)3Or BF3) and
Lewis base (pyridine py) come regulate and control catalyst according to the invention catalysis lactide or caprolactone ring-opening polymerization activity
Dynamic curve diagram.
Specific embodiment
It tests and furthers investigate more extensively by the present inventor, it was unexpectedly found that: by with acetylacetone,2,4-pentanedione
It is condensed the ligand compound of two available structures containing beta-diimine of substituted aniline molecule, then by the ligand compound and zinc
Metal precursor compound is compound, and obtained zinc metal complex can be used as catalyst and efficiently urge in the case where no initiator
Change the ring-opening polymerization of lactone.In addition, activity of the complex as catalyst in the ring-opening polymerization of catalyzing lactone
The regulation of " off/on " formula can be carried out by addition lewis acid and/or alkali.Based on above-mentioned discovery, the present invention is formd.
As a result, the present invention provides the Zn complex of formula (I) a kind of,
Wherein
R1、R2、R3、R4、R5And R6It is hydrogen, halogen, C independently of one another1-C4Alkyl, halogenated C1-C4Alkyl or C1-C4Alcoxyl
Base；
X is cyano, propiono, tertiary bytyry or benzoyl.
As used in this article, halogen includes fluorine, chlorine, bromine and iodine, preferably chlorine or bromine.
As used in this article, C1-C4Alkyl includes methyl, ethyl, propyl and its isomeric form, butyl and its isomery shape
Formula；Preferably ethyl, isopropyl or tert-butyl.
As used in this article, halogenated C1-C4Alkyl refers to above-mentioned C1-C4Alkyl, the wherein C1-C4In alkyl at least
One hydrogen atom is optionally substituted by halogen.
As used in this article, C1-C4Alkoxy refers to above-mentioned C1-C4Alkyl, wherein passing through the surplus of oxygen atom and molecule
Remaining part point connection.
Preferably, in formula (I), R1、R3、R4And R6It is C independently of one another1-C4Alkyl, halogenated C1-C4Alkyl or C1-C4
Alkoxy, and R2And R5It is hydrogen, halogen or C independently of one another1-C4Alkyl.
Preferably, in formula (I), X is cyano, propiono or tertiary bytyry.
In the present invention, the Zn complex of formula (I) can be prepared via the ligand compound of formula (II):
Wherein R1、R2、R3、R4、R5、R6It is as defined above with X,
More specifically, in organic solvent such as toluene, at 70-90 DEG C, make above-mentioned formula (II) ligand compound with it is bis- (double
Trimethyl silicon substrate) reaction of amine zinc.
Preferably, the ligand compound of the formula (II) used and the molar ratio of zinc compound are 1:1.1-2；Preferably, instead
The time answered is 12~96h；Preferably, the organic solvent used can be selected from tetrahydrofuran, n-hexane, toluene, benzene, tetrachloro
Change one of carbon, ether, 1,4- dioxane and 1,2- dichloroethanes or a variety of.
As mentioned above, the Zn complex of above-mentioned formula (I) provided by the invention can be used as catalyst for be catalyzed third friendship
The ring-opening polymerization of ester or caprolactone.For example, internal ester monomer such as lactide is dissolved in solvent under the conditions of anhydrous and oxygen-free
In, zinc catalyst of the invention is then added, is reacted at 20~80 DEG C.Preferably, solvent used in reaction can be selected from
Tetrahydrofuran, dimethylbenzene, toluene, benzene, methylene chloride, chloroform, tetrachloromethane, chlorobenzene, ether, 1,4- dioxane or 1,
2- dichloroethanes etc..
In addition, not fettered by especially theoretical, by the present inventor's research, it has also been found that, Zn complex of the invention is made
The appropriateness acidity at its zinc metal catalytic center is mostly derived from for the activity of catalyst.Therefore, Zn complex of the invention is being used
In the case where catalyst, the ring-opening polymerization of lactide or caprolactone can be in the presence of no initiator for example
It is carried out under about 30 DEG C of temperate condition, and can almost make the complete ring-opening polymerisation of internal ester monomer such as lactide.Moreover, in benefit
In the case where with zinc catalyst of the invention, a small amount of such zinc catalyst, which can be used only, can be realized the ring-opening polymerisation
Reaction, such as monomer such as lactide or caprolactone for ring-opening polymerisation and the molar ratio of zinc catalyst of the invention can be
About 100:1.
