CN103380135A - 用于内酯类开环聚合的基于n-杂环卡宾的锆络合物 - Google Patents
用于内酯类开环聚合的基于n-杂环卡宾的锆络合物 Download PDFInfo
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- CN103380135A CN103380135A CN201180059470XA CN201180059470A CN103380135A CN 103380135 A CN103380135 A CN 103380135A CN 201180059470X A CN201180059470X A CN 201180059470XA CN 201180059470 A CN201180059470 A CN 201180059470A CN 103380135 A CN103380135 A CN 103380135A
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- Prior art keywords
- halogen
- alkyl
- alkyl radical
- aryl
- alkoxy
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Links
- 238000007151 ring opening polymerisation reaction Methods 0.000 title claims abstract description 11
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 150000002596 lactones Chemical group 0.000 title claims abstract description 6
- 150000003754 zirconium Chemical class 0.000 title description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 84
- 239000003446 ligand Substances 0.000 claims description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 33
- 229910052736 halogen Inorganic materials 0.000 claims description 23
- 150000002367 halogens Chemical group 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 19
- 229910052801 chlorine Inorganic materials 0.000 claims description 17
- 150000003254 radicals Chemical class 0.000 claims description 17
- 229910052794 bromium Inorganic materials 0.000 claims description 16
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 13
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 229910052740 iodine Inorganic materials 0.000 claims description 11
- 125000004104 aryloxy group Chemical group 0.000 claims description 10
- 229910052735 hafnium Inorganic materials 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 8
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 150000001408 amides Chemical class 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- -1 alkyl nitriles Chemical class 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001983 dialkylethers Chemical class 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 6
- 229920000642 polymer Polymers 0.000 abstract description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 10
- 150000002362 hafnium Chemical class 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 2
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 28
- 239000000243 solution Substances 0.000 description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000006116 polymerization reaction Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 17
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- 239000004626 polylactic acid Substances 0.000 description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 8
- 229920000747 poly(lactic acid) Polymers 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- JDIIGWSSTNUWGK-UHFFFAOYSA-N 1h-imidazol-3-ium;chloride Chemical compound [Cl-].[NH2+]1C=CN=C1 JDIIGWSSTNUWGK-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 238000005809 transesterification reaction Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 4
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 235000014655 lactic acid Nutrition 0.000 description 4
