CN107973914A - A kind of mixture metal organic framework photochemical catalyst for controllable free-radical polymerisation - Google Patents
A kind of mixture metal organic framework photochemical catalyst for controllable free-radical polymerisation Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 68
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 239000003054 catalyst Substances 0.000 title claims description 8
- 239000000463 material Substances 0.000 claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 52
- 239000013110 organic ligand Substances 0.000 claims description 18
- -1 (ethynyl pyridine) anthracenes Chemical class 0.000 claims description 14
- 239000013384 organic framework Substances 0.000 claims description 11
- 229940113088 dimethylacetamide Drugs 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- ZHBOFZNNPZNWGB-UHFFFAOYSA-N 9,10-bis(phenylethynyl)anthracene Chemical compound C1=CC=CC=C1C#CC(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C#CC1=CC=CC=C1 ZHBOFZNNPZNWGB-UHFFFAOYSA-N 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- NDBYHKKGKAWTJG-UHFFFAOYSA-N acetic acid;cadmium;dihydrate Chemical compound O.O.[Cd].CC(O)=O NDBYHKKGKAWTJG-UHFFFAOYSA-N 0.000 claims description 2
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 2
- 150000001661 cadmium Chemical class 0.000 claims 2
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims 1
- 239000012046 mixed solvent Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 8
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000003504 photosensitizing agent Substances 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 238000011160 research Methods 0.000 abstract description 3
- 230000007704 transition Effects 0.000 abstract description 3
- LPUCKLOWOWADAC-UHFFFAOYSA-M tributylstannyl 2-methylprop-2-enoate Chemical compound CCCC[Sn](CCCC)(CCCC)OC(=O)C(C)=C LPUCKLOWOWADAC-UHFFFAOYSA-M 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 230000001960 triggered effect Effects 0.000 abstract 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 38
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 29
- 238000012360 testing method Methods 0.000 description 18
- 239000013078 crystal Substances 0.000 description 17
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 16
- 239000003446 ligand Substances 0.000 description 14
- LGZXYFMMLRYXLK-UHFFFAOYSA-N mercury(2+);sulfide Chemical compound [S-2].[Hg+2] LGZXYFMMLRYXLK-UHFFFAOYSA-N 0.000 description 14
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 12
- 239000003643 water by type Substances 0.000 description 11
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 10
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 9
- 239000012043 crude product Substances 0.000 description 9
- 239000004926 polymethyl methacrylate Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 3
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000007210 heterogeneous catalysis Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- IUXIOXCOPJFKMQ-UHFFFAOYSA-N 2-bromo-4-methylpentane Chemical compound CC(C)CC(C)Br IUXIOXCOPJFKMQ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- WJCRZORJJRCRAW-UHFFFAOYSA-N cadmium gold Chemical compound [Cd].[Au] WJCRZORJJRCRAW-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical group CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000012917 MOF crystal Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- HSSXFLMPEOEFRM-UHFFFAOYSA-N N1=C(C=CC=C1)C#CC=1C2=CC=CC=C2C(=C2C=CC=CC=12)C#CC1=NC=CC=C1 Chemical compound N1=C(C=CC=C1)C#CC=1C2=CC=CC=C2C(=C2C=CC=CC=12)C#CC1=NC=CC=C1 HSSXFLMPEOEFRM-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- ARFLASKVLJTEJD-UHFFFAOYSA-N ethyl 2-bromopropanoate Chemical compound CCOC(=O)C(C)Br ARFLASKVLJTEJD-UHFFFAOYSA-N 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The new mixture metal-organic framework materials of the present invention are used for the crossing domain for triggering controllable free-radical polymerisation research to belong to chemistry, material science and polymer science under visible light.The present invention has synthesized a kind of new pillared type metal-organic framework materials (NNUP1) with visible absorption with compounding method, which has in wide visible-range absorbs.In addition, the compound is demonstrated by good solvent stability.The atom transition free radical polymerization reaction of Tri- n -butyltin methacrylate monomer can be triggered under visible light using NNUP1 as photosensitizer.Polymer molecular weight prepared by reaction is controllable, and molecular weight distribution is relatively narrow, and product still keeps end active to trigger polymerization again.
