CN114456199A - Asymmetric multidentate monophenol oxygen-based metal halide and preparation method and application thereof - Google Patents
Asymmetric multidentate monophenol oxygen-based metal halide and preparation method and application thereof Download PDFInfo
- Publication number
- CN114456199A CN114456199A CN202210076002.3A CN202210076002A CN114456199A CN 114456199 A CN114456199 A CN 114456199A CN 202210076002 A CN202210076002 A CN 202210076002A CN 114456199 A CN114456199 A CN 114456199A
- Authority
- CN
- China
- Prior art keywords
- multidentate
- asymmetric
- monophenol
- metal
- halide
- Prior art date
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Links
- INKDAKMSOSCDGL-UHFFFAOYSA-N [O].OC1=CC=CC=C1 Chemical compound [O].OC1=CC=CC=C1 INKDAKMSOSCDGL-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910001507 metal halide Inorganic materials 0.000 title claims abstract description 5
- 150000005309 metal halides Chemical class 0.000 title claims abstract description 5
- 239000011701 zinc Substances 0.000 claims abstract description 104
- 229910052751 metal Inorganic materials 0.000 claims abstract description 64
- 239000002184 metal Substances 0.000 claims abstract description 62
- -1 zinc halide Chemical class 0.000 claims abstract description 61
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 43
- 239000011777 magnesium Substances 0.000 claims abstract description 35
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 33
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 33
- 239000003446 ligand Substances 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920000728 polyester Polymers 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 10
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 8
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 8
- 150000002596 lactones Chemical class 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 134
- 239000003054 catalyst Substances 0.000 claims description 59
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 31
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 26
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000000460 chlorine Substances 0.000 claims description 13
- 239000003208 petroleum Substances 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 239000011592 zinc chloride Substances 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 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 claims description 3
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 claims description 3
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000012312 sodium hydride Substances 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- WMJMABVHDMRMJA-UHFFFAOYSA-M [Cl-].[Mg+]C1CCCCC1 Chemical compound [Cl-].[Mg+]C1CCCCC1 WMJMABVHDMRMJA-UHFFFAOYSA-M 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000006356 dehydrogenation reaction Methods 0.000 claims 1
- CQRPUKWAZPZXTO-UHFFFAOYSA-M magnesium;2-methylpropane;chloride Chemical compound [Mg+2].[Cl-].C[C-](C)C CQRPUKWAZPZXTO-UHFFFAOYSA-M 0.000 claims 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical group [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 claims 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 238000007142 ring opening reaction Methods 0.000 claims 1
- 235000005074 zinc chloride Nutrition 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 31
- 238000003786 synthesis reaction Methods 0.000 abstract description 19
- 230000015572 biosynthetic process Effects 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000012694 Lactone Polymerization Methods 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 4
- 239000002685 polymerization catalyst Substances 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 54
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 48
- 238000009826 distribution Methods 0.000 description 33
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 19
- 239000002904 solvent Substances 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 12
- 229920000747 poly(lactic acid) Polymers 0.000 description 11
- 238000004983 proton decoupled 13C NMR spectroscopy Methods 0.000 description 11
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 150000004696 coordination complex Chemical class 0.000 description 4
- 229920005565 cyclic polymer Polymers 0.000 description 4
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- FMUYQRFTLHAARI-UHFFFAOYSA-N 2,4-bis(2-phenylpropan-2-yl)phenol Chemical compound C=1C=C(O)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 FMUYQRFTLHAARI-UHFFFAOYSA-N 0.000 description 1
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 1
- RCAZDYKIEASENU-UHFFFAOYSA-N 2-(dimethylamino)-5-methylbenzaldehyde Chemical compound CN(C)C1=CC=C(C)C=C1C=O RCAZDYKIEASENU-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- LDZHTQSBXDDUFB-UHFFFAOYSA-M potassium;4-aminobenzenesulfonate Chemical class [K+].NC1=CC=C(S([O-])(=O)=O)C=C1 LDZHTQSBXDDUFB-UHFFFAOYSA-M 0.000 description 1
- 238000006049 ring expansion reaction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000002636 symptomatic treatment Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
- 239000002699 waste material Substances 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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic System without C-Metal linkages
-
- 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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
- C07F3/02—Magnesium 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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
- C07F3/06—Zinc compounds
-
- 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
-
- 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
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
Abstract
The invention discloses an asymmetric multidentate monophenol oxygen-based metal halide, a preparation method thereof and application thereof in catalyzing ring-opening polymerization of lactone. The preparation method comprises the following steps: reacting the ligand with a hydrogen-withdrawing reagent to generate metal salt of the corresponding ligand, and then reacting the metal salt with a metal raw material compound in an organic medium to obtain zinc halide (I); the neutral ligand is reacted with a grignard reagent in an organic medium to obtain the magnesium halide (II). The complex is a high-efficiency lactone polymerization catalyst, has high tolerance to impurities, and can be used for the polymerization of unpurified lactones; particularly has good catalytic effect on rac-lactide polymerization. The invention relates to asymmetric multidentate monophenol oxylsThe advantages of the metal halide are obvious: the raw materials are easy to obtain, the synthesis is simple, the product yield is high, the catalytic activity is high, the unpurified monomers can be catalyzed to synthesize the high molecular weight cyclic polyester, the harsh polymerization conditions are not required, and the requirements of industrial departments can be met. The structural formula is shown as follows.
Description
Technical Field
The invention relates to asymmetric multidentate monophenol oxygen-based metal zinc and magnesium halides, and application of the complexes in lactone polymerization.
Background
In recent years, the use of large quantities of polymer plastic products such as polyolefin has caused a great consumption of petroleum resources. Meanwhile, polyolefin materials cannot be degraded under natural conditions, and the waste incineration disposal also causes a serious environmental pollution problem. The novel polymer materials including polylactide are gradually receiving attention from people due to good degradability and wide raw material sources (corn stalks and waste materials). In addition, the polymer has excellent physical and mechanical properties, so that the polymer is convenient to process and can be applied to various fields from industry to civil plastic products, food packages, industrial and civil fabrics and the like. Meanwhile, the polyester material has good biocompatibility and can be used as a medical suture, a drug carrier and the like in the field of biomedicine.
Cyclic polyesters have many different physical properties than their linear counterparts, including glass transition temperature, melting temperature, morphology, melt viscosity, thermal stability, compatibility, hydrodynamic volume, and intrinsic viscosity. In addition, the biological properties of cyclic polyesters have a high potential for biomedical applications. For example, cyclic polyesters used in drug delivery systems have a longer blood circulation time than their linear analogs, which may result in controlled release of the drug and better symptomatic treatment. In addition, the unique properties of cyclic polyesters are widely used in industry. For example, the incorporation of small amounts of cyclic polymers into the polymer, which adjusts the viscoelastic and thermal properties of the resulting homopolymer blend, provides significant advantages.
Currently, a variety of catalysts have been used for the synthesis of cyclic polyesters, including carbene catalysts, metallic tin, aluminum catalysts, and the like. However, these catalysts are generally sensitive, resulting in poor controllability and easy decomposition during the polymerization process, limiting their industrial application, and the resulting cyclic polymers have relatively low molecular weight. For example, in 2006, the Waymouth group achieved the synthesis of cyclic polylactide by the zwitterionic ring-expansion mechanism using N-heterocyclic carbene organic catalysts, but only catalyzed 200 equivalents of purified rac-lactide to give molecular weights of 2.6X 10 due to the catalyst's extreme sensitivity4g/mol of polymer (Angew. chem. int. Ed.,2007,46, 2627-. In 2008, the Kricheldorf group reported N-methylimidazole catalysts that can produce cyclic polylactides at high temperatures by zwitterionic end-to-end cyclization, but only oligomers were obtained, and that are poorly catalytic active (Macromolecules,2008,41, 7812-. 2017, Wu groupA series of extremely sensitive sodium and potassium sulfanilate complexes are reported, and the ring-opening polymerization of rac-lactide is catalyzed to obtain a cyclic polymer under the reaction condition of no alcohol, but the molecular weight is only 1.4 multiplied by 104g/mol, and an isotacticity of only 0.63(Macromolecules,2017,50, 83-96). Although some catalysts have better activity and isotactic selectivity for lactone ring-opening polymerization, linear polymers cannot be obtained, for example, in 2018-.