- 239000004310 lactic acid Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical group C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 3
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 3
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 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 2
- 125000001309 chloro group Chemical class Cl* 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
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- 239000000155 melt Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- JJTUDXZGHPGLLC-ZXZARUISSA-N (3r,6s)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-ZXZARUISSA-N 0.000 description 1
- XBQHMDPUHANFFH-UHFFFAOYSA-N 2,4-ditert-butyl-6-[3-(3,5-ditert-butyl-2-hydroxyphenyl)-1,2,3a,4,5,6,7,7a-octahydrobenzimidazol-1-ium-1-yl]phenol;chloride Chemical compound [Cl-].CC(C)(C)C1=CC(C(C)(C)C)=CC(N2C3CCCCC3[NH+](C2)C=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)=C1O XBQHMDPUHANFFH-UHFFFAOYSA-N 0.000 description 1
- CRIXBZAOMTXXJY-UHFFFAOYSA-N 2,4-ditert-butyl-6-[3-(3,5-ditert-butyl-2-hydroxyphenyl)benzimidazol-3-ium-1-yl]phenol;chloride Chemical compound [Cl-].CC(C)(C)C1=CC(C(C)(C)C)=CC(N2C3=CC=CC=C3[N+](C=3C(=C(C=C(C=3)C(C)(C)C)C(C)(C)C)O)=C2)=C1O CRIXBZAOMTXXJY-UHFFFAOYSA-N 0.000 description 1
- OMLHCPASYKDSDP-CLJLJLNGSA-N 2-(n-[(1r,2r)-2-aminocyclohexyl]-3,5-ditert-butyl-2-hydroxyanilino)-4,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N([C@H]2[C@@H](CCCC2)N)C=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)=C1O OMLHCPASYKDSDP-CLJLJLNGSA-N 0.000 description 1
- RBMHUYBJIYNRLY-UHFFFAOYSA-N 2-[(1-carboxy-1-hydroxyethyl)-hydroxyphosphoryl]-2-hydroxypropanoic acid Chemical compound OC(=O)C(O)(C)P(O)(=O)C(C)(O)C(O)=O RBMHUYBJIYNRLY-UHFFFAOYSA-N 0.000 description 1
- FYGFQAJDFJYPLK-UHFFFAOYSA-N 3-butyloxiran-2-one Chemical compound CCCCC1OC1=O FYGFQAJDFJYPLK-UHFFFAOYSA-N 0.000 description 1
- YYAMOMYEENPVSP-UHFFFAOYSA-N 4-[(4-sulfamoylphenyl)methyl]benzenesulfonamide Chemical compound C1=CC(S(=O)(=O)N)=CC=C1CC1=CC=C(S(N)(=O)=O)C=C1 YYAMOMYEENPVSP-UHFFFAOYSA-N 0.000 description 1
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 description 1
- KRSSDSVKULEWRH-UHFFFAOYSA-M CC(C)O[Zr]Cl Chemical compound CC(C)O[Zr]Cl KRSSDSVKULEWRH-UHFFFAOYSA-M 0.000 description 1
- FKNHCFCLZFESRE-UHFFFAOYSA-M Cl[Zr]CC1=CC=CC=C1 Chemical compound Cl[Zr]CC1=CC=CC=C1 FKNHCFCLZFESRE-UHFFFAOYSA-M 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 1
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
- 238000004639 Schlenk technique Methods 0.000 description 1
- 235000021536 Sugar beet Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000006345 epimerization reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- 229920001580 isotactic polymer Polymers 0.000 description 1
- SCEZYJKGDJPHQO-UHFFFAOYSA-M magnesium;methanidylbenzene;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C1=CC=CC=C1 SCEZYJKGDJPHQO-UHFFFAOYSA-M 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001434 poly(D-lactide) Polymers 0.000 description 1
- 229920001432 poly(L-lactide) Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000009870 specific binding Effects 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- 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
- C07F7/28—Titanium compounds
-
- 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
