CN103864659A - 手性亚胺酚氧基锌、镁化合物及其制备方法和应用 - Google Patents
手性亚胺酚氧基锌、镁化合物及其制备方法和应用 Download PDFInfo
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- CN103864659A CN103864659A CN201410090168.6A CN201410090168A CN103864659A CN 103864659 A CN103864659 A CN 103864659A CN 201410090168 A CN201410090168 A CN 201410090168A CN 103864659 A CN103864659 A CN 103864659A
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- rac
- alkyl
- zinc
- lactide
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- -1 phenol oxyl zinc Chemical compound 0.000 title claims abstract description 52
- 150000002681 magnesium compounds Chemical class 0.000 title claims abstract description 31
- 150000002466 imines Chemical class 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 114
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000003446 ligand Substances 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 7
- 150000002596 lactones Chemical class 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 312
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 141
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 128
- 239000011701 zinc Substances 0.000 claims description 121
- 238000006243 chemical reaction Methods 0.000 claims description 97
- 239000011777 magnesium Chemical group 0.000 claims description 75
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 64
- 229910052725 zinc Inorganic materials 0.000 claims description 60
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 57
- 239000003921 oil Substances 0.000 claims description 47
- 125000000217 alkyl group Chemical group 0.000 claims description 40
- 229910052749 magnesium Inorganic materials 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 239000002585 base Substances 0.000 claims description 15
- 125000003368 amide group Chemical group 0.000 claims description 14
- 150000002431 hydrogen Chemical class 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- INKDAKMSOSCDGL-UHFFFAOYSA-N [O].OC1=CC=CC=C1 Chemical compound [O].OC1=CC=CC=C1 INKDAKMSOSCDGL-UHFFFAOYSA-N 0.000 claims description 13
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 150000002736 metal compounds Chemical class 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 claims description 5
- PHRABVHYUHIYGY-UHFFFAOYSA-N 1-methylnaphthalene Chemical group C1=CC=C2C([CH2])=CC=CC2=C1 PHRABVHYUHIYGY-UHFFFAOYSA-N 0.000 claims description 4
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 4
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 4
- 229960004217 benzyl alcohol Drugs 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 2
- ZNKKJQSIIWYNCD-UHFFFAOYSA-N CC[Zn]OC(C)C Chemical compound CC[Zn]OC(C)C ZNKKJQSIIWYNCD-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- QXTIBZLKQPJVII-UHFFFAOYSA-N triethylsilicon Chemical compound CC[Si](CC)CC QXTIBZLKQPJVII-UHFFFAOYSA-N 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
- 238000009826 distribution Methods 0.000 abstract description 45
- 229920000747 poly(lactic acid) Polymers 0.000 abstract description 24
- 239000002994 raw material Substances 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000002685 polymerization catalyst Substances 0.000 abstract description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 239000004626 polylactic acid Substances 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 112
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 90
- 239000002904 solvent Substances 0.000 description 57
- 229910052786 argon Inorganic materials 0.000 description 56
- 239000000126 substance Substances 0.000 description 52
- 239000000284 extract Substances 0.000 description 51
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 46
- 238000001556 precipitation Methods 0.000 description 45
- 230000009466 transformation Effects 0.000 description 45
- 238000001291 vacuum drying Methods 0.000 description 45
- 239000003054 catalyst Substances 0.000 description 34
- 229920000642 polymer Polymers 0.000 description 31
- 238000005481 NMR spectroscopy Methods 0.000 description 18
- 239000007787 solid Substances 0.000 description 17
- 238000001953 recrystallisation Methods 0.000 description 12
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000010992 reflux Methods 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 7
- 244000061458 Solanum melongena Species 0.000 description 7
- 235000002597 Solanum melongena Nutrition 0.000 description 7