From the above, it is still a great challenge to synthesize cyclic polyesters, and the reported catalysts are poorly tolerant to moisture, oxygen and impurities in the monomers, are easily deactivated, and only cyclic polylactones of low molecular weight can be obtained. Therefore, at present, there is an urgent need to develop a catalyst which has a high tolerance to water and oxygen and can catalyze ring-opening polymerization of a large equivalent amount of monomers to obtain cyclic polyester without purifying the monomers, so as to meet the requirements in the actual production process.
The invention provides an asymmetric multidentate monophenol oxygroup metal zinc and magnesium halide catalyst, which can realize the ring-opening polymerization of industrial grade lactone without purification, synthesize and obtain high molecular weight cyclic polyester, has extremely strong tolerance to impurities in a monomer, and can meet the requirements of industrial departments. Meanwhile, the catalyst has the advantages of convenient synthesis route, high product yield and higher activity.
Disclosure of Invention
The invention aims to disclose an asymmetric multidentate monophenol oxygen-based metal zinc and magnesium halide.
The second purpose of the invention is to disclose a preparation method of asymmetric multidentate monophenol oxygen-based metal zinc and magnesium halide.
The invention also aims to disclose the application of asymmetric multidentate monophenol oxygen-based metal zinc and magnesium halide as a catalyst in lactone polymerization.
The technical idea of the invention is as follows:
research shows that synthesizing high activity and high isotactic selectivity catalyst is key to obtaining excellent cyclic polylactide. The polydentate phenolic compound is used as a ligand, and substituent groups are introduced into a plurality of sites, so that the effects of adjusting the steric hindrance of the metal center and the Lewis acidity can be achieved, and the catalytic performance of the metal complex can be adjusted. In the structure of the metal complex catalyst, in addition to the influence of the steric and electronic factors of the polydentate ligand on the catalytic performance of the metal complex, the kind of initiating group attached to the metal center also influences the stability and activity of the metal complex catalyst. Compared with a metal-silicon amino bond, the metal-halogen bond is relatively inert, so that the high-efficiency catalyst integrating the properties of high activity, high selectivity, insensitivity to water, oxygen and the like is hopefully screened by combining the regulation and control of each substituent of the polydentate ligand and introducing the metal-halogen bond as an initiating group. In order to effectively realize the initiation of metal-halogen bonds, the cyclohexene oxide is used as a solvent, and the cyclization of a polymer chain in the polymerization process is promoted, so that the cyclic polyester with high molecular weight is finally obtained, and the commercial application value of the cyclic polyester is improved.
The invention provides asymmetric multidentate monophenol oxygen-based metal zinc, magnesium halide (I) and (II), which are characterized by having the following general formulas:
in the formulae (I), (II):
R1～R4each represents hydrogen, C1～C20Alkyl of linear, branched or cyclic structure, C7～C30Mono-or poly-aryl-substituted alkyl of (a), halogen;
R5represents ethylene or methylene;
X1～X2represents C1～C12Alkoxy of linear, branched or cyclic structure, C1～C12Alkyl substituted amine groups of linear, branched or cyclic structure;
X3represents halogen.
More particularly, in the formulae (I) and (II), R1～R4Is hydrogen, C1～C10Alkyl of linear, branched or cyclic structure, C7～C20Mono-or poly-aryl-substituted alkyl of (a), halogen; x1～X2Is C1～C6Alkoxy of linear, branched or cyclic structure, C1～C6Alkyl substituted amine groups of linear, branched or cyclic structure; x3Is chlorine, bromine or iodine.
In the formulae (I) and (II), R1～R4Preferably hydrogen, methyl, tert-butyl, cumyl, triphenylmethyl or chlorine; r5Preferably an ethylene group; x1～X2Preferably methoxy group and dimethylamino group; x3Chlorine is preferred.
Preferred asymmetric multidentate monophenoloxy metal zinc halides are of the formula:
preferred asymmetric multidentate monophenoloxy metal magnesium halides have the formula:
the above preferred asymmetric multidentate monophenol oxygroup metal zinc, magnesium halide has the corresponding asymmetric multidentate monophenol ligand compound of the formula:
the preparation method of the asymmetric multidentate monophenol oxygen-based metal zinc halide (I) is as follows:
reacting an asymmetric multidentate monophenol ligand compound shown in a formula (III) with a hydrogen extraction reagent to obtain metal salt of a corresponding ligand, then reacting the metal salt with a metal raw material compound in an organic medium to generate an asymmetric multidentate monophenol oxygroup metal zinc halide, wherein the reaction temperature is-75-80 ℃, preferably 0-40 ℃, the reaction time is 8-72 hours, preferably 16-48 hours, and then collecting a compound (I) from a reaction product;
substituent R in the above preparation method1～R5And X1～X2Corresponding groups to the asymmetric multidentate monophenol oxo metal zinc halide (I) according to any one of claims 1 to 3;
the hydrogen drawing reagent is C1～C4An alkali metal alkyl compound of (a), sodium hydride, or potassium hydride;
the metal starting compound has the general formula Zn (X)3)2，X3Corresponding groups of the asymmetric multidentate monophenol oxygroup metal zinc halide (I) according to any one of claims 1 to 3;
the mass ratio of the asymmetric multidentate monophenol ligand compound (III) to the hydrogen-withdrawing reagent is 1: 1.5-2.5; the mass ratio of the metal salt of the asymmetric multidentate monophenol ligand compound to the metal raw material compound is 1: 1.0-1.5;
the organic medium is one or two of tetrahydrofuran, diethyl ether, toluene, benzene, petroleum ether and n-hexane.
The preparation method of the asymmetric multidentate monophenol oxygen-based metal magnesium halide (II) is as follows:
reacting an asymmetric multidentate monophenol ligand compound shown in a formula (III) with a Grignard reagent in an organic medium to generate an asymmetric multidentate monophenol oxygen-based metal magnesium halide, wherein the reaction temperature is-75-80 ℃, preferably 0-40 ℃, the reaction time is 8-72 hours, preferably 16-48 hours, and then collecting a compound (II) from a reaction product;
substituent R in the above preparation method1～R5And X1～X2Corresponding to each corresponding group of the asymmetric multidentate monophenol oxygen-based metal magnesium halide (II) as claimed in any one of claims 1 to 3;
the Grignard reagent has the general formula R6Mg(X3)，R6Is C1～C6Alkyl of straight, branched or cyclic structure, X3Corresponding groups satisfying the asymmetric multidentate monophenol oxygen-based metal magnesium halide (II) described in any one of claims 1 to 3;
the mass ratio of the asymmetric multidentate monophenol ligand compound (III) to the Grignard reagent is 1: 1.0-1.5;
the organic medium is one or two of tetrahydrofuran, diethyl ether, toluene, benzene, petroleum ether and n-hexane.
Among the above-mentioned preparation methods, the asymmetric multidentate monophenol ligand compound represented by formula (III) can be synthesized by referring to the method disclosed in patent CN 109879810 a.
The asymmetric multidentate monophenol oxygen-based metal zinc and magnesium halide is a high-efficiency lactone polymerization catalyst, has high catalytic activity, and can be used for ring-opening polymerization of L-lactide, D-lactide, rac-lactide, meso-lactide, epsilon-caprolactone, beta-butyrolactone and alpha-methyltrimethylene cyclic carbonate to obtain cyclic polyester.
