CN111282597A - Catalyst, preparation method and application thereof, cyclic carbon dioxide-based polycarbonate and preparation method thereof - Google Patents
Catalyst, preparation method and application thereof, cyclic carbon dioxide-based polycarbonate and preparation method thereof Download PDFInfo
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- CN111282597A CN111282597A CN202010156466.6A CN202010156466A CN111282597A CN 111282597 A CN111282597 A CN 111282597A CN 202010156466 A CN202010156466 A CN 202010156466A CN 111282597 A CN111282597 A CN 111282597A
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- carbon dioxide
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 111
- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 72
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 67
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 65
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 21
- 239000003446 ligand Substances 0.000 claims description 78
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 75
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 56
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 38
- 238000006482 condensation reaction Methods 0.000 claims description 35
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims description 30
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims description 30
- 150000003752 zinc compounds Chemical class 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 26
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 26
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 24
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 239000011701 zinc Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- -1 alkyl zinc Chemical compound 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 238000006467 substitution reaction Methods 0.000 claims description 12
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 5
- 125000004092 methylthiomethyl group Chemical group [H]C([H])([H])SC([H])([H])* 0.000 claims description 4
- MQNPENQYQXUCOX-UHFFFAOYSA-N C=1C=CC=CC=1C[Zn]CC1=CC=CC=C1 Chemical compound C=1C=CC=CC=1C[Zn]CC1=CC=CC=C1 MQNPENQYQXUCOX-UHFFFAOYSA-N 0.000 claims description 3
- GITRLZWECMONDK-UHFFFAOYSA-N CN(C)CC[Zn]CCN(C)C Chemical compound CN(C)CC[Zn]CCN(C)C GITRLZWECMONDK-UHFFFAOYSA-N 0.000 claims description 3
- QZVQZIPXUZCNIP-UHFFFAOYSA-N CN(C)C[Zn]CN(C)C Chemical compound CN(C)C[Zn]CN(C)C QZVQZIPXUZCNIP-UHFFFAOYSA-N 0.000 claims description 3
- OSUFLWLTUNYQMN-UHFFFAOYSA-N COCC[Zn]CCOC Chemical compound COCC[Zn]CCOC OSUFLWLTUNYQMN-UHFFFAOYSA-N 0.000 claims description 3
- JMFFSUWYUQPKLC-UHFFFAOYSA-N COC[Zn]COC Chemical compound COC[Zn]COC JMFFSUWYUQPKLC-UHFFFAOYSA-N 0.000 claims description 3
- QAFVLMLZAIRSKG-UHFFFAOYSA-N CSCC[Zn]CCSC Chemical compound CSCC[Zn]CCSC QAFVLMLZAIRSKG-UHFFFAOYSA-N 0.000 claims description 3
- LBNUJYWNWRUVBM-UHFFFAOYSA-N CSC[Zn]CSC Chemical compound CSC[Zn]CSC LBNUJYWNWRUVBM-UHFFFAOYSA-N 0.000 claims description 3
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 3
- FRLYMSHUDNORBC-UHFFFAOYSA-N diisopropylzinc Chemical compound [Zn+2].C[CH-]C.C[CH-]C FRLYMSHUDNORBC-UHFFFAOYSA-N 0.000 claims description 3
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 claims description 3
- MKRVHLWAVKJBFN-UHFFFAOYSA-N diphenylzinc Chemical compound C=1C=CC=CC=1[Zn]C1=CC=CC=C1 MKRVHLWAVKJBFN-UHFFFAOYSA-N 0.000 claims description 3
- HEPBQSXQJMTVFI-UHFFFAOYSA-N zinc;butane Chemical compound [Zn+2].CCC[CH2-].CCC[CH2-] HEPBQSXQJMTVFI-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- BYYXHWABFVUKLO-UHFFFAOYSA-N zinc;2-methylpropane Chemical compound [Zn+2].C[C-](C)C.C[C-](C)C BYYXHWABFVUKLO-UHFFFAOYSA-N 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 24
- 239000004593 Epoxy Substances 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 6
- 238000012648 alternating copolymerization Methods 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 66
- 238000001228 spectrum Methods 0.000 description 35
- 229920000642 polymer Polymers 0.000 description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 32
- 229910052739 hydrogen Inorganic materials 0.000 description 32
- 239000001257 hydrogen Substances 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 11
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 230000000977 initiatory effect Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 6
- 238000012544 monitoring process Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 238000003780 insertion Methods 0.000 description 5
- 230000037431 insertion Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- WORJRXHJTUTINR-UHFFFAOYSA-N 1,4-dioxane;hydron;chloride Chemical compound Cl.C1COCCO1 WORJRXHJTUTINR-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cis-cyclohexene Natural products C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 125000002587 enol group Chemical group 0.000 description 3
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 238000012795 verification Methods 0.000 description 3
- CCEFMUBVSUDRLG-KXUCPTDWSA-N (4R)-limonene 1,2-epoxide Natural products C1[C@H](C(=C)C)CC[C@@]2(C)O[C@H]21 CCEFMUBVSUDRLG-KXUCPTDWSA-N 0.000 description 2
- WEEGYLXZBRQIMU-UHFFFAOYSA-N 1,8-cineole Natural products C1CC2CCC1(C)OC2(C)C WEEGYLXZBRQIMU-UHFFFAOYSA-N 0.000 description 2
- 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 2
- GJEZBVHHZQAEDB-UHFFFAOYSA-N 6-oxabicyclo[3.1.0]hexane Chemical compound C1CCC2OC21 GJEZBVHHZQAEDB-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- CCEFMUBVSUDRLG-XNWIYYODSA-N Limonene-1,2-epoxide Chemical compound C1[C@H](C(=C)C)CCC2(C)OC21 CCEFMUBVSUDRLG-XNWIYYODSA-N 0.000 description 2
- 229920002732 Polyanhydride Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 229920005565 cyclic polymer Polymers 0.000 description 2
- 238000006352 cycloaddition reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- KYHHMFUFEIHUHB-UHFFFAOYSA-N di-tert-butylzinc Chemical compound CC(C)(C)[Zn]C(C)(C)C KYHHMFUFEIHUHB-UHFFFAOYSA-N 0.000 description 2
- 229910000071 diazene Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000011369 resultant mixture Substances 0.000 description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 2
- XDLDASNSMGOEMX-RWQOXAPSSA-N C1(=CC=CC=C1)[2H].C1=CC=CC=C1 Chemical class C1(=CC=CC=C1)[2H].C1=CC=CC=C1 XDLDASNSMGOEMX-RWQOXAPSSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002466 imines Chemical group 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
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Classifications
-
- 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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/06—Zinc compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
-
- 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
- B01J2531/02—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
-
- 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
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a catalyst, a preparation method and application thereof, cyclic carbon dioxide-based polycarbonate and a preparation method thereof, and belongs to the technical field of carbon dioxide-based polycarbonate. The catalyst provided by the invention can realize epoxy monomer (meso-CHO) and CO2Alternating copolymerization of (regioselective polycarbonate)>99%) and exhibits high activity (TOF)>3200h‑1) The catalyst of the invention can be used for preparing cyclic CO for the first time2Based on polycarbonate and for the first time synthesizing a mixture containing continuous CO which is conventional in inverse thermodynamics2CO of a unit2Based Polycarbonate (PCHC).
Description
Technical Field
The invention relates to the technical field of carbon dioxide-based polycarbonate, in particular to a catalyst, a preparation method and application thereof, cyclic carbon dioxide-based polycarbonate and a preparation method thereof.
