CN106633019A - 钴络合物在内酯、丙烯酸酯活性聚合及两单体共聚中的应用 - Google Patents
钴络合物在内酯、丙烯酸酯活性聚合及两单体共聚中的应用 Download PDFInfo
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- CN106633019A CN106633019A CN201610944140.3A CN201610944140A CN106633019A CN 106633019 A CN106633019 A CN 106633019A CN 201610944140 A CN201610944140 A CN 201610944140A CN 106633019 A CN106633019 A CN 106633019A
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- catalyst
- polymerization
- acrylate
- monomer
- multiple tooth
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- 239000000178 monomer Substances 0.000 title claims abstract description 50
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 28
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 12
- 150000002596 lactones Chemical class 0.000 title claims abstract description 9
- 150000001868 cobalt Chemical class 0.000 title abstract 4
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- -1 cyclic lactone Chemical class 0.000 claims abstract description 32
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 17
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 8
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 8
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 48
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 30
- 229910052786 argon Inorganic materials 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 24
- 150000004700 cobalt complex Chemical class 0.000 claims description 17
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 14
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 4
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 3
- 229960004217 benzyl alcohol Drugs 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims 3
- 150000002989 phenols Chemical class 0.000 claims 2
- HLGBMTYGLRQFJR-UHFFFAOYSA-N 3,3-dimethyl-2-methylidenebutanoic acid;prop-2-enoic acid Chemical class OC(=O)C=C.CC(C)(C)C(=C)C(O)=O HLGBMTYGLRQFJR-UHFFFAOYSA-N 0.000 claims 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims 1
- 125000005396 acrylic acid ester group Chemical group 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 229910052752 metalloid Inorganic materials 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims 1
- 239000012985 polymerization agent Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 28
- 239000003446 ligand Substances 0.000 abstract description 16
- 238000009826 distribution Methods 0.000 abstract description 8
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- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 3
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- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 73
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
