CN111393460B - Zinc coordination compound of flavone derivative and preparation method and application thereof - Google Patents
Zinc coordination compound of flavone derivative and preparation method and application thereof Download PDFInfo
- Publication number
- CN111393460B CN111393460B CN202010313676.1A CN202010313676A CN111393460B CN 111393460 B CN111393460 B CN 111393460B CN 202010313676 A CN202010313676 A CN 202010313676A CN 111393460 B CN111393460 B CN 111393460B
- Authority
- CN
- China
- Prior art keywords
- complex
- zinc
- temperature
- flavone
- reactant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011701 zinc Substances 0.000 title claims abstract description 33
- 150000002212 flavone derivatives Chemical class 0.000 title claims abstract description 15
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 15
- 150000001875 compounds Chemical class 0.000 title claims abstract description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 239000000376 reactant Substances 0.000 claims abstract description 10
- 239000004593 Epoxy Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 7
- 150000005676 cyclic carbonates Chemical class 0.000 claims abstract description 7
- DZJHBPLOAIXZPY-UHFFFAOYSA-N 2-(4-carboxyphenyl)-3-hydroxy-4-oxochromene-6-carboxylic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=C(O)C(=O)C2=CC(C(O)=O)=CC=C2O1 DZJHBPLOAIXZPY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000003751 zinc Chemical class 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000007789 sealing Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 9
- YCEXFKMSRPXVPJ-UHFFFAOYSA-N [Zn].O1C2=CC=CC=C2C(=O)C=C1C1=CC=CC=C1 Chemical class [Zn].O1C2=CC=CC=C2C(=O)C=C1C1=CC=CC=C1 YCEXFKMSRPXVPJ-UHFFFAOYSA-N 0.000 claims 1
- 229930003935 flavonoid Natural products 0.000 claims 1
- 150000002215 flavonoids Chemical class 0.000 claims 1
- 235000017173 flavonoids Nutrition 0.000 claims 1
- 238000011534 incubation Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- GAMYVSCDDLXAQW-AOIWZFSPSA-N Thermopsosid Natural products O(C)c1c(O)ccc(C=2Oc3c(c(O)cc(O[C@H]4[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O4)c3)C(=O)C=2)c1 GAMYVSCDDLXAQW-AOIWZFSPSA-N 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 229930003944 flavone Natural products 0.000 abstract description 6
- 235000011949 flavones Nutrition 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 6
- VHBFFQKBGNRLFZ-UHFFFAOYSA-N vitamin p Natural products O1C2=CC=CC=C2C(=O)C=C1C1=CC=CC=C1 VHBFFQKBGNRLFZ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000011968 lewis acid catalyst Substances 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000012621 metal-organic framework Substances 0.000 description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005859 coupling reaction Methods 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 6
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 150000002118 epoxides Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 2
- 238000006352 cycloaddition reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- HOEMHZBNQZZUPF-UHFFFAOYSA-N 2-(4-carboxyphenyl)-3-hydroxy-4-oxochromene-6-carboxylic acid zinc Chemical compound C1=CC(=CC=C1C2=C(C(=O)C3=C(O2)C=CC(=C3)C(=O)O)O)C(=O)O.[Zn] HOEMHZBNQZZUPF-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000005200 wet scrubbing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention relates to the field of material synthesis, and discloses a flavone derivative-zinc complex and a preparation method thereof, wherein the preparation method comprises the following steps: s1, mixing N, N-dimethylformamide and methanol to obtain a reaction solvent; s2, mixing 3-hydroxy-6, 4' -flavone dicarboxylic acid, zinc salt crystals and the reaction solvent, and sealing to obtain a reactant; s3, sequentially heating, preserving heat and cooling the reactant to be reacted to obtain yellow blocky crystals; s4, washing and drying the yellow blocky crystal to obtain the complex; the invention also discloses that the complex captures and converts CO at normal pressure 2 The use of (a); the complex has a unique open Zn site and a smooth pore channel structure, and can adsorb a large amount of CO at normal temperature 2 And as a Lewis acid catalyst to CO 2 A nano-reactor which reacts with epoxy compound at normal temperature and normal pressure to generate cyclic carbonate; meanwhile, the high stability of the Zn sites also enables the Zn sites to have excellent recovery performance in the catalytic reaction and separation processes.