Description
Technical field
The invention belongs to chemistry, materials chemistry, polymer chemistry technical field, and in particular to a kind of stabilization based on anthracene
The preparation method of the mixture metal-organic framework materials of yl pyridines and biphenyl dicarboxylic acid and its free radical induced under visible light
The application of polymerisation.
Background technology
Atom transition free radical polymerization reaction (ATRP) is the controllable polymerization method to grow up in recent years.ATRP is a kind of
Living radical reacts, and the concentration of free radical is controlled in very low scope by reversible balance, reduces biradical termination reaction,
Improve the molecular weight and molecualr weight distribution of product.Compared with other types of polymerization are reacted, the polymerizable monomer of radical polymerization is more,
Reaction condition is gentle, easy to control, less sensitive to impurity, and MOLECULE DESIGN ability is stronger, realizes that industrialized production is easy, for activity
Polymerization opens up a new way.But ATRP used catalysts are mostly homogeneous catalyst at present, catalyst amount is big, holds
Easily aoxidized, be difficult to remove in the product, for the solvent majority of polymerisation with toxic, these shortcomings all limit atom in addition
The development and application of transferring free-radical polymerization.
Metal-organic framework materials (MOFs) be it is a kind of by inorganic metal node and organic bridging ligand by coordination from group
The obtained novel nano porous material with periodic structure is filled, it has had the performance of inorganic and organic materials concurrently.MOFs has
There is the features such as big specific surface area, porosity, component is various.Therefore it possesses what other inorganic porous materials cannot compare
Advantage.From the perspective of ligands, MOFs has single point matched somebody with somebody with mixture.Usually in mixture synthesis, although metal ion
Coordination mode between ligand is more various, but controllability is poor.And pillared method compensate for these deficiencies, have following excellent
Point：Target product architectural feature is more controllable, the pillared ligand of functionalization can realize the functionalization of crystal structure.In addition, MOFs exists
Many aspects have good application prospect, particularly in heterogeneous catalysis aspect of performance.But using MOFs as catalyst application
In macromolecular synthetic reaction research still in the primary stage, the report that MOFs is applied to photoinduction polymerisation is even more few
Occur.Based on this, we have synthesized a kind of mixture metal-organic framework materials with pillared layered structure of new photoresponse.
On the one hand in this metal organic framework visible absorption is realized containing functionalized pillared ligand；On the other hand this MOFs materials
Material has oxidation-reduction quality, and the photogenerated charge isolated under photoinduction effect being capable of long-term existence；We attempt real in ATRP
Realized in testing using this visible light-responded MOFs materials as heterogeneous catalysis by ATRP reactions to important life
Controllable polymerization is carried out with the Tri- n -butyltin methacrylate monomer of productive value, prepares important polymeric articles --- poly- methyl-prop
Olefin(e) acid.
The content of the invention
The object of the present invention is to provide a kind of synthesis of the new cadmium metal organic frame photochemical catalyst comprising mixed ligand
Method, in wide visible range, this novel photocatalyst can be with for the light absorbs of prepared metal organic frame photochemical catalyst
Trigger ATRP reaction synthesis polymethyl methacrylates as heterogeneous photosensitizer.The reaction effect is obvious and with controllable
Property.
New mixed cadmium metal-organic framework materials of the present invention be by (ethynyl pyridine) anthracenes of 9,10- bis- and 4,
4 '-biphenyl acid cadmium is synthesized using solvent thermal process, simple and convenient, is easily enlarged production.
The present invention provides the novel metal organic framework material as photosensitizer in induction atom transfer radical polymerization side
The application in face.