The asymmetric multidentate monophenol oxygen-based metal zinc and magnesium halide has extremely strong stability, and can be used for ring-opening polymerization of unpurified L-lactide, D-lactide, rac-lactide, meso-lactide, epsilon-caprolactone, beta-butyrolactone and alpha-methyltrimethylene cyclic carbonate to obtain high molecular weight cyclic polyester.
When the asymmetric multidentate monophenol oxygen-based metal zinc and magnesium halide is used for catalyzing rac-lactide polymerization, the cyclic polylactide with high molecular weight and an isotactic block structure can be obtained.
Taking the asymmetric multidentate monophenol oxygen-based metal zinc halide or the asymmetric multidentate monophenol oxygen-based metal magnesium halide as a catalyst and epoxy cyclohexane as a solvent to polymerize lactide to obtain cyclic polylactide; the ratio of the amount of the catalyst to the amount of the monomer during polymerization is 1:1 to 300000, preferably 1:200 to 150000.
Taking the asymmetric multidentate monophenol oxygen-based metal zinc halide or the asymmetric multidentate monophenol oxygen-based metal magnesium halide as a catalyst and epoxy cyclohexane as a solvent, polymerizing lactide which is not purified to obtain cyclic polylactide; the ratio of the amount of the catalyst to the amount of the monomer during polymerization is 1:1 to 300000, preferably 1:200 to 150000.
The asymmetric multidentate monophenol oxygen-based metal zinc halide or asymmetric multidentate monophenol oxygen-based metal magnesium halide is used as a catalyst, epoxy cyclohexane is used as a solvent, and epsilon-caprolactone is polymerized to obtain a cyclic polymer; the amount ratio of the catalyst to the monomer is 1:1 to 300000, preferably 1:200 to 150000.
Lactide is taken as an example to illustrate the structure of the cyclic polyester synthesized by the invention, which is shown as the formula (IV):
wherein n is an integer greater than 2.
The formation of cyclic polyester is illustrated by taking the asymmetric multidentate monophenol oxygen-based metal zinc and magnesium halide as a catalyst and taking the polymerization of lactide as an example:
in the polymerizations as shown in examples 10-20, when high monomer conversion was achieved, the resulting polylactide product was subjected to molecular weight determination by gel permeation chromatography, which determinedThe number average molecular weight value is far smaller than the number average molecular weight of a theoretical polymerization product with a linear structure, and the molecular weight distribution is narrow. For the polymerization shown in example 31, a sample was taken at a low monomer conversion of 28% by1H NMR and MALDI-TOF mass spectrometry analysis of the structure of the oligomers obtained in1No end groups ascribed to linear polymers were observed in H NMR, whereas the molecular weight sequence in MALDI-TOF mass spectrometry conformed to the structure of cyclic polylactide, i.e., to the structure of formula (IV); the polymerization described in example 32 was further subjected to sampling at a high monomer conversion of 91%, and the isolated polymer was subjected to MALDI-TOF mass spectrometry to determine a molecular weight sequence which still conforms to the structure of cyclic polylactide, i.e., having the structure shown in formula (IV). As described above, the asymmetric multidentate monophenol oxygen-based metal zinc or magnesium halide of the present invention is used as a catalyst to catalyze lactide polymerization to obtain cyclic polylactide.
The asymmetric multidentate monophenol oxygen-based metal zinc halide or asymmetric multidentate monophenol oxygen-based metal magnesium halide is used as a catalyst to catalyze epsilon-caprolactone to polymerize, and a polymer with a ring structure is also obtained. For the polymer obtained in example 301H NMR and MALDI-TOF mass spectrometry analysis confirmed that the compound also has a cyclic structure. The asymmetric multidentate monophenol oxygen-based metal zinc and magnesium halide has universality on different lactone monomers when catalyzing lactone polymerization to synthesize cyclic polylactone.
The catalyst provided by the invention has the advantages of cheap raw materials, simple and convenient preparation, stable property in the polymerization process, high catalytic activity, strong tolerance to water, oxygen and other impurities, capability of catalyzing the ring-opening polymerization of industrial grade lactone with the equivalent weight of 150000 or more to obtain the cyclic polyester with high molecular weight and certain regularity, and great commercial and industrial application value. The invention is further illustrated, but not limited, by the following examples.
Detailed Description
The invention relates to an asymmetric multidentate monophenol ligand compound shown as a formula (III), such as L1-4H and L9H, etc., can be synthesized by referring to the method disclosed in patent CN 101698648A.
Example 1
Synthesis of complex Zn1
In a glove box, L1H (654mg, 1.7mmol) was added to a Schlenk flask, and 15mL of anhydrous tetrahydrofuran was added to dissolve the ligand, followed by accurately weighing NaH (82mg, 3.4mmol), which was added portion-wise slowly to the Schlenk flask and reacted for 12H. Filtering redundant NaH by using filter paper, and accurately weighing anhydrous ZnCl2(232mg, 1.7mmol) was added portionwise to the filtrate and the reaction was continued for 12 h. The mixture was then filtered, the solid was drained and recrystallized from dichloromethane and n-hexane to yield a white solid which was detected by nuclear magnetic resonance as complex Zn1(416mg, 50.5%).
1H NMR(400MHz,CDCl3):δ7.43–7.35(m,1H),7.31(dd,3J＝7.4,4J＝1.4Hz,1H),7.01(m,1H),7.00–6.98(m,1H),6.97(d,3J＝8.4Hz,1H),6.50(d,4J＝1.8Hz,1H),4.43(d,4J＝14.2Hz,1H),4.23(d,4J＝12.2Hz,1H),4.07(d,4J＝14.2Hz,1H),3.81(s,3H),3.38(d,4J＝12.2Hz,1H),2.99–2.88(m,1H),2.74(dt,4J＝14.1,3J＝3.7Hz,1H),2.67–2.60(m,1H),2.58(s,3H),2.37–2.27(m,1H),2.14(s,3H),2.07(s,3H),1.44(s,9H).13C{1H}NMR(CDCl3,100MHz):δ164.4,158.7,139.1,134.2,130.3,130.5,128.5,122.8,121.8,120.7,120.1,111.2,59.1,58.1,55.6,52.5,48.8,46.0,45.5,35.2,29.9,20.8.Anal.Calcd.for C24H35ClN2O2Zn:C,59.51；H,7.28；N,5.78.Found:C,59.10；H,7.42；N,5.67％.
Example 2
Synthesis of complex Zn2
Except that the raw material adopts L2H (602mg, 0.95mmol), NaH (46mg, 1.9mmol) and anhydrous ZnCl2(129mg, 0.95mmol) and the same procedure as in example 1 except that recrystallization from dichloromethane and n-hexane was carried out to obtain a white solid, which was then drained to obtain Zn2 complex (249mg, 43.5%)。
1H NMR(400MHz,CDCl3):δ7.45(d,3J＝7.5Hz,2H),7.37(t,3J＝7.1Hz,1H),7.29(d,3J＝2.1Hz,1H),7.24–7.04(m,9H),7.02–6.89(m,2H),6.51(d,4J＝2.2Hz,1H),4.34(d,2J＝14.3Hz,1H),4.14(d,2J＝12.2Hz,1H),3.98(d,2J＝14.3Hz,1H),3.76(s,3H),3.21(d,3J＝12.2Hz,1H),2.79(m,1H),2.56(m,1H),2.37(m,1H),2.27(s,3H),2.04(m,1H),1.91(s,3H),1.63(s,9H),1.05(s,3H).13C{1H}NMR(CDCl3,100MHz):δ164.3,158.7,152.3,150.47,137.4,135.5,134.2,130.5,128.7,127.1,127.7,127.2,126.8,126.2,125.3,124.6,121.2,120.7,120.2,111.2,59.1,57.8,55.5,52.2，48.4,44.9,43.3,42.3,42.1,31.2,26.4.Anal.Calcd.for C37H45ClN2O2Zn·1.6CH2Cl2:C,58.95；H,6.18；N,3.56.Found:C,58.58；H,5.79；N,4.15％.