Background
Development of CO2Polycarbonate is a practical and efficient means of mitigating the greenhouse effect and relieving the fossil energy crisis since 1969 when ZnEt was used by Inoue et al2/H2The O system realizes the epoxy and the CO for the first time2From the polymerization of (2), CO2Based on polycarbonateSynthetic studies have received much attention, and epoxy monomers include, but are not limited to, Propylene Oxide (PO), cyclohexene oxide (CHO), cyclopentene oxide (CPO), and Limonene Oxide (LO), among others. Among them, PO and CHO epoxy monomers have the most extensive advantages due to their wide sources and low prices, and are particularly attractive. In the presence of epoxy monomers and CO2In the reaction of (2), there are two problems of product selectivity and regioselectivity: product selectivity refers to the epoxy monomer and CO2Two reactions occur: one is cycloaddition to generate small molecular cyclic carbonate product, and the other is epoxy monomer and CO2To obtain a polycarbonate product; regioselectivity means that in the copolymerization reaction, there are three different processes: one is epoxy monomer and CO2Completely alternating copolymerization of CO2The synthesis of polycarbonate is aimed at, the second is that in the course of polymerization the epoxy monomer is continuously ring-opened to form polyether and doped in the polycarbonate, and the third is CO2Successive insertions forming polyanhydrides, but since the reaction does not occur thermodynamically and the polyanhydride structure is unstable, the reaction between epoxy monomers and CO2CO in the copolymerization of (2)2The process of continuous insertion is not reported.
In a plurality of epoxy monomers with CO2Among the catalytic systems for copolymerization, the organometallic catalytic systems developed to be mature at present are roughly classified into four types, i.e., a binary Salen (Co/Cr)/anionic salt system represented by Darensbourg and ludwig soldiers, a beta-diimine double zinc system represented by Coates and Rieger, a phenolate (Zn/Mg/Fe/In) system represented by Williams, a cyano (Co/Zn) system represented by zhanghong, a heterogeneous catalyst other than the cyano (Co/Zn) catalyst, and homogeneous catalytic systems. In the main stream catalytic systems, high product selectivity and regioselectivity are shown, namely, a high-selectivity alternating copolymerization product can be obtained, a small molecular cycloaddition product and a polyether unit can be well inhibited, wherein the beta-diimine zinc system shows ultrahigh activity, and the conversion frequency (TOF) is as high as 150,000h-1. In the case of the epoxy monomer CHO, since it is of meso configuration (meso-CHO), it has 2 chiral carbon centers, with CO2Polycyclohexene carbonate (PCHC) obtained by copolymerizationAnd the problem of stereocontrol exists, and the chiral Salen (Co/Cr)/anion salt binary system developed by Lu soldiers as a representative can further realize stereoselectivity control, so that isotactic/syndiotactic PCHC can be obtained selectively. To date, in CO2Copolymerization with epoxy to give CO2Base polymers developed, except for continuous CO2The unit polyester cannot be synthesized due to thermodynamic limitation, and the rest is related to products and the microstructure control is completely and efficiently realized.
Macroscopically, at present, CO2The base polycarbonates are all linear polymers. Polymer molecules have macroscopically linear (including branched) and cyclic components. There is currently no cyclic CO2The polycarbonate base is reported. In the existing catalytic systems, homogeneous or heterogeneous, single or binary, the core part of the polymerization mechanism is a coordination insertion mechanism, i.e. the Lewis acid center (metal center) is first reacted with epoxy or CO2Coordination activation occurs, initiating groups (OR co-ligands from the metals in the unit system, usually M-OH, M-OR, M-O)2COR, R represents alkyl, M-N (TMS)2(ii) a Or from anions X in binary systems-X represents halogen) to the activated epoxy or CO2On carbon (b) to initiate polymerization and to effect stepwise coordination insertion to chain termination (addition of acid H)+Or trace amount of H in the coating system2O quench). Thus, the initiating group is located at one end of the final polymer chain as one of the end groups, the other end group being the polar group-OH upon quenching, and all of the resulting polymers are linear.
Linear and cyclic polymer molecules directly affect the properties of the polymeric material. Cyclic CO2The synthesis of polycarbonate-based materials has hitherto remained a blank for the synthesis of cyclic CO2New catalytic systems based on polycarbonates have yet to be developed.
Disclosure of Invention
The invention aims to provide a catalyst, a preparation method and application thereof, cyclic carbon dioxide-based polycarbonate and a preparation method thereof, wherein the catalyst can be used for catalytically synthesizing a polycarbonate containing continuous CO2A cyclic carbon dioxide-based polycarbonate of a unit.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a catalyst for synthesizing cyclic carbon dioxide-based polycarbonate, which has a structure shown in a formula I:
wherein R is alkyl or alkyl derivatives.
Preferably, the R includes Me, Et, iPr, nBu, tBu, Ph, Bn, -CH2OCH3、-CH2N(CH3)2、-CH2SCH3、-CH2CH2N(CH3)2、-CH2CH2OCH3or-CH2CH2SCH3。
The invention provides a preparation method of a catalyst for synthesizing cyclic carbon dioxide-based polycarbonate, which comprises the following steps:
mixing 4, 4-diaminodiphenylmethane, acetylacetone, p-toluenesulfonic acid and toluene, and carrying out a first hydroxylamine condensation reaction to obtain a first ligand;
mixing the ethanol solution of the first ligand, the hydrochloric acid solution of 1, 4-dioxane and 4, 4-diaminodiphenylmethane, and carrying out a second hydroxylamine condensation reaction to obtain a second ligand;
mixing the solution of the second ligand and the solution of a zinc compound, and carrying out substitution reaction to obtain a catalyst for synthesizing the cyclic carbon dioxide-based polycarbonate;
the zinc compound in the solution of the zinc compound comprises zinc compounds of alkyl zinc or alkyl derivatives.
Preferably, in the raw materials of the first hydroxylamine condensation reaction, the dosage ratio of 4, 4-diaminodiphenylmethane, acetylacetone, p-toluenesulfonic acid and toluene is (11.6-24.0) g to 12mL (1.0-100) g (1.0-3.0) L;
the first hydroxylamine condensation reaction is carried out under the reflux condition, the temperature of the first hydroxylamine condensation reaction is 80-130 ℃, and the time is 0.5-2 h.
Preferably, in the raw materials of the second hydroxylamine condensation reaction, the dosage ratio of the first ligand in the ethanol solution of the first ligand, the hydrochloric acid solution of dioxane and 4, 4-diaminodiphenylmethane is 3g (4.2-8.4) mL (1.65-3.3) g; the concentration of hydrochloric acid in the hydrochloric acid solution of dioxane is 4.0 mol/L.
Preferably, the second hydroxylamine condensation reaction is carried out under a reflux condition, the temperature of the second hydroxylamine condensation reaction is 80-90 ℃, and the time is 4-12 hours.
Preferably, the zinc alkyl comprises dimethyl zinc, diethyl zinc, diisopropyl zinc, di-n-butyl zinc, di-tert-butyl zinc, diphenyl zinc or dibenzyl zinc; the zinc compound of the alkyl derivative comprises bis (methoxymethyl) zinc, bis (methoxyethyl) zinc, bis (methylthiomethyl) zinc, bis (methylthioethyl) zinc, bis (dimethylaminomethyl) zinc or bis (dimethylaminoethyl) zinc; the molar ratio of the second ligand in the solution of the second ligand to the zinc compound in the solution of the zinc compound is 1 (2-3);
the temperature of the substitution reaction is 90-110 ℃, and the time is 24-48 h.
The invention provides an application of the catalyst in the technical scheme or the catalyst prepared by the preparation method in the technical scheme in the synthesis of cyclic carbon dioxide-based polycarbonate.
The invention provides cyclic carbon dioxide-based polycarbonate, which has a structure shown in a formula II:
wherein n represents the number of repeating units and n is a positive integer.
The invention provides a preparation method of the cyclic carbon dioxide-based polycarbonate in the technical scheme, which comprises the following steps:
mixing the cyclohexene oxide anhydrous solution with a catalyst, introducing carbon dioxide, and carrying out polymerization reaction under anhydrous and anaerobic conditions to obtain cyclic carbon dioxide-based polycarbonate;
the catalyst is the catalyst for synthesizing the cyclic carbon dioxide-based polycarbonate in the technical scheme or the catalyst for synthesizing the cyclic carbon dioxide-based polycarbonate prepared by the preparation method in the technical scheme.
