CN115260217B - Bridged bisoxazoline rare earth metal catalyst, preparation method and application - Google Patents
Bridged bisoxazoline rare earth metal catalyst, preparation method and application Download PDFInfo
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- CN115260217B CN115260217B CN202210996297.6A CN202210996297A CN115260217B CN 115260217 B CN115260217 B CN 115260217B CN 202210996297 A CN202210996297 A CN 202210996297A CN 115260217 B CN115260217 B CN 115260217B
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- Prior art keywords
- rare earth
- earth metal
- bisoxazoline
- bridged
- metal catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 41
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 38
- 239000003446 ligand Substances 0.000 claims abstract description 30
- -1 cyclic lactone Chemical class 0.000 claims abstract description 24
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 11
- 125000001424 substituent group Chemical group 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 15
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 14
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 claims description 5
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 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 4
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical group C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 150000002596 lactones Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 150000001414 amino alcohols Chemical class 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 51
- 239000000243 solution Substances 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229920001610 polycaprolactone Polymers 0.000 description 6
- 239000004632 polycaprolactone Substances 0.000 description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229920000747 poly(lactic acid) Polymers 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 3
- DDAPSNKEOHDLKB-UHFFFAOYSA-N 1-(2-aminonaphthalen-1-yl)naphthalen-2-amine Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3N)=C(N)C=CC2=C1 DDAPSNKEOHDLKB-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- LUIZPARUXKOQBR-UHFFFAOYSA-N bromobenzene 4,5-dihydro-1,3-oxazole Chemical compound BrC1=CC=CC=C1.O1C=NCC1 LUIZPARUXKOQBR-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 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 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 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
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 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
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/083—Syntheses without formation of a Si-C bond
-
- 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
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0244—Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/35—Scandium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/36—Yttrium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/38—Lanthanides other than lanthanum
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of catalysis, and relates to a bridged bisoxazoline rare earth metal catalyst, a preparation method and application thereof. The rare earth metal catalyst prepared by the invention takes amino alcohol which is cheap and easy to obtain and easy to modify as a raw material, and the synthesized ligands with different bridging structures and different substituents can directly react with rare earth metal alkylate, so that the catalyst is easy to separate and purify and has high yield. The catalyst can be directly used for catalyzing ring-opening polymerization of cyclic lactone at room temperature, and has higher catalytic activity.
Description
Technical Field
The invention belongs to the technical field of catalysis, and relates to a bridged bisoxazoline rare earth metal catalyst, a preparation method and application thereof.
Background
The polyester material is a typical representative of degradable high polymer material, is a biological-based high polymer applied to production and living, is different from the problems of high exploitation cost, difficult degradation of polymers and the like faced by some petroleum-based plastic products, has abundant sources, low price, good biocompatibility and capability of realizing biodegradation, and is widely applied to the fields of food packaging, medical equipment and the like. In recent years, research on ring-opening polymerization of cyclic lactones catalyzed by rare earth metal catalysts is attracting more and more attention from researchers. The Cui subject group reports rare earth metal catalysts with dialkyl initiating groups, which can catalyze ring-opening polymerization of epsilon-CL with high activity, and the synthesized polymer has narrower molecular weight distribution (pdi=1.17). (organometallics, 2008,27,5889-5893). The Zhou subject group reports that bisphenol tetradentate rare earth catalyst bridged by carbon atoms catalyzes epsilon-CL to realize high activity at room temperature, and the catalytic system is a controllable system and accords with coordination-insertion mechanism. (RSC advance, 2016,6,22269-22276). In addition, polymer materials with different physical properties can be prepared by regulating the microstructure of the polymer. Therefore, it is of great importance to design a class of high performance catalysts that catalyze the polymerization of cyclic lactones.
Disclosure of Invention
The invention aims to provide a preparation method of a bridged bisoxazoline rare earth metal catalyst and application thereof in the field of ring-opening polymerization of cyclic lactone, wherein the rare earth metal catalyst has an adjustable bridged framework.