Example 3
Synthesis of complex Zn3
Except that the raw material adopts L3H (687mg, 1.61mmol), NaH (77mg, 3.22mmol) and anhydrous ZnCl2(219mg, 1.61mmol) in the same manner as in example 1, and was recrystallized from methylene chloride and n-hexane to give a white solid, which was then dried by suction to give Zn3 complex (373mg, 44.0%).
1H NMR(400MHz,CDCl3):δ7.41(t,3J＝7.8Hz,1H),7.35(d,3J＝7.2Hz,1H),7.21(t,3J＝7.6Hz,1H),7.04(t,3J＝7.4Hz,1H),6.98(d,3J＝8.3Hz,1H),6.65(d,4J＝1.9Hz,1H),4.44(d,2J＝14.2Hz,1H),4.24(d,2J＝12.1Hz,1H),4.08(d,2J＝14.0Hz,1H),3.82(s,3H),3.42(d,2J＝12.1Hz,1H),2.89(t,3J＝11.5Hz,1H),2.80(d,2J＝14.2Hz,1H),2.65–2.58(m,1H),2.56(s,3H),2.34(d,J＝10.6Hz,1H),2.03(s,3H),1.46(s,9H),1.22(s,9H).13C{1H}NMR(CDCl3,100MHz):δ164.1,158.7,138.4,134.3,130.6,126.5,126.4,124.7,121.2,120.8,120.3,111.2,59.3,58.1,55.5,52.8,48.4,45.8,35.5,34.0,31.9,29.9.Anal.Calcd.for C27H41ClN2O2Zn·0.2CH2Cl2:C,60.12；H,7.68；N,5.15.Found:C,60.24；H,7.69；N,5.03％.
Example 4
Synthesis of complex Zn4
Except that the raw material adopts L4H (722mg, 1.89mmol), NaH (91mg, 3.78mmol) and anhydrous ZnCl2(258mg, 1.89mmol) in the same manner as in example 1, and then recrystallized from methylene chloride and n-hexane to give a white solid, which was then dried by suction to obtain Zn4 complex (347mg, 38.2%).
1H NMR(400MHz,CDCl3):δ7.44–7.37(m,1H),7.28(dd,3J＝8.2,4J＝2.0Hz,2H),7.06–6.94(m,2H),6.71(d,4J＝2.5Hz,1H),4.42(d,2J＝14.2Hz,1H),4.23(d,2J＝12.6Hz,1H),4.03(d,2J＝14.2Hz,1H),3.82(s,3H),3.44(d,2J＝12.6Hz,1H),3.01–2.88(m,1H),2.73(dt,2J＝14.1,4J＝3.5Hz,1H),2.61(s,3H),2.51–2.41(m,1H),2.3–2.29(m,1H),2.17(s,3H).13C{1H}NMR(CDCl3,100MHz):δ158.6,134.0,131.0,130.1,129.8,129.1,128.3,125.7,124.3,120.9,119.3,111.4,58.2,57.5,55.6,52.9,48.5,45.9,44.8.58.2,57.5,55.6,52.9,48.5,45.9,44.8.Anal.Calcd.for C19H23Cl3N2O2Zn·0.1CH2Cl2:C,46.66；H,4.76；N,5.70.Found:C,46.20；H,4.84；N,5.68％.
Example 5
Synthesis of complex Zn9
Except that the raw material adopts L9H (541mg, 1.19mmol), NaH (57mg, 2.38mmol) and anhydrous ZnCl2(162mg, 1.19mmol) in the same manner as in example 1, and was recrystallized from methylene chloride and n-hexane to give a white solid, which was then dried by suction to obtain Zn9 complex (213mg, 32.3%).
1H NMR(400MHz,CDCl3):δ7.19(d,4J＝1.9Hz,1H),7.03(d,4J＝1.9Hz,1H),6.99(d,4J＝2.1Hz,1H),6.50(d,4J＝2.1Hz,1H),4.38(d,2J＝14.3Hz,1H),4.11(d,2J＝12.2Hz,1H),4.02(d,2J＝14.3Hz,1H),3.75(s,3H),3.31(d,2J＝12.2Hz,1H),2.79–2.68(m,2H),2.56(s,3H),2.49(m,1H),2.35(s,3H),2.32(m,1H),2.15(s,3H),2.07(s,3H),1.44(s,9H),1.39(s,9H).13C{1H}NMR(CDCl3,100MHz):δ164.3,157.7,143.5,139.2,133.1,132.6,130.4,129.5,128.5,125.1,122.9,121.9,63.4,59.0,58.4,53.7,48.6,46.0,45.4,35.2,35.1,31.2,29.9,21.2,20.8.Anal.Calcd.for C29H45ClN2O2Zn:C,62.81；H,8.18；N,5.05.Found:C,62.48；H,8.31；N,4.98％.
Example 6
Synthesis of complex Zn15
(1) N- [2- (N, N-dimethylamino) ethyl ] -N- [2- (N, N-dimethylamino) benzyl ] methylamine
5-methyl-2- (N, N-dimethylamino) benzaldehyde (10.3g, 68.8mmol) was charged into a 100mL three-necked flask and dissolved in 30mL dry methanol, and N, N-dimethylethylenediamine (8.1g, 89.5mmol) was added with stirring followed by heating to reflux for 24h, and the reaction was followed by TLC. The reaction was placed in an ice-water bath and sodium borohydride (3.9g, 103.3mmol) was added in portions, the reaction exothermed and a large number of bubbles were formed. Stirred at room temperature for 12 h. The reaction was quenched by adding 10mL of water to the reaction flask. Extraction was carried out three times with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the solvent and excess N, N-dimethylethylenediamine were distilled off under reduced pressure to give about 10.5g of a yellow oily liquid, which was directly subjected to the next reaction without further purification.
(2) Ligand L15Synthesis of H
Reacting N- [2- (N, N-dimethylamino) ethyl]-N- [2- (N, N-dimethylamino) benzyl]Methylamine (0.8g, about 3.86mmol) was charged into a 100mL three-necked flask, followed by addition of paraformaldehyde (0.346g, 11.6mmol) and 4-methyl-2-tert-butylphenol (0.634g, 3.86mmol), dissolution in 50mL of methanol, followed by heating under reflux for 24 h. After the reaction is finished, the solvent is distilled off, and white solid L is obtained by column chromatography (PE: EA is 20:1) separation15H(0.89g，58％)。
1H NMR(400MHz,CDCl3):δ7.38(d,3J＝7.6Hz,1H),7.22–7.15(m,1H),7.08(d,3J＝7.6Hz,1H),7.02(m,1H),6.97(s,1H),6.71(s,1H),3.72(s,2H),3.68(s,2H),2.64(s,6H),2.55–2.48(m,2H),2.45–2.37(m,2H),2.23(s,3H),2.10(s,6H),1.43(s,9H).13C{1H}NMR(CDCl3,100MHz):δ154.2,153.5,136.3,132.6,131.0,128.0,127.9,126.8,126.6,123.6,123.0,119.2,58.3,56.6,53.2,50.7,45.5,45.4,34.7,29.7,21.0.Anal.Calcd.For C25H39N3O:C,75.52；H,9.89；N,10.57.Found:C,75.45；H,9.67；N,10.41％.
(3) Synthesis of complex Zn15
Except that the raw material adopts L15H (637mg, 1.60mmol), NaH (77mg, 3.20mmol) and anhydrous ZnCl2(218mg, 1.60mmol) and the same operation as in example 1 were carried out, and recrystallization was carried out with methylene chloride and n-hexane to obtain a white solid, which was then dried by suction to obtain Zn15 complex (423mg, 53.1%).