The invention provides a catalyst for synthesizing cyclic carbon dioxide-based polycarbonate, which can realize epoxy monomer (meso-CHO) and CO2Alternating copolymerization of (regioselective polycarbonate)>99%) and exhibits high activity (TOF)>3200h-1) The cyclic carbon dioxide-based polycarbonate can be obtained by the carboxyl bridging retaining ring formed by carbon dioxide when a chain is terminated by the polymerization initiated by the carbon dioxide synergistically activated by bimetal in the environment of epoxy monomer, while in the prior art, under the initiation of an initiating group (the initiating group is a co-ligand of metal or an additional initiator), trace H in a system is subjected to a coordination insertion mechanism2O or added acid H+To quench the polymer chain to obtain linear CO2Based on a polycarbonate.
The invention provides a cyclic carbon dioxide-based polycarbonate, and cyclic CO is prepared for the first time by adopting the catalyst of the invention2Based on polycarbonate, and bimetal synergistically activates carbon dioxide to initiate polymerization in the presence of epoxy monomer, carboxyl bridging snap ring formed by carbon dioxide is used for first synthesizing continuous CO-containing conventional reverse thermodynamics2CO of a unit2Based Polycarbonate (PCHC).
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a first ligand prepared in example 1;
FIG. 2 is a nuclear magnetic hydrogen spectrum of a second ligand prepared in example 1;
FIG. 3 is a nuclear magnetic hydrogen spectrum of the catalyst prepared in example 1;
FIG. 4 is a nuclear magnetic hydrogen spectrum of PCHC prepared in example 5;
FIG. 5 is a Mark-Houwink plot of the PCHC prepared in example 5 versus a linear PCHC of the prior art;
FIG. 6 shows the respective use of12CO2And13CO2a maldi-tof comparison plot of PCHC synthesized according to the method of example 1;
FIG. 7 shows the 3 consecutive COs produced in example 12Cell-linked PCHC structure diagram;
FIG. 8 is a nuclear magnetic reaction monitoring hydrogen spectrum of the catalyst prepared in example 1 with monomer meso-CHO;
FIG. 9 shows the catalyst prepared in example 1 with CO2Monitoring a hydrogen spectrum by nuclear magnetic reaction;
FIG. 10 shows the catalyst prepared in example 1 with CO2Monitoring a carbon spectrogram through nuclear magnetic reaction;
FIG. 11 shows the nuclear magnetic monitored hydrogen spectrum of the catalytic copolymerization of the catalyst prepared in example 1;
FIG. 12 is a nuclear magnetic hydrogen spectrum of PCHC prepared in example 6;
FIG. 13 is a Mark-Houwink plot of the PCHC prepared in example 6 versus a linear PCHC of the prior art;
FIG. 14 is a nuclear magnetic hydrogen spectrum of PCHC prepared in example 7;
FIG. 15 is a Mark-Houwink plot of the PCHC prepared in example 7 versus a prior art linear PCHC;
FIG. 16 is a nuclear magnetic hydrogen spectrum of PCHC prepared in example 8;
FIG. 17 is a Mark-Houwink plot of the PCHC prepared in example 8 versus a prior art linear PCHC;
FIG. 18 is a nuclear magnetic hydrogen spectrum of the catalyst prepared in example 9;
FIG. 19 is a nuclear magnetic hydrogen spectrum of PCHC prepared in example 10;
FIG. 20 is a Mark-Houwink plot of the PCHC prepared in example 10 versus a prior art linear PCHC;
FIG. 21 shows a schematic view of a process using12CO2Maldi-tof plot of PCHC synthesized according to example 10.
Detailed Description
The invention provides a catalyst for synthesizing cyclic carbon dioxide-based polycarbonate, which has a structure shown in a formula I:
wherein R is alkyl or alkyl derivatives.
In the present invention, in the structure of formula I, R preferably includes Me, Et, iPr, nBu, tBu, Ph, Bn, -CH2OCH3、-CH2N(CH3)2、-CH2SCH3、-CH2CH2N(CH3)2、-CH2CH2OCH3or-CH2CH2SCH3More preferably, Me or Et is used. When R is preferably Me, Et, iPr, nBu, tBu, Ph, Bn, -CH2N(CH3)2、-CH2OCH3、-CH2SCH3、-CH2CH2N(CH3)2、-CH2CH2OCH3or-CH2CH2SCH3When the catalysts are represented by (BDI-ZnMe)2、(BDI-ZnEt)2、(BDI-ZniPr)2、(BDI-ZnnBu)2、(BDI-ZntBu)2、(BDI-ZnPh)2、(BDI-ZnBn)2、(BDI-ZnCH2N(CH3)2)2、(BDI-ZnCH2OCH3)2、(BDI-ZnCH2SCH3)2、(BDI-ZnCH2CH2N(CH3)2)2、(BDI-ZnCH2CH2OCH3)2、(BDI-ZnCH2CH2SCH3)2。
In the catalyst with the structure of the formula I, the organometallic active site Zn-CO-ligand contains alkyl (such as Me, Et, iPr, nBu or tBu) or alkyl derivative group CO-ligand, and in the presence of epoxy monomer, double zinc is synergistic, carbon dioxide is activated to form Zn-O active site to start polymerization, and further, CHO, CO and the like2Activated by Zn coordination of active sites in sequence, inserted into a polymer chain to realize chain growth, and in the reaction termination process, the polymerization active sites form a cyclic polymer through bridging carboxyl buckles formed by carbon dioxide fixed by coordination between double metalsBecause the ring-opening reaction of CHO is a speed-determining step, the polymer chain is kept in a structure after the last molecule of carbon dioxide is inserted when the chain is terminated, the head and the tail of the whole buckle molecular chain are all carboxyl structures formed by carbon dioxide, and after the buckle is terminated, the special cyclic polycarbonate with three continuous carbon dioxide units (one molecule of which is a structure in an adjacent repeating unit) is finally realized.
The catalyst provided by the invention changes the mechanism of polymerization initiation and termination by virtue of the steric hindrance and the design of the CO-ligand, can efficiently catalyze the polymerization of carbon dioxide and epoxy monomer, is the same as the existing method, and is polymerized in an anhydrous and oxygen-free environment, and can ensure that a polymer chain is not quenched by water molecules into a chain polymer under the condition of changing the initiation mechanism, so that the polymer containing continuous CO is obtained2A cyclic carbon dioxide-based polycarbonate of a unit.
The invention provides a preparation method of a catalyst for synthesizing cyclic carbon dioxide-based polycarbonate, which comprises the following steps:
mixing 4, 4-diaminodiphenylmethane, acetylacetone, p-toluenesulfonic acid and toluene, and carrying out a first hydroxylamine condensation reaction to obtain a first ligand;
mixing the ethanol solution of the first ligand, the hydrochloric acid solution of 1, 4-dioxane and 4, 4-diaminodiphenylmethane, and carrying out a second hydroxylamine condensation reaction to obtain a second ligand;
mixing the solution of the second ligand and the solution of a zinc compound, and carrying out substitution reaction to obtain a catalyst for synthesizing the cyclic carbon dioxide-based polycarbonate;
the zinc compound in the solution of the zinc compound comprises zinc compounds of alkyl zinc or alkyl derivatives.
In the present invention, the required raw materials are all commercially available products well known to those skilled in the art, unless otherwise specified.