The technical scheme of the invention is as follows:
a bridged bisoxazoline rare earth metal catalyst has the following structural formula:
Wherein Ln is a rare earth metal, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, or lutetium;
R 1 is a substituent on the carbon linked to nitrogen on the oxazoline heterocycle, which is a hydrogen atom or methyl;
r 2 is a substituent on the carbon attached to the nitrogen on the oxazoline heterocycle, which is a hydrogen atom, methyl, isopropyl, tert-butyl, phenyl, benzyl or adamantyl;
R 3 is a group directly connected with rare earth metal, and is a methyl, ethyl, isopropyl, n-butyl, tert-butyl, phenyl, benzyl, trimethylsilyl, alkoxy, indenyl, fluorenyl or halogen atom; wherein, halogen atoms are Cl, br and I;
l is an auxiliary ligand directly connected with rare earth metal, and is tetrahydrofuran, anisole, dimethyl ether, diethyl ether, tetrahydropyran or triethylamine; wherein m=0 to 2;
n is the number of bridging methylene groups, n=2 to 6.
The preparation method of the bridged bisoxazoline rare earth metal catalyst comprises the following steps:
(1) Preparation of bridged bisoxazoline ligands
Under the condition of nitrogen, dissolving an o-bromobenzene-oxazoline, a diamino compound, tris (dibenzylideneacetone) dipalladium, 1 '-binaphthyl-2, 2' -bisdiphenylphosphine and sodium tert-butoxide in a toluene solution with the concentration of 0.1-1.0M, heating and refluxing for 12 hours, and separating to obtain a bridged bisoxazoline ligand; wherein, the mol ratio of the o-bromobenzene-oxazoline, the diamino compound, the tris (dibenzylideneacetone) dipalladium, the 1,1 '-binaphthyl-2, 2' -bisdiphenylphosphine and the sodium tert-butoxide is 2:1:0.02:0.04:3; the diamino compound is ethylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, 1, 5-pentylene diamine, 1, 6-hexamethylenediamine or 1,1 '-binaphthyl-2, 2' -diamine;
(2) Preparation of bridged bisoxazoline rare earth metal catalysts
Under the condition of nitrogen protection and low temperature, dissolving bridging ligand in toluene solution with the concentration of 0.01-0.1M, dissolving alkyl metal in n-hexane solution with the concentration of 0.01-0.1M, and then mixing the two solutions to react for 1-3 hours to obtain the bridging bisoxazoline rare earth metal catalyst, wherein the molar ratio of the bridging bisoxazoline ligand to the alkyl rare earth metal is 1:1-1.2; the volume ratio of toluene to n-hexane is 1:2-6.
A bridged bisoxazoline rare earth metal catalyst is applied to ring-opening polymerization reaction of cyclic lactone, and the steps of the catalytic polymerization reaction are as follows:
Stirring the rare earth metal catalyst and the cyclic lactone in a good solvent for 30s-12h under the protection of nitrogen, adding a chain terminator to terminate the reaction after a certain time, separating out reaction liquid in a separating-out liquid, settling to obtain a solid polymer, and then vacuum drying the obtained polymer to constant weight at 30-70 ℃; the concentration of the rare earth metal catalyst in the reaction system is 1 multiplied by 10 -3~5×10-2 mol/L, and the molar ratio of the cyclic lactone to the rare earth metal catalyst is 50-5000:1.
The cyclic lactone types are L-lactide, D-lactide, rac-lactide, meso-lactide, beta-butyrolactone, epsilon-caprolactone and gamma-valerolactone; when the cyclic lactone is L-lactide, D-lactide, rac-lactide, meso-lactide, epsilon-caprolactone or gamma-valerolactone, the polymerization time is 5-30min; when the cyclic lactone is beta-butyrolactone, the polymerization time is 1-3h.
The good solvent is one or more of benzene, toluene, chlorobenzene, dichloromethane or tetrahydrofuran.