- 229960000935 dehydrated alcohol Drugs 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 230000002194 synthesizing effect Effects 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- JIJLESMARNPCRJ-VIFPVBQESA-N CCCCN1CCC[C@@]1(C)N Chemical compound CCCCN1CCC[C@@]1(C)N JIJLESMARNPCRJ-VIFPVBQESA-N 0.000 description 4
- 150000004696 coordination complex Chemical class 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- RRIQVLZDOZPJTH-UHFFFAOYSA-N 3,5-di-tert-butyl-2-hydroxybenzaldehyde Chemical compound CC(C)(C)C1=CC(C=O)=C(O)C(C(C)(C)C)=C1 RRIQVLZDOZPJTH-UHFFFAOYSA-N 0.000 description 3
- 229920003232 aliphatic polyester Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- YJQIQTZIUDTKFC-LBPRGKRZSA-N (2s)-1-benzyl-2-methylpyrrolidin-2-amine Chemical compound C[C@@]1(N)CCCN1CC1=CC=CC=C1 YJQIQTZIUDTKFC-LBPRGKRZSA-N 0.000 description 2
- OZZQHCBFUVFZGT-UHFFFAOYSA-N 2-(2-hydroxypropanoyloxy)propanoic acid Chemical compound CC(O)C(=O)OC(C)C(O)=O OZZQHCBFUVFZGT-UHFFFAOYSA-N 0.000 description 2
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- UNRBEYYLYRXYCG-ZETCQYMHSA-N [(2s)-1-ethylpyrrolidin-2-yl]methanamine Chemical compound CCN1CCC[C@H]1CN UNRBEYYLYRXYCG-ZETCQYMHSA-N 0.000 description 2
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical group NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 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
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 1
- 0 CCC(*12*3(C(C)=*)Oc(c(C(C)*(C)CC)cc(*(C)C)c4)c4C(*(CC)CC)=*3CC1CCC2)N Chemical compound CCC(*12*3(C(C)=*)Oc(c(C(C)*(C)CC)cc(*(C)C)c4)c4C(*(CC)CC)=*3CC1CCC2)N 0.000 description 1
- 208000003643 Callosities Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010020649 Hyperkeratosis Diseases 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
- QCTXENUBAFDBER-UHFFFAOYSA-N [O].NC1=C(C=CC=C1)O Chemical compound [O].NC1=C(C=CC=C1)O QCTXENUBAFDBER-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 238000012271 agricultural production Methods 0.000 description 1
- 150000001413 amino acids Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229920001580 isotactic polymer Polymers 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002989 phenols Chemical group 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000003356 suture material Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D207/08—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon radicals, substituted by hetero atoms, attached to ring carbon atoms
- C07D207/09—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
-
- 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 Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- C—CHEMISTRY; METALLURGY
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
本发明公开了一类手性亚胺酚氧基锌、镁化合物及其制备方法和在催化内酯开环聚合中的应用。其制备方法包括如下步骤:将中性配体直接与金属原料化合物在有机介质中反应,然后经过滤,抽干,重结晶步骤获得目标化合物。本发明的手性亚胺酚氧基锌、镁化合物是高效的内酯开环聚合催化剂,可用于催化丙交酯、ε-己内酯等的聚合反应;特别对于外消旋丙交酯可以得到较高杂规度的聚乳酸。本发明的手性亚胺酚氧基锌、镁化合物的优点十分明显:原料易得,合成路线简单,目标产物收率高,具有较高的催化活性,能获得高分子量及窄分子量分布的聚丙交酯,能够满足工业部门的需要。其结构式如下所示。
Description
技术领域
本发明涉及一类手性亚胺酚氧基锌、镁化合物,以及这类化合物在内酯聚合中的应用。
背景技术
作为一类可以代替传统聚烯烃材料的聚合物,脂肪族聚酯具有良好的生物相容性和可降解性,且原料来源于可再生资源,因而受到了广泛关注。目前被大量研究的脂肪族聚酯中,聚乳酸尤其引人瞩目,一方面其原料乳酸可由玉米等农作物发酵而得,另一方面聚乳酸可以被自然界中的微生物降解、参与自然界的碳循环,属于环境友好型聚合物。聚乳酸优良的可加工性更使其成为最具有发展潜力的脂肪族聚酯,在工农业生产和生物医药等领域(如药物的缓释材料、医用缝合材料等)具有广阔的应用前景。近年来,由结构明确金属络合物催化剂引发的乳酸二聚体(丙交酯)立体选择性开环,进一步拓展了聚乳酸的微观链结构,使得其机械加工、热稳定性能等得到显著提高,使得在更广泛的应用领域替代传统聚烯烃材料成为可能。
乳酸二聚体即丙交酯主要包括L-丙交酯、D-丙交酯、内消旋丙交酯三种异构体,1:1的L-丙交酯和D-丙交酯混合物为外消旋丙交酯。其中L-丙交酯和外消旋丙交酯可以由农作物通过发酵工程较廉价获取用于工业生产。不同的丙交酯单体通过金属络合物催化剂催化可以得到不同微观结构的聚乳酸。由L-丙交酯可以制得等规聚乳酸,等规聚乳酸具有170-180℃和较好的结晶度。而外消旋丙交酯通过开环聚合可以得到无规、杂规、嵌段等规聚合物和等规立体复合物。其中嵌段等规和立体复合聚乳酸具有比等规聚乳酸更高的熔点和机械性能;杂规聚丙交酯为无定形体,虽然机械强度和加工性能较差,但其具有比等规聚乳酸更快的降解速率,在药物缓释等领域有较多的应用。相对于无规聚乳酸,由高立体选择性催化剂通过聚合得到的等规立体复合物和杂规聚乳酸都有较高的应用价值。因此,研究开发外消旋丙交酯高活性、高立体选择性聚合催化剂成为该领域的研究热点。锌、镁络合物对丙交酯聚合具有高催化活性、高可控性等特点,此外,锌、镁作为人体必需元素,其无色无毒以及具有生物相容性等特点也符合聚丙交酯在食品包装及医药领域的要求,因此锌、镁等环境友好型金属的络合物催化剂研究开发更成为该领域广泛关注的研究热点。
Coates小组在2001年发表了利用β-二亚胺配体通过烷氧基桥联的锌、镁络合物(BDI)Zn(OiPr)和(BDI)Mg(OiPr)催化外消旋丙交酯聚合分别获得高分子量的杂规聚丙交酯和无规聚丙交酯(J.Am.Chem.Soc.2001,123,3229)。Chisholm小组报道了含有醚键三齿β-二亚胺配体锌、镁络合物,催化外消旋丙交酯聚合过程中锌络合物得到了较高杂规度聚丙交酯,镁络合物需要在四氢呋喃中才有较高的杂规选择性(Inorg.Chem.2005,44,8004)。Hillmyer和Tolman研究组在2003年报道合成了乙氧基双核锌络合物,该络合物对外消旋丙交酯开环聚合具有很高的催化剂活性,可以在20分钟内聚合1500当量丙交酯得到分子量为130kg·mol-1的聚乳酸,是至今为止锌络合物中活性最高的催化剂之一(J.Am.Chem.Soc.2003,125,11350)。Lin小组合成了三齿席夫碱配体锌络合物,在THF溶剂中,能够催化外消旋丙交酯聚合得到杂规聚合物,降低温度至-55℃后杂规度可以达到0.91(Macromolecules,2006,39,3745)。