-
- 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
- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
- C08F261/12—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated acetals or ketals
-
- 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
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/74—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals
- C08F4/76—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
本发明报道了新的基于N-杂环卡宾的锆(或铪)络合物及其作为用于内酯类开环聚合的催化剂的用途。这些新的催化剂是稳定和通用的并且发挥控制聚合物分子量和/或立体化学的作用并且显示高反应性(对照用于低温应用)。尤其是，新的催化剂显示增强的活性且同时显示比现有技术使用的催化剂更佳的选择性。
Description
近年来，聚乳酸(PLA)和相关聚合物，如聚已内酯或聚丁内酯因其高度通用的应用范围及其生物可降解性而已经受到关注。来源于100%可再生的资源，例如玉米和甜菜、PLA和相关聚酯类作为基于油的聚合物的替代品对于环境保护仍然是非常令人感兴趣的。然而，尽管其极佳的性质的平衡，但是商业化应用从历史上来看受限于高生产成本以及与聚烯烃等效物相比更差的性能特性。迄今为止，PLA仅在商品应用中替代基于石油的塑料方面取得了有限的成功，其中大部分最初的应用限于生物医学应用，例如缝合线。
无论如何，目前由大公司推动的在方法研发中的近期进展(Technische biopolymere,Hans-Josef Endres和Andrea Siebert-Raths,ISBN978-3-446-41683-3,(2009))将导致生产成本显著下降并且使得PLA成为未来的有活力的大规模使用（large-volume）的塑料。
PLA可以通过乳酸的直接缩合和通过环丙交酯二聚体的开环聚合制备。因为直接缩合途径是平衡反应，所以在聚合的后期阶段中除去痕量水的困难通常限制了可通过这种方法得到的最终分子量。
迄今为止，大部分工作致力于开环聚合，不过，Mitsui ToatsuChemicals已获得使用高沸点溶剂以驱动在直接酯化方法中除去水来得到高分子量PLA的共沸蒸馏方法的专利(美国专利US5,194,473.Mitsui Toatsu,(1990))。
Cargill Dow LLC已研发了用于生产基于乳酸的聚合物的低成本连续方法。该方法结合了在熔体中而非在溶液中合成丙交酯和PLA的主要环境和经济益处(美国专利US5,258,488和相关专利，Cargill,Inc.(1993))。该方法从乳酸水溶液的连续缩合反应开始以生产低分子量PLA预聚物。
接下来，使用锡催化将预聚物转化成丙交酯立体异构体的混合物以提高分子内环化反应的速率和选择性。然后通过真空蒸馏纯化熔化的丙交酯混合物。最后，使用熔体中的锡-催化的开环丙交酯聚合生产PLA高分子量聚合物，完全排除了使用高成本和对环境不友好的溶剂的应用。
从现有技术中已知的方法的不利之处尤其在于需要几个步骤，因为需要通过真空蒸馏的另一个纯化步骤，从而分离外消旋和内消旋丙交酯，这不仅耗费时间，而且耗费能量。
一般认为使用辛酸锡聚合丙交酯通过具有丙交酯开环的配位-插入机理而发生，以将两个乳酸分子添加到聚合物链的生长端。通常，采用辛酸锡催化的丙交酯聚合观察到了高分子量聚合物、良好反应速率和低水平的外消旋化。
聚合的典型条件是180±210℃、100±1000ppm的辛酸锡浓度和2±5h以达到约95%的转化率。聚合是催化剂和丙交酯二者的一级反应。往往使用含羟基的引发剂，如1-辛醇以控制分子量和加速反应。可以使用类似反应条件制备丙交酯与其他环状单体，如己内酯的共聚物。这些单体因末端生长聚合机理而可以用于制备无规聚合物或嵌段聚合物。
尽管辛酸盐催化的聚合导致良好的转化率，但是在基于天然产物的聚合物中锡的毒性和存在不能被忽视。此外，该方法需要相对高的温度。
聚酯合成中的常见副反应是酯交换，其中聚合物链的裂解和再形成导致分子量分布变宽，其在理论上被描述为单体转化率的函数。酯交换程度是任何LA聚合体系的重要选择性标准。在不连续A-B嵌段共聚酯类的制备中特别需要最低程度的酯交换，其中酯交换会危害共聚物的结构完整性。酯交换的出现对更具有活性且由此选择性更低的聚合催化剂而言尤其可以变成问题。在以三种立体异构体存在的LA的聚合中的立体选择性对控制而言也是重要的，因为材料的性质极大地取决于聚合物的等规度。只要聚合催化剂不影响单体或聚合物中手性中心的差向异构化，则等规PLA(PDLA或PLLA)可以通过分别使用纯的D-或L-LA获取。
选择性问题对D/L-LA混合物的聚合而言更为重要，其中增殖的金属醇盐中心可以显示对增强特定的立体异构体的偏向性。等规聚合物片段因这样的立体选择性反应产生。考虑到用于行为良好的LA聚合的一些一般实验标准，理想催化剂的属性包括高活性、与增殖相关的快速引发、最低程度的酯交换和控制由LA立体异构体任意混合物制备的PLA的立体化学纯度的能力。在充分限定的催化体系中构效关系的系统性反褶积对设计具有这些有益特征的聚合催化剂而言是重要的。
用于均相催化的配体设计基于利用与金属中心的连接单元（ligating units）的特定结合特性和特定充分限定的分子形状的靶向。其依赖于构成多齿配体体系的分子结构单元的空间和电子特性的结合。这种方法往往用于研发新的分子催化剂。
N-杂环卡宾类已成为用于研发均相催化剂的配体的新家族。它们是通过NCN碳键的强σ-供体且目前广泛用作膦类似物。已证实它们与大部分后过渡金属形成的M-C键是动力学惰性的，由此赋予它们用于配体设计的专用基元。相反地，使用具有前过渡金属的NHC配体是临时的，部分是因为易于从高氧化态过渡金属中解离N-杂环配体。这种假设使得前过渡金属和NHC的化学更难以研究。因此，为了降低配体解离的倾向，并入由阴离子配体围绕的中性卡宾供体的二齿或三齿NHC供体体系潜在地显示为富有希望的辅助配体。
本发明的目的在于研发新的基于N-杂环卡宾的锆(或铪)络合物及其作为用于内酯类开环聚合的催化剂的用途。新的催化剂是稳定的和通用的并且发挥控制聚合物分子量和/或立体化学的作用且显示高反应性(对照用于低温应用)。尤其是，新催化剂显示增强的活性且同时显示比现有技术使用的催化剂更佳的选择性。因为聚合物材料的物理性质直接受限于其分子量，所以控制聚合物分子量在本合成方法中具有巨大的重要性。
现已令人惊讶地发现，具有特定的二(羟基芳基-取代的)N-杂环卡宾配体的潜在的三齿配位的([L,X2]-型螯合物)，结合了这些配体的新的一系列锆(或铪)络合物是用于催化环酯类(丙交酯类,α-己内酯)开环聚合的最有效和最具选择性的化合物。更令人惊讶地，它们凸显了另外报道的基于等效的钛的络合物的性能(选择性、转换性)(Zelikoff,Ayellet L.;Kopilov,Jacob;Goldberg,Israel;Coates,Geoffrey W.;Kol,Moshe.Chem.Com.,(2009),(44),6804-6806;Romain,Charles;Brelot,Lydia;Bellemin-Laponnaz,Stephane;Dagorne,Samuel.Organometallics(2010),29(5),1191-1198)，并且在开环聚合条件下显示较高的稳定性和耐用性。