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- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 22
- 238000001914 filtration Methods 0.000 description 21
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 238000011160 research Methods 0.000 description 8
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 7
- 229920000747 poly(lactic acid) Polymers 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 229930040373 Paraformaldehyde Natural products 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 229920002866 paraformaldehyde Polymers 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 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 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 235000011054 acetic acid Nutrition 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 3
- 125000005909 ethyl alcohol group Chemical group 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 125000000218 acetic acid group Chemical class C(C)(=O)* 0.000 description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- FMUYQRFTLHAARI-UHFFFAOYSA-N 2,4-bis(2-phenylpropan-2-yl)phenol Chemical class 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- MRBKEAMVRSLQPH-UHFFFAOYSA-N 3-tert-butyl-4-hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1 MRBKEAMVRSLQPH-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 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
- JOOMLFKONHCLCJ-UHFFFAOYSA-N N-(trimethylsilyl)diethylamine Chemical compound CCN(CC)[Si](C)(C)C JOOMLFKONHCLCJ-UHFFFAOYSA-N 0.000 description 1
- NSGDYZCDUPSTQT-UHFFFAOYSA-N N-[5-bromo-1-[(4-fluorophenyl)methyl]-4-methyl-2-oxopyridin-3-yl]cycloheptanecarboxamide Chemical compound Cc1c(Br)cn(Cc2ccc(F)cc2)c(=O)c1NC(=O)C1CCCCCC1 NSGDYZCDUPSTQT-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 241001104043 Syringa Species 0.000 description 1
- 235000004338 Syringa vulgaris Nutrition 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- SFOSJWNBROHOFJ-UHFFFAOYSA-N cobalt gold Chemical compound [Co].[Au] SFOSJWNBROHOFJ-UHFFFAOYSA-N 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 1
- 238000001647 drug administration Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006197 hydroboration reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- KAHVZNKZQFSBFW-UHFFFAOYSA-N n-methyl-n-trimethylsilylmethanamine Chemical compound CN(C)[Si](C)(C)C KAHVZNKZQFSBFW-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/46—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
- C07C215/48—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups
- C07C215/50—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups with amino groups and the six-membered aromatic ring, or the condensed ring system containing that ring, bound to the same carbon atom of the carbon chain