2010年,本小组报道了多齿胺基酚氧基镁、锌络合物,其中镁络合物对丙交酯显示了超高活性,在甲苯中能够迅速催化大量丙交酯单体聚合,得到等规倾向的聚合物,是目前催化丙交酯聚合速率最快的催化剂(Macromolecules,2010,43,6535–6537),锌络合物也得到偏等规的聚合物(Dalton Trans.,2010,39,7897)。为获得高等规选择性,研究者尝试在络合物配体骨架上引入手性因素,2007年Darensbourg报道了非环状单手性中心氨基酸衍生的亚胺酚氧基锌络合物,但对外消旋丙交酯聚合表现出较高的杂规选择性(Inorg.Chem.,2010,49,2360)。Lin小组合成了含有手性环己二胺桥联的单阴离子Salen型配体镁络合物,催化外消旋丙交酯聚合得到略显等规的聚丙交酯,Pm=0.54~0.67(Polymer,2005,46,9784)。2009年,Mehrkhodavandi课题组合成了含有手性环己二胺结构的三齿席夫碱配体锌乙基络合物,其对外消旋丙交酯具有活性,但选择性很低(Organometallics,2009,28,1309)。2012年,Otero报道了含有手性的杂异蟹型锌络合物,对外消旋丙交酯有活性聚合特征,得到杂规度不高的聚合物(Organometallics,2012,31,4191)。本小组在2013年首次报道了利用脯氨酸衍生的手性胺基酚氧基锌络合物(Chem.Comm.,2013,49,8686),实现了锌络合物较等规选性催化外消旋丙交酯聚合,得到了具有熔点和一定结晶性的嵌段聚丙交酯。
金属络合物在外消旋丙交酯聚合领域中的应用已经取得了较大突破,通对改变周围的电子和空间位阻对金属中心进行巧妙设计,一定程度上实现了不同立体结构聚丙交酯的合成。作为环境友好型聚合物,人们在合成聚丙交酯时更倾向使用生物相容性金属的络合物(锌、镁等),但到目前为止,锌、镁等络合物作为内酯酯开环聚合催化剂,对外消旋丙交酯只表现出了较高的杂规选择性,具有较高等规选择性的催化剂还很少被报道。因此,有关锌、镁络合物催化剂的研究工作有待于进一步开展,以合成集高活性、高立体选择性为一体的高效催化剂。
发明内容
本发明目的之一在于公开一类手性亚胺酚类配体及其锌、镁化合物。
本发明目的之二在于公开手性亚胺酚类配体及其锌、镁化合物的制备方法。
本发明目的之三在于公开手性亚胺酚氧基锌、镁化合物作为催化剂在内酯聚合中的应用。
本发明的技术构思:
目前,文献报道的高选择性锌、镁络合物对外消旋丙交酯开环聚合都是通过链端控制机理得到杂规聚乳酸。其中包括一些手性催化剂,它们没有利用手性中心控制机理表现出相应的选择性。因此,本发明在配体结构中引入手性脯氨酸衍生的多手性中心骨架,该手性NNO三齿配体与金属配位后,能产生一个手性N原子和手性金属中心,加上配体本身的固有碳手性,可以得到多手性中心的金属络合物,以实现在单体与金属中心配位时起到手性诱导效果,从而获得对催化外消旋丙交酯有高立体选择性的锌、镁催化剂。此外,以酚亚胺为基本骨架,在多手性中心配体骨架基础上,改变其上各相关取代基,可以起到调整金属中心的空间位阻和路易斯酸性,从而筛选出集高活性、高选择性于一体的高效催化剂。
本发明提供的手性亚胺酚类配体(I)及其金属锌、镁化合物(II),具有以下通式:
式(I)、(II)中:
R1~R2分别代表氢,C1~C20直链、支链或环状结构的烷基,C1~C20直链或支链结构的烷氧基,C7~C30单或多芳基取代的烷基,C6~C18的芳基,卤素;R1~R2也可分别代表取代硅基SiR6R7R8,其中R6~R8分别为C1~C10直链、支链或环状结构的烷基,C7~C20单或多芳基取代的烷基,C6~C18的芳基,R6、R7和R8可以相同或不同;
R3代表氢,C1~C20直链、支链或环状结构的烷基,C6~C18的芳基;
R4代表C1~C20直链、支链或环状结构的烷基,C7~C30单或多芳基取代的烷基,C6~C18的芳基;
R5代表C1~C10直链、支链或环状结构的烷基;R5代表胺基NR9R10,其中R9~R10分别为C1~C6直链、支链或环状结构的烷基,三甲基硅基,三乙基硅基,二甲基氢硅基,R9和R10可以相同或不同;R5代表烷氧基OR11,其中R11为C1~C10直链、支链或环状结构的烷基,C7~C20单或多芳基取代的烷基;
M代表锌、镁。
手性亚胺酚类配体(I)及其金属锌、镁化合物(II),其特征在于,R1~R2优选为氢,C1~C8直链、支链或环状结构的烷基,C1~C8直链或支链结构的烷氧基,C7~C20单或多芳基取代的烷基,C6~C12的芳基,卤素;R1~R2代表取代硅基SiR6R7R8时,R6~R8优选为C1~C6直链、支链或环状结构的烷基,C7~C12单或多芳基取代的烷基,C6~C12的芳基;
R3代表氢,C1~C8直链、支链或环状结构的烷基,C6~C12的芳基;
R4代表C1~C8直链、支链或环状结构的烷基,C7~C20单或多芳基取代的烷基,C6~C12的芳基;
R5代表C1~C6直链、支链或环状结构的烷基,二(三甲基硅)胺基,二(三乙基硅)胺基,二(二甲基氢硅)胺基;R5代表烷氧基OR11时,其中R11优选为C1~C6直链、支链或环状结构的烷基,苄基,(1-萘基)甲基,(9-蒽基)甲基。
式(I)、(II)中,手性亚胺酚类配体(I)及其金属锌、镁化合物(II),其特征在于,R1~R2优选为氢、甲基、异丙基、叔丁基、枯基、三苯甲基、三甲基硅基,三苯基硅基或卤素;R3优选为氢、甲基;R4优选为甲基、乙基、异丙基、正丁基、正辛基、苄基、(1-萘基)甲基;R5优选为二(三甲基硅)胺基,乙基,正丁基,异丙氧基,苄氧基。
优选的手性亚胺酚类配体,其结构式如下:
优选的手性亚胺酚类配体金属锌、镁化合物结构为:
本发明的手性亚胺酚类配体(I)及其锌、镁化合物(II)制备方法如下步骤:
将式(III)所示的手性N-取代-2-氨基甲基四氢吡咯与取代水杨醛(IV)在乙醇或甲醇中发生西佛碱反应,反应温度为25~150℃,反应时间为2~72小时,然后从反应产物中收集手性亚胺酚类配体化合物(I);
任选的,再将式(I)所示的手性亚胺酚类配体化合物与锌或镁的金属原料化合物在有机溶剂中反应,反应温度为0~100℃,反应时间为2~96小时,然后从反应产物中收集目标手性亚胺酚氧基锌或镁化合物(II);
反应式中取代基R1~R5与满足本发明的手性亚胺酚类配体(I)及其金属锌、镁化合物(II)的各相应基团一致;金属原料化合物具有通式M(R5)(R12),M=Zn、Mg,R12为反应中离去的基团,其要求与R5一致,R5和R12可以相同或不同。
锌或镁的金属原料化合物优选二乙基锌、乙基异丙氧基锌、二{二(三甲基硅)胺基}锌、二正丁基镁、二{二(三甲基硅)胺基}镁;
手性亚胺酚类配体化合物与金属原料化合物的摩尔比为1:0.5~1.5。
所述的有机溶剂选自四氢呋喃、乙醚、甲苯、苯、石油醚和正己烷中的一种或两种。
本发明所述的手性亚胺酚类配体锌、镁化合物是一种高效的内酯聚合催化剂,可用于L-丙交酯,D-丙交酯,rac-丙交酯,meso-丙交酯,己内酯,β-丁内酯的聚合反应,聚合方式为溶液聚合和熔融聚合。
以本发明手性亚胺酚氧基锌、镁化合物为催化剂,使丙交酯在-39~130℃下聚合,聚合时催化剂与单体的摩尔比为1:1~10000,优选1:100~1000。
以本发明手性亚胺酚氧基锌、镁化合物为催化剂,在醇存在的条件下,使丙交酯在-39~130℃下聚合,聚合时催化剂与醇以及单体摩尔比为1:1~50:1~10000;所述的醇为C1~C10直链、支链或环状结构的烷基醇,苄醇。
以本发明手性亚胺酚氧基锌、镁化合物为催化剂,在醇存在下或不加醇,使β-丁内酯在-39~50℃下共聚合;所述的醇为C1~C10直链、支链或环状结构的烷基醇,苄醇。
本发明提供的催化剂其配体原料易得,催化剂制备方便、性质稳定,同时具有较高的催化活性及高立体选择性,易获得高立体规整度、高分子量的聚内酯。能够满足工业部门的要求,有着广泛的应用前景。下面通过实例进一步说明本发明,但本发明不限于此。
具体实施方式
手性原料(S)-1-乙基-2-氨基甲基四氢吡咯,(S)-1-正丁基-2-氨基甲基四氢吡咯的合成可参考文献(Bioorg.Med.Chem.1998,6,1759)进行。
实施例1
配体L1的合成
在100mL茄型瓶中加入3-异丙基水杨醛1.65g,30mL无水乙醇,(S)-1-乙基-2-氨基甲基四氢吡咯1.35g,加热回流24小时。无水硫酸镁干燥,抽除溶剂及过量的低沸点反应物得黄色粘稠液体。无须进一步处理即得纯产物(2.51g,91.6%)。
1H NMR(CDCl3,400MHz):δ13.86(s,1H),8.36(s,1H),7.25(d,J=6.4Hz,1H),7.09(d,J=2.4Hz,1H),3.74(ddd,J=11.8,4.1,0.9Hz,1H),3.36(dd,J=11.8,8.8Hz,1H),3.07(sept,1H),3.01–2.90(m,2H),2.56(dt,J=8.9,6.6Hz,1H),2.01–1.77(m,2H),1.76–1.69(m,2H),1.45(s,9H),1.31(s,9H),1.15(d,J=6.5Hz,3H),1.05(d,J=6.4Hz,3H).13C{1H}NMR(CDCl3,100MHz):δ166.3,158.2,139.8,136.6,126.7,125.8,117.9,65.1,60.5,51.2,48.8,35.0,34.1,31.5,29.5,29.4,23.4,22.2,17.8.Anal.Calcd.For C17H26N2O:C,74.41;H,9.55;N,10.21.Found:C,74.54;H,9.69;N,10.15%.
实施例2
配体L2的合成
在100mL茄型瓶中加入3,5-二叔丁基水杨醛2.34g,30mL无水乙醇,(S)-1-丁基-2-氨基甲基四氢吡咯1.60g,加热回流24小时。无水硫酸镁干燥,抽除溶剂及过量低沸点原料得黄色粘稠液体(3.58g,96.1%)。
1H NMR(CDCl3,400MHz):δ13.86(s,1H),8.36(s,1H),7.37(d,J=2.4Hz,1H),7.09(d,J=2.4Hz,1H),3.81(dd,J=11.7,4.6Hz,1H),3.41(dd,J=11.7,7.8Hz,1H),3.21–3.12(m,1H),2.82(ddd,J=11.7,9.5,6.9Hz,1H),2.75–2.65(m,1H),2.27(ddd,J=11.8,9.2,5.4Hz,0H),2.23–2.17(m,2H),1.96(ddd,J=16.1,12.1,8.2Hz,1H),1.85–1.78(m,1H),1.78–1.70(m,2H),1.69–1.60(m,1H),1.57–1.46(m,2H),1.44(s,9H),1.31(s,9H),0.90(t,J=7.3Hz,3H).13C{1H}NMR(CDCl3,100MHz):δ166.4,158.2,139.8,136.4,126.7,125.7,117.9,64.7,64.3,55.3,54.4,35.0,34.1,31.5,30.1,29.5,29.4,22.8,20.7,14.0.Anal.Calcd.For C24H39N2O:C,77.58;H,10.58;N,7.54.Found:C,77.26;H,10.76;N,7.48%.