The method comprises the steps of mixing 4, 4-diaminodiphenylmethane, acetylacetone, p-toluenesulfonic acid and toluene, and carrying out a first hydroxylamine condensation reaction to obtain a first ligand. In the invention, the dosage ratio of the 4, 4-diaminodiphenylmethane to the acetylacetone to the p-toluenesulfonic acid to the toluene is preferably (11.6-24.0) g to 12mL (1.0-100) g to (1.0-3.0) L, and more preferably 11.6g to 12mL to 1.0g to 1L. The mixing process is not particularly limited in the invention, and the raw materials can be uniformly mixed by selecting the process well known in the field. In the invention, the p-toluenesulfonic acid is used for acidifying acetylacetone, thereby being beneficial to stabilizing an enol structure and generating subsequent hydroxylamine condensation.
In the invention, the first hydroxylamine condensation reaction is preferably carried out under a reflux condition, and the temperature of the first hydroxylamine condensation reaction is preferably 80-130 ℃, and more preferably 90-100 ℃; the time is preferably 0.5 to 2 hours, and more preferably 1.0 to 1.5 hours. In the first hydroxylamine condensation reaction process, p-toluenesulfonic acid is acidified with acetylacetone to form an enol structure, one enol group and one amino group of 4, 4-diaminodiphenylmethane are subjected to hydroxylamine condensation, one molecule of water is removed, and an imine structure is generated.
After the first hydroxylamine condensation reaction is completed, saturated NaHCO is preferably used in the present invention3The resulting mixture was washed with aqueous solution, the solvent was removed by rotary evaporation, and the solid was washed with hexane to give the first ligand.
After the first ligand is obtained, the ethanol solution of the first ligand, the hydrochloric acid solution of dioxane and 4, 4-diaminodiphenylmethane are mixed for a second hydroxylamine condensation reaction to obtain a second ligand. In the invention, the dosage ratio of the first ligand, the hydrochloric acid solution of dioxane and the 4, 4-diaminodiphenylmethane in the ethanol solution of the first ligand is preferably 3g (4.2-8.4) mL (1.65-3.3) g, and more preferably 3g:4.2mL:1.65 g; the concentration of hydrochloric acid in the hydrochloric acid solution of dioxane is preferably 4.0 mol/L. In the invention, the dosage ratio of the first ligand to ethanol in the ethanol solution of the first ligand is preferably 3g: 120-250 mL. The present invention utilizes a hydrochloric acid solution of dioxane to acidify the two hydroxyl groups of the first ligand. In the invention, the second hydroxylamine condensation reaction is preferably carried out under a reflux condition, the temperature of the second hydroxylamine condensation reaction is preferably 80-90 ℃, more preferably 85 ℃, and the time is preferably 4-12 h, more preferably 6-10 h. In the second hydroxylamine condensation reaction process, two hydroxyl groups on the acidified first ligand are subjected to hydroxylamine condensation with two amino groups of one molecule of 4, 4-diaminodiphenylmethane respectively, one molecule of water is removed, and secondary amine is generated.
After the second hydroxylamine condensation reaction is completed, the invention disperses the obtained solid in water and adds NaHCO3Then extracting by using dichloromethane, and taking an organic phase for spin drying to obtain a second ligand. The present invention has no special limitation on the dispersing, extracting and spin-drying processes, and processes well known in the art can be selected. The amount of the sodium bicarbonate is not particularly limited in the invention, and the sodium bicarbonate can be added according to the dosage relationship well known in the art, and the residual hydrochloric acid in the reaction is neutralized by the sodium bicarbonate in the invention.
After the second ligand is obtained, the solution of the second ligand and the solution of a zinc compound are mixed for substitution reaction to obtain the catalyst for synthesizing the cyclic carbon dioxide-based polycarbonate. In the present invention, the zinc compound in the solution of the zinc compound includes zinc compounds of alkyl zinc or alkyl derivatives; the alkyl zinc preferably comprises dimethyl zinc, diethyl zinc, diisopropyl zinc, di-n-butyl zinc, di-tert-butyl zinc, diphenyl zinc or dibenzyl zinc, the zinc compound of the alkyl derivative comprises bis (methoxymethyl) zinc, bis (methoxyethyl) zinc, bis (methylthiomethyl) zinc, bis (methylthioethyl) zinc, bis (dimethylaminomethyl) zinc or bis (dimethylaminoethyl) zinc, and the molar ratio of the second ligand in the solution of the second ligand to the zinc compound in the solution of the zinc compound is preferably 1 (2-3), more preferably 1: 2; the solvent of the solution of the second ligand is preferably toluene or tetrahydrofuran, and the dosage ratio of the second ligand to the solvent is preferably 525mg:200 mL; the solvent of the solution of the zinc compound is preferably toluene or tetrahydrofuran, and the concentration of the zinc compound in the solution of the zinc compound is preferably 1 mol/L.
In the invention, the temperature of the substitution reaction is preferably 90-110 ℃, more preferably 95-100 ℃, and the time is preferably 24-48 h, more preferably 30-40 h. In the process of substitution reaction, one alkyl of the alkyl zinc is used for removing hydrogen of secondary amine in the second ligand to generate a molecule of methane, and simultaneously the rest alkyl zinc and the hydrogen-removed second ligand generate a zinc alkyl compound.
After the substitution reaction is finished, the solvent in the substitution reaction product is preferably pumped to dryness to obtain the catalyst for synthesizing the cyclic carbon dioxide-based polycarbonate.
In the present invention, the preparation process of the catalyst for synthesizing cyclic carbon dioxide-based polycarbonate is as follows (taking R ═ Me as an example):
wherein, the compound shown in the structural formula a is the first ligand, the compound shown in the structural formula b is the second ligand, and the complex shown in the structural formula c is the catalyst with the structure shown in the formula I.
The invention provides an application of the catalyst in the technical scheme or the catalyst prepared by the preparation method in the technical scheme in the synthesis of cyclic carbon dioxide-based polycarbonate. The method of the present invention is not particularly limited, and any method known in the art may be used.
The invention provides cyclic carbon dioxide-based polycarbonate, which has a structure shown in a formula II:
wherein n represents the number of repeating units and n is a positive integer.
The value range of n is not particularly limited in the present invention.
In the present invention, the cyclic carbon dioxide-based polycarbonate contains continuous CO2And (4) units.
The invention provides a preparation method of the cyclic carbon dioxide-based polycarbonate in the technical scheme, which comprises the following steps:
mixing the cyclohexene oxide anhydrous solution with a catalyst, introducing carbon dioxide, and carrying out polymerization reaction under anhydrous and anaerobic conditions to obtain cyclic carbon dioxide-based polycarbonate;
the catalyst is the catalyst for synthesizing the cyclic carbon dioxide-based polycarbonate in the technical scheme or the catalyst for synthesizing the cyclic carbon dioxide-based polycarbonate prepared by the preparation method in the technical scheme.
In the present invention, cyclohexene oxide (meso-CHO) in said cyclohexene oxide anhydrous solution is treated with CaH before use2Drying for 48h, and then carrying out reduced pressure distillation purification. The conditions for the reduced pressure distillation are not particularly limited in the present invention, and a process well known in the art may be selected. In the invention, the solvent of the cyclohexene oxide solution is preferably toluene, and the concentration of the cyclohexene oxide anhydrous solution is preferably 1.0-2.0 mol/L. In the invention, the molar ratio of cyclohexene oxide to catalyst in the cyclohexene oxide anhydrous solution is preferably (100-4000): 1, more preferably (200-1600): 1, and even more preferably (400-800): 1. In the invention, the pressure of the system after the carbon dioxide is introduced is preferably 1-40 bar, more preferably 10-30 bar, and further preferably 20 bar. The invention ensures the anaerobic environment by charging carbon dioxide, and the reaction reagent does not use water, thereby achieving the anhydrous and anaerobic environment.