本发明由此涉及基于N-杂环卡宾的锆(或铪)的络合物及其作为用于内酯类开环聚合的催化剂的用途。
更具体地，本发明涉及催化方法以通过使用本文所述的基于N-杂环卡宾的锆或铪的络合物获得基于作为主要单体单元的丙交酯、己内酯的聚酯类。
在下文中，如果不另外指明，则"卤素"表示F、Cl、Br或I，优选F、Cl或Br，更优选F或Cl，甚至更优选Cl；如果不另外指明，则"烷基"表示直链和支链烷基；"烷氧基"表示直链和支链烷氧基;任意的烷基和环烷基是未取代的或被卤素取代。
本发明涉及式(I)化合物：
其中：
M选自Zr或Hf；
R1选自卤素(Cl、Br、F、I)、C1-C10烷基、C1-C10烷氧基、芳基、苄基(Bn)、芳氧基、苄氧基或式N(R7)(R8)的酰胺；
R2是任选的并且是配位溶剂，例如四氢呋喃、乙醚、水、乙腈、二甲胺或其他弱配位配体；
X选自卤素(Cl、Br、F、I)、C1-C10烷基、C1-C10烷氧基、芳基、苄基(Bn)、芳氧基、苄氧基或式N(R7)(R8)的酰胺；
R3和R4彼此独立地选自氢、C1-C10烷基、C5-C10环烷基，其中的所述烷基基团任选被卤素(Cl、Br、F、I)取代；C1-C10烷氧基、未取代的苯基或取代的苯基(其中取代基是卤素、C1-C10烷基或硝基)；
R5和R6彼此独立地选自氢、C1-C10烷基、C5-C10环烷基，其中的所述烷基基团任选被卤素(Cl、Br、F、I)取代；未取代的苯基或取代的苯基(其中取代基是卤素、C1-C10烷基或硝基)；
R5和R6可以任选地连接在一起以形成不饱和的或饱和的5－6元环，其中该环可以具有一个或多个手性中心；
R7和R8彼此独立地选自C1-C10烷基、C5-C10环烷基、未取代的苯基或取代的苯基(其中取代基是卤素、C1-C10烷基或硝基)。
在优选的方面，本发明涉及式(I)化合物，
其中，
M选自Zr；
R1选自Cl、Br、C3-C4烷氧基、芳氧基；
R2是任选的并且是配位溶剂，例如四氢呋喃、乙醚、二甲胺；
X选自Cl、Br、C3-C4烷氧基、芳氧基、苄氧基、C4-C5烷基或苄基；
R3和R4彼此独立地选自氢、CH3、C2H5、C3H7、C4H9；
R5和R6彼此独立地选自氢、CH3、C2H5、C3H7、C4H9；
R5和R6可以任选地连接在一起以形成不饱和或饱和的6元环，在饱和时，该环可以具有两个手性中心；可以使用的典型原料是R,R-S,S-R,S环己二胺；
R7和R8彼此独立地选自C1-C10烷基、C5-C10环烷基。
迄今为止已通过包括使"游离"卡宾螯合配体盐与MCl4或ClxM(OR)4-x(M=Zr,Hf)反应的"经典的"盐置换途径产生了通过结合了N-杂环卡宾的螯合配体(二齿螯合物或三齿螯合物)支持的锆和铪络合物制备配体和络合物。然而，该方法存在两个主要缺陷：
(i)在将螯合配体配位至金属前必须产生通常稳定性差的"游离"卡宾;和
(ii)可能形成不期望的均配（homoleptic）双加合络合物。总之，这两个因素可以显著地降低反应收率。
在本发明中，已经通过包括邻-羟基芳基-取代的咪唑啉鎓与ClxZr(OR)4-x的反应的醇消除路线(图3)研发了双酚盐-N-杂环卡宾4族络合物的直接和高收率一步合成。上述方法允许获得各种4族氯代和/或醇盐衍生物。
特别地，后面的氯络合物还易于以极佳收率转化成相应的烷基和/或醇盐衍生物(图5)。因此，易于在从咪唑啉鎓前体开始的一步或两步合成步骤中以高收率得到各种各样的双酚盐-N-杂环卡宾4族络合物。或者，如图6中所示，在锆衍生物的情况下，使邻-羟基芳基-取代的咪唑啉鎓前配体脱质子且随后用MCl4进行盐置换可以提供相应的金属络合物，虽然收率低于使用醇消除法获得的收率。
优选通过使1当量的金属前体，如金属醇盐、金属酰胺、金属烷基或金属卤素前体的溶液与1当量的相应配体的沸腾溶液反应制备式(I)的锆和铪络合物。按照标准方法分离沉淀。
在该方法中使用的溶剂优选选自C1-C8醇类、二烷基醚氧化物、烷基腈类、芳族化合物、二甲基甲酰胺、N-甲基吡咯烷酮或这些溶剂的混合物。特别优选非质子溶剂，如THF、甲苯或卤化溶剂，如二氯甲烷等，只举出几例。
该方法在10－150℃温度，优选介于室温和140℃之间进行。然后将反应混合物至少搅拌几分钟直到24小时。反应时间和反应温度取决于单体和溶剂(如果使用的话)。反应可以以不加其它溶剂的方式（neat）进行。
实施例：
除非有指示，否则全部操作在干燥氮气的惰性气氛中使用标准Schlenk技术进行。通过标准方法纯化和干燥溶剂。全部试剂为可商购的并且如收到时使用。1H和13C NMR光谱在Bruker Avance300光谱仪上在300MHz和75MHz记录并且使用残留质子溶剂峰参比。在FT-IR Perkin Elmer1600上获得红外光谱。质谱由"service despectrométrie de masse de l'UniversitéLouis Pasteur"记录。元素分析通过"service commun d'analyseélémentaire of the StrasbourgChemistry Department"进行。
配体合成：氯化N,N'-二(2-羟基-3,5-二-叔丁基苯基)-4,5-二氢-咪唑鎓(1)
于室温在空气中向N,N-双(2-羟基-53,5-二-叔丁基苯基)乙二胺(5.0g,10.7mmol)在MeOH(150ml)中的溶液中滴加2.10ml浓HCl(10M)。在白色固体完全溶解后，将溶液在减压下蒸发并在真空中干燥以产生相应的二盐酸盐。不将其分离或表征。向得到的固体中添加原甲酸三乙酯(50ml)并将烧瓶在室温在N2下搅拌1天。添加乙醚(50ml)并将白色固体过滤，用乙醚洗涤两次以提供期望的产物(5.22g，10.1mmol，94%)。1H NMR(300MHz,CDCl3)δ9.32(s,2H),8.16(s,1H),7.37(d,J=2.3Hz,2H),6.95(d,J=2.4Hz),4.64(s,4H),1.43(s,18H),1.29(s,18H);13C NMR(75MHz,CDCl3)δ158.8,148.7,143.1,140.3,125.3,123.9,119.7,51.7,35.5,34.3,31.1,29.3.HRMS(ESI)m/z:实测值479.3632，计算值[C31H47N2O2]+479.3638.
氯化N,N'-二(2-羟基-3,5-二-叔丁基苯基)-八氢苯并咪唑鎓(2)。
于室温在空气中向N,N-双(2-羟基-3,5-二-叔丁基苯基)-反式-1,2-环己二胺(2.0g,3.8mmol)在MeOH(40ml)中的溶液中滴加0.8ml浓HCl(10M)。在白色固体完全溶解后，将溶液在减压下蒸发并在真空中干燥以产生相应的二盐酸盐。不将其分离或表征。向得到的固体中添加原甲酸三乙酯(10ml)并将烧瓶在室温在N2下搅拌1天。添加乙醚(50ml)并将白色固体过滤，用乙醚洗涤两次以提供期望的产物(1.42g，2.5mmol，66%)。1H NMR(300MHz,CDCl3)δ9.31(s,2H),8.33(s,1H),7.36(d,J=2.4Hz,2H),6.86(d,J=2.4Hz,2H),4.59(m,2H),2.3-19(m,4H),1.42(s,18H),1.29(s,18H);13C NMR(75MHz,CD2Cl2)δ159.9,149.1,142.8,141.4,125.5,123.3,119.5,70.9,35.6,34.3,31.4,29.6,27.8,23.9.HRMS(ESI)m/z:实测值531.3949，计算值[C35H51N2O2]+531.3951.