The chain terminator is methanol, ethanol, propanol, n-butanol, isobutanol, tertiary butanol or the solution containing HCl, wherein the volume ratio of the HCl to the solution is 5% -10%: 1.
The filtrate is methanol, ethanol, propanol, n-butanol, isobutanol, tertiary butanol or the solution containing HCl, wherein the volume ratio of the HCl to the solution is 5% -10%: 1.
The invention has the beneficial effects that: (1) The bridged bisoxazoline ligand is simple and easy to synthesize and operate and easy to modify; (2) The bridged bisoxazoline rare earth metal catalyst has simple preparation method, the ligand can directly react with alkyl rare earth metal, and the catalyst is easy to separate and purify; (3) The bridged bisoxazoline rare earth metal catalyst can be directly applied to ring-opening polymerization of cyclic lactones.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of ligand (MePh) 2-(CH2)4.
FIG. 2 is a nuclear magnetic hydrogen spectrum of catalyst (MePh) 2-(CH2)4-Y(CH2SiMe3).
FIG. 3 is a nuclear magnetic hydrogen spectrum of ligand (MePh) 2-Ph4.
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of catalyst (MePh) 2-Ph4-Y(CH2SiMe3) (THF).
FIG. 5 is a GPC chart of polycaprolactone.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described below with reference to examples.
Example 1
Preparation of catalyst (MePh) 2-(CH2)4-Y(CH2SiMe3)
(1) Preparation of ligand (MePh) 2-(CH2)4
O-bromobenzene-oxazoline (1 g,3.94 mmol), 1, 4-butanediamine (0.1736 g,1.97 mmol), tris (dibenzylideneacetone) dipalladium (0.07 g,0.0787 mmol), 1 '-binaphthyl-2, 2' -bisdiphenylphosphine (0.098 g,0.1576 mmol) and sodium tert-butoxide (0.618 g,5.91 mmol) were added in sequence to a Schlenk flask under nitrogen, dissolved in 25ml toluene and heated at 95℃under reflux for 24h, after the reaction was completed, the solvent was removed by filtration and column chromatography gave 1.21g of ligand in 71.0% yield. The nuclear magnetic hydrogen spectrum of the ligand is shown in figure 1. (2) Preparation of catalyst (MePh) 2-(CH2)4-Y(CH2SiMe3)
Ligand (MePh) 2-(CH2)4 (0.1 g,0.2304 mmol) was dissolved in 1ml toluene and yttrium alkyl (0.1138 g,0.2304 mmol) was dissolved in 3ml n-hexane under nitrogen, stirred and mixed at-30 ℃, slowly warmed to room temperature for 2h, filtered, and the solvent was removed under vacuum to give catalyst 0.956g in 68.2% yield. The nuclear magnetic hydrogen spectrum of the catalyst is shown in figure 2.
Example 2
Preparation of catalyst (MePh) 2-(CH2)4-Lu(CH2SiMe3)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure was analogous to the method of example 1, except that Lu (CH 2SiMe3)3(THF)2 instead of Y (CH 2SiMe3)3(THF)2) was used, giving 0.11g of catalyst, 69.8% yield.
Example 3
Preparation of catalyst (MePh) 2-(CH2)4-Sc(CH2SiMe3)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure was analogous to the method in example 1, except that Sc (CH 2SiMe3)3(THF)2 was used instead of Y (CH 2SiMe3)3(THF)2, giving a catalyst of 0.12g, 71.8% yield).
Example 4
Preparation of catalyst (iPrPh)2-(CH2)4-Y(CH2SiMe3)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure was analogous to the method in example 1, except that ligand (iPrPh)2-(CH2)4 was used instead of ligand (MePh) 2-(CH2)4, giving 0.09g of catalyst in 58.4% yield.
Example 5
Preparation of catalyst (PhPh) 2-(CH2)4-Y(CH2SiMe3)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure was analogous to the method in example 1, except that ligand (PhPh) 2-(CH2)4 was used instead of ligand (MePh) 2-(CH2)4, giving catalyst 0.078g, 58.1% yield.