After the carbon dioxide is charged, the reaction kettle is preferably put into an oil bath kettle for polymerization reaction after the pressure is stabilized. In the present invention, the polymerization reaction is preferably carried out at 90 ℃ for 1 hour. After the polymerization reaction is completed, the present invention preferably washes the obtained polymer with HCl/MeOH (0.1mol/L hydrochloric acid methanol solution, hydrochloric acid concentration of 0.1mol/L) solution to obtain cyclic carbon dioxide based polycarbonate.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
4, 4-diaminodiphenylmethane (11.6g,58.4mmol, 1)0eq), acetylacetone (12mL,117mmol,2.0eq), and p-toluenesulfonic acid (1.0g,5.8mmol,0.01eq) were refluxed at 130 ℃ for 2h in 1L toluene to perform a first hydroxylamine condensation reaction using saturated NaHCO3Washing the resulting mixture with an aqueous solution, removing the solvent by rotary evaporation, and washing with hexane to obtain a solid having an earthy yellow color of 19g, i.e., the first ligand, in a yield of 90%; nuclear magnetic hydrogen spectrum (500 MHz) of the first ligand1H NMR benzene-d6) See FIG. 1; the nuclear magnetic data are: δ 13.07(s,2H, -OH), δ 6.77-6.79(d, J ═ 10.0Hz,4H, C-H), δ 6.67-6.69(d, J ═ 10.0Hz,4H, C-H), δ 5.00(s,2H, C-H), δ 3.55(s,2H, CH, -OH), δ 6.77-6.79(d, J ═ C-H), δ 5.00(s,2H, C-H), δ 3.55(s,2H, CH, H2),δ2.05(s,6H,CH3),δ1.55(s,6H,CH3) According to the nuclear magnetic spectrum information, the structure of the compound is the structure of the target first ligand;
dissolving the first ligand (3g,8.3mmol,1.0eq) in 120mL ethanol, adding dropwise a dioxane HCl solution (hydrochloric acid concentration of 4.0M,4.2mL,16.8mmol,2.0eq), then adding 4, 4-diaminodiphenylmethane (1.65g,8.3mmol,1.0eq), refluxing at 90 deg.C overnight, performing a second hydroxylamine condensation reaction, dispersing the obtained solid in water, adding NaHCO3Extracting with dichloromethane, and spin-drying the organic phase to obtain 1.6g of yellow powder, namely a second ligand, with the yield of 37%; nuclear magnetic hydrogen spectrum (500 MHz) of the second ligand1H NMR benzene-d6) See FIG. 2; the nuclear magnetic data are: δ 13.51(s,2H, -NH), δ 6.75-6.76(d, J ═ 5.0Hz,8H, C-H), δ 6.57-6.58(d, J ═ 5.0Hz,8H, C-H), δ 4.79(s,2H, C-H), δ 3.57(s,4H, CH, H2),δ1.88(s,12H,CH3) According to the nuclear magnetic spectrum information, the structure of the compound is the structure of a target second ligand;
the second ligand (525mg,1mmol,1.0eq) was dissolved in 200mL of anhydrous toluene and ZnMe was added dropwise2(2mL,2mmol,2.0eq) in toluene at 90 ℃ for 24h, and the toluene was drained to give 620mg of a yellow solid powder, the catalyst, noted as (BDI-ZnMe)2The yield is 90%; nuclear magnetic hydrogen spectrum (500 MHz) of the catalyst1H NMRbenzene-d6) See FIG. 3; the nuclear magnetic data are: δ 6.87-6.85(d, J ═ 10.0Hz,8H, C-H), δ 6.62-6.60(d, J ═ 10.0Hz,8H, C-H), δ 4.84(s,2H, C-H), δ 3.53(s,4H, CH), δ 6.8H, C-H, J ═ C-H, y2),δ1.95(s,12H,CH3)δ-1.37(s,6H,Zn-CH3) According to the nuclear magnetic spectrum information, the structure of the compound is a target catalyst (BDI-ZnMe)2And (5) structure.
Example 2
4, 4-diaminodiphenylmethane (24.0g,117.0mmol,2.0eq), acetylacetone (12mL,117mmol,2.0eq) and p-toluenesulfonic acid (100.0g,580.0mmol,1.0eq) were refluxed at 100 ℃ for 2h in 1L of toluene to perform a first hydroxylamine condensation reaction using saturated NaHCO3Washing the resultant mixture with an aqueous solution, removing the solvent by rotary evaporation, and washing with hexane to obtain a solid of yellowish brown color (20.1 g, i.e., the first ligand) at a yield of 95%; nuclear magnetic hydrogen spectrum (500 MHz) of the first ligand1H NMRbenzene-d6) See FIG. 1;
dissolving the first ligand (3g,8.3mmol,1.0eq) in 250mL ethanol, adding dropwise a dioxane HCl solution (hydrochloric acid concentration of 4.0M, 8.4mL, 33.6mmol, 4.0eq), then adding 4, 4-diaminodiphenylmethane (1.65g,8.3mmol,1.0eq), refluxing at 90 deg.C overnight, performing a second hydroxylamine condensation reaction, dispersing the obtained solid in water, adding NaHCO3Extracting with dichloromethane, and spin-drying the organic phase to obtain yellow powder 0.91g, which is the second ligand, with a yield of 21%; nuclear magnetic hydrogen spectrum (500 MHz) of the second ligand1H NMR benzene-d6) See FIG. 2;
the second ligand (525mg,1mmol,1.0eq) was dissolved in 200mL tetrahydrofuran and ZnMe was added dropwise2(3.0mL, 3.0mmoL, 3.0eq) of tetrahydrofuran was subjected to a substitution reaction at 110 ℃ for 24h, and the tetrahydrofuran was dried to give 620mg of a yellow solid powder, i.e., a catalyst, identified as (BDI-ZnMe)2The yield is 90%; nuclear magnetic hydrogen spectrum (500 MHz) of the catalyst1H NMR benzene-d6) See fig. 3.
Example 3
4, 4-diaminodiphenylmethane (24.0g,117.0mmol,2.0eq), acetylacetone (12mL,117mmol,2.0eq) and p-toluenesulfonic acid (100.0g,580.0mmol,1.0eq) were refluxed at 130 ℃ for 0.5h in 1L of toluene to carry out a first hydroxylamine condensation reaction using saturated NaHCO3The resulting mixture was washed with an aqueous solution, the solvent was removed by rotary evaporation, and washing was carried out with hexane to obtain 13.1g of a yellowish solid, i.e.First ligand, yield 62%; nuclear magnetic hydrogen spectrum (500 MHz) of the first ligand1H NMRbenzene-d6) See FIG. 1;
dissolving the first ligand (3g,8.3mmol,1.0eq) in 120mL ethanol, adding dropwise a dioxane HCl solution (hydrochloric acid concentration of 4.0M, 8.4mL, 33.6mmol, 4.0eq), then adding 4, 4-diaminodiphenylmethane (2.4g, 4.012.45mmol,1.5eq), refluxing at 90 deg.C overnight, performing a second hydroxylamine condensation reaction, dispersing the resulting solid in water, adding NaHCO, adding3Extracting with dichloromethane, and spin-drying the organic phase to obtain yellow powder 1.0g, namely the second ligand, with a yield of 25%; nuclear magnetic hydrogen spectrum (500 MHz) of the second ligand1H NMR benzene-d6) See FIG. 2;
the second ligand (525mg,1mmol,1.0eq) was dissolved in 200mL tetrahydrofuran and ZnMe was added dropwise2(2mL,2mmol,2.0eq) of tetrahydrofuran solution at 100 ℃ for 24h, and the tetrahydrofuran was dried to give 620mg of a yellow powder solid, the catalyst, identified as (BDI-ZnMe)2The yield is 90%; nuclear magnetic hydrogen spectrum (500 MHz) of the catalyst1H NMRbenzene-d6) See fig. 3.