Description
Technical Field
The invention relates to the field of material synthesis, in particular to a zinc complex serving as a flavone derivative and a preparation method and application thereof.
Background
85% of energy required by human life comes from the combustion of fossil fuel, which is a non-renewable resource and is exhausted after decades of years as reserves are reduced day by day, so that the society is particularly urgent to seek renewable resources. On the other hand, the increasing carbon dioxide in the atmosphere, as a major greenhouse gas, has led to severe climate change over the last decades. However, carbon dioxide is a good renewable resource, so in order to reduce carbon dioxide emissions, it is also an urgent task to develop a feasible carbon dioxide capture and storage technology.
Amine-based wet scrubbing systems are currently used commercially to capture and store carbon dioxide, but their high energy costs, high corrosiveness and low efficiency have prompted the search for better methods for capturing and storing carbon dioxide.
In recent years, CO is introduced 2 As C 1 The research on the further conversion of raw materials into organic carbon, such as dimethyl carbonate, cyclic urethane, N' -disubstituted urea compounds, methanol, formic acid and other chemical products, is gradually rising. Among these chemicals, cyclic carbonates formed by combining epoxides with carbon dioxide have attracted increasing attention due to their wide application in pharmaceutical and fine chemical industries, and their inherent advantages of good solubility, high boiling point, and degradability. Although various homogeneous catalysts have been used commercially to synthesize cyclic carbonates, these processes require further separation of the product and recovery of the catalyst. Therefore, heterogeneous catalysts such as zeolite, titanosilicate, metal oxide, ion exchange resin, etc. are used in many cases to catalyze CO 2 The study of the coupling reaction of (2) has been carried out. However, effective chemical fixation often requires harsh conditions of high pressure, high temperature, etc. to allow the reaction to occur, thereby increasing energy consumption.
At present, metal-organic framework Materials (MOFs) have good structural controllability, high specific surface area and functionalized pore channel structures, and show great application potential in the fields of adsorption, catalysis, sensing, drug delivery and the like. Although there have been many references to MOFs as heterogeneous Lewis acid catalysts to catalyze CO 2 The chemical conversion of (2) is reported, but most of them require high-pressure or high-temperature reaction conditions to achieve higher catalytic efficiency; although a small fraction of several MOFs also appear to catalyze CO under mild reaction conditions 2 The performance of coupling reactions, most of which are also based on noble metal sites in expensive metal macrocycle complexes. In addition, in the epoxide with CO 2 In the coupling reaction, the open metal sites in the MOFs act as Lewis acid catalytic centers, however, the open metal sites in most of the MOFs are latent and can only be obtained by degassing, not intrinsic open metal sites. Thus, the novel intrinsic open metal site catalytic centers in MOFs were investigated to react epoxides with CO 2 The coupling under mild conditions is an urgent need for developing efficient novel catalysts.
In conclusion, IThere is a need for a catalyst that can react epoxide with CO 2 The coupling occurs under mild conditions, and the heterogeneous catalyst has inherent open metal site catalytic center, low cost and high catalytic efficiency.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a flavone derivative-zinc complex, a preparation method and application thereof so as to enable epoxide and CO to be mixed 2 The coupling occurs under mild conditions, and the catalyst has the effects of inherent open metal site catalytic center, low cost and high catalytic efficiency.
The purpose of the invention is realized by the following technical scheme: a zinc complex of flavone derivative has the following structural formula:
by the technical scheme, the complex has a unique open Zn site and a smooth pore channel structure, and can adsorb a large amount of CO at normal temperature 2 And as a Lewis acid catalyst to CO 2 The nano-reactor reacts with epoxy compound at normal temperature and normal pressure to generate cyclic carbonate, so that the purpose of leading the epoxy compound and CO to react is achieved 2 The coupling is carried out under mild conditions, and the catalyst has the effects of inherent open metal site catalytic center, low cost and high catalytic efficiency; meanwhile, the high stability of the Zn sites also enables the Zn sites to have excellent recovery performance in the catalytic reaction and separation processes.