The present invention is achieved by the following technical solutions：
A kind of visible light-responded cadmium metal organic framework material, its molecular formula are (following for Cd (BPEA) (BPDC) DMF
Abbreviation NNUP1), which belongs to rhombic system, Pca21Space group.Its structural formula is as follows：
The preparation method of the cadmium metal organic framework material NNUP1 used in the visible light-inducing ATRP reactions of the present invention,
Comprise the following steps：Four nitric hydrate cadmiums and (ethynyl pyridine) anthracenes of organic ligand 9,10- bis- and 4,4 '-biphenyl acid are dissolved in
In organic solvent, cadmium metal organic framework material is obtained when 65~100 DEG C of reactions 48~144 are small；The organic solvent is
N, N '-dimethyl formamide/deionized water, N, N '-dimethyl acetamide/deionized water, or N, N '-dimethyl formamide/N,
N '-dimethyl acetamide/deionized water；Six nitric hydrate cadmiums, organic ligand 9,10- bis- (pyridinylethynyl) anthracene, 4,4 '-biphenyl
The molar ratio of diacid is 1:0.5~5:0.5~5.N, the molar ratio of N '-dimethyl formamide/deionized water is 1:0.8~2.7,
N, the molar ratio of N '-dimethyl acetamide/deionized water is 1:0.6~3.9, or N, N '-dimethyl formamide/N, N '-diformazan
The molar ratio of yl acetamide/deionized water is 1:0:5~17:0.11~55.
The present invention is to the methyl methacrylate Raolical polymerizable that is induced under visible light as photosensitizer using NNUP1
Performance is tested.Specific testing procedure and result are (1) sampling, and MOF crystal uses N respectively, N '-dimethyl formamide,
Ethanol is dried after cleaning and weighed, and takes a certain amount of methyl methacrylate (MMA), N, N, N ', N ", N " '-pentamethyl divinyl three
Amine (PMDETA), isobutyl ethyl bromide (EBiB) and copper bromide (CuBr2) and place them into rear uniformly mixed in reaction tube；
(2) radiation of visible light initiated polymerization, when radiation of visible light 8 is small at room temperature by mixture；(3) by resulting polymers in alcohol
Deng being separated out in poor solvent.Test result shows that the novel metal organic framework material induces MMA atoms under simulated solar irradiation
Transferring free-radical polymerization effect is fine, and reaction has good controllability, and MOF material recoverables.
The cadmium metal organic framework material preparation method of the present invention is simple, and synthesis scope is wide and yield is high；Contrast mesh at the same time
There is larger fragrance to be total to for preceding substantial amounts of metal-organic framework materials, the organic ligand in the new cadmium metal organic framework material
Yoke, can form effective light absorbs in whole visible region, and efficient visible light induction is carried out by the charge migration of ligand
Atom transition free radical polymerization reaction, and then lamp sunlight can be made full use of；In heterogeneous catalysis performance side
Face, mixture metal-organic framework material is with good stability, and recycling can be repeated several times, and can reduce metal and urge
The dosage of agent, has good application prospect.
Brief description of the drawings
Fig. 1 is the novel metal organic framework material structure diagram；The ball of color from deep to shallow represent respectively nitrogen-atoms,
Oxygen atom, carbon atom and cadmium atom；
Fig. 2 is the ultraviolet-ray visible absorbing of the novel metal organic framework material and 9,10- bis- (ethynyl pyridine) anthracene ligand
Spectrogram；
Fig. 3 is ln ([M0]/[M]) the kinetics relation figure that changes over time；
The visible light-initiated ATRP that Fig. 4 is MMA reacts the relation that middle-molecular-weihydroxyethyl and molecular weight distribution change with conversion ratio
Figure；
Fig. 5 is the gel chromatography analysis chart of sample before and after propagation process；Before solid line is reaction, after dotted line is reaction
's；
Fig. 6 is the response diagram of light-operated ATRP；
Fig. 7 is the thermogravimetric curve figure of the novel metal organic framework material；
Fig. 8 is powder x-ray diffraction (PXRD) figure of the novel metal organic framework material；
Fig. 9 is the Fourier Transform Infrared Spectroscopy figure of the novel metal organic framework material；
Embodiment
The present invention is described in further detail with embodiment below in conjunction with attached drawing, it should be pointed out that its purpose only exists
In the protection domain for being best understood from present disclosure and being not intended to limit the present invention.