实施例3
配体L3的合成
在100mL茄型瓶中加入3,5-二枯基水杨醛3.58g,30mL无水乙醇,(S)-1-丁基-2-氨基甲基四氢吡咯1.60g,加热回流24小时。无水硫酸镁干燥,抽除溶剂及低沸点原料得黄色粘稠液体(4.71g,94.8%)。
1H NMR(CDCl3,400MHz):δ13.45(s,1H),8.21(s,1H),7.31(d,J=2.4Hz,1H),7.28(s,1H),7.27(s,1H),7.26(s,1H),7.23(s,1H),7.21(s,1H),7.19(d,J=4.6Hz,3H),7.16(d,J=1.9Hz,1H),7.10(d,J=6.8Hz,1H),7.00(d,J=2.3Hz,1H),3.64(dd,J=11.7,4.7Hz,1H),3.27(dd,J=11.7,7.7Hz,1H),3.09(td,J=6.5,3.1Hz,1H),2.73–2.64(m,1H),2.63–2.53(m,1H),2.22–2.10(m,2H),1.82(dd,J=12.3,8.1Hz,1H),1.69(s,6H),1.66(s,3H),1.64(s,3H),1.55–1.44(m,2H),1.40(ddd,J=10.0,7.6,3.6Hz,2H),1.30–1.24(m,2H),0.85(t,J=7.3Hz,3H).13C{1H}NMR(CDCl3,100MHz):165.9,157.9,150.8,150.7,139.3,136.0,128.8,128.0,127.7,126.7,125.6,125.0,118.0,64.4,64.4,55.3,54.4,42.4,42.1,31.0,29.4,31.0,30.9,29.5,29.2,22.8,20.7,14.0.Anal.Calcd.For C34H43N2O:C,82.38;H,8.74;N,5.65.Found:C,82.00;H,8.97;N,5.63%.
实施例4
配体L4的合成
在100mL茄型瓶中加入3,5-二叔丁基水杨醛2.34g,30mL无水乙醇,(S)-1-苄基-2-氨基甲基四氢吡咯1.90g,加热回流24小时。无水硫酸镁干燥,抽除溶剂及低沸点原料得淡黄色粘稠液体(3.67g,90.4%)。
1H NMR(CDCl3,400MHz):δ13.84(s,1H),8.24(s,1H),7.31(d,J=2.1Hz,1H),7.29–7.12(m,5H),7.02(d,J=2.2Hz,1H),3.98(d,J=13.1Hz,1H),3.71(dd,J=11.8,4.1Hz,1H),3.45–3.40(m,1H),3.38(d,J=13.1Hz,1H),2.96–2.87(m,1H),2.83-2.74(m,1H),2.21(dd,J=16.4,8.7Hz,1H),2.00–1.88(m,1H),1.76–1.56(m,2H),1.39(s,9H),1.25(s,9H).Anal.Calcd.For C27H37N2O:C,79.95;H,9.19;N,6.91.Found:C,79.72;H,9.28;N,7.02%.
实施例5
配体L5的合成
在100mL茄型瓶中加入3,5-二枯基水杨醛3.58g,30mL无水乙醇,(S)-1-苄基-2-氨基甲基四氢吡咯1.90g,加热回流24小时。加热回流24小时。无水硫酸镁干燥,抽除溶剂及低沸点原料得淡黄色粘稠液体(4.98g,93.8%)。
1H NMR(CDCl3,400MHz):δ13.55(s,1H),8.19(s,1H),7.34(d,J=2.4Hz,1H),7.33–7.28(m,4H),7.28-7.24(m,5H),7.24–7.18(m,5H),7.16–7.10(m,1H),7.02(d,J=2.3Hz,1H),3.93(d,J=13.1Hz,1H),3.64(dd,J=11.8,4.4Hz,1H),3.43–3.34(m,1H)3.36(d,J=13.2Hz,1H),2.93(ddd,J=9.2,6.0,3.4Hz,1H),2.87–2.73(m,1H),2.23(dd,J=17.1,8.5Hz,1H),1.94–1.85(m,1H),1.75-1.66(m,2H),1.73(s,6H),1.70(s,3H),1.67(s,3H),1.66–1.61(m,1H).13C{1H}NMR(CDCl3,100MHz):δ166.1,158.0,150.8,150.6,139.6,139.2,136.0,128.8,128.1,128.0,127.7,126,8,126.7,125.6,124.9,118.0,64.0,63.9,59.6,54.6,42.4,42.1,30.9,30.9,29.6,29.1,29.6,22.8.Anal.Calcd.For C37H41N2O:C,83.89;H,7.80;N,5.29.Found:C,83.68;H,7.92;N,5.23%.
实施例6
配体L6的合成
在100mL茄型瓶中加入3,5-二叔丁基水杨醛2.34g,,30mL无水乙醇,(S)-1-异丙基-2-氨基甲基四氢吡咯1.45g,加热回流24小时。加热回流24小时。加热回流24小时。无水硫酸镁干燥,抽除溶剂及低沸点原料得淡黄色粘稠液体(3.14g,87.6%)。
1H NMR(CDCl3,400MHz):δ13.88(s,1H),8.35(s,1H),7.37(d,J=2.4Hz,1H),7.09(d,J=2.4Hz,1H),3.74(ddd,J=11.8,4.1,0.9Hz,1H),3.36(dd,J=11.8,8.8Hz,1H),3.07(sept,1H),3.01–2.90(m,2H),2.56(dt,J=8.9,6.6Hz,1H),2.01–1.77(m,2H),1.76–1.69(m,2H),1.45(s,9H),1.31(s,9H),1.15(d,J=6.5Hz,3H),1.05(d,J=6.4Hz,3H).13C{1H}NMR(CDCl3,100MHz):δ166.3,158.2,139.8,136.6,126.7,125.8,117.9,65.1,60.5,51.2,48.8,35.0,34.1,31.5,29.5,29.4,23.4,22.2,17.8.Anal.Calcd.For C23H37N2O:C,77.04;H,10.68;N,7.81.Found:C,76.89;H,10.51;N,7.73%.
实施例7
配体L7的合成
在100mL茄型瓶中加入3-三苯甲基-5-甲基水杨醛3.78g,30mL无水乙醇,(S)-1-正丁基-2-氨基甲基四氢吡咯1.56g,加热回流24小时。无水硫酸镁干燥,抽除溶剂后用加醇重结晶得黄色固体(4.24g,82.2%)。
1H NMR(400MHz,C6D6):δ10.59(s,1H),7.56(d,J=7.5Hz,6H),7.35(d,4J=1.6Hz,1H),7.14-7.08(m,9H),7.02(t,3J=7.3Hz,3H),6.93-6.88(d,3J=6.4Hz,2H),6.74(d,4J=1.6Hz,1H),3.62(d,2J=13.4Hz,1H),3.42(d,2J=13.4Hz,1H),3.29(d,2J=12.8Hz,1H),3.15(d,2J=12.8Hz,1H),2.82-2.75(m,1H),2.49-2.39(m,1H),2.24(d,3J=5.3Hz,2H),2.15(s,3H),2.11-2.03(m,1H),1.83-1.75(m,1H),1.68(dd,2J=16.6,3J=9.0Hz,1H),1.38(m,1H),1.33-1.11(m,6H),1.05(m,1H),0.84(t,3J=7.0Hz).13C{1H}NMR(100MHz,C6D6):154.9,147.2,138.4,134.8,132.3,131.7,130.1129.9,128.9,127.8,127.7,127.1,126.1,123.1,64.3,63.3,60.4,59.6,57.4,55.5,54.3,31.6,30.1,23.1,21.4,21.3,14.7.Anal.Calcd.for C43H48N2O:C,84.82;H,7.95;N,4.60.Found:C,84.75;H,7.80;N,4.62%.
实施例8
锌络合物Zn1的合成
在氩气保护下,于50mL Schlenk瓶内加入Zn[N(SiMe3)2]2(0.386g,1.00mmol),3mL甲苯,再慢慢加入配体L1(0.274g,1.00mmol)的甲苯溶液,室温搅拌,过滤,抽去溶剂重结晶得黄色固体Zn1(0.328g,产率:65.7%)。
1H NMR(C6D6,400MHz):δ7.42(s,1H),7.28(d,3J=7.2Hz,1H),6.88(dd,3J=7.8Hz,4J=1.8Hz,1H),6.62(t,3J=7.5Hz,1H),3.93(m,3J=6.9Hz,1H),3.26-3.16(m2H),2.51-2.39(m,2H),2.32(qd,2J=12.7,3J=7.2Hz,1H),2.25-2.15(m1H),2.04-1.95(m,1H),1.43(d,3J=6.9Hz,3H),1.39(d,3J=6.9Hz,3H),1.41-1.32(m,1H),1.17-1.02(m,2H),0.96(t,3J=7.2Hz,3H),0.75-0.65(m,1H),0.38(s,18H).Anal.Calcd.for C23H43N3OSi2Zn:C,55.34;H,8.68;N,8.42.Found:C,54.86;H,8.35;N,8.23%.