Example 6
Preparation of catalyst (MePh) 2-(CH2)2-Y(CH2SiMe3)
(1) Synthesis of ligand (MePh) 2-(CH2)2
The ligand was prepared in the same manner as in example 1, as follows:
the procedure was analogous to the method of example 1, except that ethylenediamine was used instead of 1, 4-butanediamine, 1.53g of ligand was obtained, in 70% yield.
(2) Synthesis of catalyst (MePh) 2-(CH2)2-Y(CH2SiMe3)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure was analogous to the method of example 1, giving 0.12g of catalyst in 85.6% yield.
Example 7
Preparation of catalyst (MePh) 2-(CH2)2-Lu(CH2SiMe3)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure was analogous to that in example 1, except that Lu (CH 2SiMe3)3(THF)2 was used instead of Y (CH 2SiMe3)3(THF)2, giving 0.11g of catalyst, 65.0% yield).
Example 8
Preparation of catalyst (MePh) 2-(CH2)2-Sc(CH2SiMe3)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure was analogous to the method in example 1, except that Sc (CH 2SiMe3)3(THF)2 was used instead of Y (CH 2SiMe3)3(THF)2, giving 0.10g of catalyst, 62.3% yield).
Example 9
Preparation of catalyst (MePh) 2-Ph4-Y(CH2SiMe3) (THF)
(1) Synthesis of ligand (MePh) 2-Ph4
The ligand was prepared in the same manner as in example 1, as follows:
The procedure was analogous to the method of example 1, except that 1,1 '-binaphthyl-2, 2' -diamine was used instead of 1, 4-butanediamine, 1.53g of ligand was obtained, yield 70%. The nuclear magnetic hydrogen spectrum of the ligand is shown in figure 3.
(2) Synthesis of catalyst (MePh) 2-Ph4-Y(CH2SiMe3) (THF)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure was analogous to the method of example 1, giving 0.12g of catalyst in 85.6% yield. The nuclear magnetic hydrogen spectrum of the catalyst is shown in fig. 4.
Example 10
Preparation of catalyst (MePh) 2-Ph4-Lu(CH2SiMe3) (THF)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure was analogous to the method in example 1, except that Lu (CH 2SiMe3)3(THF)2 was used instead of Y (CH 2SiMe3)3(THF)2, giving 0.09g of catalyst, 55.0% yield).
Example 11
Preparation of catalyst (MePh) 2-Ph4-Sc(CH2SiMe3) (THF)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure was analogous to the method of example 1, except that Sc (CH 2SiMe3)3(THF)2 was used instead of Y (CH 2SiMe3)3(THF)2, giving 0.08g of catalyst, 45.4% yield).
Example 12
Preparation of catalyst (MePh) 2-(CH2)4 -Y (Cl) (THF)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure was analogous to the method of example 1, except that YCl 3(THF)2 was used instead of Y (CH 2SiMe3)3(THF)2, giving 0.09g of catalyst, 50.8% yield.
Example 13
Preparation of catalyst (iPrPh)2-(CH2)4 -Y (Cl) (THF)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure is analogous to the method in example 1, except that ligand (iPrPh)2-(CH2)4 is used instead of ligand (MePh) 2-(CH2)4 and YCl 3(THF)2 is used instead of Y (CH 2SiMe3)3(THF)2) to give product 0.08g in 47.1% yield.
Example 14
Preparation of catalyst (PhPh) 2-(CH2)4 -Y (Cl) (THF)
The procedure for the preparation of the catalyst was the same as in example 1, the catalyst being prepared as follows:
The procedure is analogous to the method in example 1, except that ligand (PhPh) 2-(CH2)4 is used instead of ligand (MePh) 2-(CH2)4 and YCl 3(THF)2 is used instead of Y (CH 2SiMe3)3(THF)2, giving product 0.09g, 52.2% yield.