氯化N,N'-二(2-羟基-3,5-二-叔丁基苯基)-苯并咪唑鎓(3).
在室温在氮气下向N,N-双(3,5-二-叔丁基-2-羟基苯基)-1,2-苯二胺(4.9g,9.5mmol)在MeOH(50ml)中的溶液中滴加1.9ml浓HCl(10M)。搅拌1小时后，将固体通过过滤分离，用己烷洗涤并干燥(约5g相应的二盐酸盐)。向得到的固体中添加原甲酸三乙酯(50ml)并将烧瓶在室温在N2下搅拌1天。添加乙醚(20ml)并过滤固体，从MeOH/乙醚中重结晶以提供期望的产物(2.1g,3.7mmol,39%)。1H NMR(300MHz,CDCl3)δ9.28(s,2H),9.04(s,1H),7.61-7.57(m,4H),7.55(d,J=2.4Hz,2H),7.15(d,J=2.4Hz,2H),1.48(s,18H),1.34(s,18H));13C NMR(75MHz,CDCl3)δ149.3,143.0,141.8,141.4,132.4,127.8,126.9,120.9,114.5,35.85,34.5,31.5,29.6.HRMS(ESI)m/z：实测值527.3637，计算值[C35H47N2O2]+527.3638.
锆和铪络合物合成
LZr(Cl)(OiPr)(THF),L=配体(1)
在室温用移液管将Zr(OiPr)4、iPrOH(752,6mg,1.94mol)的THF溶液(5mL)添加到搅拌的氯化咪唑鎓盐1(1.0g,1.94mmol)的THF溶液(100ml)中。在添加锆试剂后，最初无色的溶液缓慢地变成黄/绿色。将该反应混合物在室温搅拌过夜并蒸发至干以定量地产生黄/绿色固体残余物L1Zr(Cl)(OiPr)(THF)，如通过NMR光谱法所测定。如果需要的话，则可以通过THF/戊烷(1/5)重结晶应用纯化步骤(1,14g,80%收率)。
1H NMR(300MHz,CD2Cl2)δ:7.21(d,J=2.2Hz,2H,芳基-H),6.98(d,J=2.2Hz,2H,芳基-H),4.48-4.21(m,4H,NCH2),4.18(hept,J=6.2Hz,1H,OiPr),3.76-3.63(m,4H,THF),1.77-1.69(m,4H,THF),1.56(s,18H,tBu),1.37(s,18H,tBu),0.94(d,J=6.3Hz,6H,CH3-OiPr).13C NMR(75MHz,CD2Cl2)δ:200.0(NCN),149.1(Cipso,O-芳基),139.8(Cquat,芳基),138.2(Cquat,芳基),130.6(Cquat,芳基),119.8(CH,芳基),112.7(CH,芳基),73.9(CH,OiPr),70.2(CH2,THF),48.1(CH2,NCH2),36.0(Cquat,tBu),34.8(Cquat,tBu),31.9(CH3,tBu),30.2(CH3,tBu),26.6(CH3,OiPr),25.7(CH2,THF).
LHf(Cl)(OiPr)(THF),L=配体(1)
在室温用移液管将Hf(OiPr)4、iPrOH(230,5mg,0.485mol)的THF溶液(4mL)添加到搅拌的氯化咪唑鎓盐1(250.0mg,0.485mmol)的THF溶液(20ml)中。在添加铪试剂后，最初无色的溶液缓慢地变成黄/绿色。将该反应混合物在室温搅拌过夜并蒸发至干以得到黄/绿色固体残余物。在将粗产物从THF/戊烷(1/5)中重结晶后获得黄色固体状纯的L1Hf(Cl)(OiPr)(THF)(267.1mg,67%收率)。
1H NMR(300MHz,CD2Cl2)δ:7.22(d,J=2.2Hz,2H,芳基-H),6.97(d,J=2.2Hz,2H,芳基-H),4.46-4.22(m,5H,NCH2和OiPr),3.79-3.70(m,4H,THF),1.73-1.66(m,4H,THF),1.55(s,18H,tBu),1.37(s,18H,tBu),0.92(d,J=6.3Hz,6H,CH3-OiPr).13C NMR(75MHz,CD2Cl2)δ:203.7(NCN),149.4(Cipso,O-芳基),139.7(Cquat,芳基),138.9(Cquat,芳基),130.7(Cquat,芳基),119.9(CH,芳基),112.6(CH,芳基),72.8(CH,OiPr),71.5(CH2,THF),48.1(CH2,NCH2),35.9(Cquat,tBu),34.8(Cquat,tBu),31.9(CH3,tBu),30.2(CH3,tBu),26.9(CH3,OiPr),25.6(CH2,THF).
LZr(OiPr)2,L=配体(1)
在手套箱中，在室温通过微量注射器将LiOiPr(2M的THF溶液,68.2μl,0.136mmol)添加到预冷却的(-35℃)的氯异丙氧基锆络合物LZr(Cl)(OiPr)(THF)(100.0mg,0.136mmol)的THF溶液(15mL)中。最初的淡黄色溶液在几分钟的过程中变得更亮。将该反应混合物升温至室温并搅拌过夜以产生黄色溶液。蒸发至干，然后添加甲苯，通过玻璃料上的硅藻土过滤得到的悬浮液，蒸发后产生粗的浅绿色固体。将后面的固体用戊烷洗涤，获得LZr(OiPr)2，如通过NMR光谱法所测定。
1H NMR(300MHz,CD2Cl2)δ:7.05(d,J=2.2Hz,2H,芳基-H),6.91(d,J=2.2Hz,2H,芳基-H),4.46-4.00(m,6H,NCH2和CH-OiPr),1.36(s,18H,tBu),1.29(d,J=6.3Hz,6H,CH3-OiPr),1.26(s,18H,tBu),0.68(d,J=6.3Hz,6H,CH3-OiPr).δ:201.8(NCN),151.1(Cipso,O-芳基),138.2(Cquat,芳基),137.7(Cquat,芳基),130.9(Cquat,芳基),9.3(CH,芳基),112.2(CH,芳基),71.8(CH,OiPr),70.2(CH,OiPr),47.9(CH2,NCH2),36.0(Cquat,tΒιι),34.8(Cquat,tBu),31.9(CH3,tBu),30.9(CH3,tBu),27.1(CH3,OiPr),26.3(CH3,OiPr).