Further, since having lewis acid binding site on Zn complex of the invention, therefore Zn complex of the invention is urged
Agent be catalyzed the ring-opening polymerization of lactide or caprolactone activity can by addition lewis acid and/or lewis base into
The adjusting of row zinc metal catalytic center acidity.For example, in the reaction system, by adding lewis acid, can be closed with zinc impregnation
The coordination of object skeleton in conjunction with and so that catalyst is lost activity, to effectively terminate polymerization process；And the complex bound Louis
This acid is also easy to separate from zinc compound skeleton by the lewis base of addition, lives so that catalyst restores catalysis
Property, restart so as to polymerization process.It therefore, can be by way of simply adding Lewis Acids and Bases to polymerization process
Carry out the control of " off/on ".
In the present invention, it is preferred to which the lewis acid used can be BF3、BCl3、BBr3Or (C6F5)3Deng the road used
This easy alkali can be pyridine, imidazoles or 2,6- lutidines etc..
It should be understood that within the scope of the invention, above-mentioned each technical characteristic of the invention and have in below (eg embodiment)
It can be combined with each other between each technical characteristic of body description, to form a new or preferred technical solution.As space is limited, exist
This is no longer repeated one by one.
Embodiment
Following examples merely illustrate different aspect of the invention, the data provided include that the synthesis of ligand, metal are matched
Close the synthesis of object and the ring-opening polymerisation applied to lactide and caprolactone, the wherein synthesis of metal complex, ring-opening polymerisation
Journey is carried out under anhydrous and oxygen-free, and the substance of all sensitivities is stored in -30 DEG C of glove box refrigerator, and all solvents all pass through
Stringent dry water removal, lactide uses methylene chloride and n-hexane recrystallization purifying, after the hydrogenated calcium of caprolactone is 12 hours dry
Vacuum distillation purifying obtain, bis- (double trimethyl silicon substrates) amine zinc precursor zinc compounds according to document [Rivillo D, Guly á s H,
Benet-Buchholz J,et al.Angewandte Chemie International Edition,2007,46(38):
7247-7250.] synthesis obtains, is not particularly illustrated, and all raw materials directly use after buying.
Silica gel column chromatography uses the silica gel of 200-300 mesh；Nuclear-magnetism detection Bruker 400MHz nuclear-magnetism instrument；Element point
Analysis is measured by China Science & Technology University's physics and chemistry center；Molecular weight and molecualr weight distribution is measured by gel permeation chromatography (GPC)
(polystyrene type pillar, HR2 and HR4, box temperature are 40 DEG C, are pumped using Water 1515 and Water 2414；Mobile phase is tetrahydro
Furans, flow velocity are 1.0 milliliters per minute, use the polystyrene of polydispersion for standard)；Mass spectrum Thermo LTQ
Orbitrap XL (ESI+) or P-SIMS-Gly of Bruker Daltonics Inc (EI+) measurement；Single crystal X diffraction point
Analysis uses Oxford Diffraction Gemini S Ultra CCD single crystal diffraction instrument, Cu K α
Room temperature radiation；The synthesis of beta-diimine ligand reference literature (see, for example, [Allen SD, Moore DR, Lobkovsky EB,
Coates GW.J Organomet Chem,2003,683:137-148]、[Tong R,Cheng JJ.Macromolecules,
2012,45:2225-2232]、[Doyle DL,Hitchcock PB,Lappert MF,Li G.J Organomet Chem,
2009,694:2611-2617] etc.), such as required beta-diimine ligand compound can be obtained by scheme as follows,
P-methyl benzenesulfonic acid used in it is catalyst, and toluene or tetrahydrofuran are reaction dissolvent, by 2,6-DIPA, second
The reaction of the reaction reagents such as acyl acetone and n-BuLi.These reactions can be for example with oil bath heating device, reflux point
It is carried out in the Schlenk bottle of water installations.