1H NMR(400MHz,CDCl3):δ7.35–7.30(m,1H),7.30–7.26(m,1H),7.24–7.19(m,1H,),7.11(t,3J＝7.4Hz,1H),6.91(d,4J＝2.1Hz,1H),6.41(d,4J＝2.1Hz,1H),4.49(d,2J＝14.1Hz,1H),4.18(d,2J＝12.1Hz,1H),3.98(d,2J＝14.1Hz,1H),3.27(d,2J＝12.2Hz,1H),2.88–2.78(m,1),2.71(dt,2J＝14.0,4J＝3.7Hz,1H),2.58(s,6H),2.47(m,1H),2.25(s,6H),2.22–2.18(m,1H),2.07(s,3H),1.36(s,9H).13C{1H}NMR(CDCl3,100MHz):δ164.3,155.0,139.0,133.9,130.4,130.2,128.4,127.0,124.4,122.8,121.8,121.0,68.03,59.2,58.2,53.1,47.3,45.8,44.9,35.2,29.8,25.68,20.7.Anal.Calcd.for C25H38ClN3OZn:C,60.37；H,7.70；N,8.45.Found:C,60.03；H,7.74；N,8.57％.
Example 7
Synthesis of complex Zn16
(1) Ligand L16Synthesis of H
Except that the reactant is N- [2- (N, N-dimethylamino) ethyl]-N- [2- (N, N-dimethylamino) benzyl]Methylamine (6.6g, 31.9mmol), paraformaldehyde (2.87g, 95.7mmol) and 2, 4-dicumylphenol (10.53g, 31.9mmol), the remaining procedure is followed with ligand L15H is the same. Subjecting to column chromatography (PE: EA: 20:1) to obtain white solid L16H(7.01g，38.2％)。
1H NMR(400MHz,CDCl3):δ7.25–7.08(m,10H),7.03(dd,J＝8.0,0.8Hz,1H),6.95–6.89(m,1H),6.87(m,1H),6.76(d,4J＝2.3Hz,1H),3.59(s,2H),3.56(s,2H),2.55(s,6H),2.41–2.32(m,2H),2.23–2.18(m,2H),1.98(s,6H),1.68(d,J＝3.6Hz,12H).13C{1H}NMR(CDCl3,100MHz):δ153.8,153.5,151.8,151.7,139.5,135.4,132.5,131.2,127.9,127.7,126.9,126.5,126.4,125.9,125.4,124.7,124.7,123.5,122.8,119.1,58.0,56.2,53.2,50.4,45.4,45.3,42.6,42.2,31.2,29.6).Anal.Calcd.For C38H49N3O:C,80.95；H,8.76；N,7.45.Found:C,80.90；H,8.68；N,7.40％.
(2) Synthesis of complex Zn16
Except that the raw material adopts L16H (302mg, 0.54mmol), NaH (26mg, 1.08mmol) and anhydrous ZnCl2(74mg, 0.54mmol) in the same manner as in example 1, and was recrystallized from methylene chloride and n-hexane to give a white solid, which was then dried by suction to obtain Zn16 complex (153mg, 43.0%).
1H NMR(400MHz,CDCl3):δ7.45(d,3J＝7.3Hz,2H),7.37(td,3J＝7.8,4J＝1.6Hz,1H),7.28(d,4J＝2.1Hz,1H),7.26(m,1H),7.25–7.09(m,9H),7.07(t,3J＝7.3Hz,1H),6.50(d,4J＝2.5Hz,1H),4.50(d,2J＝14.1Hz,1H),4.15(d,2J＝12.1Hz,1H),3.93(d,2J＝14.1Hz,1H),3.19(d,2J＝12.1Hz,1H),2.77(td,2J＝12.4,4J＝3.4Hz,1H),2.59(s,6H),2.56(m,1H),2.35–2.24(m,1H),1.99(dd,3J＝10.0,4J＝3.0Hz),1.93(s,3H),1.65(s,3H),1.61(d,J＝3.5Hz,12H).13C{1H}NMR(CDCl3,100MHz):δ164.3,155.0,152.3,150.4,137.4,135.5,133.9,130.2,128.7,127.8,127.6,127.2,127.1,126.7,126.3,125.3,124.5,124.4,121.3,121.1,59.4,57.8,52.8,45.8,44.3,42.3,42.0,31.3,31.2,26.3.Anal.Calcd.for C38H48ClN3OZn·0.5CH2Cl2:C,65.49；H,6.99；N,5.95.Found:C,65.38；H,6.99；N,5.87％.
Example 8
Synthesis of complex Zn18
(1) Ligand L18Synthesis of H
Except that the reactant is N- [2- (N, N-dimethylamino) ethyl]-N- [2- (N, N-dimethylamino) benzyl]Methylamine (6.7g, 32.4mmol), paraformaldehyde (2.91g, 97.1mmol) and 2, 4-dichlorophenol (5.28g, 32.4mmol), the remaining procedures were performed with ligand L15H is the same. Obtaining yellow solid L through column chromatography (PE: EA is 20:1)18H(6.5g，50.6％)。
1H NMR(400MHz,CDCl3):δ7.29(dd,3J＝7.6Hz,4J＝1.5Hz,1H),7.24(d,4J＝2.6Hz,1H),7.18(td,3J＝8.0,4J＝1.6Hz,1H),7.06(dd,3J＝8.0,4J＝1.0Hz,1H),7.00(td,3J＝8.0,4J＝1.6Hz,1H),6.94(d,4J＝2.6Hz,1H),3.65(s,2H),3.63(s,2H),2.59(s,6H),2.54–2.44(m,4H),2.15(s,6H).13C{1H}NMR(CDCl3,100MHz):δ153.6,152.9,132.0,131.0,128.6,128.2,128.0,126.3,123.3,122.4,121.9,119.2,56.0,55.5,53.2,49.5,45.3,44.9.Anal.Calcd.For C20H24Cl2N3O:C,60.61；H,6.87；N,10.60.Found:C,60.66；H,6.83；N,10.52％.
(2) Synthesis of complex Zn18
Except that the raw material adopts L18H (724mg, 1.83mmol), NaH (88mg, 3.66mmol) and anhydrous ZnCl2(249mg, 1.83mmol) in the same manner as in example 1, and then recrystallized from methylene chloride and n-hexane to give a white solid, which was then dried by suction to obtain Zn18 complex (310mg, 34.3%).
1H NMR(400MHz,CDCl3):δ7.44–7.37(m,1H),7.30(m,3H),7.19(t,3J＝7.4Hz,1H),6.68(d,4J＝2.7Hz,1H),4.54(d,2J＝14.1Hz,1H),4.25(d,2J＝12.6Hz,1H),4.03(d,2J＝14.1Hz,1H),3.38(d,2J＝12.6Hz,1H),2.97–2.88(m,1H),2.77(dt,2J＝14.1,4J＝3.6Hz,1H),2.64(s,6H),2.46(m,6H),2.34(m,1H),2.28(dt,2J＝13.2,4J＝3.6Hz,1H).13C{1H}NMR(CDCl3,100MHz):δ160.8,155.0,133.9,130.6,130.2,129.8,126.3,125.6,124.6,124.1,121.3,118.6,58.3,57.8,53.6,46.7,45.8,45.4.Anal.Calcd.for C20H26ClN3OZn·0.2CH2Cl2:C,47.28；H,5.19；N,8.19.Found:C,47.26；H,5.40；N,8.00％.