LZr(Cl)(NMe2)(THF),L=配体(1)
通过注射器将氯化咪唑鎓盐L(250.0mg,0.485mmol)的预冷却的THF溶液(25mL,-78℃)滴加到在-78℃冷却的Zr(NMe2)4(129,8mg,0.485mmol)的THF溶液(5mL)中。在添加锆试剂后，最初无色的溶液缓慢地变成黄/绿色，然后升温至室温并搅拌过夜。蒸发至干，得到黄/棕色残余物，所述残余物在THF/戊烷(1/5)中重结晶之后产生黄色粉末状纯的L1Zr(Cl)(NMe2)(THF)。
1H NMR(300MHz,CD2Cl2)δ:7.26(d,J=2.2Hz,2H,芳基-H),7.03(d,J=2.2Hz,2H,芳基-H),4.52-4.24(m,4H,CH2),3.66-3.52(m,4H,THF),2.82(s,6H,N-CH3),1.68-1.62(m,4H,THF),1.60(s,18H,tBu),1.37(s,18H,tBu).13C NMR(75MHz,CD2Cl2)δ:202.9(NCN),148.2(Cipso,O-芳基),140.4(Cquat,芳基),138.4(Cquat,芳基),131.3(Cquat,芳基),119.9(CH,芳基),112.9(CH,芳基),70.6(CH2,THF),48.2(CH2,NCH2),45.4(CH3,NCH3),36.0(Cquat,tBu),34.9(Cquat,tBu),31.9(CH3,tBu),30.5(CH3,tBu),25.6(CH2,THF).
LZr(Cl)(NMe2)(HNMe2),L=配体(1)
通过注射器将氯化咪唑鎓盐L(250.0mg,0.485mmol)的预冷却的CH2Cl2溶液(25mL,-78℃)滴加到在-78℃冷却的Zr(NMe2)4(129,8mg,0.485mmol)的THF溶液(5mL)中。在添加锆试剂后，最初无色的溶液缓慢地变成黄/绿色，然后升温至室温并搅拌过夜。蒸发至干，得到绿色残余物，所述残余物在二氯甲烷/戊烷(1/5)中重结晶后得到绿色粉末状纯的L1Zr(Cl)(NMe2)(HNMe2)(186,4mg,60%收率)。
1H NMR(300MHz,C6D6)δ:7.54(d,J=2.2Hz,2H,芳基-H),6.81(d,J=2.2Hz,2H,芳基-H),3.36-3.19(m,4H,CH2),3.14(s,6H,N-CH3),1.88(s,18H,tBu),1.42(s,18H tBu),1.69(br,6H,HNMe2).
LZr(Cl)(Bn),L=配体(1)
通过注射器将Zr(Bn)4(177.0mg,0.388mmol)的预冷却的甲苯溶液(20mL,-35℃)滴加到在-35℃冷却的氯化咪唑鎓盐L(200.0mg,0.388mmol)的甲苯悬浮液(20mL)中。在添加铪试剂后，最初无色的溶液缓慢地变成黄色，然后升温至室温并搅拌过夜。蒸发至干，得到黄色残余物，所述残余物用戊烷洗涤后得到淡黄色粉末状纯的L1Zr(Cl)(Bn)。
1H NMR(300MHz,CD2Cl2):δ7.30(d,2H,J=2.2Hz,芳基-H),6.93(d,2H,J=2.2Hz,芳基-H),6.65-6.45(m,3H,Bn),6.28-6.17(m,2H,Bn),4.26-4.00(m,4H,CH2),2.89(s,2H,Bn),1.66(s,18H,tBu),1.39(s,18H,tBu).13C NMR(75MHz,CD2Cl2)204.3(Cquat,NCN),147.3(Cquat),142.0(Cquat),138.2(Cquat),131.9(Cquat),131.7(Cquat),131.6(CH),128.6(CH),124.0(CH),119.8(CH),112.2(CH),62.5(CH2,Bn),48.5(CH2,NCH2),36.0(Cquat,tBu),35.0(Cquat,tBu),31.9(CH3,tBu),30.3(CH3,tBu).