Example 15
Implementation of the polymerization reaction
In a glove box, (MePh) 2-(CH2)4-Y(CH2SiMe3) (10 μmol,6.09 mg) of catalyst and ε -caprolactone (2 mmol,228.3 mg) were added sequentially to a 20mL reaction flask, 2mL toluene solvent was added, and the reaction was stirred at room temperature for 5min; the polymerization termination process is as follows: adding a chain terminator to terminate the reaction; the reaction solution is separated out by absolute ethyl alcohol, solid polymer is obtained by sedimentation, and finally, the polymer is dried to constant weight in vacuum at 45 ℃ to obtain 206.0mg of polycaprolactone, the conversion rate is 99%, and the catalytic activity is 2376.h -1. The polycaprolactone GPC chart is shown in FIG. 5.
Example 16
The procedure is as in example 15, except that the catalyst is replaced by (MePh) 2-(CH2)4-Lu(CH2SiMe3) (MePh) 2-(CH2)4-Y(CH2SiMe3 to give 212.3mg of polycaprolactone with a conversion of 99% and a catalytic activity of 2376.h -1.
Example 17
The procedure is as in example 15, except that the catalyst is replaced by (MePh) 2-(CH2)4-Sc(CH2SiMe3) (MePh) 2-(CH2)4-Y(CH2SiMe3 to give 209.5mg of polycaprolactone with a conversion of 90% and a catalytic activity of 2160.h -1.
Example 18
The procedure is as in example 15, except that the catalyst is replaced by (MePh) 2-Ph4-Y(CH2SiMe3) (THF) (MePh) 2-(CH2)4-Y(CH2SiMe3 to give 210.5mg of polycaprolactone with a conversion of 99% and a catalytic activity of 1188.h -1.
Example 19
In a glove box, (MePh) 2-(CH2)4-Y(CH2SiMe3) (10 μmol,6.09 mg) of catalyst and rac-lactide (2 mmol,288.3 mg) were sequentially added to a 20mL reaction flask, 2mL THF solvent was added and the reaction stirred at room temperature for 10min; the polymerization termination process is as follows: adding a chain terminator to terminate the reaction; and (3) separating out the reaction solution by using absolute ethyl alcohol, settling to obtain a solid polymer, and finally, vacuum drying the polymer at 45 ℃ to constant weight to obtain 256.4mg of polylactide, wherein the conversion rate is 99%, and the catalytic activity is 1188.h -1.
Example 20
The procedure is as in example 19, except that the catalyst is replaced with (MePh) 2-(CH2)4-Lu(CH2SiMe3) (MePh) 2-(CH2)4-Y(CH2SiMe3 to give 203.8mg of polylactide with a conversion of 99% and a catalytic activity of 1188.h -1.
Example 21
The procedure is as in example 19, except that the catalyst is replaced with (MePh) 2-(CH2)4-Sc(CH2SiMe3) (MePh) 2-(CH2)4-Y(CH2SiMe3 to give 202.1mg of polylactide with a conversion of 99% and a catalytic activity of 1188.h -1.
Example 22
The procedure is as in example 19, except that the catalyst is replaced by (MePh) 2-Ph4-Y(CH2SiMe3) (THF) (MePh) 2-(CH2)4-Y(CH2SiMe3 to give 235.5mg of polylactide with a conversion of 98% and a catalytic activity of 1176.h -1.
Example 23
In a glove box, (MePh) 2-(CH2)4-Y(CH2SiMe3) (10. Mu. Mol,6.09 mg) of the catalyst and β -butyrolactone (2 mmol,172 mg) were sequentially added to a 20mL reaction flask, 2mL of toluene solvent was added, and the reaction was stirred at room temperature for 3 hours; the polymerization termination process is as follows: adding a chain terminator to terminate the reaction; the solid polymer is separated out from the reaction liquid by absolute ethyl alcohol, the obtained polymer is washed by absolute ethyl alcohol for multiple times, finally, the polymer and 45 ℃ are dried to constant weight in vacuum, 140.8mg of polybutyrolactone is obtained through reaction, and the conversion rate is 90.2%.