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/54—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
- C07C217/56—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by singly-bound oxygen atoms
- C07C217/58—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by singly-bound oxygen atoms with amino groups and the six-membered aromatic ring, or the condensed ring system containing that ring, bound to the same carbon atom of the carbon chain
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/80—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from iron group metals or platinum group metals
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Abstract
本发明公开了一种多齿脂肪族胺基双酚类配体钴络合物及在内酯开环聚合中的应用。其制备方法如下：将配体(I)与Co(OAc)2﹒4H2O反应，然后从反应产物中收集目标产物(II)。本发明所阐述的多功能钴络合物含有多齿脂肪族胺基双酚配体，是一种高效的内酯开环聚合催化剂，也可以有效控制丙烯酸酯类单体进行活性自由基聚合，还可以催化环内酯与丙烯酸酯类单体进行共聚。本发明的多齿脂肪族胺基双酚类配体钴络合物的优点十分明显：原料易得，合成路线简单，易于分离纯化，聚合条件温和，同时具有高催化活性与不死聚合的特点。催化所得的聚合物具有较高分子量，较窄的分子量分布，能够满足工业部门的需要。其结构具有以下通式：
Description
技术领域
本发明涉及一类低价格、高活性、多功能钴金属络合物催化剂的制备，以及这类络合物在环内酯开环不死聚合、丙烯酸酯活性自由基聚合及内酯和丙烯酸酯共聚中的应。
背景技术
随着高分子材料的迅速发展，塑料垃圾与日俱增，废弃聚合物导致的“白色污染”成为人们所面临的难题。这不符合我国政府提出的“可持续发展”的政策。所以，用可生物降解的聚合物（包括聚丙交酯以及聚丙烯酸酯类）来替代现有以石化材料为原料的聚合物成为我国乃至世界研究的主流与热点。
聚丙交酯（又名聚乳酸，PLA）是以可再生淀粉植物为原料，具有良好降解特性和生物相容性的绿色合成高分子材料。此外，因其具有独特的理化性质，使其被广泛应用在医疗卫生、日用品等领域。它摆脱了人们对石油资源的依赖，产生制造过程对环境造成的污染很小，并且能在自然界中的微生物、水、酸、碱等作用下能完全分解，降解产生的CO2和水能重返自然，有可靠的生物安全性。其目前已经被美国FDA(Foodand Drug Administration，食品和药物管理局)批准用于生物医用高分子材料，PLA是迄今科研、应用最热门的化学合成生物降解高分子材料。聚丙交酯大规模合成与应用对解决目前全世界所面临的环境问题、资源问题将起到积极的推动作用。如今，通过金属有机络合物催化丙交酯进行可控开环聚合是得到高分子量聚丙交酯行之有效的方法。
过渡金属钴络合物具有合成方法简单，固体在空气中比较稳定，价格便宜等优点，最先被用于电化学的研究，但是随着对于金属钴性质的进一步研究，金属钴催化剂也被应用到丙交酯聚合的研究中。近年来有国内外研究者对钴金属络合物催化丙交酯聚合进行了研究。Guojun Liu等人研究了将(Salen)Co用于二氧化碳、环氧丙烷以及其他环氧化合物的共聚，发现其能达到较高的TOF值（TOF,4400-14 000h-1）并能得到了分子量分布较窄的共聚物(Mw/Mn=1.11～1.27)。(Macromolecules 2010,43,903–908)。Bun Yeoul Lee等人研究了把(Salen)Co用于二氧化碳、环氧丙烷以及邻苯二甲酸酐共聚，并发现了(Salen)Co可以用于不死聚合。并能得到分子量较高（Mn=170000～350000g/mol）和分子量分布较窄的共聚物（Mw/Mn=1.05～1.5）(Beilstein J.Org.Chem.2014,10,1787–1795)。Bernhard Rieger等人报道合成了胺基双酚配体的钴络合物，并用于二氧化碳和环氧化合物的共聚。在共聚研究中发现，配体酚上取代基对于反应的转化率y有很大影响（0～95%），所得到的共聚合物具有较窄的分子量分布（Mw/Mn=1.35～1.49）。但其达不到较高的分子量（Mn=1600～6700g/mol）(Eur.J.Inorg.Chem.2015,1766–1774)。Christophe M.Thomas等人合成了一系列氨基三酚配体的钴络合物，用其催化丙交酯开环聚合，并在聚合反应过程中加入苄醇，得到了分子量分布较窄的聚合物（Mw/Mn=1.07～1.21）。但该类络合物的活性很低，不能达到较高的转化率(7～60%)，也不能达到较高的分子量（Mn=2300～7300g/mol）。(Dalton Trans.,2014,43,4550)。John A.Gladysz等人合成了新型钴有络合物，用其催化丙交酯开环聚合，并深入研究了在加入对苯基苄醇时丙交酯开环聚合的反应机理(ACS Catal.2014,4,1134-1138)。
利用金属有机催化剂调节丙烯酸酯类单体的活性自由基聚合的相关报道很少。付雪峰等将（Salen）Co（II）运用到活性自由基聚合当中（Macromolecules2015,48,5132-5139.）得到了分子量分布较窄的聚合物。关于环内酯和丙烯酸酯共聚的研究只有一篇利用辛酸亚锡催化进行丙交酯和丙烯酸叔丁酯共聚的报道（RSC Adv.2016,6,31934-31946），而利用钴金属络合物催化剂进行环内酯和丙烯酸酯类单体进行共聚还没有相关报道。