Synthesis example 1:2- ((2,6- diisopropyl) amino) -3- cyano -4- ((2,6- diisopropyl phenyl) imino group) -2-
The synthesis of amylene
Under nitrogen protection, 2- ((2,6- diisopropyl) amino) -4- ((2,6- diisopropyls are added in Schlenk bottles
Phenyl) imino group) -2- amylene (1.8 grams, 4.3 mMs), then it is added 90 milliliters of tetrahydrofuran.It will passing through liquid nitrogen/acetone
After mixture solution is cooled to -78 DEG C, slowly to reaction system be added n-BuLi (2.5 mol/Ls, 5.16 mMs, 2.06
Milliliter), after five minutes in -78 DEG C of reactions, reaction is warmed to room temperature and is reacted again 1 hour.It is cooled to -78 DEG C again later, it will be molten
Reaction system is added dropwise in the p-toluenesulfonyl cyanide (0.82 gram, 4.52 mMs) of 30 milliliters of tetrahydrofurans, is then warmed to
Room temperature reaction 10 hours.To after reaction, walk solvent with Rotary Evaporators rotation, then obtained solid with methylene chloride dissolution
Body after extraction, is separated organic phase simultaneously with separatory funnel later with saturated sodium-chloride water solution by organic extractant phase three times
It is dry with anhydrous sodium sulfate, and after being spin-dried for solvent, it is crystallized with n-hexane at -20 DEG C come purified product (1.48 grams, 78%).
1H NMR(400MHz,C6D6) δ=14.14 (1H, s, NH), 7.07 (6H, m, ArH), 2.93 (4H, m, J=
6.5Hz,CHMe2),1.98(6H,s,a-CH3), 1.02 (12H, d, J=6.5Hz, CHMeMe, CHMeMe).
13C NMR(100MHz,C6D6): δ=167.4,142.2,139.0,126.8,123.9,121.5,81.4,28.7,
24.2,23.3,19.8。
Elemental analysis: calculate C, 81.21；H,9.31；N,9.47；Actual measurement: C, 81.28；H,9.20；N,9.49.
HRMS (m/z): C is calculated30H41N3:443.3300；Actual measurement: 443.3308 [M+H]+。
Synthesis example 2:2- ((2,6- diisopropyl) amino) -3- tertiary bytyry -4- ((2,6- diisopropyl phenyl) imido
Base) -2- amylene synthesis
Under nitrogen protection, 2- ((2,6- diisopropyl) amino) -4- ((2,6- diisopropyls are added in Schlenk bottles
Phenyl) imino group) -2- amylene (4.18 grams, 10 mMs), then it is added 100 milliliters of tetrahydrofuran.Passing through liquid nitrogen/acetone
After being cooled to -78 DEG C, n-BuLi (2.5 mol/Ls, 11.2 mMs, 4.5 milliliters) slowly are added into reaction system, in -
78 DEG C of reactions after five minutes, reaction are warmed to room temperature down and is reacted again 1 hour.- 78 DEG C are cooled to again later, by trimethyl second
Reaction system is added dropwise in acyl chlorides (1.3 milliliters, 10.5 mMs), then warms to room temperature reaction 12 hours.To the end of reacting
Afterwards, solvent is walked with Rotary Evaporators rotation, with methylene chloride dissolved solid, is extracted three times with saturated sodium-chloride water solution later, extraction
After taking, organic phase is separated with separatory funnel and is dried with anhydrous sodium sulfate, and after being spin-dried for solvent, with n-hexane -20
DEG C crystallization come purified product (4.47 grams, 89%).