A preparation method of a zinc complex of a flavone derivative comprises the following steps:
s1, mixing N, N-dimethylformamide and methanol to obtain a reaction solvent;
s2, mixing 3-hydroxy-6, 4' -flavone dicarboxylic acid, zinc salt crystals and the reaction solvent, and sealing to obtain a reactant;
s3, sequentially heating, preserving heat and cooling the reactant to be reacted to obtain yellow blocky crystals;
and S4, washing and drying the yellow blocky crystal to obtain the complex.
Further, in S1, the volume ratio of N, N-dimethylformamide to methanol is 3.
Further, in S2, the zinc salt crystals include Zn (NO) 3 ) 2 ·2.5H 2 O。
Further, in S2, the 3-hydroxy-6, 4' -flavone dicarboxylic acid is reacted with Zn (NO) 3 ) 2 ·2.5H 2 The mass ratio of O is 3.
Further, in S3, the temperature rise specifically includes: the temperature of the reactants was increased to 90 ℃ within 300 min.
Further, in S3, the heat preservation time is 5000min.
Further, in S3, the cooling specifically includes: the temperature was reduced from 90 ℃ to 30 ℃ within 600 min.
A flavone derivative-zinc complex is used for capturing and converting CO at normal pressure 2 The use of (1).
Further, the complex is used for capturing CO at normal temperature and normal pressure 2 And catalyze CO 2 With an epoxy compound to form a cyclic carbonate.
The beneficial effects of the invention are:
1. the zinc coordination compound of the flavone derivative can adsorb a large amount of CO at normal temperature through the unique open Zn site and unobstructed pore structure 2 And as a Lewis acid catalyst to CO 2 The nano-reactor reacts with epoxy compound at normal temperature and normal pressure to generate cyclic carbonate, so that the purpose of leading the epoxy compound and CO to react is achieved 2 The coupling is carried out under mild conditions, and the catalyst has the effects of inherent open metal site catalytic center, low cost and high catalytic efficiency.
2. According to the flavone derivative-zinc complex, the generation reaction conditions of the complex are determined by analogy with temperature control parameters in the synthesis process of a metal-organic framework complex, and meanwhile, the optimum time length and the temperature critical value of the temperature rise stage and the temperature drop stage are determined by fully considering the characteristics of complex synthesis in the temperature rise stage and the temperature drop stage, so that a powerful basis is provided for the industrial production of the complex.
3. The high stability of Zn site of the flavone derivative-Zn complex of the invention also makes it have excellent recovery performance in the catalytic reaction and separation process.
Drawings
FIG. 1 is a schematic representation of a ball and stick model of a zinc complex which is a flavone derivative according to the present invention;
FIG. 2 is an infrared spectrum of a zinc complex as a flavone derivative according to the present invention;
FIG. 3 is N of the complex prepared in example 1 2 Adsorption isotherm plot (77K);
FIG. 4 is CO of the complex prepared in example 1 2 Suction attached sheets (273K, 298K);
FIG. 5 shows that the complexes prepared in the respective comparative examples catalyze CO separately 2 Comparison of substrate conversion when reacted with propylene oxide to propylene carbonate.
Detailed Description
The technical solutions of the present invention are further described in detail below with reference to the accompanying drawings, but the scope of the present invention is not limited to the following descriptions.
Example 1
A preparation method of a zinc complex of a flavone derivative comprises the following steps:
s1, mixing N, N-dimethylformamide and methanol in a volume ratio of 3;
s2, taking 4.90mg of 3-hydroxy-6, 4' -flavone dicarboxylic acid and 4.50mg of Zn (NO) 3 ) 2 ·2.5H 2 Mixing O with 2mL of reaction solvent, and filling the mixture into a glass tube for vacuum sealing to obtain a reactant to be reacted;
s3, placing the reactant in an oven, raising the temperature of the oven from room temperature to 90 ℃ within 300min, keeping the temperature at 90 ℃ for 5000min, reducing the temperature from 90 ℃ to 30 ℃ within 600min, and finally cutting off a glass tube to obtain light yellow blocky crystals;
s4, washing the light yellow blocky crystals by using N, N-dimethylformamide and drying in vacuum to obtain the complex with the yield of 65%.