Example 4
4, 4-diaminodiphenylmethane (24.0g,117.0mmol,2.0eq), acetylacetone (12mL,117mmol,2.0eq) and p-toluenesulfonic acid (100.0g,580.0mmol,1.0eq) were refluxed at 100 ℃ for 2h in 1L of toluene to perform a first hydroxylamine condensation reaction using saturated NaHCO3Washing the resultant mixture with an aqueous solution, removing the solvent by rotary evaporation, and washing with hexane to obtain a solid having a yellowish brown color (10.1 g, i.e., the first ligand) in a yield of 48%; nuclear magnetic hydrogen spectrum (500 MHz) of the first ligand1H NMRbenzene-d6) See FIG. 1;
dissolving the first ligand (3g,8.3mmol,1.0eq) in 250mL ethanol, adding dropwise a dioxane HCl solution (hydrochloric acid concentration of 4.0M, 8.4mL, 33.6mmol, 4.0eq), then adding 4, 4-diaminodiphenylmethane (1.65g,8.3mmol,1.0eq), refluxing at 80 ℃ overnight, performing a second hydroxylamine condensation reaction, dispersing the obtained solid in water, adding NaHCO3Extraction with dichloromethane, spin-drying of the organic phase to give 2.8g of a yellow powder, secondBiligand, yield 65%; nuclear magnetic hydrogen spectrum (500 MHz) of the second ligand1H NMR benzene-d6) See FIG. 2;
the second ligand (525mg,1mmol,1.0eq) was dissolved in 200mL tetrahydrofuran and ZnMe was added dropwise2(3.0mL, 3.0mmoL, 3.0eq) of tetrahydrofuran was subjected to a substitution reaction at 90 ℃ for 48h, and the tetrahydrofuran was dried to give a yellow powdery solid 537mg, i.e., the catalyst, identified as (BDI-ZnMe)2Yield 78%; nuclear magnetic hydrogen spectrum (500 MHz) of the catalyst1H NMR benzene-d6) See fig. 3.
Example 5
Cyclohexene oxide (meso-CHO) was treated with CaH2Drying for 48h, and distilling and purifying under reduced pressure for later use;
dissolving the treated meso-CHO in toluene to obtain meso-CHO solution (2.0M);
the meso-CHO solution and the catalyst prepared in example 1 were charged into a reaction vessel at a cyclohexene oxide to catalyst molar ratio of 800:1, sealed (cyclohexene oxide 4mmoL, catalyst 0.005mmoL), and charged with CO2Adjusting CO2The pressure is 30bar, after the pressure is stable, the reaction kettle is placed into an oil bath pot to be heated for 1h at 90 ℃ for polymerization reaction, and the obtained product is washed by HCl/MeOH solution (0.1mol/L hydrochloric acid methanol solution, the hydrochloric acid concentration is 0.1mol/L) to obtain the polycarbonate cyclohexene ester (PCHC).
Structure and performance testing
1) Molecular weight measurement of the PCHC prepared in example 5 revealed that the absolute molecular weight of the PCHC was 26.3kDa, Mw was 28.7kDa, and PDI (polymer dispersibility index) was 1.09, indicating that the molecular weight distribution of the polymer was uniform.
2) Nuclear magnetic characterization of the PCHC prepared in example 5 (500 MHz)1H NMR CDCl3) The nuclear magnetic hydrogen spectrum is shown in FIG. 4.
3) Testing of PCHC annular structure:
with linear PCHC of the same molecular weightlinearFor viscosity comparison, log η (using [ η ]]Representation) [ η ]]Cyclic/[ η]The range of linearity ≦ 0.7 may prove to be a cyclic structure, where η represents the intrinsic viscosity;
the PCHC prepared in example 5 is designated PCHC1Wherein PCHClinearRepresents a linear polymer, prepared in the literature references (Angew. chem. int. Ed.2013,52, 11594-11598); Mark-Houwink curves (viscosity versus molecular weight) for both polymers are shown in FIG. 5;
after calculation, [ η ]]PCHC1/[η]PCHClinearThis demonstrates that the PC HC prepared in example 5 is a cyclic structure, 0.68.
4) PCHC 3 continuous CO2Unit determination
The PCHC prepared in example 5 was isotopically labeled and subjected to the mass-tof end group verification, and the results are shown in FIG. 6, and as can be seen by analysis,13CO2in contrast to12CO2Repeat units increased from 142 to 143, end group molecular weights increased from 88 to 90, and end groups determined to be 2 CO2Combined with the cyclic structure of 3), the structure of the final polymer is shown in FIG. 7 as 3 consecutive COs2The units are connected.
Verification example
The mechanism of the invention is verified and confirmed:
1) catalyst (BDI-ZnMe)2meso-CHO cannot be activated alone: monomer and catalyst are mixed according to the molar ratio meso-CHO/(BDI-ZnMe)2＝2:1(meso-CHO 0.005mmol、(BDI-ZnMe)20.0025mmol) to obtain a system before reaction; reacting the reaction precursor system at 40 ℃ for 24h to obtain a reacted system, and simultaneously reacting the reacted system in deuterated toluene tol-d8Middle soluble catalyst (BDI-ZnMe)2As a blank control, the hydrogen spectra of the three systems are shown in FIG. 8: (1H N MR 500MHz，tol-d8Monitoring, wherein a is a blank control, b is a pre-reaction control, and c is a post-reaction system); as can be seen from the analysis in FIG. 8, the components of the system before and after the reaction did not change, indicating that the catalyst (B DI-ZnMe)2The monomer meso-CHO cannot be activated alone.
2) Catalyst (BDI-ZnMe)2Can not activate CO alone2：
Contacting the catalyst with CO2Respectively, are subjected to nuclear magnetic testing (NMR)1H 500MHz，13C400 MHz monitoring, benzene-d6) The results are shown in FIGS. 9-10, where a is blank: in deuterated benzene (benzene-d)6) In solution of CO2(ii) a b is blank control: in the benzene-d6Middle soluble catalyst (BDI-ZnMe)2(ii) a c is catalyst (BDI-ZnMe)2With 1bar CO2Reacting at 40 ℃ for 24h to obtain a system; d is catalyst (BDI-ZnMe)2With 20bar CO2The reaction was carried out at 40 ℃ for 24 h.
As can be seen from the analysis in FIGS. 9 to 10, the components of the system before and after the reaction did not change, indicating that the catalyst (BDI-ZnMe)2Can not activate CO alone2。
3) Catalyst (BDI-ZnMe)2Catalyzing copolymerization reaction while keeping the structure of the catalyst unchanged:
separately subjecting different systems of monomer and catalyst to nuclear magnetic testing: (1H NMR 500MHz monitoring, tol-d8) The results are shown in FIG. 11; wherein, a is a blank control of the reaction kettle, b is monomer and catalyst according to the molar ratio meso-CHO/(BDI-ZnMe)22: 1; c is monomer and catalyst in molar ratio meso-CHO/(BDI-ZnMe)2After mixing 2:1, 20bar CO was charged2And reacting at 40 ℃ for 24 hours to obtain the system. From the analysis of the figure, the catalyst (BDI-ZnMe)2The structure of the catalyst can be kept unchanged while catalyzing copolymerization reaction. Thus, the present catalytic system enables initiation and polymerization processes to be achieved in the presence of both epoxy monomer and carbon dioxide.
Example 6
Cyclohexene oxide (meso-CHO) was treated with CaH2Drying for 48h, and distilling and purifying under reduced pressure for later use;
dissolving the treated meso-CHO in toluene to obtain meso-CHO solution (2.0M);
the meso-CHO solution and the catalyst prepared in example 2 were charged into a reaction vessel at a cyclohexene oxide to catalyst molar ratio of 800:1, sealed (cyclohexene oxide 4.0mmoL, catalyst 0.005mmoL), and charged with CO2Adjusting CO2The pressure is 40bar, after the pressure is stable, the reaction kettle is put into an oil bath pot to be heated for 1 hour at 90 ℃ for polymerization reactionThe obtained product is washed by HCl/MeOH solution (0.1mol/L hydrochloric acid methanol solution, hydrochloric acid concentration is 0.1mol/L) to obtain the polycarbonate cyclohexene ester (PCHC).