综上所述，金属钴络合物是一类的高效多功能催化剂，设计合成新型结构的钴金属络合物，为实现金属钴络合物催化环内酯的开环不死聚合，丙烯酸酯活性自由基聚合及其共聚提供理论依据，为推动可降解聚合物的工业应用奠定实验基础。
发明内容
本发明目的之一在于公开一类脂肪族胺基双酚类配体及其金属钴的络合物，以丰富现在催化聚合技术。
本发明目的之二在于公开脂肪族胺基双酚类金属钴络合物作为催化剂在环内酯的开环不死聚合，丙烯酸酯活性自由基聚合及其共聚反应中的应用。
本发明的技术构思：
本发明尝试用脂肪族胺基双酚配体与四水合醋酸钴反应，在配体芳环上引入各种不同取代基，调节电子和空间效应，引入不同的配体结构，使之在聚合条件下更好地与单体结合，从而提高催化剂活性。实验结果表明，通过改变配体结构和聚合条件，这类钴化合物能够产生较高分子量、较窄分子量分布的聚合物。本发明提供的脂肪族胺基双酚类配体(I)及其金属钴的络合物(II)，其特征在于，具有以下通式：
式(I)、(II)中：
n=2～3；R5为甲基或乙基
R1～R2～R3～R4为氢或C1～C4直链、支链结构的烷基、烷氧基、枯基或卤素中的一种或两种。R1～R2～R3～R4为优选氢、叔丁基、甲氧基、枯基或卤素的一种或两种。
本发明的脂肪族胺基双酚类配体(I)及其与金属钴络合物(II)制备方法如下步骤：
当R1=R3；R2=R4时：
将式（III）所示的芳香酚、脂肪胺和多聚甲醛在乙醇中反应，回流温度为70～85℃，反应时间为4～15小时，然后从反应产物中收集化合物（I）。
芳香酚与脂肪胺的摩尔比为2:1。
当R1≠R3；R2≠R4时：
先将式（IV）所示的芳香醛和脂肪胺反应，反应时间为2～9小时，之后加入硼氢化钠后反应6～12小时，然后加入式（III）所示的芳香酚，乙醇还有多聚甲醛继续在70～85℃下回流反应8～13小时。
芳香醛、脂肪胺与芳香酚的摩尔比为1:1:0.8。
再将式（I）所示的脂肪族胺基双酚类配体化合物与四水合醋酸钴在有机介质中反应，生成多齿脂肪族胺基双酚类钴络合物，反应温度为25～110℃，优选40～65℃，反应时间为2～48小时，然后从反应产物中收集目标化合物（II）。
脂肪族胺基双酚类配体化合物与四水合醋酸钴的摩尔比为1:1。
所述的有机介质选自甲醇、乙醇、正丙醇或异丙醇中的一种。
多齿脂肪族胺基双酚类金属钴络合物的应用，其特征在于，用于己内酯、丙交酯或β-丁内酯等内酯的开环聚合。
本发明所述的多齿脂肪族胺基双酚类金属钴络合物是一种高效的耐醇内酯开环聚合不死催化剂，使内酯为己内酯、L-丙交酯、rac-丙交酯在140℃聚合，聚合时催化剂与单体以及苄醇的摩尔比为1:500～10000:0～216。
改变聚合条件，催化剂的聚合活性有不同程度的改变。最优聚合条件为：聚合温度为140℃条件下熔融聚合；聚合时间为1.5～15h。
本发明所述的多齿脂肪族胺基双酚类金属钴络合物能够在偶氮二异丁腈（AIBN）存在下，有效控制丙烯酸酯活性自由基聚合，使丙烯酸酯为丙烯酸叔丁酯（tBA）、丙烯酸甲酯等在60℃聚合，聚合时催化剂与单体摩尔比为1:750～3000。
本发明所述的多齿脂肪族胺基双酚类金属钴络合物是一种高效的环内酯和丙烯酸酯类单体进行共聚的催化剂，L-丙交酯在140℃聚合，聚合时催化剂与单体摩尔比为1:300～500，然后再加入偶氮二异丁腈（AIBN），丙烯酸叔丁酯（tBA）或丙烯酸甲酯等在60℃进行共聚，聚合时催化剂与丙烯酸酯单体摩尔比为1:750～1500。
本发明提供的催化剂原料易得，制备方便，在空气中性质稳定，同时在空气中依旧具有较高的催化活性，易获得高分子量及分布较窄的聚内酯。能够满足工业部门的需要，有着广泛的应用前景。下面通过实例进一步说明本发明，但本发明包括但不限于此。
具体实施方式：
实施例1
合成配体化合物L1
在100mL三口烧瓶中加入多聚甲醛(1.80g,0.06mol)，15mL无水乙醇，4-甲氧基-2-叔丁基苯酚(5.40g,0.03mol)，加一滴冰乙酸搅拌15分钟，再加N,N-二甲基乙胺（1.206g,0.165mol），加热回流8小时。将溶液冷却转移到100ml锥形瓶中，静置结晶，得到产物为白色针状晶体，即配体L1。
1H NMR(500MHz,CDCl3)δ6.81(d,J=3.0Hz,2H,ArH),6.48(d,J=3.0Hz,2H,ArH),3.78–3.71(m,6H,N(CH3)2),3.59(d,J=9.7Hz,4H,ArCH2N),2.57(dd,J=11.1,4.5Hz,4H,NCH2CH2),2.29(d,J=15.1Hz,6H,ArOCH3),1.39(s,18H,Ar-C(CH3)3).
实施例2
合成配体化合物L2
在100ml三口烧瓶中加入3,5-二叔丁基水杨醛(2.343g,0.01mol），N,N-二甲胺基乙胺（0.7312g,0.01mol）加热回流3小时，待冷却到室温后加入25ml无水甲醇搅拌溶解，之后加入硼氢化钠（0.7587g,0.02mol）和10滴冰乙酸在室温反应10小时。待反应完成后，旋出溶剂，将剩余物加入30ml乙酸乙酯溶解后倒入分液漏斗中，加水后分液，取有机层旋干。之后在烧瓶中加入多聚甲醛(0.60g,0.02mol)，15mL无水乙醇，4-甲氧基-2-叔丁基苯酚(1.44g,0.008mol)，加热回流18小时。将溶液冷却转移到100ml锥形瓶中，静置结晶，得到产物为白色针状晶体，即配体L2。
1H NMR(500MHz,CDCl3)δ7.21(d,J=2.4Hz,1H,ArH),6.88(d,J=2.4Hz,1H,ArH),6.80(d,J=3.1Hz,1H,ArH),6.49(d,J=3.0Hz,1H,ArH),3.75(d,J=5.7Hz,3H,ArOCH3),3.62(s,2H,ArCH2N),3.59(s,2H,ArCH2N),2.58(dd,J=11.0,4.9Hz,4H,NCH2CH2),2.30(s,6H,N(CH3)2),1.40(d,J=5.4Hz,9H,Ar-C(CH3)3),1.39(s,9H,Ar-C(CH3)3),1.30–1.27(m,9H,Ar-C(CH3)3).