1H NMR(400MHz,CDCl3) δ=13.04 (s, 1H, NH), 7.13 (s, 6H, ArH), 3.10 (m, 4H, CHMe2),
1.67(s,6H,a-CH3),1.30(s,9H,COMe3), 1.20 (d, J=6.4Hz, 12H, CHMeMe), 1.12 (d, J=5.4Hz,
12H,CHMeMe)。
13C NMR(100MHz,CDCl3): δ=209.6,167.8,146.0,136.6,136.4,124.4,123.5,
123.4,68.6,45.8,28.1,28.0,26.5,24.3,23.9,23.5,23.4,20.1。
Elemental analysis: calculate C, 81.22；H,10.02；N,5.57；Actual measurement: C, 81.24；H,9.98；N,5.61.
HRMS (m/z): C is calculated34H50N2O:502.3923, actual measurement: 502.3928 [M+H]+。
Synthesis example 3:2- ((2,6- diisopropyl) amino) -3- cyano -4- ((2,6- diisopropyl phenyl) imino group) -2-
Amylene closes the synthesis of bis- (trimethyl silicon substrate) amido Zn complexes (catalyst 1)
Under nitrogen protection, 2- ((2,6- diisopropyl) amino) -3- cyano -4- ((2,6- is added in Schlenk bottles
Diisopropyl phenyl) imino group) -2- amylene (0.88 gram, 2 mMs), 4 milliliters of toluene stirring and dissolvings are then added.Then will
In (0.92 gram, 2.4 mMs) addition reaction system of bis- (trimethyl silicon substrate) amido zinc, then by oil bath heating to 85 DEG C it is anti-
It answers 18 hours.After reaction, a large amount of white solid is generated.After solvent is drained under reduced pressure, in the gloves of nitrogen protection
Solid is washed three times in case with toluene, is drained under then depressurizing, obtain as white solid required product (1.27 grams, yield
95%).
1H NMR(400MHz,CDCl3) δ=7.27-7.20 (m, 6H, ArH), 2.97-2.85 (m, 4H, CHMe2),2.21
(s,6H,a-CH3), 1.33-1.28 (d, J=6.8Hz, 12H, CHMeMe), 1.16-1.12 (d, J=6.7Hz, 12H,
CHMeMe),-0.36(s,18H,SiMe3,SiMe3)。
13C NMR(101MHz,CDCl3):δ176.31,150.25,149.77,147.52,147.03,142.05,
140.55,139.08,139.11,136.55,136.47,128.32,124.64,78.14,29.13,24.01,23.38,
22.12。
Elemental analysis: calculate C, 64.69；H,8.75；N,8.38；Survey C, 64.55；H,8.93；N,8.28.
Synthesis example 4:2- ((2,6- diisopropyl) amino) -3- tertiary bytyry -4- ((2,6- diisopropyl phenyl) imido
Base) -2- amylene closes the synthesis of bis- (trimethyl silicon substrate) amido Zn complexes (catalyst 2)
Under nitrogen protection, 2- ((2,6- diisopropyl) amino) -3- tertiary bytyry -4- is added in Schlenk bottles
((2,6- diisopropyl phenyl) imino group) -2- amylene (1.06 grams, 2 mMs) is then added 4 milliliters of toluene and stirs molten
Solution.Then, will be bis- in (0.92 gram, 2.4 mMs) addition reaction system of (trimethyl silicon substrate) amido zinc, then add via oil bath
Heat to 85 DEG C react 72 hours.After reaction, a large amount of white solid is generated.After solvent is drained under reduced pressure, in nitrogen
By 1 milliliter of n-hexane dissolution of resulting solid in the glove box of protection, it is subsequently placed in refrigerator in -30 DEG C of freezing and crystallizings, most
The required product (0.99 gram, yield 63%) as light yellow solid is obtained eventually.
1H NMR(400MHz,CDCl3) δ=7.24-7.13 (m, 6H, Ar-H), 3.28-3.12 (m, 2H, CHMe2),
3.03-2.92(m,2H,CHMe2),1.78(s,6H,α-CH3), 1.36-1.31 (d, J=6.4Hz, 6H, CHMe2),1.31-
1.25 (d, J=6.4Hz, 6H, CHMe2),1.27(s,9H,COMe3), 1.25-1.20 (d, J=6.4Hz, 6H, CHMe2),
1.09-1.02 (d, J=6.4Hz, 6H, CHMe2),-0.16(s,9H,SiMe3),-0.48(s,9H,SiMe3)。
13C NMR(100MHz,CDCl3):δ217.27,165.85,143.88,142.67,141.40,126.20,
124.67,123.94,108.64,77.36,47.69,29.83,28.76,27.91,25.43,24.88,24.83,23.67,
23.53,5.47,5.12,2.64。
Elemental analysis: calculate C, 66.04；H,9.28；N,5.78；Survey C, 65.91；H,9.55；N,5.71.