Embodiment 1
The preparation of novel metal organic framework material 9,10- bis- (ethynyl pyridine) anthracene -4,4 '-biphenyl dicarboxylic acid cadmium：Take
0.016mmol Cd(NO)2·4H2O, 0.015mmol BPDC0.015mmol BPEA, are added in 20mL vials, to reaction
In mixture add 0.014mol N, N '-dimethyl formamide (DMF) 0.0043mol N, N '-dimethyl acetamide (DMA) and
Bottle, is put into 85 DEG C of baking ovens reacts 72h afterwards, it is thick to obtain porous cadmium metal organic framework material by 0.022mol deionized waters
Product；The porous cadmium metal organic framework material crude product is washed after drying at room temperature with ethanol, obtains Chinese red flake crystalline
The porous cadmium metal organic framework material of body --- purifying, yield are 86% (being calculated with the amount of the pillared ligand of anthryl).
The cell parameter of the new cadmium metal organic framework material is 14.7963 (8), 21.0944 (11), 29.8645
(16),90,90,90.The novel metal organic framework materials belong to rhombic system, Pca21Space group.
Fig. 1 be the novel porous cadmium metal organic framework material shape appearance figure, form layer be cadmium metal and with cadmium be coordinated
4,4 '-biphenyl acid, the structure of pillared part is ligand 9,10- bis- (ethynyl pyridine) anthracene.
Fig. 2 is the UV-visible absorption spectrum of the novel metal organic framework material and the pillared ligand of anthryl, passes through spectrum
Peak can be seen that the material because anthryl ligand has visible absorption, which absorbs in visible region
Scope is wider than anthryl ligand.
As shown in the PXRD spectrograms of Fig. 8, black line is the new cadmium metal organic backbone simulated by single crystal structural data
XRD spectra, the gray line of compound are the PXRD spectrograms of the metal organic framework compound of synthesis, contrast and can be found that：Two width XRD are composed
Figure peak position fits like a glove, and the compound for illustrating synthesis is pure phase, without impurity.
Fig. 9 is the infrared spectrum of the novel porous cadmium metal organic framework material, also may be used by the characteristic value of spectral peak
There is and be coordinated situation to qualitatively judge anthryl ligand.
Embodiment 2
Take 0.016mmol Cd (NO)2·4H2O, 0.008mmol BPDC, 0.015mmol BPEA, are added to 4-dram's
In bottle, 0.014mol N, N '-dimethyl formamide (DMF), 0.0043mol N, N '-diformazan are added into reaction mixture
Bottle, is put into 85 DEG C of baking ovens reacts 72h afterwards, obtain porous cadmium metal by yl acetamide (DMA) and 0.022mol deionized waters
Organic framework material crude product；The porous cadmium metal organic framework material crude product is washed after drying at room temperature with ethanol, is obtained
The porous cadmium metal organic framework material of Chinese red flat crystal --- purifying, yield is for 78% (with organic ligand 9,10- bis-
The amount of (ethynyl pyridine) anthracene is calculated).
Embodiment 3
Take 0.032mmol Cd (NO)2·4H2O, 0.015mmol BPDC, 0.015mmol BPEA, are added to 4-dram's
In bottle, 0.014mol N, N '-dimethyl formamide (DMF), 0.0043mol N, N '-diformazan are added into reaction mixture
Bottle, is put into 85 DEG C of baking ovens reacts 72h afterwards, obtain porous cadmium metal by yl acetamide (DMA) and 0.022mol deionized waters
Organic framework material crude product；The porous cadmium metal organic framework material crude product is washed after drying at room temperature with ethanol, is obtained
The porous cadmium metal organic framework material of Chinese red flat crystal --- purifying, yield is for 65% (with organic ligand 9,10- bis-
The amount of (ethynyl pyridine) anthracene is calculated).