Structure and performance testing
1) Molecular weight measurement of the PCHC prepared in example 6 revealed that the absolute molecular weight of the PCHC was 25.7kDa, Mw was 28.6kDa, and PDI (polymer dispersibility index) was 1.11, indicating that the molecular weight distribution of the polymer was uniform.
2) Nuclear magnetic characterization of the PCHC prepared in example 6 (500 MHz)1H NMR CDCl3) The nuclear magnetic hydrogen spectrum is shown in FIG. 12.
3) Testing of PCHC annular structure:
with linear PCHC of the same molecular weightlinearFor viscosity comparison, log η (using [ η ]]Representation) [ η ]]Cyclic/[ η]The range of linearity ≦ 0.7 may prove to be a cyclic structure, where η represents the intrinsic viscosity;
the PCHC prepared in example 6 is designated PCHC2Wherein PCHClinearRepresents a linear polymer, prepared in the literature references (Angew. chem. int. Ed.2013,52, 11594-11598); Mark-Houwink curves (viscosity versus molecular weight) for both polymers are shown in FIG. 13;
after calculation, [ η ]]PCHC2/[η]PCHClinearThis demonstrates that the PC HC prepared in example 6 is a cyclic structure, as 0.67.
Example 7
Cyclohexene oxide (meso-CHO) was treated with CaH2Drying for 48h, and distilling and purifying under reduced pressure for later use;
dissolving the treated meso-CHO in toluene to obtain meso-CHO solution (2.0M);
the meso-CHO solution and the catalyst prepared in example 3 were charged into a reaction vessel at a cyclohexene oxide to catalyst molar ratio of 800:1, sealed (cyclohexene oxide 4mmoL, catalyst 0.005mmoL), and charged with CO2Adjusting CO2The pressure is 20bar, after the pressure is stable, the reaction kettle is placed into an oil bath pot to be heated for 1h at 90 ℃ for polymerization reaction, and the obtained product is washed by HCl/MeOH solution (0.1mol/L hydrochloric acid methanol solution, the concentration of hydrochloric acid is 0.1mol/L) to obtainPolycyclohexene carbonate (PCHC).
Structure and performance testing
1) Molecular weight measurement of the PCHC prepared in example 7 revealed that the absolute molecular weight of the PCHC was 25.2kDa, Mw was 27.9kDa, and PDI (polymer dispersibility index) was 1.11, indicating that the molecular weight distribution of the polymer was uniform.
2) Nuclear magnetic characterization of the PCHC prepared in example 7 (500 MHz)1H NMR CDCl3) The nuclear magnetic hydrogen spectrum is shown in FIG. 14.
3) Testing of PCHC annular structure:
with linear PCHC of the same molecular weightlinearFor viscosity comparison, log η (using [ η ]]Representation) [ η ]]Cyclic/[ η]The range of linearity ≦ 0.7 may prove to be a cyclic structure, where η represents the intrinsic viscosity;
the PCHC prepared in example 7 is designated PCHC3Wherein PCHClinearRepresents a linear polymer, prepared in the literature references (Angew. chem. int. Ed.2013,52, 11594-11598); Mark-Houwink curves (viscosity versus molecular weight) for both polymers are shown in FIG. 15;
after calculation, [ η ]]PCHC3/[η]PCHClinearThis demonstrates that the PC HC prepared in example 7 is a cyclic structure, 0.68.
Example 8
Cyclohexene oxide (meso-CHO) was treated with CaH2Drying for 48h, and distilling and purifying under reduced pressure for later use;
dissolving the treated meso-CHO in toluene to obtain meso-CHO solution (2.0M);
the meso-CHO solution and the catalyst prepared in example 4 were charged into a reaction vessel at a cyclohexene oxide to catalyst molar ratio of 800:1, sealed (cyclohexene oxide 4mmoL, catalyst 0.005mmoL), and charged with CO2Adjusting CO2The pressure is 10bar, after the pressure is stable, the reaction kettle is placed into an oil bath pot to be heated for 1h at 90 ℃ for polymerization reaction, and the obtained product is washed by HCl/MeOH solution (0.1mol/L hydrochloric acid methanol solution, the hydrochloric acid concentration is 0.1mol/L) to obtain the polycarbonate cyclohexene ester (PCHC).
Structure and performance testing
1) Molecular weight measurement of the PCHC prepared in example 8 revealed that the absolute molecular weight of the PCHC was 31.6kDa, Mw was 32.2kDa, and PDI (polymer dispersibility index) was 1.02, indicating that the molecular weight distribution of the polymer was uniform.
2) Nuclear magnetic characterization of the PCHC prepared in example 8 (500 MHz)1H NMR CDCl3) The nuclear magnetic hydrogen spectrum is shown in FIG. 16.
3) Testing of PCHC annular structure:
with linear PCHC of the same molecular weightlinearFor viscosity comparison, log η (using [ η ]]Representation) [ η ]]Cyclic/[ η]The range of linearity ≦ 0.7 may prove to be a cyclic structure, where η represents the intrinsic viscosity;
the PCHC prepared in example 8 is designated PCHC4Wherein PCHClinearRepresents a linear polymer, prepared in the literature references (Angew. chem. int. Ed.2013,52, 11594-11598); Mark-Houwink curves (viscosity versus molecular weight) for both polymers are shown in FIG. 17;
after calculation, [ η ]]PCHC4/[η]PCHClinearThis demonstrates that the PC HC prepared in example 8 is a cyclic structure.
Example 9
The procedure for synthesizing the first ligand and the second ligand is exactly the same as in example 1, and the catalyst of this example is synthesized directly using the second ligand synthesized in example 1:
the second ligand (525mg,1mmol,1.0eq) was dissolved in 200mL of anhydrous toluene, and ZnEt was added dropwise2(2mL,2mmol,2.0eq) in toluene at 90 ℃ for 24h, and the toluene was drained to give 645mg of a yellow powder as a solid, i.e., the catalyst, noted as (BDI-ZnEt)2The yield is 90%; nuclear magnetic hydrogen spectrum (500 MHz) of the catalyst1H NMRbenzene-d6) See FIG. 18; the nuclear magnetic data are: δ 6.87-6.86(d, J ═ 5.0Hz,8H, C-H), δ 6.63-6.62(d, J ═ 5.0Hz,8H, C-H), δ 4.82(s,2H, C-H), δ 3.53(s,4H, CH), δ 6.4, C-H, J, C-H, C2),δ1.93(s,12H,CH3)δ0.39-0.36(t,J＝7.5Hz,6H,(ZnCH2)-CH3)δ-0.29-0.34(dd,J1＝10.0Hz,J2＝15.0Hz,4H,Zn-CH2(CH3) According to the nuclear magnetic spectrum information, the structure of the compound is the target catalyst (BDI-ZnEt)2And (5) structure.
Example 10
Cyclohexene oxide (meso-CHO) was treated with CaH2Drying for 48h, and distilling and purifying under reduced pressure for later use;
dissolving the treated meso-CHO in toluene to obtain meso-CHO solution (2.0M);
the meso-CHO solution and the catalyst prepared in example 9 were charged into a reaction vessel at a cyclohexene oxide to catalyst molar ratio of 800:1, sealed (cyclohexene oxide 4mmoL, catalyst 0.005mmoL), and charged with CO2Adjusting CO2The pressure is 30bar, after the pressure is stable, the reaction kettle is placed into an oil bath pot to be heated for 1h at 90 ℃ for polymerization reaction, and the obtained product is washed by HCl/MeOH solution (0.1mol/L hydrochloric acid methanol solution, the hydrochloric acid concentration is 0.1mol/L) to obtain the polycarbonate cyclohexene ester (PCHC).