Example 9
Synthesis of complex Mg16
In a glove box, 0.5mL of a solution of cyclohexylmagnesium chloride in tetrahydrofuran (2mmol/L) was added to a Schlenk flask, followed by slow dropwise addition of ligand L dissolved therein16A solution of H (563mg, 1mmol) in 15mL of dry tetrahydrofuran was reacted for 12H. The mixture was then filtered, the solid was drained and recrystallized from dichloromethane and n-hexane to precipitate a white solid as Mg16 complex (318Mg, 51.2%) by nuclear magnetic resonance.
1H NMR(400MHz,DMSO-d6):δ6.95–7.36(m,14H),6.88(d,1H),6.24(d,1H),4.39(s,1H),3.76(s,1H),3.48(s,1H),2.85(s,1H),2.53(s,6H),1.91–2.23(m,4H),1.66–1.88(m,6H),1.50–1.65(m,6H),1.34–4.49(m,6H).Anal.Calcd.for C38H48ClmMgN3O·0.2CH2Cl2:C,62.22；H,7.98；N,8.57.Found:C,61.10；H,8.29；N,8.93％.
Example 10
Under argon atmosphere, unpurified racemic lactide (0.144g, 1.00mmol) was charged to a polymerization flask, and 0.5mL of a solution of catalyst Zn1 in cyclohexene oxide was metered into the polymerization flask. [ rac-LA]0＝2.0M，[Zn]0＝0.01M，[Zn]0:[rac-LA]01: 200. Controlling the reaction temperature to be 80 +/-1 ℃, adding petroleum after reacting for 33 minutesThe reaction was terminated with ether. The solvent was removed by suction, the residue was dissolved in dichloromethane, methanol was added to precipitate the polymer, which was subsequently washed with methanol and dried in vacuo for 24 h. Conversion rate: 90%, Mn＝1.7×104g/mol, molecular weight distribution PDI of 1.25, isotacticity Pm＝0.50。
Example 11
The same procedure as in example 10 was repeated except that the catalyst was replaced with Zn2, the reaction temperature was controlled to 80. + -. 1 ℃ and the reaction temperature was controlled to [ rac-LA ]]0＝2.0M，[Zn]0＝0.01M，[Zn]0:[rac-LA]0After 36 minutes of reaction, conversion: 95%, Mn＝2.4×104g/mol, molecular weight distribution PDI of 1.27, isotacticity Pm＝0.57。
Example 12
The same procedure as in example 10 was repeated except that the catalyst was replaced with Zn3, the reaction temperature was controlled to 80. + -. 1 ℃ and the reaction temperature was controlled to [ rac-LA ]]0＝2.0M，[Zn]0＝0.01M，[Zn]0:[rac-LA]0After 37 minutes of reaction, conversion: 95%, Mn＝1.9×104g/mol, molecular weight distribution PDI of 1.31, isotacticity Pm＝0.55。
Example 13
The same procedure as in example 10 was repeated except that the catalyst was replaced with Zn4, the reaction temperature was controlled to 80. + -. 1 ℃ and the reaction temperature was controlled to [ rac-LA ]]0＝2.0M，[Zn]0＝0.01M，[Zn]0:[rac-LA]0After 30 minutes of reaction, conversion: 95%, Mn＝2.1×104g/mol, molecular weight distribution PDI of 1.27, isotacticity Pm＝0.50。
Example 14
The same procedure as in example 10 was repeated except that the catalyst was replaced with Zn9, the reaction temperature was controlled to 80. + -. 1 ℃ and the reaction temperature was controlled to [ rac-LA ]]0＝2.0M，[Zn]0＝0.01M，[Zn]0:[rac-LA]0After 68 minutes of reaction, conversion: 93%, Mn＝1.6×104g/mol, molecular weight distribution PDI 1.34, isotacticity Pm＝0.59。
Example 15
Except that the catalyst was changed to Zn15The procedure of example 10 was followed, with the reaction temperature being controlled to 80. + -. 1 ℃ and the reaction temperature being controlled to [ rac-LA ]]0＝2.0M，[Zn]0＝0.01M，[Zn]0:[rac-LA]0After 41 minutes of reaction, conversion: 93%, Mn＝2.1×104g/mol, molecular weight distribution PDI 1.34, isotacticity Pm＝0.50。
Example 16
The same procedure as in example 10 was repeated except that the catalyst was replaced with Zn16, the reaction temperature was controlled to 80. + -. 1 ℃ and the reaction temperature was controlled to [ rac-LA ]]0＝2.0M，[Zn]0＝0.01M，[Zn]0:[rac-LA]0After 42 minutes of reaction, conversion: 93%, Mn＝2.1×104g/mol, molecular weight distribution PDI of 1.22, isotacticity Pm＝0.59。
Example 17
The same procedure as in example 10 was repeated except that the catalyst was replaced with Zn18, the reaction temperature was controlled to 80. + -. 1 ℃ and the reaction temperature was controlled to [ rac-LA ]]0＝2.0M，[Zn]0＝0.01M，[Zn]0:[rac-LA]0After 36 minutes of reaction, conversion: 95%, Mn＝2.1×104g/mol, molecular weight distribution PDI of 1.31, isotacticity Pm＝0.50。
Example 18
Under argon atmosphere, unpurified racemic lactide (0.144g, 1.00mmol) was charged to a polymerization flask, and 0.5mL of a solution of catalyst Zn2 in cyclohexene oxide was metered into the polymerization flask. [ rac-LA]0＝2.0M，[Zn]0＝0.01M，[Zn]0:[rac-LA]01: 200. Controlling the reaction temperature to be 25 +/-1 ℃, and adding petroleum ether to terminate the reaction after reacting for 3 days. The solvent was removed by suction, the residue was dissolved in dichloromethane, methanol was added to precipitate the polymer, which was subsequently washed with methanol and dried in vacuo for 24 h. Conversion rate: 84%, Mn＝2.0×104g/mol, molecular weight distribution PDI 1.16.
Example 19
The same procedure as in example 18 was repeated except that the catalyst was replaced with Zn3, the reaction temperature was controlled to 25. + -. 1 ℃ and the reaction temperature was controlled to [ rac-LA ]]0＝2.0M，[Zn]0＝0.01M，[Zn]0:[rac-LA]0＝1:200, 3 days after reaction, conversion: 95%, Mn＝1.9×104g/mol, molecular weight distribution PDI 1.18.
Example 20
The same procedure as in example 18 was repeated except that the catalyst was replaced with Zn4, the reaction temperature was controlled to 25. + -. 1 ℃ and the reaction temperature was controlled to [ rac-LA ]]0＝2.0M，[Zn]0＝0.01M，[Zn]0:[rac-LA]0After 3 days reaction, conversion: 93%, Mn＝1.9×104g/mol, molecular weight distribution PDI of 1.15, isotacticity Pm＝0.57。
Example 21
The same procedure as in example 18 was repeated except that the catalyst was replaced with Zn9, the reaction temperature was controlled to 25. + -. 1 ℃ and the reaction temperature was controlled to [ rac-LA ]]0＝2.0M，[Zn]0＝0.01M，[Zn]0:[rac-LA]0After 4 days reaction, conversion: 95%, Mn＝2.1×104g/mol, molecular weight distribution PDI of 1.18, isotacticity Pm＝0.68。
Example 22
The same procedure as in example 18 was repeated except that the catalyst was replaced with Zn15, the reaction temperature was controlled to 25. + -. 1 ℃ and the reaction temperature was controlled to [ rac-LA ]]0＝2.0M，[Zn]0＝0.01M，[Zn]0:[rac-LA]0After 4 days of reaction, conversion: 92%, Mn＝2.2×104g/mol, molecular weight distribution PDI 1.17.