实施例3
合成配体化合物L3
在100ml三口烧瓶中加入水杨醛(1.22g,0.01mol），N,N-二乙胺基乙胺（1.16g,0.01mol）加热3小时，待冷却到室温后加入25ml无水甲醇搅拌溶解，后加入硼氢化钠（0.7587g,0.02mol）和10滴冰乙酸在室温反应10小时。待反应完成后，旋出溶剂，将剩余物加入30ml乙酸乙酯溶解后倒入分液漏斗中，加水后分液，取有机层旋干。之后在烧瓶中加入多聚甲醛(0.60g,0.02mol)，15mL无水乙醇，2,4-二枯基苯酚(2.64g,0.008mol)，加一滴冰乙酸搅拌15分钟，加热回流18小时。将溶液冷却转移到100ml锥形瓶中，静置结晶，得到产物为白色固体，即配体L3。
1H NMR(500MHz,CDCl3)δ7.28–7.26(m,5H,Ar-H),7.22–7.17(m,5HAr-H),7.15–7.12(m,1H，Ar-H),7.11–7.05(m,1H，Ar-H),6.93(d,J=7.4Hz,1H，Ar-H),6.82(d,J=8.1Hz,1H，Ar-H),6.75(dd,J=7.0,1.7Hz,1H，Ar-H),6.72(dd,J=7.4,1.1Hz,1H，Ar-H),3.55(s,2H,ArCH2N),3.49(s,1H,ArCH2N),2.50–2.43(m,4H，NCH2CH2),2.35(q,J=7.1Hz,4H，N(CH2)2(CH3)2),1.67(s,6H，Ar-CH3),1.65(s,6H，Ar-CH3),0.83(dt,J=11.7,7.1Hz,6H，N(CH2)2(CH3)2).
实施例4
合成络合物C1
在氩气保护下，于100mL Schlenk瓶内加入L1（0.472g，1.0mmol），甲醇20mL，20℃条件下加入Co(OAc)2﹒4H2O（0.249g，1.0mmol）和Et3N(0.277ml，2.2mmol)，加热至50℃并搅拌2小时，溶液呈紫色。代冷却至室温后，得到紫色固体C1。
1H NMR(500MHz,CDCl3)δ6.78(s,2H,ArH),6.47(s,2H,ArH),3.89(s,2H,Ar-CH2-N),3.57(s,1H,Ar-CH2-N),2.56(s,4H,NCH2CH2),2.27(s,3H,OCH3),1.47(s,6H,ArOCH3),1.36(s,9H,Ar-C(CH3)3),1.25(s,9H,Ar-C(CH3)3),0.87(s,6H,N(CH3)2).
实施例5
合成络合物C2
在氩气保护下，于100mL Schlenk瓶内加入L2（0.472g，1.0mmol），甲醇20mL，20℃条件下加入Co(OAc)2﹒4H2O（0.249g，1.0mmol）和Et3N(0.277ml，2.2mmol)，加热至55℃并搅拌3小时，溶液呈深紫色。冷却至室温后放入-20℃的低温箱中，得深紫色固体C2。
1H NMR(500MHz,CDCl3)δ7.22(d,J=2.3Hz,2H,ArH),6.91(d,J=2.3Hz,2H,ArH),4.63–4.56(m,1H,OCH(CH3)2),3.80(s,2H,Ar-CH2-N),3.77(s,2H,Ar-CH2-N),3.67–3.62(m,4H,NCH2CH2O),2.41(s,2H,NCH2CH2CH2N),2.25(s,4H,NCH2CH2O),2.05(s,2H,NCH2CH2CH2N),1.86(s,2H,NCH2CH2CH2N),1.40(s,18H,Ar-C(CH3)3),1.28(s,18H,Ar-C(CH3)3),1.22(d,J=6.1Hz,12H,OCH(CH3)2).
实施例6
合成络合物C3
在氩气保护下，于100mL Schlenk瓶内加入L3（0.5648g，1.0mmol），甲醇20mL，20℃条件下加入Co(OAc)2﹒4H2O（0.249g，1.0mmol）和Et3N(0.277ml，2.2mmol)，加热至55℃并搅拌3小时，溶液呈浅紫色。冷却至室温后放入0℃的低温箱中，得到浅紫色固体C3。
1H NMR(500MHz,CDCl3)δ7.66(s,5H,ArH),7.30(d,J=14.6Hz,5H,ArH),7.18(s,2H,ArH),6.77(d,J=33.5Hz,4H,ArH),3.58(s,2H,Ar-CH2-N),3.57(s,2H,Ar-CH2-N),2.66(s,6H,N(CH2CH3)2),1.26(d,J=10.7Hz,3H,Ar-CH3),1.10(s,9H,Ar-CH3),0.90–0.79(m,4H,N(CH2CH3)2).