Structure and performance testing
1) Molecular weight measurement of the PCHC prepared in example 10 revealed that the absolute molecular weight of the PCHC was 27.5kDa, Mw was 30.6kDa, and PDI (polymer dispersibility index) was 1.11, indicating that the molecular weight distribution of the polymer was uniform.
2) Nuclear magnetic characterization of the PCHC prepared in example 10 (500 MHz)1H NMR CDCl3) The nuclear magnetic hydrogen spectrum is shown in FIG. 19.
3) Testing of PCHC annular structure:
with linear PCHC of the same molecular weightlinearFor viscosity comparison, log η (using [ η ]]Representation) [ η ]]Cyclic/[ η]The range of linearity ≦ 0.7 may prove to be a cyclic structure, where η represents the intrinsic viscosity;
the PCHC prepared in example 10 is designated PCHC5Wherein PCHClinearRepresents a linear polymer, prepared in the literature references (Angew. chem. int. Ed.2013,52, 11594-11598); Mark-Houwink curves (viscosity versus molecular weight) for both polymers are shown in FIG. 20;
after calculation, [ η ]]PCHC5/[η]PCHClinearThis demonstrates that the PCHC prepared in example 10 is 0.7A cyclic structure.
4) PCHC 3 continuous CO2Unit determination
The PCHC prepared in example 10 was subjected to maldi-tof end group verification, the results are shown in FIG. 21, and the analysis shows that the PCHC was used12CO2The end group molecular weight of (A) was 88, the results were in agreement with those of example 5, and were 3 consecutive COs2The units are connected.
From the above embodiments, the invention provides a catalyst, a preparation method and an application thereof, a cyclic carbon dioxide-based polycarbonate and a preparation method thereof, and belongs to the technical field of carbon dioxide-based polycarbonates. The catalyst provided by the invention can realize epoxy monomer (meso-CHO) and CO2Alternating copolymerization of (regioselective polycarbonate)>99%) and exhibits high activity (TOF)>3200h-1) The catalyst of the invention can be used for preparing cyclic CO for the first time2Based on polycarbonate and for the first time synthesizing a mixture containing continuous CO which is conventional in inverse thermodynamics2CO of a unit2Based Polycarbonate (PCHC).
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A catalyst for synthesizing cyclic carbon dioxide-based polycarbonate has a structure shown in formula I:
wherein R is alkyl or alkyl derivatives.
2. The catalyst of claim 1, wherein R comprises Me, Et, iPr, nBu, tBu, Ph, Bn, -CH2OCH3、-CH2N(CH3)2、-CH2SCH3、-CH2CH2N(CH3)2、-CH2CH2OCH3or-CH2CH2SCH3。
3. The method for preparing a catalyst for the synthesis of cyclic carbon dioxide-based polycarbonate according to claim 1 or 2, comprising the steps of:
mixing 4, 4-diaminodiphenylmethane, acetylacetone, p-toluenesulfonic acid and toluene, and carrying out a first hydroxylamine condensation reaction to obtain a first ligand;
mixing the ethanol solution of the first ligand, the hydrochloric acid solution of 1, 4-dioxane and 4, 4-diaminodiphenylmethane, and carrying out a second hydroxylamine condensation reaction to obtain a second ligand;
mixing the solution of the second ligand and the solution of a zinc compound, and carrying out substitution reaction to obtain a catalyst for synthesizing the cyclic carbon dioxide-based polycarbonate;
the zinc compound in the solution of the zinc compound comprises zinc compounds of alkyl zinc or alkyl derivatives.
4. The preparation method according to claim 3, wherein the amount of 4, 4-diaminodiphenylmethane, acetylacetone, p-toluenesulfonic acid, and toluene used in the raw material for the first hydroxylamine condensation reaction is (11.6-24.0) g to 12mL (1.0-100) g (1.0-3.0) L;
the first hydroxylamine condensation reaction is carried out under the reflux condition, the temperature of the first hydroxylamine condensation reaction is 80-130 ℃, and the time is 0.5-2 h.
5. The preparation method according to claim 3, wherein the amount of the first ligand, the hydrochloric acid solution of dioxane and 4, 4-diaminodiphenylmethane in the ethanol solution of the first ligand is 3g (4.2-8.4) mL (1.65-3.3) g; the concentration of hydrochloric acid in the hydrochloric acid solution of dioxane is 4.0 mol/L.
6. A preparation method according to claim 3 or 5, wherein the second hydroxylamine condensation reaction is performed under reflux conditions, and the temperature of the second hydroxylamine condensation reaction is 80-90 ℃ for 4-12 hours.
7. The production method according to claim 3, wherein the zinc alkyl comprises dimethyl zinc, diethyl zinc, diisopropyl zinc, di-n-butyl zinc, di-t-butyl zinc, diphenyl zinc or dibenzyl zinc; the zinc compound of the alkyl derivative comprises bis (methoxymethyl) zinc, bis (methoxyethyl) zinc, bis (methylthiomethyl) zinc, bis (methylthioethyl) zinc, bis (dimethylaminomethyl) zinc or bis (dimethylaminoethyl) zinc; the molar ratio of the second ligand in the solution of the second ligand to the zinc compound in the solution of the zinc compound is 1 (2-3);
the temperature of the substitution reaction is 90-110 ℃, and the time is 24-48 h.
8. Use of the catalyst according to claim 1 or 2 or the catalyst prepared by the preparation method according to any one of claims 3 to 7 in the synthesis of cyclic carbon dioxide-based polycarbonate.
9. A cyclic carbon dioxide-based polycarbonate having a structure represented by formula II:
wherein n represents the number of repeating units and n is a positive integer.
10. The method for producing a cyclic carbon dioxide-based polycarbonate according to claim 9, comprising the steps of:
mixing the cyclohexene oxide anhydrous solution with a catalyst, introducing carbon dioxide, and carrying out polymerization reaction under anhydrous and anaerobic conditions to obtain cyclic carbon dioxide-based polycarbonate;
the catalyst is the catalyst as described in claim 1 or 2 or the catalyst prepared by the preparation method as described in any one of claims 3 to 7.
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| CN113336932A (en) * | 2021-07-16 | 2021-09-03 | 郑州大学第一附属医院 | Metal coordination catalyst for synthesizing carbon dioxide-based biodegradable material and application thereof |
| CN113429556A (en) * | 2021-07-19 | 2021-09-24 | 郑州大学第一附属医院 | Catalyst for synthesizing biocompatible material by carbon dioxide-epoxy compound copolymerization |
| CN113444236A (en) * | 2021-07-16 | 2021-09-28 | 郑州大学第一附属医院 | Catalyst for synthesizing biodegradable plastic and application thereof |
| CN113461927A (en) * | 2021-07-19 | 2021-10-01 | 郑州大学第一附属医院 | Catalyst for preparing carbon dioxide-based degradable polycarbonate and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113336932A (en) * | 2021-07-16 | 2021-09-03 | 郑州大学第一附属医院 | Metal coordination catalyst for synthesizing carbon dioxide-based biodegradable material and application thereof |
| CN113444236A (en) * | 2021-07-16 | 2021-09-28 | 郑州大学第一附属医院 | Catalyst for synthesizing biodegradable plastic and application thereof |
| CN113429556A (en) * | 2021-07-19 | 2021-09-24 | 郑州大学第一附属医院 | Catalyst for synthesizing biocompatible material by carbon dioxide-epoxy compound copolymerization |
| CN113461927A (en) * | 2021-07-19 | 2021-10-01 | 郑州大学第一附属医院 | Catalyst for preparing carbon dioxide-based degradable polycarbonate and application thereof |
| CN113461927B (en) * | 2021-07-19 | 2023-03-10 | 郑州大学第一附属医院 | Catalyst for preparing carbon dioxide-based degradable polycarbonate and application thereof |
| CN113429556B (en) * | 2021-07-19 | 2023-03-10 | 郑州大学第一附属医院 | Catalyst for synthesizing biocompatible material by carbon dioxide-epoxy compound copolymerization |
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