实施例9
锌络合物Zn2的合成
在氩气保护下,于50mL Schlenk瓶内加入Zn[N(SiMe3)2]2(0.386g,1.00mmol),3mL甲苯,再慢慢加入配体L2(0.373g,1.00mmol)的甲苯溶液,室温搅拌,用正己烷重结晶,得黄色固体Zn2(0.358g,产率:60.0%)。
1H NMR(C6D6,400MHz):δ7.63(d,1H,4J=2.7Hz,ArH),7.50(s,1H,HC=N),6.92(d,1H,4J=2.7Hz,ArH),3.32(dd,1H,2J=11.3Hz,3J=4.8Hz),3.23(m,1H,CH),2.59(dd,1H,2J=11.4Hz,3J=4.0Hz,)2.49(td,1H,2J=12.32Hz,3J=4.41Hz),2.36(m,2H,)2.15(td,1H2J=11.0Hz,3J=7.0Hz)1.70-1.83(m,1H)1.76(s,9H),1.35(s,9H),1.03-1.32(m,6H),0.88(t,3H,3J=7.2Hz),0.71-0.78(m,1H),0.373(s,18H).13C{1H}NMR(C6D6,100MHz):169.0,168.2,142.2,134.7,129.7,118.1,65.1,60.1,58.3,56.2,36.1,34.0,31.7,30.0,28.5,28.4,23.8,21.0,14.1,5.8.Anal.Calcd.For C30H56N3OSi2Zn:C,60.42;H,9.47;N,7.05.Found:C,60.19;H,9.54;N,7.10%.
实施例10
锌络合物Zn3的合成
在氩气保护下,于50mL Schlenk瓶内加入Zn[N(SiMe3)2]2(0.386g,1.00mmol),3mL甲苯,再慢慢加入配体L3(0.497g,1.00mmol)的甲苯溶液,室温搅拌,用正己烷重结晶,得红色固体Zn3(0.465g,产率:64.5%)。
1H NMR(C6D6,400MHz):δ7.56(d,4J=2.3Hz,1H),7.41–7.34(m,4H),7.33(s,1H),7.19(d,J=7.5Hz,2H),7.12(s,1H),7.00-7.20(m,4H),6.90(d,4J=2.4Hz,1H),3.33(dd,2J=10.7Hz,3J=4.2Hz,1H),2.74–2.64(m,1H),2.39(d,J=11.6Hz,2H),2.33–2.16(m,2H),2.02(s,3H),1.97–1.84(m,1H),1.71(s,3H),1.70(s,6H),1.57(m,1H),1.04-1.13(m,4H),0.92-1.97(m,2H),0.86(t,J=6.8Hz,3H),0.52-0.60(m,1H),0.29(s,18H).13C{1H}NMR(C6D6,100MHz):δ168.2,167.2,152.6,151.5,142.3,134.3,131.7,130.3,127.7,127.3,126.2,125.9,124.4,118.3,65.1,60.2,58.1,56.0,43.1,42.5,31.3,31.2,28.7,28.1,24.0,21.0(-CH2CH2CH2CH3),14.0,5.9.Anal.Calcd.For C40H60N3OSi2Zn:C,66.68;H,8.39;N,5.83.Found:C,66.55;H,8.61;N,5.81%.
实施例11
锌络合物Zn5的合成
在氩气保护下,于50mL Schlenk瓶内加入二乙基锌的己烷溶液(1.00mL,1.00mmol),3mL甲苯,再慢慢加入配体L5(0.530g,1.00mmol)的甲苯溶液,室温搅拌,用甲苯和正己烷重结晶,得黄色固体Zn5(0.412g,产率:66.0%)。
1H NMR(400MHz,C6D6):δ7.66(d,J=2.3Hz,1H),7.52(d,J=7.2Hz,2H),7.45(d,J=7.3Hz,2H),7.41–7.32(m,2H),7.29–7.17(m,8H),7.14–7.07(m,3H),7.07–7.00(m,1H),6.94(d,J=2.3Hz,1H),3.43(d,J=12.6Hz,1H),3.04(d,J=12.7Hz,1H),2.60(d,J=6.1Hz,2H),2.49–2.38(m,1H),2.31–2.18(m,2H),1.92(s,3H),1.91(s,3H),1.78(s,6H),1.74–1.68(m,1H),1.42(t,J=7.8Hz,3H),1.19–1.04(m,3H),0.77–0.66(m,1H),0.41–0.26(m,3H).Anal.Calcd.For C39H46N2OZn:C,75.04;H,7.43;N,4.49.Found:C,74.81;H,7.47;N,4.42%.
实施例12
锌络合物Zn6的合成
在氩气保护下,于50mL Schlenk瓶内加入Zn[N(SiMe3)2]2(0.386g,1.00mmol),3mL甲苯,再慢慢加入配体L6(0.359g,1.00mmol)的甲苯溶液,室温搅拌,用甲苯和正己烷混合溶剂重结晶,得黄色固体Zn6(0.3.65g,产率:62.6%)。
1H NMR(C6D6,400MHz):δ7.65(d,1H,4J=1.8Hz,ArH),7.50(s,1H,HC=N),6.93(d,1H,4J=2.7Hz,ArH),3.61(dt,1H,2J=11.3Hz,3J=6.6Hz,)3.17(dd,1H,2J=11.3Hz,3J=5.5Hz),3.00(m,1H,),2.65(dd,1H,2J=11.4Hz,3J=4.6Hz,)2.53(t,1H,3J=5.3Hz),2.33(dt,2J=11.2Hz,3J=7.8Hz,,2H,)1.77(s,9H)1.35(s,9H),1.29(m,1H),1.10(m,1H),1.04(d,1H,3J=6.7Hz),0.78,(m,1H),0.59(d,3H,3J=6.1Hz,),0.39(s,18H).13C{1H}NMR(C6D6,100MHz):169.3,168.3,142.2,134.7,129.7,118.0,61.3,59.3,55.8,53.7,36.1,34.0,31.7,30.1,30.0,24.7,21.3,17.1,5.8.Anal.Calcd.For C29H54N3OSi2Zn:C,59.81;H,9.35;N,7.22.Found:C,59.96;H,9.76;N,7.04%.
实施例13
锌络合物Zn7的合成
在氩气保护下,于50mL Schlenk瓶内加入Zn[N(SiMe3)2]2(0.386g,1.00mmol),3mL甲苯,再慢慢加入配体L7(0.517g,1.00mmol)的甲苯溶液,室温搅拌,过滤,抽去溶剂正己烷重结晶得黄色固体Zn7(0.488g,产率:65.8%)。
1H NMR(400MHz,C6D6):δ7.58–7.44(m,7H),7.41(s,1H),7.15–7.07(m,5H),7.02(t,J=7.1Hz,3H),6.73(s,1H),3.53(dd,J=10.6,3.9Hz,1H),2.53(td,J=12.6,4.1Hz,1H),2.42–2.29(m,3H),2.26–2.12(m,1H),2.08(s,2H),1.89(dd,J=17.4,7.4Hz,1H),1.78–1.62(m,1H),1.32–0.93(m,5H),0.88(t,J=7.1Hz,3H),0.76(tt,J=14.8,7.5Hz,1H),0.51(td,J=12.3,6.1Hz,1H),0.19(s,18H).Anal.Calcd.for C42H57N3OSi2Zn:C,68.03;H,7.75;N,5.67.Found:C,67.97;H,7.67;N,5.54%.