实施例7
在氩气保护下，将0.1mL甲苯，2.0mmolrac-丙交酯加入到20mL Schlenk瓶中，再加入所述的催化剂C1，[Co]0:[rac-LA]0=1:1000，140℃搅拌反应4h。降温终止反应，过滤后将聚合物在50℃真空干燥12小时。单体转化率：92.4%，分子量Mn=1.01×105，PDI=1.16。
实施例8
在氩气保护下，于20mL Schlenk瓶中加2.0mmolrac-丙交酯，0.1mL甲苯，再加入所述的催化剂C1和苄醇，使[Co]0:[rac-LA]0:[BnOH]=1:500:1，140℃搅拌反应4h。降温终止反应，过滤后将聚合物在60℃真空干燥12小时。单体转化率：95.2%，分子量Mn=3.64×104，PDI=1.11。
实施例9
在空气中，于20mLSchlenk瓶中加2.0mmolrac-丙交酯，0.1mL甲苯，再加入所述的催化剂C1和苄醇，使[Co]0:[rac-LA]0:[BnOH]=1:1000:1，140℃搅拌反应4h。降温终止反应，过滤后将聚合物在60℃真空干燥12小时。单体转化率：72.6%，分子量Mn=1.14×105，PDI=1.16。
实施例10
氩气保护下，于20mL Schlenk瓶中加2.0mmolrac-丙交酯，0.1mL甲苯，再加入所述的催化剂C1和苄醇，使[Co]0:[rac-LA]0:[BnOH]=1:500:216，140℃搅拌反应4h。降温终止反应，过滤后将聚合物在60℃真空干燥12小时。单体转化率：97.1%。
实施例11
氩气保护下，于20mL Schlenk瓶中加2.0mmolrac-丙交酯，0.1mL甲苯，再加入所述的催化剂C1和苄醇，使[Co]0:[rac-LA]0:[BnOH]=1:10000:50，140℃搅拌反应4h。降温终止反应，过滤后将聚合物在60℃真空干燥12小时。单体转化率：75.7%，分子量Mn=4.6×104，PDI=1.35。
实施例12
在空气中，于20mL Schlenk瓶中加2.0mmolrac-丙交酯，0.1mL甲苯，再加入所述的催化剂C2，[Co]0:[rac-LA]0=1:500，140℃搅拌反应4h。降温终止反应，过滤后将聚合物在60℃真空干燥12小时。单体转化率：88.5%，分子量Mn=5.3×104，PDI=1.50。
实施例13
在空气中，于20mL Schlenk瓶中加2.0mmolrac-丙交酯，0.1mL甲苯，再加入所述的催化剂C2和苄醇，使[Co]0:[rac-LA]0:[BnOH]=1:500:1，140℃搅拌反应4h。降温终止反应，过滤后将聚合物在60℃真空干燥12小时。单体转化率：95.2%，分子量Mn=4.8×104，PDI=1.40。
实施例14
氩气保护下，于20mL Schlenk瓶中加2.0mmolrac-丙交酯，0.1mL甲苯，再加入所述的催化剂C2，[Co]0:[rac-LA]0=1:1500，140℃搅拌反应6.5h。降温终止反应，过滤后将聚合物在60℃真空干燥12小时。单体转化率：70.7%，分子量Mn=1.2×105，PDI=1.20。
实施例15
氩气保护下，于20mL Schlenk瓶中加2.0mmolrac-丙交酯，0.1mL甲苯，再加入所述的催化剂C2和苄醇，使[Co]0:[rac-LA]0:[BnOH]=1:500:1，140℃搅拌反应3h。降温终止反应，过滤后将聚合物在60℃真空干燥12小时。单体转化率：89.5%，分子量Mn=6.4×104，PDI=1.33。
实施例16
氩气保护下，于20mL Schlenk瓶中加2.0mmolrac-丙交酯，0.1mL甲苯，再加入所述的催化剂C3，[Co]0:[rac-LA]0=1:500，140℃搅拌反应4h。降温终止反应，过滤后将聚合物在60℃真空干燥12小时。单体转化率：80.4%，分子量Mn=5.5×104，PDI=1.50。
实施例17