Embodiment 4
Take 0.008mmol Cd (NO)2·4H2O, 0.015mmol BPDC, 0.015mmol BPEA, are added to 4-dram's
In bottle, 0.014mol N, N '-dimethyl formamide (DMF), 0.0043mol N, N '-diformazan are added into reaction mixture
Bottle, is put into 85 DEG C of baking ovens reacts 72h afterwards, obtain porous cadmium metal by yl acetamide (DMA) and 0.022mol deionized waters
Organic framework material crude product；The porous cadmium metal organic framework material crude product is washed after drying at room temperature with ethanol, is obtained
The porous cadmium metal organic framework material of Chinese red flat crystal --- purifying, yield is for 53% (with organic ligand 9,10- bis-
The amount of (ethynyl pyridine) anthracene is calculated).
Embodiment 5
Take 0.016mmol Cd (NO)2·4H2O, 0.015mmol BPDC, 0.030mmol BPEA, are added to 4-dram's
In bottle, 0.014mol N, N '-dimethyl formamide (DMF), 0.0043mol N, N '-diformazan are added into reaction mixture
Bottle, is put into 85 DEG C of baking ovens reacts 72h afterwards, obtain porous cadmium metal by yl acetamide (DMA) and 0.022mol deionized waters
Organic framework material crude product；The porous cadmium metal organic framework material crude product is washed after drying at room temperature with ethanol, is obtained
The porous cadmium metal organic framework material of Chinese red flat crystal --- purifying, yield is for 58% (with organic ligand 9,10- bis-
The amount of (ethynyl pyridine) anthracene is calculated).
Embodiment 6
With 0.016mol N, N '-dimethyl formamide (DMF) and 0.022mol deionized waters replace 0.014mol N, N '-
Dimethylformamide (DMF), 0.0043mol N, N '-dimethyl acetamide (DMA) and 0.022mol deionized waters, repeat to implement
Example 1 obtains Chinese red flat crystal --- the porous cadmium metal organic framework material of purifying, yield for 76% (with organic ligand 9,
The amount of 10- bis- (ethynyl pyridine) anthracene is calculated).
Embodiment 7
With 0.016mol N, N '-dimethyl acetamide (DMA) and 0.022mol deionized waters replace 0.014mol N, N '-
Dimethylformamide (DMF), 0.0043mol N, N '-dimethyl acetamide (DMA) and 0.022mol deionized waters, repeat to implement
Example 1, obtains Chinese red flat crystal --- and the porous cadmium metal organic framework material of purifying, yield is for 67% (with organic ligand
The amount of 9,10- bis- (ethynyl pyridine) anthracene is calculated).
Embodiment 8
With 0.016mol N, N '-dimethyl formamide (DMF) and 0.066mol deionized waters replace 0.014mol N, N '-
Dimethylformamide (DMF), 0.0043mol N, N '-dimethyl acetamide (DMA) and 0.022mol deionized waters, repeat to implement
Example 1, obtains Chinese red flat crystal --- and the porous cadmium metal organic framework material of purifying, yield is for 80% (with organic ligand
The amount of 9,10- bis- (ethynyl pyridine) anthracene is calculated).
Embodiment 9
With 65 DEG C of replacements, 85 DEG C of repetition embodiments 1, Chinese red flat crystal is obtained --- the porous cadmium metal of purifying is organic
Framework material, yield are 65% (with organic ligand 9, the amount of 10- bis- (ethynyl pyridine) anthracene is calculated).
Embodiment 10
With 100 DEG C of replacements, 85 DEG C of repetition embodiments 1, Chinese red flat crystal is obtained --- the porous cadmium metal of purifying is organic
Framework material, yield are 60% (with organic ligand 9, the amount of 10- bis- (ethynyl pyridine) anthracene is calculated).
Embodiment 11
Replace 72h to repeat embodiment 1 with reaction time 48h, obtain Chinese red flat crystal --- the porous cadmium gold of purifying
Belong to organic framework material, yield is 72% (with organic ligand 9, the amount of 10- bis- (ethynyl pyridine) anthracene is calculated).