实施例14
镁络合物Mg1的合成
在氩气保护下,于50mL Schlenk瓶内加入Mg[N(SiMe3)2]2(0.345g,1.00mmol),3mL甲苯,再慢慢加入配体L1(0.274g,1.00mmol)的甲苯溶液,室温搅拌,过滤,抽去溶剂正己烷重结晶得黄色固体Mg1(0.268g,产率:58.6%)。
1H NMR(C6D6,400MHz):δ7.49(s,1H),7.32(dd,3J=7.2Hz,4J=1.6Hz,1H),6.97(dd,3J=7.8Hz,4J=1.8Hz,1H),6.67(t,3J=7.5Hz,1H),3.89(m3J=6.9Hz,1H),3.15-3.05(m,2H),2.53(dd,2J=11.9,3J=5.9Hz,1H),2.21(q,3J=7.2Hz,2H),2.18-2.13(m1H),1.99(td,2J=11.4,3J=6.9Hz,1H),1.44(d,3J=6.9Hz,3H),1.42(d,3J=6.9Hz,3H),1.30-1.20(m,1H),1.15-1.05(m,2H),0.88(t,3J=7.2Hz,3H),0.78-0.69(m,1H),0.37(s,18H).Anal.Calcd.forC23H43MgN3OSi2:C,60.30;H,9.46;N,9.17.Found:C,59.99;H,9.36;N,9.23%.
实施例15
镁络合物Mg2的合成
在氩气保护下,于50mL Schlenk瓶内加入Mg[N(SiMe3)2]2(0.345g,1.00mmol),3mL甲苯,再慢慢加入配体L2(0.373g,1.00mmol)的甲苯溶液,室温搅拌,用正己烷重结晶,得黄色固体Mg2(0.341g,产率:61.3%)。
1H NMR(C6D6,400MHz):δ7.67(d,4J=2.7Hz,1H),7.57(s,1H),7.01(d,4J=2.7Hz,1H),3.26–3.09(m,2H),2.74(dd,2J=11.9Hz,3J=5.5Hz,1H),2.35(td,2J=12.2Hz,3J=4.6Hz,2H),2.26–2.09(m,2H),1.77(s,9H),1.74–1.66(m,1H),1.37(s,9H),1.27(m,2H),1.17(m,3H),1.09–1.00(m,1H),0.83(t,3J=7.2Hz,3H),0.36(s,18H).13C{1H}NMR(C6D6,100MHz):δ170.0,167.4,141.5,134.7,129.3,128.0,127.8,119.8,66.0,59.8,57.7,55.9,35.9,34.0,31.7,29.9,29.9,27.6,23.5,20.8,13.9,5.0.Anal.Calcd.For C30H56N3OSi2Mg:C,64.89;H,10.17;N,7.59.Found:C,64.84;H,10.28;N,7.40%.
实施例16
镁络合物Mg4的合成
在氩气保护下,于50mL Schlenk瓶内加入Mg[N(SiMe3)2]2(0.345g,1.00mmol),3mL甲苯,再慢慢加入配体L4(0.407g,1.00mmol)的甲苯溶液,室温搅拌,过滤,抽去溶剂重结晶得淡黄色固体Mg4(0.322g,产率:54.6%)。
1H NMR(C6D6,400MHz):δ7.69(d,4J=2.7Hz,1H),7.51(s,1H),7.10-7.02(m,5H),6.90(d,4J=2.7Hz,1H),3.86(s2H),3.46(dd,2J=12.2Hz,3J=4.3Hz,1H),3.02-3.12(m1H),2.56-2.70(m2H),2.23-2.32(m1H),1.80(s,9H),1.41-1.38(m1H),1.38(s,9H),0.8-1.1(m3H),0.37(s,18H).Anal.Calcd.for C33H55Mg N3OSi2:C,68.27;H,9.87;N,6.63.Found:C,68.32;H,9.91;N,6.78%.
实施例17
镁络合物Mg6的合成
在氩气保护下,于50mL Schlenk瓶内加入Mg[N(SiMe3)2]2(0.345g,1.00mmol),3mL甲苯,再慢慢加入配体L6(0.359g,1.00mmol)的甲苯溶液,室温搅拌,用甲苯和正己烷重结晶,得黄色固体Mg6(0.289g,产率:53.3%)。
1H NMR(C6D6,400MHz):δ7.68(d,J=2.7Hz,1H),7.55(s,1H),7.03(d,4J=2.7Hz,1H),3.34–3.22(m,1H),3.05-3.20(m,1H),2.84(dt,2J=13.1,3J=6.6Hz,1H),2.72(dd,2J=11.3,3J=4.4Hz,1H),2.52–2.40(m,1H),2.33–2.20(m,1H),1.78(s,9H),1.38(s,9H),1.33–1.20(m,1H),1.09(ddd,2J=18.9,3J=9.1,4J=4.8Hz,2H),0.98(d,3J=6.6Hz,3H),0.79(ddd,2J=13.7,3J=9.6,4J=4.1Hz,1H),0.49(d,3J=6.4Hz,3H),0.39(s,18H),0.11–0.06(m,1H).13C{1H}NMR(C6D6,100MHz):170.2,167.5,141.6,134.8,129.4,119.8,60.9,60.1,55.5,53.4,36.0,34.1,31.9,31.8,29.8,24.7,21.3,16.9,5.8.Anal.Calcd.For C29H54N3OSi2Mg:C,64.35;H,10.06;N,7.76.Found:C,64.28;H,10.33;N,7.67%.
实施例18
镁络合物Mg7的合成
在氩气保护下,于50mL Schlenk瓶内加入Mg[N(SiMe3)2]2(0.345g,1.00mmol),3mL甲苯,再慢慢加入配体L7(0.517g,1.00mmol)的甲苯溶液,室温搅拌,用甲苯和正己烷重结晶,得白色固体Mg7(0.420g,产率:60.0%)。
1H NMR(400MHz,C6D6):δ7.58–7.44(m,7H),7.41(s,1H),7.15–7.07(m,5H),7.02(t,J=7.1Hz,3H),6.73(s,1H),3.53(dd,J=10.6,3.9Hz,1H),2.53(td,J=12.6,4.1Hz,1H),2.42–2.29(m,3H),2.26–2.12(m,1H),2.08(s,2H),1.89(dd,J=17.4,7.4Hz,1H),1.78–1.62(m,1H),1.32–0.93(m,5H),0.88(t,J=7.1Hz,3H),0.76(tt,J=14.8,7.5Hz,1H),0.51(td,J=12.3,6.1Hz,1H),0.19(s,18H).