氩气保护下，于20mL Schlenk瓶中加2.0mmolrac-丙交酯，0.1mL甲苯，再加入所述的催化剂C3和苄醇，使[Co]0:[rac-LA]0:[BnOH]=1:500:1，140℃搅拌反应4h。降温终止反应，过滤后将聚合物在60℃真空干燥12小时。单体转化率：81.5%，分子量Mn=2.86×104，PDI=1.40。
实施例18
氩气保护下，于20mL Schlenk瓶中加2.0mmol丙烯酸叔丁酯，再加入所述的催化剂C1及AIBN，不加溶剂的条件下，使[tBA]0:[AIBN]0:[Co]0=3000:10:1，60℃搅拌反应1h。降温终止反应，过滤后将聚合物在60℃真空干燥12小时。单体转化率：95.8%，分子量Mn=3.44×105，PDI=1.50。
实施例19
氩气保护下，于20mL Schlenk瓶中加2.0mmol丙烯酸叔丁酯，再加入所述的催化剂C2、AIBN及甲醇，单体浓度为16.0M，使[tBA]0:[AIBN]0:[Co]0=5000:10:1，60℃搅拌反应2.5h。降温终止反应，过滤后将聚合物在60℃真空干燥12小时。单体转化率：93.0%，分子量Mn=6.18×105，PDI=1.50。
实施例20
氩气保护下，于20mL Schlenk瓶中加2.0mmol丙烯酸叔丁酯，再加入所述的催化剂C2、AIBN及甲醇，单体浓度为16.0M，使[tBA]0:[AIBN]0:[Co]0=3000:6:1，60℃搅拌反应1h。降温终止反应，过滤后将聚合物在60℃真空干燥12小时。单体转化率：92.4%，分子量Mn=5.61×105，PDI=1.43。
实施例21
氩气保护下，于20mL Schlenk瓶中加2.0mmol丙烯酸叔丁酯，再加入所述的催化剂C2、AIBN及甲醇，单体浓度为16.0M，使[tBA]0:[AIBN]0:[Co]0=750:1:1，60℃搅拌反应1h。降温终止反应，过滤后将聚合物在60℃真空干燥12小时。单体转化率：53.3%，分子量Mn=4.98×104，PDI=1.40。
实施例22
氩气保护下，于20mL Schlenk瓶中加2.0mmol丙烯酸叔丁酯，再加入所述的催化剂C2、AIBN及甲醇，单体浓度为1.0M，使[tBA]0:[AIBN]0:[Co]0=750:1:1，60℃搅拌反应24h。降温终止反应，过滤后将聚合物在60℃真空干燥12小时。单体转化率：19.9%，分子量Mn=1.72×104，PDI=1.03。
实施例22
氩气保护下，于20mL Schlenk瓶中加2.0mmol丙烯酸叔丁酯，再加入所述的催化剂C3、AIBN及甲醇，单体浓度为16.0M，使[tBA]0:[AIBN]0:[Co]0=750:1:1，60℃搅拌反应0.33h。降温终止反应，过滤后将聚合物在60℃真空干燥12小时。单体转化率：66.9%，分子量Mn=4.43×104，PDI=1.73。
实施例23
氩气保护下，进行共聚反应。于20mL Schlenk瓶中加L-丙交酯，0.1mL甲苯，再加入所述的催化剂C1，使[Co]0:[L-LA]0=1:300，140℃搅拌反应3h。降温，加入丙烯酸叔丁酯、AIBN，无溶剂条件下，使[tBA]0:[AIBN]0:[Co]0=1500:1:1，60℃搅拌反应15h。降温终止反应，过滤后将聚合物在60℃真空干燥12小时。LA单体转化率为80.1%，tBA单体转化率为78.1，分子量Mn=8.88×103，PDI=1.38。
实施例24
氩气保护下，进行共聚反应。于20mL Schlenk瓶中加L-丙交酯，0.1mL甲苯，再加入所述的催化剂C1，使[Co]0:[L-LA]0=1:300，140℃搅拌反应3h。降温，加入丙烯酸叔丁酯、AIBN及甲醇，单体浓度为8.0M，使[tBA]0:[AIBN]0:[Co]0=1500:1:1，60℃搅拌反应15h。降温终止反应，过滤后将聚合物在60℃真空干燥12小时。LA单体转化率为90.2%，tBA单体转化率为78.5，分子量Mn=3.56×104，PDI=1.49。