Claims (9)
1. The bridged bisoxazoline rare earth metal catalyst is characterized by comprising the following structural formula: wherein Ln is rare earth metal, scandium, yttrium or lutetium;
R 1 is a substituent on the carbon linked to nitrogen on the oxazoline heterocycle, which is a hydrogen atom or methyl;
R 2 is a substituent on the carbon linked with nitrogen on the oxazoline heterocycle and is a hydrogen atom, methyl, isopropyl or phenyl;
R 3 is a group directly connected with rare earth metal and is trimethylsilyl or Cl;
l is an auxiliary ligand directly connected with rare earth metal and is tetrahydrofuran; wherein m=0 to 2;
n is the number of bridging methylene groups, and n=2 to 6.
2. The use of a bridged bisoxazoline rare earth metal catalyst according to claim 1 in ring-opening polymerization of lactones, characterized by the steps of:
Under the protection of nitrogen, stirring the bridged bisoxazoline rare earth metal catalyst and the cyclic lactone in a good solvent for 30s-12h, adding a chain terminator to terminate the reaction after a certain time, separating out the reaction solution in the separated liquid, settling to obtain a solid polymer, and then vacuum drying the obtained solid polymer to constant weight at 30-70 ℃; the concentration of the bridged bisoxazoline rare earth metal catalyst in the reaction system is 1 multiplied by 10 -3~5×10-2 mol/L, and the molar ratio of the cyclic lactone to the rare earth metal catalyst is 50-5000:1;
The cyclic lactone is L-lactide, D-lactide, rac-lactide, meso-lactide, beta-butyrolactone, ɛ -caprolactone or gamma-valerolactone.
3. The use of a bridged bisoxazoline rare earth metal catalyst according to claim 2 in ring opening polymerization of a cyclic lactone, wherein the polymerization time is 5-30min when the cyclic lactone is L-lactide, D-lactide, rac-lactide, meso-lactide, ɛ -caprolactone or γ -valerolactone; when the cyclic lactone is beta-butyrolactone, the polymerization time is 1-3h.
4. The use of a bridged bisoxazoline rare earth metal catalyst according to claim 2 or 3 in ring-opening polymerization of cyclic lactones, wherein the good solvent is one or more of benzene, toluene, chlorobenzene, dichloromethane and tetrahydrofuran.
5. The use of a bridged bisoxazoline rare earth metal catalyst according to claim 2 or 3 in a ring-opening polymerization of a cyclic lactone, wherein the chain terminator is methanol, ethanol, propanol, n-butanol, isobutanol, t-butanol or the solution containing HCl, wherein the volume ratio of HCl to the solution is 5% -10%: 1.
6. The use of a bridged bisoxazoline rare earth metal catalyst according to claim 4 in a ring-opening polymerization of a cyclic lactone, wherein the chain terminator is methanol, ethanol, propanol, n-butanol, isobutanol, t-butanol or the solution containing HCl, wherein the volume ratio of HCl to the solution is 5% -10%: 1.
7. The use of a bridged bisoxazoline rare earth metal catalyst according to claim 2,3 or 6, wherein the filtrate is methanol, ethanol, propanol, n-butanol, isobutanol, t-butanol or a solution containing HCl, wherein the volume ratio of HCl to the solution is 5% -10%: 1.
8. The use of a bridged bisoxazoline rare earth metal catalyst according to claim 4, wherein the filtrate is methanol, ethanol, propanol, n-butanol, isobutanol, tert-butanol or the solution containing HCl, wherein the volume ratio of HCl to the solution is 5% -10%: 1.
9. The use of a bridged bisoxazoline rare earth metal catalyst according to claim 5, wherein the filtrate is methanol, ethanol, propanol, n-butanol, isobutanol, tert-butanol or the solution containing HCl, wherein the volume ratio of HCl to the solution is 5% -10%: 1.
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