实施例19
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Zn1的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0:[rac-LA]0=1:200。控制反应温度25℃,反应300分钟,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:97%,Mn=6.53×104g/mol,分子量分布PDI=1.49,Pm=0.51。
实施例20
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。量取催化剂Zn1的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应5分钟,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:99%,Mn=2.91×104g/mol,分子量分布PDI=1.13,Pm=0.51。
实施例21
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.216g,1.50mmol),用1.4mL甲苯溶解,加入0.02mL异丙醇甲苯溶液。量取催化剂Zn1的甲苯溶液0.1mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.00066M,[Zn]0:[iPrOH]0:[rac-LA]0=1:1:1500。控制反应温度25℃,反应120分钟,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:96%,Mn=1.4×105g/mol,分子量分布PDI=1.13,Pm=0.50。
实施例22
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL四氢呋喃溶解。量取催化剂Zn1的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0:[rac-LA]0=1:200。控制反应温度25℃,反应250分钟,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:96%,Mn=5.5×104g/mol,分子量分布PDI=1.54,Pm=0.51。
实施例23
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL四氢呋喃溶解,加入0.1mL异丙醇四氢呋喃溶液。量取催化剂Zn1的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应5分钟,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:97%,Mn=2.7×104g/mol,分子量分布PDI=1.09,Pm=0.52。
实施例24
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Zn2的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0:[rac-LA]0=1:200。控制反应温度25℃,反应420分钟,加入石油醚终止反应。抽除溶剂残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:91%,Mn=5.9×104g/mol,分子量分布PDI=1.62,Pm=0.53。
实施例25
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。量取催化剂Zn2的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应35分钟,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:99%,Mn=2.6×104g/mol,分子量分布PDI=1.13,Pm=0.54。
实施例26
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL四氢呋喃溶解。量取催化剂Zn2的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0:[rac-LA]0=1:200。控制反应温度25℃,反应300分钟,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:96%,Mn=4.5×104g/mol,分子量分布PDI=1.41,所得聚合物偏杂规Pr=0.60。
实施例27
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL四氢呋喃溶解,加入0.1mL异丙醇四氢呋喃溶液。量取催化剂Zn2的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应20分钟,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:95%,Mn=2.9×104g/mol,分子量分布PDI=1.13,所得聚合物偏杂规Pr=0.58。
实施例28
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Zn3的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0:[rac-LA]0=1:200。控制反应温度25℃,反应8小时,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:95%,Mn=5.4×104g/mol,分子量分布PDI=1.44,Pr=0.61。
实施例29
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。量取催化剂Zn3的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应40分钟,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:95%,Mn=2.7×104g/mol,分子量分布PDI=1.16,Pr=0.62。
实施例30
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Zn6的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0:[rac-LA]0=1:200。控制反应温度25℃,反应7小时,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:86%,Mn=6.3×104g/mol,分子量分布PDI=1.57,Pr=0.56。
实施例31
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。量取催化剂Zn6的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应1小时,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:93%,Mn=3.7×104g/mol,分子量分布PDI=1.18,Pr=0.56。
实施例32
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL四氢呋喃溶解。量取催化剂Zn6的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0:[rac-LA]0=1:200。控制反应温度25℃,反应8小时,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:84%,Mn=7.4×104g/mol,分子量分布PDI=1.40,所得聚合物偏杂规Pr=0.60。
实施例33
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL四氢呋喃溶解,加入0.1mL异丙醇四氢呋喃溶液。量取催化剂Zn6的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应1小时,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:85%,Mn=2.3×104g/mol,分子量分布PDI=1.15,所得聚合物杂规度Pr=0.59。
实施例34
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Zn7的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0:[rac-LA]0=1:200。控制反应温度25℃,反应10小时,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:84%,Mn=4.9×104g/mol,分子量分布PDI=1.66,所得聚合物杂规度Pr=0.73。
实施例35
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。量取催化剂Zn7的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应1.5小时,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:95%,Mn=2.7×104g/mol,分子量分布PDI=1.12,所得聚合物杂规度Pr=0.73。
实施例36
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL四氢呋喃溶解。量取催化剂Zn7的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0:[rac-LA]0=1:200。控制反应温度25℃,反应9小时,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:85%,Mn=7.1×104g/mol,分子量分布PDI=1.45,所得聚合物杂规度Pr=0.77。
实施例37
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL四氢呋喃溶解,加入0.1mL异丙醇四氢呋喃溶液。量取催化剂Zn7的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应1小时,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:86%,Mn=3.0×104g/mol,分子量分布PDI=1.09,所得聚合物杂规度Pr=0.77。
实施例38
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Zn7的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0:[rac-LA]0=1:200。控制反应温度–38℃,反应7天,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:66%,所得聚合物杂规度Pr=0.76。
实施例39
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL四氢呋喃溶解,加入0.1mL异丙醇四氢呋喃溶液。量取催化剂Zn7的四氢呋喃溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Zn]0=0.005M,[Zn]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度–38℃,反应5天,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:96%,Mn=4.2×104g/mol,分子量分布PDI=1.4,所得聚合物杂规度Pr=0.80。
实施例40
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Mg1的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[rac-LA]0=1:200。控制反应温度25℃,反应300分钟,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:92%,Mn=4.7×104g/mol,分子量分布PDI=1.41,所得聚合物偏杂规Pr=0.53。
实施例41
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。量取催化剂Mg1的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应0.5小时,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:95%,Mn=3.3×104g/mol,分子量分布PDI=1.12,所得聚合物偏杂规Pr=0.54。
实施例42
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL四氢呋喃溶解。量取催化剂Mg1的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[rac-LA]0=1:200。控制反应温度25℃,反应200分钟,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:95%,Mn=5.2×104g/mol,分子量分布PDI=1.47,所得聚合物偏杂规Pr=0.58。
实施例43
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL四氢呋喃溶解,加入0.1mL异丙醇四氢呋喃溶液。量取催化剂Mg1的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应20小时,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:96%,Mn=3.1×104g/mol,分子量分布PDI=1.17,所得聚合物偏杂规Pr=0.58。
实施例44
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Mg2的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[rac-LA]0=1:200。控制反应温度25℃,反应10.5小时,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:96%,Mn=5.5×104g/mol,分子量分布PDI=1.39,所得聚合物偏杂规Pr=0.60。
实施例45
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。量取催化剂Mg2的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应25分钟,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:95%,Mn=2.6×104g/mol,分子量分布PDI=1.26,所得聚合物偏杂规Pr=0.60。
实施例46