Fig. 1 show according to the present embodiment 4 prepare catalyst 2 X-ray diffraction mono-crystalline structures schematic diagram, wherein N1,
N2 and N3 respectively indicates 3 nitrogen-atoms in the complex structure；O1 indicates 1 oxygen atom in the complex structure；Sil and
Si2 respectively indicates 2 silicon atoms in the complex structure；Zn1 indicates 1 zinc metallic atom in the ligand structure.This is matched
Hydrogen atom is not shown on the diagram in body structure, other carbon atoms are not specifically labeled on the diagram.
Compare synthesis example 5: 2- ((2,6- diisopropyl) amino) -3- cyanogen of (pentafluorophenyl group) borine of lewis acid three coordination
Base -4- ((2,6- diisopropyl phenyl) imino group) -2- amylene closes bis- (trimethyl silicon substrate) amido Zn complexes (catalyst 3)
Synthesis
Under nitrogen protection, in Schlenk bottles be added synthesis example 3 obtained in catalyst 1 (0.333 gram, 0.5 mmoles
You), 4 milliliters of methylene chloride and stirring and dissolving is then added.Then, by three (pentafluorophenyl group) borines (0.256 gram, 0.5 mmoles
You) in addition system, react 30 minutes at room temperature.It, will in the glove box of nitrogen protection after solvent is drained under reduced pressure
Resulting solid washs three times with n-hexane, and then decompressing and extracting obtains the required product as white solid (0.297 gram, produce
Rate 51%).
1H NMR (400MHz, CDCl3): δ=7.38-7.10 (m, 6H, Ar-H), 2.80 (m, 4H, CHMe2), 2.04 (s,
6H, α-CH3), 1.39-1.28 (d, J=6.7Hz, 12H, CHMe2), 1.18-1.07 (d, J=6.7Hz, 12H, CHMe2) ,-
0.35(s,18H,SiMe3)。
13C NMR (101MHz, CDCl3): δ=175.40,149.73,149.29,147.22,146.93,140.68,
140.25,138.98,138.81,136.45,136.27,128.24,124.80,78.06,29.25,24.04,23.66,
22.12,2.01,0.70,0.22。
19F NMR(376MHz,CDCl3):δ-132.51,-132.57,-156.65,-156.71,-156.76,-
163.28,-163.34,-163.39。
Elemental analysis: calculate C, 54.95；H,4.95；N,4.75；Actual measurement: C, 54.72；H,5.08；N,4.61.
Fig. 2 is the X-ray diffraction mono-crystalline structures schematic diagram for the catalyst 3 that according to the present invention prepared by control synthesis example 5, wherein
N1, N2, N3 and N4 respectively indicate 4 nitrogen-atoms in the complex structure；B1 indicates 1 boron original in the complex structure
Son；Si1 and Si2 respectively indicates 2 silicon atoms in the complex structure；Zn1 indicates that 1 zinc metal in the ligand structure is former
Son；C2, C3 and C4 indicate to cooperatively form pentacyclic three carbon atoms, and hydrogen atom in the ligand structure with N1, N2 and Zn1
It does not show on the diagram, other carbon atoms are not specifically labeled on the diagram.