Embodiment 12
Replace 72h to repeat embodiment 1 with reaction time 144h, obtain Chinese red flat crystal --- the porous cadmium gold of purifying
Belong to organic framework material, yield is 89% (with organic ligand 9, the amount of 10- bis- (ethynyl pyridine) anthracene is calculated).
Embodiment 13
Four nitric hydrate cadmiums in case study on implementation 1 are replaced with anhydrous caddy, the experiment of case 1 is repeated, obtains less
The porous cadmium metal organic framework material of the flat crystal of Chinese red --- purifying, yield is for 42% (with organic ligand 9,10- bis-
The amount of (ethynyl pyridine) anthracene is calculated).
Embodiment 14
Four nitric hydrate cadmiums in case study on implementation 1 are replaced with acetic acid dihydrate cadmium, the experiment of case 1 is repeated, obtains smaller
Chinese red flat crystal --- the porous cadmium metal organic framework material of purifying, yield is 46% (with organic ligand 9,10-
The amount of two (ethynyl pyridine) anthracenes is calculated).
Embodiment 15
Four nitric hydrate cadmiums in case study on implementation 1 are replaced with cadmium sulfate, the experiment of case 1 is repeated, obtains less Exocarpium Citri Rubrum
The porous cadmium metal organic framework material of the flat crystal of color --- purifying, yield is for 35% (with organic ligand 9, bis- (second of 10-
Alkynyl pyridine) amount of anthracene calculated).
Photoinduction ATRP is tested：(1) sample, NNUP1 crystal uses N respectively, and N '-dimethyl formamide, ethanol dry after cleaning
It is dry to weigh, take a certain amount of methyl methacrylate (MMA), N, N, N ', N ", N " '-pentamethyl-diethylenetriamine (PMDETA),
Isobutyl ethyl bromide (EBiB) and copper bromide (CuBr2) and place them into rear uniformly mixed in reaction tube.(2) by mixture
Radiation of visible light initiated polymerization at room temperature；(3) resulting polymers are precipitated in the poor solvents such as alcohol.Test result table
The bright novel metal organic framework material induces MMA atom transfer radical polymerization effects fine under simulated solar irradiation, reaction
With good controllability, NNUP1 material recoverables.
Embodiment 16
The NNUP1 sample 20mg obtained in case 1 are weighed, measure MMA 2mL (18.6mmol), EBiB13 μ L
(0.093mmol), CuBr211.6 μ L (0.056mmol) of 4.1mg (0.019mmol), PMDETA in reaction tube, and by it
Be dissolved in 0.5mL (9.62mmol) acetonitrile.When using radiation of visible light mixture reaction 8 small at room temperature.Test result shows
The novel metal organic framework material induces the effect of ATRP fine under visible light, gained polymethyl methacrylate (PMMA)
Molecular weight distributing index (PDI) be 1.11, reaction there is good controllability.
Embodiment 17
MMA, EBiB, CuBr are measured by embodiment 162, PMDETA, be simply not added with NNNUP1 samples.Experimental procedure is the same as implementation
Example 16.Test result shows that when being not added with the novel metal organic framework material ATRP reactions of MMA cannot carry out.
Embodiment 18
NNUP1, MMA, CuBr are measured by embodiment 162, PMDETA, be simply not added with EBiB.Experimental procedure is the same as embodiment 16.
Test result shows that when being not added with EBiB the ATRP reactions of MMA cannot carry out.
Embodiment 19
NNUP1, MMA, EBiB, CuBr are measured by embodiment 162, simply it is not added with PMDETA.Experimental procedure is the same as embodiment 16.
Test result shows that when being not added with PMDETA the ATRP reactions of MMA cannot carry out.
Embodiment 20
NNUP1, MMA, EBiB, PMDETA are measured by embodiment 16, is simply not added with CuBr2.Experimental procedure is the same as embodiment 16.
Test result shows be not added with CuBr2When, the PDI of PMMA is 1.79, and reaction is uncontrollable.