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL四氢呋喃溶解。量取催化剂Mg2的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[rac-LA]0=1:200。控制反应温度25℃,反应8小时,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:96%,Mn=6.5×104g/mol,分子量分布PDI=1.52,所得聚合物偏杂规Pr=0.61。
实施例47
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL四氢呋喃溶解,加入0.1mL异丙醇四氢呋喃溶液。量取催化剂Mg2的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应20分钟,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:97%,Mn=2.8×104g/mol,分子量分布PDI=1.13,所得聚合物偏杂规Pr=0.60。
实施例48
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Mg4的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[rac-LA]0=1:200。控制反应温度25℃,反应10.5小时,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:96%,Mn=5.5×104g/mol,分子量分布PDI=1.39,所得聚合物偏杂规Pr=0.60。
实施例49
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。量取催化剂Mg4的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应45分钟,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:88%,Mn=2.4×104g/mol,分子量分布PDI=1.19,所得聚合物偏杂规Pr=0.60。
实施例50
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL四氢呋喃溶解。量取催化剂Mg4的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[rac-LA]0=1:200。控制反应温度25℃,反应4小时,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:97%,Mn=5.7×104g/mol,分子量分布PDI=1.58,所得聚合物偏杂规Pr=0.62。
实施例51
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL四氢呋喃溶解,加入0.1mL异丙醇四氢呋喃溶液。量取催化剂Mg4的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应120分钟,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:87%,Mn=3.0×104g/mol,分子量分布PDI=1.18,所得聚合物偏杂规Pr=0.62。
实施例52
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Mg6的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[rac-LA]0=1:200。控制反应温度25℃,反应12小时,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:93%,Mn=5.6×104g/mol,分子量分布PDI=1.49,所得聚合物偏杂规Pr=0.60。
实施例53
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。量取催化剂Mg6的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应50分钟,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:96%,Mn=3.4×104g/mol,分子量分布PDI=1.23,所得聚合物偏杂规Pr=0.60。
实施例54
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL四氢呋喃溶解。量取催化剂Mg6的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[rac-LA]0=1:200。控制反应温度25℃,反应7小时,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:93%,Mn=7.2×104g/mol,分子量分布PDI=1.59,所得聚合物偏杂规Pr=0.63。
实施例55
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL四氢呋喃溶解,加入0.1mL异丙醇四氢呋喃溶液。量取催化剂Mg6的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应45分钟,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:91%,Mn=3.6×104g/mol,分子量分布PDI=1.23,所得聚合物偏杂规Pr=0.63。
实施例56
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Mg7的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[rac-LA]0=1:200。控制反应温度25℃,反应18小时,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:93%,Mn=7.6×104g/mol,分子量分布PDI=1.50,所得聚合物偏杂规Pr=0.69。
实施例57
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。量取催化剂Mg7的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应120分钟,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:95%,Mn=3.1×104g/mol,分子量分布PDI=1.22,所得聚合物偏杂规Pr=0.70。
实施例58
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.5mL四氢呋喃溶解。量取催化剂Mg7的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[rac-LA]0=1:200。控制反应温度25℃,反应10小时,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:95%,Mn=5.1×104g/mol,分子量分布PDI=1.39,所得聚合物杂规度Pr=0.77。
实施例59
氩气保护下,在聚合瓶中加入外消旋丙交酯(0.144g,1.0mmol),用0.4mL四氢呋喃溶解,加入0.1mL异丙醇四氢呋喃溶液。量取催化剂Mg7的甲苯溶液0.5mL加入到聚合瓶中。[rac-LA]0=1.0M,[Mg]0=0.005M,[Mg]0:[iPrOH]0:[rac-LA]0=1:1:200。控制反应温度25℃,反应65分钟,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:94%,Mn=3.1×104g/mol,分子量分布PDI=1.16,所得聚合物杂规度Pr=0.77。
实施例60
氩气保护下,在聚合瓶中加入ε-己内酯(0.114g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Zn1的甲苯溶液0.5mL加入到聚合瓶中。[CL]0=1.0M,[Zn]0=0.005M,[Zn]0:[CL]0=1:200。控制反应温度25℃,反应50分钟,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:95%,Mn=4.2×104g/mol,分子量分布PDI=1.34。
实施例61
氩气保护下,在聚合瓶中加入ε-己内酯(0.114g,1.0mmol),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。量取催化剂Zn1的甲苯溶液0.5mL加入到聚合瓶中。[CL]0=1.0M,[Zn]0=0.005M,[Zn]0:[iPrOH]0:[CL]0=1:1:200。控制反应温度25℃,反应5分钟,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:96%,Mn=2.1×104g/mol,分子量分布PDI=1.10。
实施例63
氩气保护下,在聚合瓶中加入ε-己内酯(0.114g,1.0mmol),用0.5mL甲苯溶解。量取催化剂Mg1的甲苯溶液0.5mL加入到聚合瓶中。[CL]0=1.0M,[Zn]0=0.005M,[Zn]0:[CL]0=1:200。控制反应温度25℃,反应30分钟,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:97%,Mn=4.7×104g/mol,分子量分布PDI=1.45。
实施例64
氩气保护下,在聚合瓶中加入ε-己内酯(0.114g,1.0mmol),用0.4mL甲苯溶解,加入0.1mL异丙醇甲苯溶液。量取催化剂Mg1的甲苯溶液0.5mL加入到聚合瓶中。[CL]0=1.0M,[Zn]0=0.005M,[Zn]0:[iPrOH]0:[CL]0=1:1:200。控制反应温度25℃,反应3分钟,加入石油醚终止反应。抽除溶剂,残余物用二氯甲烷溶解,加入甲醇使聚合物沉淀析出。真空干燥24h。转化率:91%,Mn=2.2×104g/mol,分子量分布PDI=1.10。
Claims (10)
1.一类手性亚胺酚类配体(I)及其金属锌、镁化合物(II),其特征在于,具有以下通式:
式(I)、(II)中:
R1~R2分别代表氢,C1~C20直链、支链或环状结构的烷基,C1~C20直链或支链结构的烷氧基,C7~C30单或多芳基取代的烷基,C6~C18的芳基,卤素;R1~R2也可分别代表取代硅基SiR6R7R8,其中R6~R8分别为C1~C10直链、支链或环状结构的烷基,C7~C20单或多芳基取代的烷基,C6~C18的芳基,R6、R7和R8可以相同或不同;
R3代表氢,C1~C20直链、支链或环状结构的烷基,C6~C18的芳基;
R4代表C1~C20直链、支链或环状结构的烷基,C7~C30单或多芳基取代的烷基,C6~C18的芳基;
R5代表C1~C10直链、支链或环状结构的烷基;R5代表胺基NR9R10,其中R9~R10分别为C1~C6直链、支链或环状结构的烷基,三甲基硅基,三乙基硅基,二甲基氢硅基,R9和R10可以相同或不同;R5代表烷氧基OR11,其中R11为C1~C10直链、支链或环状结构的烷基,C7~C20单或多芳基取代的烷基;
M代表锌、镁。
2.根据权利要求1所述的手性亚胺酚类配体(I)及其金属锌、镁化合物(II),其特征在于,R1~R2优选为氢,C1~C8直链、支链或环状结构的烷基,C1~C8直链或支链结构的烷氧基,C7~C20单或多芳基取代的烷基,C6~C12的芳基,卤素;R1~R2代表取代硅基SiR6R7R8时,R6~R8优选为C1~C6直链、支链或环状结构的烷基,C7~C12单或多芳基取代的烷基,C6~C12的芳基;
R3优选为氢,C1~C8直链、支链或环状结构的烷基,C6~C12的芳基;
R4优选为C1~C8直链、支链或环状结构的烷基,C7~C20单或多芳基取代的烷基,C6~C12的芳基;
R5代表C1~C6直链、支链或环状结构的烷基,二(三甲基硅)胺基,二(三乙基硅)胺基,二(二甲基氢硅)胺基;R5代表烷氧基OR11时,其中R11优选为C1~C6直链、支链或环状结构的烷基,苄基,(1-萘基)甲基,(9-蒽基)甲基。
3.根据权利要求1所述的手性亚胺酚类配体(I)及其金属锌、镁化合物(II),其特征在于,R1~R2优选为氢、甲基、异丙基、叔丁基、枯基、三苯甲基、三甲基硅基,三苯基硅基或卤素;R3优选为氢、甲基;R4优选为甲基、异丙基、正丁基、正辛基、苄基、(1-萘基)甲基;R5优选为二(三甲基硅)胺基,乙基,正丁基,异丙氧基,苄氧基。
4.权利要求1~3任一项所述的手性亚胺酚类配体(I)及其金属锌、镁化合物(II)的制备方法,包括如下步骤:
将式(III)所示的手性N-取代-2-氨基甲基四氢吡咯与取代水杨醛(IV)在乙醇或甲醇中发生西佛碱反应,反应温度为25~150℃,反应时间为2~72小时,然后从反应产物中收集手性亚胺酚类配体(I);
任选的,再将式(I)所示的手性亚胺酚类配体化合物与锌或镁的金属原料化合物在有机溶剂中反应,反应温度为0~100℃,反应时间为2~96小时,然后从反应产物中收集目标手性亚胺酚氧基锌或镁化合物(II);
反应式中取代基R1~R5与权利要求1~3任一项所述的手性亚胺酚类配体(I)及其金属锌、镁化合物(II)的各相应基团一致。
5.根据权利要求4所述的方法,其特征在于,锌或镁的金属原料化合物优选二乙基锌、乙基异丙氧基锌、二{二(三甲基硅)胺基}锌、二正丁基镁、二{二(三甲基硅)胺基}镁;手性亚胺酚类配体化合物(I)与金属原料化合物的摩尔比为1:0.5~1.5;所述的有机溶剂选自四氢呋喃、乙醚、甲苯、苯、石油醚和正己烷中的一种或两种。
6.权利要求1~3任一项所述的手性亚胺酚氧基锌或镁化合物的应用,其特征在于,用于内酯的开环聚合。
7.根据权利要求6所述的应用,其特征在于,内酯选自L-丙交酯,D-丙交酯,rac-丙交酯,meso-丙交酯,ε-己内酯,β-丁内酯。
8.根据权利要求6所述的应用,其特征在于,以权利要求1~3任一项所述的手性亚胺酚氧基锌或镁化合物为催化剂,使丙交酯在-39~130℃下聚合,聚合时催化剂与单体的摩尔比为1:1~10000。
9.根据权利要求6所述的应用,其特征在于,以权利要求1~3任一项所述的手性亚胺酚氧基锌或镁化合物为催化剂,在醇存在的条件下,使丙交酯在-39~130℃下聚合,聚合时催化剂与醇以及单体摩尔比为1:1~50:1~10000;所述的醇为C1~C10直链、支链或环状结构的烷基醇,苄醇。
10.根据权利要求6所述的应用,其特征在于,以权利要求1~3任一项所述的手性亚胺酚氧基锌或镁化合物为催化剂,在醇存在的条件下,使β-丁内酯在-39~130℃下聚合,聚合时催化剂与醇以及单体摩尔比为1:1~50:1~10000;所述的醇为C1~C10直链、支链或环状结构的烷基醇,苄醇。
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CN103787943A (zh) * | 2013-05-17 | 2014-05-14 | 华东理工大学 | 手性胺基酚氧基锌、镁化合物及其制备方法和应用 |
CN104557874A (zh) * | 2014-12-16 | 2015-04-29 | 华东理工大学 | 喹啉胺基吲哚基锌、镁、钙化合物及其制备方法和应用 |
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CN116444480A (zh) * | 2022-01-07 | 2023-07-18 | 四川大学 | 一种可化学循环的高性能芳香族聚酯的制备方法 |
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