Structural characterization
The product prepared in this example is a complex of 3-hydroxy-6, 4' -flavone dicarboxylic acid-zinc, which is shown by infrared spectroscopy (as shown in fig. 1) and X-ray single crystal diffraction analysis, and is specifically represented as follows:
the complex is a triclinic system, and a space group P-1;
molecular formula of C 54 H 30 NO 23 Zn 4 Molecular weight of 1322.27;
infrared Spectrum (KBr, cm) -1 )：1658,1549,1387,1284,1221,1161,1096,875,839,784,736,685,661,645.
Test effects
1. To investigate the permanent porosity of the complexes according to the invention, the complex obtained in example 1 adsorbs N at 77K 2 The test was carried out with the following test results:
as shown in FIG. 3, the BET surface area of the complex obtained in example 1 was about 490m 2 ·g -1 Equivalent to about 566m 2 ·g -1 Langmuir surface area of (d) with the N of the complex at 77K 2 The adsorption isotherm is a typical type I isotherm. From this, it was found that the complex of the present invention had a microporous structure.
2. In order to study the complex pair CO of the present invention 2 Adsorption of CO at 273K and 298K on the complexes obtained in example 1 2 The adsorption performance is tested, and the test results are as follows:
as shown in FIG. 4, the maximum CO of the complex at 273K 2 The adsorption capacity was 32cm 3 ·g -1 And maximum CO at 298K 2 The adsorption capacity is 18cm 3 ·g -1 Calculated, the isovolumetric heat of adsorption Q of the complex st Is 33 kJ. Mol -1 . It can be seen from this that the complexes of the invention absorb CO 2 Due to CO 2 Zn in molecules and complexes 2+ Have good interaction between the open metal sites.
3. To verify that the complexes of the invention are capable of catalyzingEpoxy compounds substituted with different functional groups and CO 2 The test was conducted. The test method comprises the following steps: using the complex obtained in example 1, at room temperature and 1 atmosphere, respectively, for CO 2 Catalyzing with cycloaddition reaction of epoxybutane, epichlorohydrin, phenyl glycidyl ether or allyl glycidyl ether to obtain substrate conversion rate (yield) of each group; wherein the reaction time is 48h. The test results are shown in the following table:
as can be seen from the above table, the complex of the present invention catalyzes the reaction of butylene oxide and epichlorohydrin with CO 2 The cycloaddition of (2) all had higher substrate conversion (89% for the first group and 99% for the second group); to catalyze phenyl glycidyl ether and allyl glycidyl ether with CO 2 The substrate conversion rate almost reaches 100 percent. Therefore, the complex can efficiently catalyze epoxy compounds substituted by different functional groups and CO 2 Due to the open sites of zinc ions and the large and straight pore structure inherent in the complex structure. Meanwhile, the test experiment also aims at constructing a new type of catalyst which can efficiently fix and catalyze CO 2 The converted heterogeneous catalyst provides a new idea.
Comparative example 1
The catalytic CO is tested by adopting a ZIF-8 metal-organic framework (MOF) under the conditions of normal temperature and normal pressure 2 The substrate conversion in the reaction with propylene oxide to propylene carbonate is compared with the complex obtained in example 1.
Comparative example 2
By means of Zn 2+ Metal-organic framework Materials (MOFs) of coordinated MOFs (Zn-BDC) are tested to catalyze CO under the conditions of normal temperature and pressure 2 The substrate conversion in the reaction with propylene oxide to propylene carbonate was compared with the complex obtained in example 1.
Comparative example 3
Using Cu 2+ Coordinated Cu (tactmb) Metal-organic framework Materials (MOF) tested for catalyzing CO at ambient temperature and pressure 2 The substrate conversion in the reaction with propylene oxide to propylene carbonate was compared with the complex obtained in example 1.
The complexes obtained in comparative examples 1 to 3 and example 1 were tested under the same conditions for catalyzing CO at room temperature and pressure 2 Substrate conversion when reacting with propylene oxide to produce propylene carbonate; wherein the time of catalytic reaction is 48h, the test results are shown in the following table and fig. 5:
from this, it was found that when the catalytic reaction was carried out for 48 hours, the substrate conversion of the complex of the present invention was 99% or more, that of comparative example 1 was 48%, that of comparative example 2 was 31%, and that of comparative example 3 was 47.5%. It can be seen that the substrate conversion rate of the experimental group is much higher than that of the comparative examples 1, 2 and 3, and even higher than that of some compounds with metal-schiff base porous organic network structure which need to be catalyzed under high pressure and high temperature reaction conditions. Therefore, the complex can efficiently catalyze the epoxypropane and the CO 2 Reaction for preparing propylene carbonate, and the complex is in the presence of CO 2 The high catalytic activity exhibited in chemical immobilization and conversion is due to the unique Zn sites and open pore structure therein.