Embodiment 21
MMA, EBiB, PMDETA, CuBr are measured by embodiment 162, but the dosage of NNUP1 halves as 10mg.Experimental procedure
With embodiment 16.Test result shows that when the dosage of MOFs halves the PDI of PMMA is 1.18, and reaction has preferable controllable
Property.
Embodiment 22
MMA, EBiB, PMDETA, CuBr are measured by embodiment 162, but the dosage increase of NNUP1 is 30mg.Experimental procedure
With embodiment 16.Test result shows that in the dosage increase of MOFs the PDI of PMMA is 1.14, and reaction has preferable controllable
Property.
Embodiment 23
NNUP1, MMA, PMDETA, CuBr are measured by embodiment 162, but EBiB is replaced with the PMMA previously prepared,
The dosage of PMMA is 100.7mg (0.0095mmol, Mn=10600gmol-1).Experimental procedure is the same as embodiment 16.Test result table
Bright when replacing EBiB with PMMA, the PDI of the new PMMA of gained is 1.15, and reaction has preferable controllability.
Embodiment 24
NNUP1, MMA, EBiB, PMDETA, CuBr are measured by embodiment 162, experimental procedure is same
Embodiment 16, but light application time changes.When first placement 4 is small under dark condition, when illumination 4 is small, so
Circulating repetition 3 times.Test result shows that ATRP reactions cannot be carried out under dark condition, and ATRP reactions can under illumination condition
Carry out.
Embodiment 25
NNUP1, EBiB, PMDETA, CuBr are measured by embodiment 162, but replaced with n-butyl acrylate (n-BMA)
MMA, n-BMA dosage are 2.6mL (18.6mmol).Experimental procedure is the same as embodiment 16.Test result shows to replace MMA with n-BMA
When, the PDI of resulting polymers is 1.18, and reaction has good controllability.
Embodiment 26
NNUP1, EBiB, PMDETA, CuBr are measured by embodiment 162, but replaced with isobutyl acrylate (i-BMA)
MMA, i-BMA dosage are 2.7mL (18.6mmol).Experimental procedure is the same as embodiment 16.Test result shows to replace MMA with i-BMA
When, the PDI of resulting polymers is 1.16, and reaction has good controllability.
Embodiment 27
NNUP1, MMA, PMDETA, CuBr are measured by embodiment 162, but MMA is replaced with methacrylic acid, its dosage is
1.6mL(18.6mmol).Experimental procedure is the same as embodiment 16.When test result shows to replace MMA with methacrylic acid, gained polymerization
The PDI of thing is 1.14, and reaction has good controllability.
Embodiment 28
NNUP1, MMA, PMDETA, CuBr are measured by embodiment 162, but MMA is replaced with styrene (St), St dosages are
2.1mL (18.6mmol), replaces EBiB, EtBP dosages are 12uL (0.093mmol) with 2 bromopropionic acid ethyl ester (EtBP).Experiment step
Suddenly with embodiment 16.When test result shows to replace MMA with styrene (St), the PDI of resulting polymers is 1.12, and reaction has
Good controllability.
Embodiment 29
NNUP1, MMA, EBiB, PMDETA, CuBr are measured by embodiment 162, experimental procedure is same
Embodiment 16.NNUP1 is recycled after the completion of each reaction, as testing next time.NNUP1 materials are reused
After three times, still there is very high activity.Test result shows that the MOFs materials can be at least recycled 3 times.
Above content is that a further detailed description of the present invention in conjunction with specific preferred embodiments, it is impossible to is assert
The specific implementation of the present invention is confined to these explanations., can be according to the present invention for the common scientific research personnel of this area
Technical solution and inventive concept, make it is corresponding change and substitute, and performance or purposes are identical, should all be considered as the present invention's
Protection domain.
Claims (5)
1. the preparation side of the new mixture metal-organic framework materials NNUP1 of controllable free-radical polymerisation is catalyzed under a kind of visible ray
Method, it is characterised in that including step in detail below：
(1) by cadmium salt, (ethynyl pyridine) anthracenes of organic ligand 9,10- bis- and 4,4 '-biphenyl dicarboxylic acid according to 1:0.5~5:0.5
~5 molar ratio is added in 20mL vials, adds a certain amount of mixed solvent；
(2) under conditions of and then reaction kettle being placed on 65~100 DEG C, when reaction 48~144 is small after obtain new mixture metal and have
Machine framework material.