Application examples 1-9: the ring-opening polymerisation of catalysis lactide or caprolactone
In glove box, into the Schlenk flask with magneton, it is separately added into the catalyst 1,2 or 3 (10 of above-mentioned synthesis
Micromole) and 5 milliliters of methylene chloride.Then, into mixture solution be added rac-lactide (0.144 gram, 1 mM, from
Bellingwell company's purchase) or caprolactone (0.114 gram, 1 mM, bought from Bellingwell company).By reaction mixture in room temperature
Lower stirring, and every the solution of 0.2 milliliter of the taking-up from reaction system in 10 minutes, it is quenched with acetic acid dichloromethane solution (3 drop)
It goes out polymerization reaction.The solution of taking-up is evaporated into dry in air, is filtered by vacuum later to constant weight.Sampling is analyzed with nucleus magnetic hydrogen spectrum
Conversion ratio, and molecular weight and molecualr weight distribution is measured with GPC, specific reaction condition and result are as shown in table 1.
After completion of the reaction, obtained reaction solution is concentrated under vacuum, and with n-hexane by the polymerization in residue
Object product is precipitated, and after vacuum is drained, is analyzed by mass spectrometry to resulting polymer product, Fig. 3 shows 1 institute of application examples
The mass spectrogram of the polymer obtained.
Table 1: catalysis lactide or caprolactone ring-opening polymerisationa)
aPolymerizing condition: 10 micromole's catalyst, 1 mM of monomer, 5 milliliters of methylene chloride, 30 DEG C.
bMonomer conversion is measured with nucleus magnetic hydrogen spectrum.
cCalculate molecular weight=monomer molecule amount × (monomer concentration/catalyst concn) × conversion ratio+161.11.
dGPC numerical value is numerical value of the styrene in tetrahydrofuran, for polylactide, by the numerical value multiplied by 0.58, for
Polycaprolactone, by the numerical value multiplied by 0.56.
eResult is not detected in expression.
The result of application examples 1-8 can be seen that catalyst according to the invention 1 from table 1 and catalyst 2 can be efficiently
It is catalyzed the ring-opening polymerisation of lactide or caprolactone；It can be seen that work as from the result of application examples 9 and use catalyst 3 of the invention (i.e.
Catalyst 1 is coordinated the coordination complex combined with lewis acid) when, the catalytic activity of catalyst 1 is blocked completely, thus
The ring-opening polymerisation of lactide or caprolactone can not be catalyzed.
Fig. 4-6 respectively illustrates the power of the catalyst lactide ring-opening polymerisation of application examples 1,2 and 5 according to the present invention
It learns curve graph (relation curve i.e. between the logarithm and monomer conversion of monomer concentration ratio), wherein polymerizing condition are as follows: 10 is micro-
Mol catalyst；Catalyst concn: monomer concentration=1:100；5 milliliters of methylene chloride；30 DEG C of reaction temperature.From can in Fig. 4-6
To find out, catalyst 1 for the ring-opening polymerisation of caprolactone speed ratio for lactide ring-opening polymerisation rate faster, that is, be catalyzed
Activity is higher.
In addition, catalyst 2 has obvious by comparative catalyst 1 and catalyst 2 for the ring-opening polymerisation rate of lactide
Better activity.In addition, the present inventor has confirmed although being not shown, road is individually added into reaction system
Easy this alkali such as pyridine, does not influence the activity of the ring-opening polymerisation of catalyst lactide or caprolactone of the invention.
Fig. 7 shows the resulting polymer of one catalyzing ring-opening polymerization of lactide of catalyst using one embodiment of the invention
Molecular weight (■) and molecular weight distribution (▲) and monomer conversion between graph of relation；Fig. 8, which is shown, utilizes the present invention
The molecular weight (■) and molecular weight distribution of the resulting polymer of two catalyzing ring-opening polymerization of lactide of catalyst of one embodiment
Graph of relation between (▲) and monomer conversion；Fig. 9 shows the catalysis of catalyst one using one embodiment of the invention
Relationship between the molecular weight (■) and molecular weight distribution (▲) and monomer conversion of the resulting polymer of caprolactone ring-opening polymerisation
Curve graph, wherein polymerizing condition are as follows: 10 micromole's catalyst；Catalyst concn: monomer concentration=1:100；5 milliliters of dichloromethanes
Alkane；30 DEG C of reaction temperature.It can be seen that the increase with monomer conversion from Fig. 7-9, catalysis monomers lactide ring-opening polymerisation obtains
To the obtained molecular weight of polycaprolactone product of polylactic acid product and catalysis monomer caprolactone ring-opening polymerisation linearly increase,
And molecular weight distribution does not have significant changes, is indicated above the open loop of catalyst lactone such as lactide and caprolactone of the invention
Polymerization is that living polymerization feature, i.e. number-average molecular weight and monomer conversion are in a linear relationship.