The foregoing is illustrative of the preferred embodiments of the present invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and is not to be construed as limited to the exclusion of other embodiments, and that various other combinations, modifications, and environments may be used and modifications may be made within the scope of the concepts described herein, either by the above teachings or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. The zinc coordination compound of the flavone derivative is characterized in that the structural formula is as follows:
2. the process for preparing a zinc-flavone derivative complex according to claim 1, comprising the steps of:
s1, mixing N, N-dimethylformamide and methanol to obtain a reaction solvent;
s2, mixing 3-hydroxy-6, 4' -flavone dicarboxylic acid, zinc salt crystals and the reaction solvent, and sealing to obtain a reactant to be reacted;
s3, sequentially heating, preserving heat and cooling the reactant to be reacted to obtain yellow blocky crystals;
and S4, washing and drying the yellow blocky crystal to obtain the complex.
3. The method according to claim 2, wherein the volume ratio of N, N-dimethylformamide to methanol in S1 is 3.
4. The method according to claim 2, wherein in S2, the zinc salt crystals comprise Zn (NO) 3 ) 2 ·2.5H 2 O。
5. The method of claim 4, wherein in S2, the 3-hydroxy-6, 4' -flavonedicarboxylic acid is reacted with Zn (NO) 3 ) 2 ·2.5H 2 The mass ratio of O is 3.
6. The method according to claim 2, wherein in S3, the temperature rise is specifically: the temperature of the reactants was increased to 90 ℃ within 300 min.
7. The method of claim 2, wherein in S3, the incubation time is 5000min.
8. The method according to claim 2, wherein in S3, the temperature reduction is specifically: the temperature was reduced from 90 ℃ to 30 ℃ within 600 min.
9. The flavonoid derivative-zinc complex of claim 1, which captures and converts CO at atmospheric pressure 2 Characterized in that the complex is used for capturing CO at normal temperature and pressure 2 And catalyze CO 2 With an epoxy compound to form a cyclic carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010313676.1A CN111393460B (en) | 2020-04-20 | 2020-04-20 | Zinc coordination compound of flavone derivative and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010313676.1A CN111393460B (en) | 2020-04-20 | 2020-04-20 | Zinc coordination compound of flavone derivative and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111393460A CN111393460A (en) | 2020-07-10 |
| CN111393460B true CN111393460B (en) | 2023-01-17 |
Family
ID=71427978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010313676.1A Active CN111393460B (en) | 2020-04-20 | 2020-04-20 | Zinc coordination compound of flavone derivative and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111393460B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106423282A (en) * | 2016-09-21 | 2017-02-22 | 大连理工大学 | Preparation method and application of triphenylamino metal organic framework compound capable of catalyzing carbon dioxide-epoxy compound cycloaddition |
| CN106748994A (en) * | 2017-02-06 | 2017-05-31 | 辽宁大学 | Based on YbIIIThe metal-organic framework material of five core molecule construction units and its preparation method and application |
| WO2018153334A1 (en) * | 2017-02-22 | 2018-08-30 | 南京林业大学 | Biflavonoid-nickel complex and preparation method and application thereof |
| CN110156818A (en) * | 2019-06-24 | 2019-08-23 | 鲁东大学 | A kind of complex and its preparation method and application of chromocor derivative-copper |
-
2020
- 2020-04-20 CN CN202010313676.1A patent/CN111393460B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106423282A (en) * | 2016-09-21 | 2017-02-22 | 大连理工大学 | Preparation method and application of triphenylamino metal organic framework compound capable of catalyzing carbon dioxide-epoxy compound cycloaddition |
| CN106748994A (en) * | 2017-02-06 | 2017-05-31 | 辽宁大学 | Based on YbIIIThe metal-organic framework material of five core molecule construction units and its preparation method and application |
| WO2018153334A1 (en) * | 2017-02-22 | 2018-08-30 | 南京林业大学 | Biflavonoid-nickel complex and preparation method and application thereof |