2. according to the new mixture metal-organic framework materials that controllable free-radical polymerisation is catalyzed under a kind of visible ray of claim 1
Preparation method, it is characterised in that：Selected organic solvent includes N, and the molar ratio of N '-dimethyl formamide/deionized water is
1:0.8~2.7, N, the molar ratio of N '-dimethyl acetamide/deionized water is 1:0.6~3.9, or N, N '-dimethyl formyl
Amine/N, the molar ratio of N '-dimethyl acetamide/deionized water is 1:0:5~17:0.11~55, dosage is between 1mL~4mL.
3. according to the new mixture metal-organic framework materials that controllable free-radical polymerisation is catalyzed under a kind of visible ray of claim 1
Preparation method, it is characterised in that：Selected cadmium salt is four nitric hydrate cadmiums, anhydrous caddy, acetic acid dihydrate cadmium, cadmium sulfate
Deng.
4. the new mixture metal for being catalyzed controllable free-radical polymerisation under the visible ray prepared in accordance with the method for claim 1 has
Machine framework material；
(1) the new mixture metal of controllable free-radical polymerisation is catalyzed under the visible ray prepared in accordance with the method for claim 1
Organic framework material, it is characterised in that：The molecular formula of the new mixture metal-organic framework materials of the present invention is Cd (BPEA)
(BPDC)·DMF；
(2) the new mixture metal of controllable free-radical polymerisation is catalyzed under the visible ray prepared in accordance with the method for claim 1
Organic framework material, it is characterised in that：The new mixture metal-organic framework materials of the present invention are crystallized in rhombic system, space group
For Pca21；
(3) the new mixture metal of controllable free-radical polymerisation is catalyzed under the visible ray prepared in accordance with the method for claim 1
Organic framework material, it is characterised in that：The present invention new mixture metal-organic framework materials molecular skeleton be,
5. the new mixture metal for being catalyzed controllable free-radical polymerisation under the visible ray prepared in accordance with the method for claim 1 has
Application of the machine framework material as catalyst in terms of controllable free-radical polymerisation is catalyzed.
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| CN114524946A (en) * | 2022-02-22 | 2022-05-24 | 华南理工大学 | Zirconium-based metal organic framework material and preparation method and application thereof |
| CN116162191A (en) * | 2023-04-26 | 2023-05-26 | 清华大学 | Visible light induced photocatalytic free radical polymerization method |
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| CN104402914A (en) * | 2014-10-16 | 2015-03-11 | 东北师范大学 | Zinc metal organic framework material for catalysis degradation of organic dye under visible light |
| WO2015166015A1 (en) * | 2014-04-30 | 2015-11-05 | Imec Vzw | Method of producing a thin metal-organic framework film using vapor phase precursors |
| CN105646900A (en) * | 2016-02-02 | 2016-06-08 | 遵义医学院 | Three-ligand Cd(II) metal organic framework crystal material and preparation method |
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| WO2015166015A1 (en) * | 2014-04-30 | 2015-11-05 | Imec Vzw | Method of producing a thin metal-organic framework film using vapor phase precursors |
| CN104402914A (en) * | 2014-10-16 | 2015-03-11 | 东北师范大学 | Zinc metal organic framework material for catalysis degradation of organic dye under visible light |
| CN105646900A (en) * | 2016-02-02 | 2016-06-08 | 遵义医学院 | Three-ligand Cd(II) metal organic framework crystal material and preparation method |
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| CN114524946A (en) * | 2022-02-22 | 2022-05-24 | 华南理工大学 | Zirconium-based metal organic framework material and preparation method and application thereof |
| CN116162191A (en) * | 2023-04-26 | 2023-05-26 | 清华大学 | Visible light induced photocatalytic free radical polymerization method |
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