L1Zr(Bn)2，L=配体(1)
在手套箱中，在室温通过微量注射器将BnMgCl(1M的Et2O溶液,144.0μl,0.144mmol)添加到预冷却的(-35℃)的氯苄基锆络合物LZr(Cl)(Bn)(100.0mg,0.144mmol)的甲苯溶液(15mL)中。最初淡黄色的溶液在几分钟的过程中变成混浊。将该反应混合物升温至室温并搅拌过夜。通过玻璃料上的硅藻土过滤得到的悬浮液，然后蒸发至干，得到粗的淡黄色固体。在二氯甲烷/戊烷(1/5)中将后面的固体重结晶得到纯的L1Zr(Bn)2，如通过NMR光谱法所测定(78mg,78%收率)。
1H NMR(300MHz,CD2Cl2):δ7.27(d,2H,J=2.2Hz,芳基-H),6.92(d,2H,J=2.2Hz,芳基-H),6.83-6.74(m,4H,Bn),6.72-6.64(m,2H,Bn),6.62-6.55(m,4H,Bn),4.10(s,4H,CH2),1.94(s,4H,Bn),1.66(s,18H,tBu),1.39(s,18H,tBu).13C NMR(75MHz,CD2Cl2)205.8(Cquat,NCN),148.0(Cquat),140.9(Cquat),139.0(Cquat),137.3(Cquat),131.9(Cquat),129.3(CH),129.0(CH),122.2(CH),119.4(CH),112.7(CH),55.0(CH2,Bn),48.4(CH2,NCH2),36.1(Cquat,tBu),34.9(Cquat,tBu),31.9(CH3,tBu),30.5(CH3,tBu).
L1Hf(Cl)(Bn)
通过注射器将Hf(Bn)4(210.8mg,0.388mmol)的预冷却的甲苯溶液(5mL,-35℃)滴加到在-35℃冷却的氯化咪唑鎓盐L(200.0mg,0.388mmol)的甲苯悬浮液(20mL)中。在添加铪试剂后，最初无色的溶液缓慢地变成黄色，然后升温至室温并搅拌过夜。蒸发至干，得到黄色残余物，所述残余物用戊烷洗涤后得到淡黄色粉末状LHf(Cl)(Bn)。
1H NMR(300MHz,CD2Cl2):δ7.32(d,2H,J=2.2Hz,芳基-H),6.91(d,2H,J=2.2Hz,芳基-H),6.65-6.57(m,1H,Bn),6.56-6.47(m,2H,Bn),,6.31-6.23(m,2H,Bn),4.27-3.98(m,4H,CH2),2.64(s,2H,Bn),1.67(s,18H,tBu),1.39(s,18H,tBu).13C NMR(75MHz,CD2Cl2)209.1(Cquat,NCN),147.8(Cquat),141.8(Cquat,),138.7(Cquat),132.4(Cquat),131.5(Cquat),131.5(CH),128.3(CH),124.0(CH),119.9(CH),112.3(CH),65.9(CH2,Bn),48.5(CH2,NCH2),35.9(Cquat,tBu),35.0(Cquat,tBu),31.9(CH3,tBu),30.3(CH3,tBu).
开环聚合(ROP)法
一般聚合方法
向小瓶中装入Zr或Hf引发剂并在需要时溶于溶剂。然后添加X当量(X=M0/I0)的单体并将该反应混合物在所考虑的温度下加热期望的时间。然后将溶液用MeOH淬灭并蒸发至干。1H NMR揭示单体到聚合物的转化率。通过NMR光谱法、SEC和MALDI-TOF质谱法研究得到的物质。
-用LZr(Cl)(OiPr)(THF),L=配体(1)作为引发剂的外消旋丙交酯的立体控制聚合：
1)M0=1mol/l(条目1-4)；
2)通过1H NMR测定；
3)通过凝胶渗透色谱法(GPC)在THF中测定，确切质量。
4)通过1H同去偶合的（homodecoupled）NMR光谱测定；
Pr是外消旋键的概率。
-采用LZr(Cl)(OiPr)(THF),L=配体(1)作为引发剂β-丁内酯和ε-己内酯的聚合：
1)M0=1mol/l；
2)通过1H NMR测定；
3)通过凝胶渗透色谱法(GPC)在THF中测定，确切质量。
-采用LHf(Cl)(OiPr)(THF),L=配体(1)作为引发剂的外消旋丙交酯的立体控制聚合：
使用一般聚合方法，将100当量的外消旋丙交酯在二氯甲烷中在室温聚合15小时，转化率为约75%。经测定Pr为>0.95。
-采用外消旋-丙交酯与LZr(Cl)(Bn),L=配体(1)作为引发剂的立体控制聚合：
使用一般聚合方法，将20当量的外消旋-丙交酯在二氯甲烷中在室温聚合15小时，完全转化。
Claims (4)
1.用于作为内酯开环聚合的催化剂的式(I)的N-杂环卡宾：
其中：
M选自Zr或Hf；
R1选自卤素、C1-C10烷基、C1-C10烷氧基、芳基、苄基(Bn)、芳氧基、苄氧基或式N(R7)(R8)的酰胺；
R2是任选的并且是配位溶剂，例如四氢呋喃、乙醚、水、乙腈、二甲胺或其他弱配位配体；
X选自卤素(Cl、Br、F、I)、C1-C10烷基、C1-C10烷氧基、芳基、苄基(Bn)、芳氧基、苄氧基或式N(R7)(R8)的酰胺；
R3和R4彼此独立地选自氢、C1-C10烷基、C5-C10环烷基，其中的所述烷基基团任选被卤素(Cl、Br、F、I)取代；C1-C10烷氧基、未取代的苯基或取代的苯基(其中取代基是卤素、C1-C10烷基或硝基)；
R5和R6彼此独立地选自氢、C1-C10烷基、C5-C10环烷基，其中的所述烷基基团任选被卤素(Cl、Br、F、I)取代；未取代的苯基或取代的苯基(其中取代基是卤素、C1-C10烷基或硝基)；
R5和R6可以任选地连接在一起以形成不饱和的或饱和的5－6元环，其中该环可以具有一个或多个手性中心；
R7和R8彼此独立地选自C1-C10烷基、C5-C10环烷基、未取代的苯基或取代的苯基(其中取代基是卤素、C1-C10烷基或硝基)。
2.根据权利要求1的N-杂环卡宾，其中：
M选自Zr；
R1选自Cl、Br、C3-C4烷氧基、芳氧基；
R2是任选的并且是配位溶剂，例如四氢呋喃、乙醚、二甲胺；
X选自Cl、Br、C3-C4烷氧基、芳氧基、苄氧基、C4-C5烷基或苄基；
R3和R4彼此独立地选自氢、CH3、C2H5、C3H7、C4H9；
R5和R6彼此独立地选自氢、CH3、C2H5、C3H7、C4H9；
R5和R6可以任选地连接在一起以形成不饱和的或饱和的6元环，在饱和时，该环可以具有两个手性中心；可以使用的典型原料是R,R-S,S-R,S环己二胺；
R7和R8彼此独立地选自C1-C10烷基、C5-C10环烷基。
3.用于生产式(I)化合物的方法：