Example 23
The same procedure as in example 18 was repeated except that the catalyst was replaced with Zn16, the reaction temperature was controlled to 25. + -. 1 ℃ and the reaction temperature was controlled to [ rac-LA ]]0＝2.0M，[Zn]0＝0.01M，[Zn]0:[rac-LA]0After 4 days of reaction, conversion: 89%, Mn＝1.9×104g/mol, molecular weight distribution PDI of 1.19, isotacticity Pm＝0.69。
Example 24
The same procedure as in example 18 was repeated except that the catalyst was replaced with Zn18, the reaction temperature was controlled to 25. + -. 1 ℃ and the reaction temperature was controlled to [ rac-LA ]]0＝2.0M，[Zn]0＝0.01M，[Zn]0:[rac-LA]0After 3 days of reaction, conversion: 94%, Mn＝2.1×104g/mol, molecular weight distribution PDI 1.17.
Example 25
Under argon atmosphere, unpurified racemic lactide (0.144g, 1.00mmol) was charged to a polymerization flask, and 0.5mL of a solution of catalyst Zn16 in cyclohexene oxide was metered into the polymerization flask. [ rac-LA]0＝2.0M，[Zn]0＝0.002M，[Zn]0:[rac-LA]01: 1000. Controlling the reaction temperature to be 80 +/-1 ℃, and adding petroleum ether to terminate the reaction after the reaction is carried out for 1.4 hours. The solvent was removed by suction, the residue was dissolved in dichloromethane, methanol was added to precipitate the polymer, which was subsequently washed with methanol and dried in vacuo for 24 h. Conversion rate: 91%, Mn＝2.1×104g/mol, molecular weight distribution PDI of 1.26, isotacticity Pm＝0.55。
Example 26
Except for [ Zn ]]00.0002M and [ Zn ]]0:[rac-LA]0In addition to 1:10000, [ rac-LA ] was prepared as in example 25]0Control reaction temperature 80 ± 1 ℃ at 2.0M, after 7.6 hours of reaction, conversion: 95%, Mn＝2.2×104g/mol, molecular weight distribution PDI of 1.39, isotacticity Pm＝0.50。
Example 27
Except for [ Zn ]]00.00005M and [ Zn ]]0:[rac-LA]0Other than 1:40000, the procedure was as in example 25, [ rac-LA]0Control reaction temperature 80 ± 1 ℃ at 2.0M, after 20.8 hours of reaction, conversion: 94%, Mn＝2.1×104g/mol, molecular weight distribution PDI of 1.32, isotacticity Pm＝0.50。
Example 28
Except for [ Zn ]]00.00002M and [ Zn ]]0:[rac-LA]0Other than 1:100000, the procedure is as in example 25, [ rac-LA]0Control reaction temperature 80 ± 1 ℃ at 2.0M, conversion after 40.6 hours reaction: 96%, Mn＝2.4×104g/mol, molecular weight distribution PDI of 1.71, isotacticity Pm＝0.50。
Example 29
Except for [ Zn ]]00.000013M and [ Zn ]]0:[rac-LA]0In addition to 1:150000, the procedure is as in example 25, [ rac-LA]0Control reaction temperature 80 ± 1 ℃ at 2.0M, after 58.7 hours of reaction, conversion: 93%, Mn＝1.8×104g/mol, molecular weight distribution PDI of 1.69, isotacticity Pm＝0.50。
Example 30
Purified ε -CL (0.144g, 1.00mmol) was added to a polymerization flask under argon protection, and 0.5mL of an epoxycyclohexane solution of catalyst Zn1 was weighed and added to the polymerization flask. [ epsilon-CL]0＝2.0M，[Zn]0＝0.01M，[Zn]0:[ε-CL]01: 200. Controlling the reaction temperature to be 80 +/-1 ℃, and adding petroleum ether to terminate the reaction after reacting for 2.5 hours. The solvent was removed by suction, the residue was dissolved in dichloromethane, methanol was added to precipitate the polymer, which was subsequently washed with methanol and dried in vacuo for 24 h. Conversion rate: 75%, Mn＝1.6×104g/mol, molecular weight distribution PDI 1.35.
Example 31
Under argon atmosphere, unpurified racemic lactide (0.144g, 1.00mmol) was charged to a polymerization flask, and 0.5mL of a solution of catalyst Zn16 in cyclohexene oxide was metered into the polymerization flask. [ rac-LA]0＝2.0M，[Zn]0＝0.01M，[Zn]0:[rac-LA]01: 200. Controlling the reaction temperature to be 80 +/-1 ℃, and adding petroleum ether to terminate the reaction after 7 minutes of reaction. The solvent was removed by suction, the residue was dissolved in dichloromethane, methanol was added to precipitate the polymer, which was subsequently washed with methanol and dried in vacuo for 24 h. Conversion rate: 28%, Mn＝6.8×103g/mol, molecular weight distribution PDI 1.14.
Example 32
Under argon atmosphere, unpurified racemic lactide (0.144g, 1.00mmol) was charged to a polymerization flask, and 0.5mL of a solution of catalyst Zn16 in cyclohexene oxide was metered into the polymerization flask. [ rac-LA ]]0＝2.0M，[Zn]0＝0.1M，[Zn]0:[rac-LA]01: 20. Controlling the reaction temperature to be 80 +/-1 ℃, and adding petroleum ether to terminate the reaction after reacting for 6 minutes. The solvent is removed by suction and the residue is freed from the solvent by dichloro-benzeneThe methane was dissolved and methanol was added to precipitate the polymer, which was subsequently washed with methanol and dried under vacuum for 24 h. Conversion rate: 91%, Mn＝2.4×103g/mol, molecular weight distribution PDI 1.21.
Example 33
Purified racemic lactide (0.144g, 1.00mmol) was added to a polymerization flask under argon protection, and 0.5mL of a solution of catalyst Zn1 in cyclohexene oxide was metered into the polymerization flask. [ rac-LA]0＝2.0M，[Zn]0＝0.01M，[Zn]0:[rac-LA]01: 200. Controlling the reaction temperature to be 80 +/-1 ℃, and adding petroleum ether to terminate the reaction after reacting for 30 minutes. The solvent was removed by suction, the residue was dissolved in dichloromethane, methanol was added to precipitate the polymer, which was subsequently washed with methanol and dried in vacuo for 24 h. Conversion rate: 92%, Mn＝2.4×104g/mol, molecular weight distribution PDI 1.23.
Example 34
The same procedure as in example 33 was repeated except that the catalyst was replaced with Zn2, the reaction temperature was controlled to 80. + -. 1 ℃ and the reaction temperature was controlled to [ rac-LA ]]0＝2.0M，[Zn]0＝0.01M，[Zn]0:[rac-LA]0After 30 minutes of reaction, conversion: 91%, Mn＝2.3×104g/mol, molecular weight distribution PDI 1.14.
Example 35
The same procedure as in example 33 was repeated except that the catalyst was replaced with Zn3, the reaction temperature was controlled to 80. + -. 1 ℃ and the reaction temperature was controlled to [ rac-LA ]]0＝2.0M，[Zn]0＝0.01M，[Zn]0:[rac-LA]0After 35 minutes of reaction, conversion: 92%, Mn＝2.4×104g/mol, molecular weight distribution PDI 1.15.
Example 36
The same procedure as in example 33 was repeated except that the catalyst was replaced with Zn4, the reaction temperature was controlled to 80. + -. 1 ℃ and the reaction temperature was controlled to [ rac-LA ]]0＝2.0M，[Zn]0＝0.01M，[Zn]0:[rac-LA]0After 29 minutes of reaction, conversion: 94%, Mn＝2.4×104g/mol, molecular weight distribution PDI 1.20.
Example 37
The same procedure as in example 33 was repeated except that the catalyst was replaced with Zn9, the reaction temperature was controlled to 80. + -. 1 ℃ and the reaction temperature was controlled to [ rac-LA ]]0＝2.0M，[Zn]0＝0.01M，[Zn]0:[rac-LA]0After 60 minutes of reaction, conversion: 91%, Mn＝2.3×104g/mol, molecular weight distribution PDI 1.16.