| CN110156818A (en) * | 2019-06-24 | 2019-08-23 | 鲁东大学 | A kind of complex and its preparation method and application of chromocor derivative-copper |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111393460A (en) | 2020-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kuruppathparambil et al. | A solid solution zeolitic imidazolate framework as a room temperature efficient catalyst for the chemical fixation of CO 2 | |
| Das et al. | Construction of a bifunctional Zn (II)–organic framework containing a basic amine functionality for selective capture and room temperature fixation of CO 2 | |
| Wu et al. | Chemical fixation of CO 2 into cyclic carbonates catalyzed by bimetal mixed MOFs: the role of the interaction between Co and Zn | |
| CN107433205B (en) | Covalent organic framework supported cobalt catalyst and preparation and application thereof | |
| Abdelhamid | Removal of carbon dioxide using zeolitic imidazolate frameworks: adsorption and conversion via catalysis | |
| Li et al. | The design of a novel and resistant Zn (PZDC)(ATZ) MOF catalyst for the chemical fixation of CO 2 under solvent-free conditions | |
| Lan et al. | A facile fabrication of a multi-functional and hierarchical Zn-based MOF as an efficient catalyst for CO 2 fixation at room-temperature | |
| CN110684203B (en) | Two-dimensional bromine-containing covalent organic framework compound and preparation method thereof | |
| Zhang et al. | Thermally activated construction of open metal sites on a Zn-organic framework: An effective strategy to enhance Lewis acid properties and catalytic performance for CO2 cycloaddition reactions | |
| CN113292724B (en) | Preparation method of pyridine-rich cationic covalent triazine polymer | |
| Song et al. | Synthesis of cyclic carbonates and dimethyl carbonate using CO 2 as a building block catalyzed by MOF-5/KI and MOF-5/KI/K 2 CO 3 | |
| Song et al. | Dual-linker metal-organic frameworks as efficient carbon dioxide conversion catalysts | |
| CN114939431A (en) | CN@ZrO 2 Composite material and application thereof in catalyzing CO 2 Application in cycloaddition reaction with epoxide | |
| CN114437364B (en) | Metal-coupled triazine porous organic framework, construction method thereof and CO catalysis 2 Application of coupling with epoxide to prepare cyclic carbonate | |
| Liu et al. | Potassium iodide–polyethylene glycol catalyzed cycloaddition reaction of epoxidized soybean oil fatty acid methyl esters with CO 2 | |
| CN111560002A (en) | With CO2Catalyst for preparing cyclic carbonate compound as raw material | |
| CN114832858A (en) | Preparation process of ILs @ CTF composite material and catalytic performance of carbon dioxide cycloaddition reaction | |
| CN111185239B (en) | CO (carbon monoxide)2Preparation method and application of epoxidation fixed catalyst | |
| Liu et al. | Superhydrophobic MOFs with enhanced catalytic activity for chemical fixation of CO 2 | |
| CN111393460B (en) | Zinc coordination compound of flavone derivative and preparation method and application thereof | |
| CN111454455B (en) | Porous hybrid polymer rich in POSS (polyhedral oligomeric silsesquioxane) derived silicon hydroxyl and preparation method and catalytic application thereof | |
| CN110615895A (en) | Covalent triazine polymer and preparation method and application thereof | |
| CN102416348A (en) | Polymer supported imidazole ion catalyst as well as preparation method and application thereof | |
| CN115138386A (en) | Two-dimensional hexagonal boron nitride in CO catalysis 2 Application in cycloaddition reaction with epoxide | |
| CN108586344A (en) | Hydroxy functionalized pyrazolium ion liquid and the method for utilizing its catalytically synthesizing cyclic carbonate ester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240822 Address after: 265799 Industrial Park, En Economic Park, North First Road, Zhenxing Road, Longkou City, Yantai City, Shandong Province Patentee after: SHANDONG DAWN POLYMER Co.,Ltd. Country or region after: China Address before: No. 184 Hongqi Middle Road, Zhifu District, Yantai City, Shandong Province Patentee before: LUDONG University Country or region before: China |
|
| TR01 | Transfer of patent right |