其中，将至少1当量的Zr或Hf-金属盐溶液与1当量的相应配体的沸腾溶液反应，将该溶液在10－150℃的温度搅拌最多至24小时。
4.权利要求3的方法，其中溶剂选自C1-C8醇类、二烷基醚氧化物、烷基腈类、芳族化合物、二甲基甲酰胺、N-甲基吡咯烷酮或这些溶剂的混合物。
用于生产基于丙交酯的聚酯类的催化方法，其特征在于，将式(I)化合物用作催化剂：
其中：
M选自Zr或Hf；
R1选自卤素、C1-C10烷基、C1-C10烷氧基、芳基、苄基(Bn)、芳氧基、苄氧基或式N(R7)(R8)的酰胺；
R2是任选的并且是配位溶剂，例如四氢呋喃、乙醚、水、乙腈、二甲胺或其他弱配位配体；
X选自卤素(Cl、Br、F、I)、C1-C10烷基、C1-C10烷氧基、芳基、苄基(Bn)、芳氧基、苄氧基或式N(R7)(R8)的酰胺；
R3和R4彼此独立地选自氢、C1-C10烷基、C5-C10环烷基，其中的所述烷基基团任选被卤素(Cl、Br、F、I)取代；C1-C10烷氧基、未取代的苯基或取代的苯基(其中取代基是卤素、C1-C10烷基或硝基)；
R5和R6彼此独立地选自氢、C1-C10烷基、C5-C10环烷基，其中的所述烷基基团任选被卤素(Cl、Br、F、I)取代；未取代的苯基或取代的苯基(其中取代基是卤素、C1-C10烷基或硝基)；
R5和R6可以任选地连接在一起以形成不饱和的或饱和的5－6元环，其中该环可以具有一个或多个手性中心；
R7和R8彼此独立地选自C1-C10烷基、C5-C10环烷基、未取代的苯基或取代的苯基(其中取代基是卤素、C1-C10烷基或硝基)。
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2011
- 2011-12-05 WO PCT/EP2011/006076 patent/WO2012076140A1/en active Application Filing
- 2011-12-05 KR KR1020137017984A patent/KR20140029373A/ko not_active Application Discontinuation
- 2011-12-05 CN CN201180059470.XA patent/CN103380135B/zh not_active Expired - Fee Related
- 2011-12-05 EP EP11794041.1A patent/EP2649083A1/en not_active Withdrawn
- 2011-12-05 JP JP2013542401A patent/JP2014505027A/ja active Pending
- 2011-12-05 US US13/992,616 patent/US20130281653A1/en not_active Abandoned
Patent Citations (3)
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| CN1687176A (zh) * | 2005-04-15 | 2005-10-26 | 浙江大学 | 一种脂肪族聚酯的制备方法 |
| WO2008068258A1 (fr) * | 2006-12-06 | 2008-06-12 | Rhodia Operations | Composition comprenant un carbene et une matrice organique, son procede d'obtention et son utilisation |
| CN101665565A (zh) * | 2008-09-01 | 2010-03-10 | 南京工业大学 | 一种用卡宾衍生物催化制备聚乳酸的方法 |
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| AMANDA J. CHMURA等: "Group 4 Complexes with Aminebisphenolate Ligands and Their Application for the Ring Opening Polymerization of Cyclic Esters", 《MACROMOLECULES》 * |
| CHARLES ROMAIN等: "Non-Innocent Behavior of a Tridentate NHC Chelating Ligand Coordinated onto a Zirconium(IV) Center", 《ANGEWANDTE CHEMIE INTERNATIONAL EDITION》 * |
| CHARLES ROMAIN等: "Synthesis and Structural Characterization of a Novel Family of Titanium Complexes Bearing a Tridentate Bis-phenolate-N-heterocyclic Carbene Dianionic Ligand and Their Use in the Controlled ROP of rac-Lactide", 《ORGANOMETALLICS》 * |
| M.D. JONES等: "New titanium and zirconium initiators for the production of polylactide", 《POLYHEDRON》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105541893A (zh) * | 2016-01-05 | 2016-05-04 | 内蒙古工业大学 | 对称四齿丙胺吗啉双酚类配体锆金属络合物的合成及应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014505027A (ja) | 2014-02-27 |
| EP2649083A1 (en) | 2013-10-16 |
| US20130281653A1 (en) | 2013-10-24 |
| CN103380135B (zh) | 2016-08-31 |
| KR20140029373A (ko) | 2014-03-10 |
| WO2012076140A1 (en) | 2012-06-14 |
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