Application examples 10-13: activity regulation of Louis's bronsted lowry acids and bases bronsted lowry to catalysis lactide or caprolactone ring-opening polymerisation
In glove box, catalyst 1 or 2 (10 micromole) and two is added into the Schlenk flask with magnetic stir bar
5 milliliters of chloromethanes.Then, into mixture solution be added rac-lactide (0.144 gram, 1 mM, from Bellingwell company
Purchase) or caprolactone (0.114 gram, 1 mM, bought from Bellingwell company).Reaction is stirred at room temperature, every 10 minutes
The solution that 0.2 milliliter is taken out from reaction system, it is poly- with being quenched by methylene chloride dilution acetic acid dichloromethane solution (3 drop)
Close reaction.
After polymerization reaction carries out about 1 hour, 10 micromolar lewis acid three (pentafluorophenyl group) boron are added into system
Alkane or boron trifluoride are bought from Ann Kyrgyzstan company), continue to take out 0.2 milliliter of solution from system every 10 minutes, and
Polymerization reaction is quenched with acetic acid dichloromethane solution (3 drop).
After polymerization carries out about 2 hours, 10 micromolar lewis base pyridines are added into reaction system (from An Naiji
Company's purchase), continue to take out 0.2 milliliter of solution from system every 5-10 minute, and with acetic acid dichloromethane solution (3 drip)
Polymerization reaction is quenched.
The solution taken out every time is evaporated into dry in air, is filtered by vacuum later to constant weight.Sampling nucleus magnetic hydrogen spectrum point
Analyse conversion ratio.
Figure 10-13 is shown by adding lewis acid (B (C5F6)3Or BF3) and lewis base (pyridine Py) regulate and control root
According to the active dynamic curve diagram of catalyst lactide or caprolactone ring-opening polymerization of the invention, wherein B
(C5F6)3Indicate three (pentafluorophenyl group) borines, BF3Indicate that boron trifluoride, Py indicate pyridine.It can be seen that from Figure 10-13
It is catalyzed in the ring opening polymerisation process of lactide or caprolactone, lewis acid and lewis base, which is successively added, rate constant of polymerisation
It influences.More specifically, it is apparent that lewis acidic addition, the influence to catalyst 1 and catalyst 2 from Figure 10-13
It is consistent, the catalyst 1 after lewis acid is coordinated and catalyst 2 can all lost poly- to lactide or caprolactone open loop
The activity of conjunction；However, when then again into polymerization reaction system be added lewis base after, due to lewis base with it is lewis acidic
Coordination is better than the coordination of lewis acid Yu Zn complex catalyst of the invention, so that Zn complex catalyst of the invention
The catalytic activity of the ring-opening polymerisation of lactide or caprolactone is restored, reaction continues.In addition, can be with from Figure 10-13
It is seen that due to the addition of lewis acid and lewis base, so that Zn complex catalyst of the invention may decompose,
So that, although catalytic activity can be restored, catalytic activity cannot be restored to initial after then addition lewis base
Catalytic activity.
Above to the present invention have been described in detail, but the invention is not limited to specific embodiment parties described herein
Formula.It will be appreciated by those skilled in the art that in the case without departing from the scope of the present invention, other changes and deformation can be made.This hair
Bright range is defined by the following claims.
Claims (10)
1. a kind of Zn complex of formula (I),
Wherein
R1、R2、R3、R4、R5And R6It is hydrogen, halogen, C independently of one another1-C4Alkyl, halogenated C1-C4Alkyl or C1-C4Alkoxy；
X is cyano, propiono, tertiary bytyry or benzoyl.