实施例25
氩气保护下，进行共聚反应。于20mL Schlenk瓶中加L-丙交酯，0.1mL甲苯，再加入所述的催化剂C2，使[Co]0:[L-LA]0=1:500，140℃搅拌反应4h。降温，加入丙烯酸叔丁酯、AIBN及甲醇，单体浓度为8.0M，使[tBA]0:[AIBN]0:[Co]0=750:1:3，60℃搅拌反应12h。降温终止反应，过滤后将聚合物在60℃真空干燥12小时。LA单体转化率为90.7%，tBA单体转化率为79.4，分子量Mn=7.35×103，PDI=1.73。
实施例26
氩气保护下，进行共聚反应。于20mL Schlenk瓶中加L-丙交酯，0.1mL甲苯，再加入所述的催化剂C2，使[Co]0:[L-LA]0=1:500，140℃搅拌反应4h。降温，加入丙烯酸叔丁酯、AIBN及甲醇，单体浓度为8.0M，使[tBA]0:[AIBN]0:[Co]0=1500:1:3，60℃搅拌反应12h。降温终止反应，过滤后将聚合物在60℃真空干燥12小时。LA单体转化率为83.9%，tBA单体转化率为76.6，分子量Mn=7.91×103，PDI=1.72。
Claims (8)
1.一种多齿脂肪族胺基双酚类配体(I)及金属钴的络合物(II)，其特征在于，具有以下通式：
式(I)、(II)中：
n＝2～3；R5为甲基或乙基
R1～R2～R3～R4可以为氢或C1～C4直链、支链结构的烷基、烷氧基、枯基或卤素的一种或两种。
2.根据权利要求1所述的多齿脂肪族胺基双酚类金属钴络合物，其特征在于，R1～R2～R3～R4为氢、叔丁基、甲氧基、枯基、卤素中的一种或两种。
3.权利要求1～2任一项所述的多齿脂肪族胺基双酚类金属钴络合物的应用，其特征在于，用于己内酯、丙交酯或β-丁内酯的开环聚合。
4.权利要求1～2任一项所述的多齿脂肪族胺基双酚类金属钴络合物的应用，其特征在于，用于在偶氮二异丁腈(AIBN)存在下，控制丙烯酸叔丁酯，丙烯酸甲酯，丙烯酸乙酯等丙烯酸酯类单体进行活性自由基聚合。
5.权利要求1～2任一项所述的多齿脂肪族胺基双酚类金属钴络合物的应用，其特征在于，用于催化环内酯(例如丙交酯)和丙烯酸酯(丙烯酸叔丁酯)类单体进行共聚。
6.根据权利要求3所述的应用，其特征在于，以1～3任一项所述的多齿脂肪族胺基双酚类金属钴络合物为催化剂，在空气中或氩气保护条件下，使内酯如己内酯、丙交酯在140℃下聚合，聚合时催化剂与单体摩尔及苄醇摩尔比为1:500～10000:0～216。
7.根据权利要求4所述的应用，其特征在于，以1～2，4任一项所述的多齿脂肪族胺基双酚类金属钴络合物为催化剂，在氩气保护条件下，在偶氮二异丁腈(AIBN)存在下，使丙烯酸酯在60℃下聚合，聚合时催化剂与单体摩尔比为1:750～3000。
8.根据权利要求5所述的应用，其特征在于，以1～2，5任一项所述的多齿脂肪族胺基双酚类金属钴络合物为催化剂，在氩气保护条件下，丙交酯在140℃下开环聚合，聚合时催化剂与单体摩尔比为1:300～500；然后加入在偶氮二异丁腈(AIBN)以及丙烯酸酯在60℃下聚合，聚合时催化剂与单体摩尔比为1:750～1500，使环内酯和丙烯酸酯进行共聚。
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| CN109897072B (zh) * | 2017-12-11 | 2021-05-18 | 北京服装学院 | 一种含铁配合物及其制备及包含其的催化剂组合物和利用所述催化剂组合物的己内酯的聚合 |
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| CN109627365B (zh) * | 2018-12-04 | 2021-07-23 | 内蒙古工业大学 | 金属钴络合物催化丙烯酰胺分散聚合制备纳米微球的方法 |
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