Example 38
The same procedure as in example 33 was repeated except that the catalyst was replaced with Zn15, the reaction temperature was controlled to 80. + -. 1 ℃ and the reaction temperature was controlled to [ rac-LA ]]0＝2.0M，[Zn]0＝0.01M，[Zn]0:[rac-LA]0After 36 minutes of reaction, conversion: 94%, Mn＝2.4×104g/mol, molecular weight distribution PDI 1.22.
Example 39
The same procedure as in example 33 was repeated except that the catalyst was replaced with Zn16, the reaction temperature was controlled to 80. + -. 1 ℃ and the reaction temperature was controlled to [ rac-LA ]]0＝2.0M，[Zn]0＝0.01M，[Zn]0:[rac-LA]0After 37 minutes of reaction, conversion: 92%, Mn＝2.3×104g/mol, molecular weight distribution PDI 1.21.
Example 40
The same procedure as in example 33 was repeated except that the catalyst was replaced with Zn18, the reaction temperature was controlled to 80. + -. 1 ℃ and the reaction temperature was controlled to [ rac-LA ]]0＝2.0M，[Zn]0＝0.01M，[Zn]0:[rac-LA]0After 30 minutes of reaction, conversion: 95%, Mn＝2.5×104g/mol, molecular weight distribution PDI 1.23.
EXAMPLE 41
Purified racemic lactide (0.144g, 1.00mmol) was added to a polymerization flask under argon protection, and 0.5mL of a solution of catalyst Zn16 in cyclohexene oxide was metered into the polymerization flask. [ rac-LA]0＝2.0M，[Zn]0＝0.002M，[Zn]0:[rac-LA]01: 1000. Controlling the reaction temperature to be 80 +/-1 ℃, and adding petroleum ether to terminate the reaction after reacting for 80 minutes. The solvent was removed by suction, the residue was dissolved in dichloromethane, methanol was added to precipitate the polymer, which was subsequently washed with methanol and dried in vacuo for 24 h. Conversion rate: the content of the active ingredients in the active ingredients is 86%,Mn＝2.61×104g/mol, molecular weight distribution PDI 1.22.
Claims (10)
1. An asymmetric multidentate monophenoloxy metal zinc, magnesium halide (I) and (II) having the general formula:
in the formulae (I), (II):
R1～R4each represents hydrogen, C1～C20Alkyl of linear, branched or cyclic structure, C7～C30Mono-or poly-aryl-substituted alkyl of (a), halogen;
R5represents ethylene or methylene;
X1～X2represents C1～C12Alkoxy of linear, branched or cyclic structure, C1～C12Alkyl substituted amine groups of linear, branched or cyclic structure;
X3represents halogen.
2. The asymmetric multidentate monophenoloxy metal zinc, magnesium halide compounds (I) and (II) according to claim 1 wherein R1～R4Is hydrogen, C1～C10Alkyl of linear, branched or cyclic structure, C7～C20Mono-or poly-aryl-substituted alkyl of (a), halogen; x1～X2Is C1～C6Alkoxy of linear, branched or cyclic structure, C1～C6Alkyl substituted amine groups of linear, branched or cyclic structure; x3Is chlorine, bromine or iodine.
3. The asymmetric multidentate monophenoloxy metal zinc, magnesium halide (I) and (II) according to claim 1 wherein R is1～R4Hydrogen, methyl, tert-butyl, cumyl, triphenylmethyl or chlorine; r5Is ethyleneA group; x1～X2Methoxy and dimethylamino; x3Is chlorine.
4. A process for preparing an asymmetric multidentate monophenol oxygroup metal zinc halide (I) as claimed in any one of claims 1 to 3, comprising the steps of:
reacting an asymmetric multidentate monophenol ligand compound shown in a formula (III) with a hydrogen extraction reagent to obtain metal salt of a corresponding ligand, then reacting the metal salt with a metal raw material compound in an organic medium to generate an asymmetric multidentate monophenol oxygroup metal zinc halide, wherein the reaction temperature is-75-80 ℃, preferably 0-40 ℃, the reaction time is 8-72 hours, preferably 16-48 hours, and then collecting a compound (I) from a reaction product;
substituent R in the above preparation method1～R5And X1～X2Corresponding groups to the asymmetric multidentate monophenol oxo metal zinc halide (I) according to any one of claims 1 to 3;
the hydrogen drawing reagent is C1～C4An alkali metal alkyl compound of (a), sodium hydride, or potassium hydride;
the metal starting compound has the general formula Zn (X)3)2，X3Corresponding groups of the asymmetric multidentate monophenol oxygroup metal zinc halide (I) according to any one of claims 1 to 3;
the mass ratio of the asymmetric multidentate monophenol ligand compound (III) to the hydrogen-withdrawing reagent is 1: 1.5-2.5; the mass ratio of the metal salt of the asymmetric multidentate monophenol ligand compound to the metal raw material compound is 1: 1.0-1.5;
the organic medium is one or two of tetrahydrofuran, diethyl ether, toluene, benzene, petroleum ether and n-hexane.
5. A process for the preparation of an asymmetric multidentate monophenoloxy metal magnesium halide (II) as claimed in any one of claims 1 to 3 comprising the steps of:
reacting an asymmetric multidentate monophenol ligand compound shown in a formula (III) with a Grignard reagent in an organic medium to generate an asymmetric multidentate monophenol oxygen-based metal magnesium halide, wherein the reaction temperature is-75-80 ℃, preferably 0-40 ℃, the reaction time is 8-72 hours, preferably 16-48 hours, and then collecting a compound (II) from a reaction product;
substituent R in the above preparation method1～R5And X1～X2Corresponding groups to the asymmetric multidentate monophenol oxygen-based metal magnesium halide (II) according to any one of claims 1 to 3;
the Grignard reagent has the general formula R6Mg(X3)，R6Is C1～C6Alkyl of linear, branched or cyclic structure, X3Corresponding groups satisfying the asymmetric multidentate monophenol oxygen-based metal magnesium halide (II) described in any one of claims 1 to 3;
the mass ratio of the asymmetric multidentate monophenol ligand compound (III) to the Grignard reagent is 1: 1.0-1.5;
the organic medium is one or two of tetrahydrofuran, diethyl ether, toluene, benzene, petroleum ether and n-hexane.
6. The process according to claims 4 and 5, wherein the hydrogen abstraction agent is sodium hydride; the metal raw material compound is zinc chloride; the Grignard reagent is ethyl magnesium chloride, tert-butyl magnesium chloride or cyclohexyl magnesium chloride.
7. Use of an asymmetric multidentate monophenol oxygen based metal halide, zinc or magnesium halide, as claimed in any of claims 1-3, for ring opening polymerization of lactones and obtaining cyclic polyesters.
8. Use according to claim 7, characterized in that the lactone is selected from the group consisting of L-lactide, D-lactide, rac-lactide, meso-lactide, epsilon-caprolactone, beta-butyrolactone, alpha-methyltrimethylene cyclic carbonate and may be used without purification treatment.
9. Use according to claim 7, wherein when the asymmetric multidentate monophenol oxo metal zinc halide or asymmetric multidentate monophenol oxo metal magnesium halide according to any one of claims 1 to 3 is used as a catalyst, the ratio of the amount of the catalyst to the amount of the monomer is 1:1 to 300000, preferably 1:200 to 150000, in the ring-opening polymerization of lactide.
10. Use according to claim 7, wherein when the asymmetric multidentate monophenol oxo metal zinc halide or asymmetric multidentate monophenol oxo metal magnesium halide according to any one of claims 1 to 3 is used as a catalyst to ring-opening polymerize epsilon-caprolactone, the ratio of the amount of the catalyst to the amount of the monomer is 1:1 to 300000, preferably 1:200 to 150000.
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