2. Zn complex according to claim 1, which is characterized in that R1、R3、R4And R6It is C independently of one another1-C4Alkyl,
Halogenated C1-C4Alkyl or C1-C4Alkoxy, and R2And R5It is hydrogen, halogen or C independently of one another1-C4Alkyl.
3. Zn complex according to claim 1, which is characterized in that X is cyano, propiono or tertiary bytyry.
4. Zn complex according to claim 1, which is characterized in that the Zn complex is 2- ((2,6- diisopropyl)
Amino) -3- cyano -4- ((2,6- diisopropyl phenyl) imino group) -2- amylene closes bis- (trimethyl silicon substrate) amido zinc or 2-
((2,6- diisopropyl) amino) -3- tertiary bytyry -4- ((2,6- diisopropyl phenyl) imino group) -2- amylene closes bis- (front threes
Base silicon substrate) amido zinc.
5. a kind of ligand compound of formula (II),
Wherein R1、R2、R3、R4、R5、R6It is as defined in claim 1 with X.
6. ligand compound according to claim 5, which is characterized in that the ligand compound is 2- ((2,6- diisopropyls
Base) amino) -3- cyano -4- ((2,6- diisopropyl phenyl) imino group) -2- amylene or 2- ((2,6- diisopropyl) amino) -
3- tertiary bytyry -4- ((2,6- diisopropyl phenyl) imino group) -2- amylene.
7. a kind of method for preparing formula described in claim 1 (I) Zn complex, the method includes；
In organic solvent, at 70-90 DEG C, make formula according to claim 5 (II) ligand compound and bis- (trimethyls
Silicon substrate) reaction of amido zinc.
8. the method according to the description of claim 7 is characterized in that the ligand compound of the formula (II) used and the zinc
The molar ratio of compound is 1:1.1-2；The time of the reaction is 12-96 hours；The organic solvent be selected from tetrahydrofuran,
One of n-hexane, toluene, benzene, carbon tetrachloride, ether, 1,4- dioxane and 1,2- dichloroethanes are a variety of.
9. the Zn complex of formula described in any one of -4 (I) is used to be catalyzed opening for lactide or caprolactone according to claim 1
The purposes of cyclopolymerization reaction, wherein the Zn complex is used as the catalyst of the ring-opening polymerization.
10. purposes according to claim 9, which is characterized in that adjusted by addition lewis acid and/or lewis base
The activity of ring-opening polymerization described in the catalyst；Preferably, the lewis acid is BF3、BCl3、BBr3Or
(C6F5)3, this described alkali is pyridine, imidazoles or 2,6- lutidines.
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Cited By (1)
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|---|---|---|---|---|
| CN111925400A (en) * | 2020-08-17 | 2020-11-13 | 中国科学院长春应用化学研究所 | Redox-responsive metalloporphyrin complex, preparation method thereof and preparation method of polylactic acid |
-
2019
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Non-Patent Citations (5)
| Title |
|---|
| DAVID J. DOYLE等: "New group 14 element(IV) b-diiminates and a Sn(II) analogue", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 * |
| RONG TONG等: "Controlled Synthesis of Camptothecin-Polylactide Conjugates and Nanoconjugates", 《BIOCONJUGATE CHEM.》 * |
| RONG TONG等: "Drug-Initiated, Controlled Ring-Opening Polymerization for the Synthesis of Polymer−Drug Conjugates", 《MACROMOLECULES》 * |
| SCOTT D. ALLEN等: "Structure and reactivity of mono- and dinuclear diiminate zinc alkyl complexes", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 * |
| 赵敏慧: "二亚胺类催化剂的外界刺激调控在烯烃聚合及开环聚合中的应用", 《中国科学技术大学硕士学位论文》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111925400A (en) * | 2020-08-17 | 2020-11-13 | 中国科学院长春应用化学研究所 | Redox-responsive metalloporphyrin complex, preparation method thereof and preparation method of polylactic acid |
| CN111925400B (en) * | 2020-08-17 | 2024-03-26 | 中国科学院长春应用化学研究所 | Redox-responsive metalloporphyrin complex, preparation method thereof and preparation method of polylactic acid |
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